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CommunicationMarch 10, 2016

Interplay of Orbital and Relativistic Effects in Bismuth Oxyhalides: BiOF, BiOCl, BiOBr, and BiOI
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Chemistry of Materials

Cite this: Chem. Mater. 2016, 28, 7, 1980–1984

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https://doi.org/10.1021/acs.chemmater.6b00349

Published March 10, 2016

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The optoelectronic properties of bismuth oxyhalides have led to their utility in applications such as pigments in the cosmetics industry, (1, 2) pharmaceuticals, (3, 4) phosphors, (5) gas sensors, (6) and catalysis. (7, 8) Over the past decade, interest in this family of materials has rapidly increased, fuelled by reports of their excellent photocatalytic activity. (9-16) They have been studied as stand-alone photocatalysts, (9, 10, 17) quaternary alloys, (18, 19) and interfaced with other photocatalytically active materials. (20-22) To date, however, an understanding of the chemical trends underpinning these successes is lacking.

The BiOX series, shown in Figure 1, crystallize in the tetragonal Matlockite structure, (23, 24) which can be considered the simplest form of the Sillén-type structure and is commonly expressed as [M₂O₂][X_m]. (25) The crystal lattice consists of fluorite-like [M₂O₂] layers sandwiched between double halide [X_m] layers, to form [X–Bi–O–Bi–X] sheets, stacked in the [001] direction, with the structure held together by nonbonding van der Waals interactions along the [001] direction. It has been proposed that this structure type imparts an internal static electric field between the [M₂O₂]²⁺ and double [X]⁻ slab along the [001] direction, which aids efficient separation of the photogenerated electron–hole pairs. (9, 10, 26, 27)

Figure 1. Crystal structure of the BiOX systems (space group P4/*nmm*, D_4h symmetry) with stoichiometric X–Bi–O–Bi–X bilayers stacked along the c axis.

In this communication, we investigate the BiOX (X = F, Cl, Br, and I) series using hybrid density functional theory with explicit treatment of spin–orbit coupling effects and dispersion interactions. First, we resolve the band gap trends, where values between 3.5–3.6 eV, 2.9–3.4 eV, 2.3–2.9 eV, and 1.8–2.1 eV for BiOF, BiOCl, BiOBr, and BiOI, had been reported. (9, 11, 12, 28-32) We separate the roles of relativistic and chemical effects in determining the magnitude of the gaps and also the absolute band energies, which provides guidance for designing tailored photocatalysts.

First-principles calculations were performed in the framework of density functional theory (DFT). Special attention was paid to electron–electron interactions (using the screened hybrid HSE06 functional), (33, 34) relativistic effects (using scalar relativistic PAW pseudopotentials (35, 36) and spin–orbit coupling, SOC), and dispersion interactions (the DFT-D3 correction (37, 38)). All solid-state calculations were performed in a plane-wave basis set using the code VASP. (39, 40)

Complete structural optimizations (forces < 0.01 eV Å^–1) were performed at a series of volumes in order to calculate the equilibrium lattice parameters. Convergence with respect to k-point sampling and plane wave energy was checked, with a cutoff of 520 eV and a k-point density of 0.04 k Å found to be sufficient. To align the electronic band energies to the vacuum level, a surface–slab model (15 Å vacuum spacing) was constructed and the corresponding electrostatic potential averaged along the c-direction, using the MacroDensity package. (41-43) The (100) surface was chosen as it is a nonpolar termination that results in minimal bond cleavage and does not produce undesirable surface states.

The predicted lattice parameters for the BiOX series are shown in Table 1. The results are in good agreement with previous experimental measurements (within 1%), (11, 23, 24) taking into account that the experimental data is mostly for room temperature. The inclusion of the nonlocal dispersion correction was vital for achieving an accurate equilibrium geometry, especially as we descend down the halide group, as shown in Table S1 of the Supporting Information. Without this interaction, the error in the c parameter can grow to as much as 1 Å.

Table 1. Calculated Structural and Electronic Properties of the BiOX Series^a

material	a	c	E_g	IP	EA
BiOF	3.72 (−1.0%)	6.20 (−0.5%)	4.18	8.23	3.87
BiOCl	3.87 (−0.5%)	7.42 (+0.9%)	3.37	7.94	4.35
BiOBr	3.90 (−0.5%)	8.14 (−0.5%)	2.82	7.55	4.65
BiOI	3.98 (−0.3%)	9.15 (0.0%)	2.00	7.03	5.03

All lattice vectors are given in Å (% error with respect to room temperature diffraction measurements in parentheses), with the band gap, ionisation potential (IP), and electron affinity (EA) in eV.

Similar to the hybrid halide perovskites (44-46) and topological insulators (47, 48) which are also composed of atoms with high atomic number, it is expected that relativistic effects should play a large role in determining the electronic structure of these materials. The band structures of the BiOX series with and without the explicit treatment of SOC are plotted in Figure 2a–d. The inclusion of SOC was found to result in a net band gap reduction independent of chemical composition, with the conduction band minimum (CBM) of BiOF, BiOCl, BiOBr, and BiOI lowered by 0.39, 0.24, 0.24, and 0.22 eV, respectively. The valence band maximum (VBM) is less affected by SOC effects, with only BiOI experiencing a significant upward shift of 0.11 eV, due to larger relativistic effect on I states as group 17 is descended. As such, the effect of SOC is insufficient in explaining the trend in band gap across the series.

Figure 2. Scalar relativistic (dashed lines) and fully relativistic (black lines) electronic band structures of the BiOX series with the hybrid HSE06 functional. The highest occupied state (including spin–orbit coupling) is set to 0 eV.

Instead, analysis of the total and partial (ion decomposed) density of states for the BiOX series, shown in Figure 3, is instructive in explaining the trend in optical response seen in experiment. For BiOF, the top of the valence band is dominated by O 2p states, with the F 2p states found at higher binding energies. As the halide anion changes upon moving down group 17, the contribution of the halide p states to the VBM increases, ultimately dominating the VBM in BiOI. In all cases, the conduction band is dominated by Bi p states. It is therefore clear that the valence band composition dictates the band gap reduction down the series, in line with the binding energy of the halide p orbitals. The Bi 6s states are mainly found at the bottom of the valence band but additionally provide a small contribution toward the top of the valence band. Consistent with the revised lone pair theory, (49-51) the orbital overlap * of Bi 6s* with the O 2p and halide p states is not sufficient to warrant a structural distortion, meaning the Bi is perfectly octahedral in the Matlockite structure.

Figure 3. Fully relativistic (HSE06+SOC) electronic density of states (DOS), including projections onto ion-centered atomic orbitals (PEDOS). The highest occupied state is set to 0 eV.

From the band structures shown in Figure 2 it can be seen that the fundamental band gaps across the BiOX series are indirect. The CBM of BiOF, BiOCl, and BiOBr appears at the Z point, with the VBM positioned between Z → R. For BiOI, the CBM is situated between Γ → R, and the VBM is again situated between Z → R. The fundamental indirect band gaps are 4.18, 3.37, 2.82, and 2.00 eV for BiOF, BiOCl, BiOBr, and BiOI, respectively, which, in all cases except BiOF, are in excellent agreement with experimental measurements. (12) The calculated hole effective masses are relatively large; however, they are considerably smaller in BiOCl and BiOBr (0.8 m_e and 0.7 m_e) than in BiOF and BiOI (12.5 m_e and 1.9 m_e). The dispersion of the conduction band is noticeably less along Z → Γ (in the [001] direction) compared to Z → R ([010]), which is to be expected as Z → Γ spans across the [X–Bi–O–Bi–X] sheets, whereas Z → R is in the plane of the layers. This is reflected in the electron effective masses of BiOF, BiOCl, and BiOBr, which are significantly lower in the Z → Γ direction (0.5 m_e, 0.3 m_e, and 0.3 m_e, respectively) than along Z → R (1.0 m_e, 2.4 m_e, and 0.6 m_e, respectively).

To understand the effect of varying the halide ion on the fundamental band alignments of the BiOX series, we have plotted the valence band alignment of these materials using the slab model, (52) with the results shown in Figure 4. As expected based on the relative energy levels of the halide p-orbitals, the ionization potential (IP) of the BiOX series gets smaller as we descend down group 17. The Bi-based conduction band is also lowered on descending group 17, which can be rationalized due to the Bi p states experiencing a different Madelung potential as the ionic radius of the halide increases on moving down the group.

Figure 4. Calculated valence band alignment of the BiOX series (HSE including spin–orbit coupling). The vacuum level was aligned to the (001) surface in a slab calculation with a vacuum thickness of 15 Å. The electrostatic potentials were aligned and checked using the package MacroDensity. (53)

The alignment helps to explain some of the puzzling experimental observations in the literature. The BiOX series have been reported to display p-type conductivity (15) but unusually to also exhibit n-type behavior. (54) Our calculated electron affinity (EA) for BiOI of 5.2 eV is consistent with the EAs exhibited by many excellent n-type materials. (55-57) The larger EA of BiOI also results in a reduced overpotential for O₂/oxygen anion splitting and can explain why BiOI is not as active for the degradation of rhodamine B than BiOBr and BiOCl. (12, 58) In addition alloys between BiOCl/BiOBr (59) and BiOBr/BiOI (60) have been demonstrated to outperform the individual materials, and this can be rationalized by the ability to tailor the band edges in order to obtain an enhanced electronic alignment in the alloys.

We have demonstrated the key role of the halide anion in determining the electronic structure and properties of the bismuth oxyhalide series. The range of functionality will be further extended by also changing the chalcogenide anion, as suggested by recent reports of topological electronic states and relativistic band splitting in the bismuth tellurihalides. As such, this extended family of compounds merits further investigation.

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.6b00349.

Comparison of lattice parameters and bond lengths calculated with and without Grimme’s D3 dispersion correction (PDF)

cm6b00349_si_001.pdf (140.31 kb)

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Author Information

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Corresponding Author
- David O. Scanlon - Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom; Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom; Email: [email protected]
Authors
- Alex M. Ganose - Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom; Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom
- Madeleine Cuff - Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom
- Keith T. Butler - Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
- Aron Walsh - Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom; Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, Seoul 120-749, Korea
Notes
The authors declare no competing financial interest.

Acknowledgment

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This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk), via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202) and the UCL Legion HPC Facility (Legion@UCL). The work at UCL was supported by EPSRC (EP/N01572X/1). The work at Bath was supported by the ERC (Grant no. 277757) and the EPSRC (Grant no. EP/K016288/1, EP/L017792/1, and EP/M009580/1). D.O.S. acknowledges support from the SUPERSOLAR Solar Energy Hub (EP/J017361/1) for the provision of a flexible funding call award. A.M.G. acknowledges Diamond Light Source for the cosponsorship of a studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1). A.W. and D.O.S. acknowledge membership of the Materials Design Network.

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With careful rational optimization and substantial simplification of the syntheses of the recently reported alloys BiO(ClxBr1-x), the authors fabricated, via a very simple procedure and at room temp., a unique visible-light-driven photocatalyst with excellent activity. The alloy BiOCl0.875Br0.125 totally decompd. 15 mg/L aq. Rhodamine B soln. within 120 s upon irradn. with visible light (λ > 422 nm). The transparent substrate acetophenone was also swiftly destroyed under the above conditions. The catalyst maintained partial activity even after switching off the light source. Initial mechanistic studies clearly suggest that the mode of action of these materials is fundamentally different from previously reported photocatalytic mechanisms. Evidently, the putative mol. mechanism does not engage dye photosensitization or oxygen radicals.
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Zhang, H.; Liu, L.; Zhou, Z. Towards Better Photocatalysts: First-Principles Studies of the Alloying Effects on the Photocatalytic Activities of Bismuth Oxyhalides Under Visible Light Phys. Chem. Chem. Phys. 2012, 14, 1286– 1292 DOI: 10.1039/C1CP23516H
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Towards better photocatalysts: first-principles studies of the alloying effects on the photocatalytic activities of bismuth oxyhalides under visible light
Zhang, Haijun; Liu, Lu; Zhou, Zhen
Physical Chemistry Chemical Physics (2012), 14 (3), 1286-1292CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
Via d. functional theory computations, we studied the photocatalytic activities of pure and alloyed Bi oxyhalides (BiOXs). The dipole moments of the majority of pure and alloyed BiOXs are larger than 2.00 Debye, which can ensure their high photocatalytic efficiencies. Both the redox potentials of the photon-induced holes and the band gaps increase with an increasing content of lighter halogen atoms in the BiOXs, which competitively affects the photocatalytic efficiency. The hole mobility decreases a lot due to the hybridization of the halogen np states, while the electron mobility is not affected by such hybridization. Therefore, the alloying effect in BiOXs brings about a substantially lower electron-hole recombination rate and, accordingly, a much higher photocatalytic efficiency. Also probably O vacancies, which are energetically more favorable in alloyed BiOXs, could act as capture centers for excited electrons and, consequently, improve the sepn. of the electron-hole pairs. The findings present a reasonable explanation for the recent exptl. reports and provide some guidance for the design of alloyed BiOX photocatalysts.
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Li, J.; Yu, Y.; Zhang, L. Bismuth Oxyhalide Nanomaterials: Layered Structures Meet Photocatalysis Nanoscale 2014, 6, 8473– 8488 DOI: 10.1039/C4NR02553A
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Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis
Li, Jie; Yu, Ying; Zhang, Lizhi
Nanoscale (2014), 6 (15), 8473-8488CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
A review. In recent years, layered bismuth oxyhalide nanomaterials have received more and more interest as promising photocatalysts because their unique layered structures endow them with fascinating physicochem. properties; thus, they have great potential photocatalytic applications for environment remediation and energy harvesting. In this article, we explore the synthesis strategies and growth mechanisms of layered bismuth oxyhalide nanomaterials, and propose design principles of tailoring a layered configuration to control the nanoarchitectures for high efficient photocatalysis. Subsequently, we focus on their layered structure dependent properties, including pH-related crystal facet exposure and phase transformation, facet-dependent photoactivity and mol. oxygen activation pathways, so as to clarify the origin of the layered structure dependent photoreactivity. Furthermore, we summarize various strategies for modulating the compn. and arrangement of layered structures to enhance the photoactivity of nanostructured bismuth oxyhalides via internal elec. field tuning, dehalogenation effect, surface functionalization, doping, plasmon modification, and heterojunction construction, which may offer efficient guidance for the design and construction of high-performance bismuth oxyhalide-based photocatalysis systems. Finally, we highlight some crucial issues in engineering the layered-structure mediated properties of bismuth oxyhalide photocatalysts and provide tentative suggestions for future research on increasing their photocatalytic performance.
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Shamaila, S.; Sajjad, A. K. L.; Chen, F.; Zhang, J. WO₃ /BiOCl, a novel heterojunction as visible light photocatalyst J. Colloid Interface Sci. 2011, 356, 465– 472 DOI: 10.1016/j.jcis.2011.01.015
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Shenawi-Khalil, S.; Uvarov, V.; Fronton, S.; Popov, I.; Sasson, Y. A Novel Heterojunc-tion BiOBr/Bismuth Oxyhydrate Photocatalyst with Highly Enhanced Visible Light Photocatalytic Properties J. Phys. Chem. C 2012, 116, 11004– 11012 DOI: 10.1021/jp3009964
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Keramidas, K.; Voutsas, G.; Rentzeperis, P. The Crystal Structure of BiOCl Z. Kristallogr. - Cryst. Mater. 1993, 205, 35– 40 DOI: 10.1524/zkri.1993.205.12.35
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The crystal structure of bismuth oxychloride (BiOCl)
Keramidas, K. G.; Voutsas, G. P.; Rentzeperis, P. I.
Zeitschrift fuer Kristallographie (1993), 205 (1), 35-40CODEN: ZEKRDZ; ISSN:0044-2968.
The crystal structure of prepd. BiOCl was redetd. with 3570 obsd. reflections of which 174 were unique measured on a computer controlled Philips PW 1100 single crystal diffractometer. The structure belongs to the tetragonal space group P4/nmm and the cell consts., obtained by a least-squares calcn. from direct Θ-value measurements on the diffractometer, are a 3.8870(5) and c 7.3540(5) Å. The positional and thermal parameters, with anisotropic temp. factors, were refined by full-matrix least-squares calcns. to a final R = 9.17%. Each Bi atom is 8-coordinate by 4 O and 4 Cl atoms at distances of 2.316 Å and 3.059 Å, resp., thus forming a decahedron. The faces of the decahedron are 2 rectangles (O-O-O-O and Cl-Cl-Cl-Cl) with sides 3.487 Å and 8 isosceles triangles (4 O-Cl-O and 4 Cl-O-Cl) with side O-Cl 3.249 Å and O-O or Cl-Cl 3.487 Å. The decahedra are linked to each other by a common O-Cl edge along the a and b axes in infinite layers.
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Bannister, F.; Hey, M. The Crystal Structure Of The Bismuth Oxyhalides Mineral. Mag. 1935, 24, 49– 58 DOI: 10.1180/minmag.1935.024.149.01
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The crystal structure of the bismuth oxyhalides
Bannister, F. A.
Mineralogical Magazine and Journal of the Mineralogical Society (1876-1968) (1935), 24 (), 49-58CODEN: MIASA6; ISSN:0369-0148.
BiOCl, BiOBr and BiOI were prepd. by diffusion methods. Laue photographs indicate true tetragonal symmetry. Rotation and powder x-ray photographs indicate crystal structures of the matlockite type. The at. positions are Bi, 00u, 1/2 1/2‾u; X(Cl, Br, I), 00v, 1/2 1/2 ‾v; 0 1/2 00, 0 1/2 0. Unit cell dimensions are, BiOCl a = 3.89, c = 7.37 A.; BiOBr, a = 3.92, c = 8.11 A.; BiOI, a = 4.01, c = 9.14 A. The x-ray data for bismoclite and daubreeite are discussed.
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Kusainova, A. M.; Zhou, W.; Irvine, J. T.; Lightfoot, P. Layered Intergrowth Phases Bi₄MO₈X (X= Cl, M= Ta and X= Br, M= Ta or Nb): Structural and Electrophysical Characterization J. Solid State Chem. 2002, 166, 148– 157 DOI: 10.1006/jssc.2002.9572
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Layered intergrowth phases Bi4MO8X (X = Cl, M = Ta, and X = Br, M = Ta or Nb): structural and electrophysical characterization
Kusainova, Ardak M.; Zhou, Wuzong; Irvine, John T. S.; Lightfoot, Philip
Journal of Solid State Chemistry (2002), 166 (1), 148-157CODEN: JSSCBI; ISSN:0022-4596. (Elsevier Science)
The high-temp. structural behavior of the layered inter-growth phase Bi4TaO8Cl, belonging to the Sillen-Aurivillius family, has been studied by powder neutron diffraction. This material is ferroelec., space group P21cn, at TC < 640 K. An order-disorder transition to centrosym. space group Pmcn is found around 640 K, which involves disordering of TaO6 octahedral tilts. A second phase transition, of a first-order nature, to space group P4/mmm occurs at a temp. of ∼1038 K. The crystal structures of the bromide analogs Bi4MO8Br (M = Nb, Ta) have also been detd. at room temp.; both are isomorphous with Bi4TaO8Cl and exhibit maxima in dielec. const. at temps. of approx. 588 and 450 K, resp.
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Ai, Z.; Ho, W.; Lee, S.; Zhang, L. Efficient Photocatalytic Removal of NO in Indoor Air with Hierarchical Bismuth Oxybromide Nanoplate Microspheres Under Visible Light Environ. Sci. Technol. 2009, 43, 4143– 4150 DOI: 10.1021/es9004366
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Efficient Photocatalytic Removal of NO in Indoor Air with Hierarchical Bismuth Oxybromide Nanoplate Microspheres under Visible Light
Ai, Zhihui; Ho, Wingkei; Lee, Shuncheng; Zhang, Lizhi
Environmental Science & Technology (2009), 43 (11), 4143-4150CODEN: ESTHAG; ISSN:0013-936X. (American Chemical Society)
Hierarchical bismuth oxybromide (BiOBr) nano-plate micro-spheres were used to remove NO from indoor air under visible light irradn. BiOBr micro-spheres were synthesized with a non-aq., sol-gel method using bismuth nitrate and cetyltrimethyl ammonium bromide as precursors. For the NO degrdn. under visible light irradn. (λ >420 nm) at 400 part-per-billion concn., a typical concn. for indoor air, these non-aq., sol-gel synthesized hierarchical BiOBr micro-spheres exhibited superior photocatalytic activity to chem. pptn.-synthesized counterpart BiOBr bulk powder and Degussa TiO2 P25 and C-doped TiO2. The excellent catalytic activity and long-term activity of non-aq., sol-gel synthesized BiOBr micro-spheres were attributed to their special hierarchical structure, favorable for diffusion of NO oxidn. intermediate compds. and final products. Ion chromatog. results confirmed HNO3 was produced on the BiOBr micro-sphere surface during gas-phase NO photooxidn. Results suggested that non-aq., sol-gel synthesized BiOBr nano-plate micro-spheres are promising photocatalytic material for indoor air purifn.
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Henle, J.; Simon, P.; Frenzel, A.; Scholz, S.; Kaskel, S. Nanosized BiOX (X= Cl, Br, I) Particles Synthesized in Reverse Microemulsions Chem. Mater. 2007, 19, 366– 373 DOI: 10.1021/cm061671k
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Wang, W.; Huang, F.; Lin, X. xBiOI—(1–x)BiOCl as efficient visible-light-driven photocatalysts Scr. Mater. 2007, 56, 669– 672 DOI: 10.1016/j.scriptamat.2006.12.023
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xBiOI-(1 - x)BiOCl as efficient visible-light-driven photocatalysts
Wang, Wendeng; Huang, Fuqiang; Lin, Xinping
Scripta Materialia (2007), 56 (8), 669-672CODEN: SCMAF7; ISSN:1359-6462. (Elsevier Ltd.)
A new class of oxyhalide photocatalysts, xBiOI-(1 - x)BiOCl, were prepd. by a soft chem. method. The samples with x = 0.2-1.0 have intense absorptions in the visible light region and the optical band gaps are in the range 1.92-2.31 eV. They possess high photocatalytic activities under visible light irradn. for the degrdn. of methyl orange. This high photocatalytic activity is in close relation with the deep valance band edge position and the internal elec. fields between [Bi2O2] slabs and halogen anionic slabs.
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Wang, W.; Huang, F.; Lin, X.; Yang, J. Visible-Light-Responsive Photocatalysts xBiOBr—(1–x)BiOI Catal. Commun. 2008, 9, 8– 12 DOI: 10.1016/j.catcom.2007.05.014
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Visible-light-responsive photocatalysts xBiOBr-(1-x)BiOI
Wang, Wendeng; Huang, Fuqiang; Lin, Xinping; Yang, Jianhua
Catalysis Communications (2007), 9 (1), 8-12CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
A new class of oxyhalide photocatalysts xBiOBr-(1-x)BiOI prepd. by a soft chem. method were characterized by X-ray diffraction and UV-Vis diffuse reflectance spectra. They are all visible-light-responsive materials with the bandgaps ranging from 1.92 to 2.91 eV. Methyl orange (MO) photocatalytic degrdn. expts. showed that BiOBr possessed a higher photocatalytic activity than P25 (TiO2) under UV illumination and iodine-modified BiOBr exhibited high photocatalytic activities under visible-light irradn. The high photocatalytic activity is in close relation with the deep valance band edge position and the internal elec. fields between [Bi2O2] slabs and halogen anionic slabs.
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Chen, L.; Yin, S.-F.; Huang, R.; Zhou, Y.; Luo, S.-L.; Au, C.-T. Facile Synthesis of BiOCl Nano-Flowers of Narrow Band Gap and their Visible-Light-Induced Photocatalytic Property Catal. Commun. 2012, 23, 54– 57 DOI: 10.1016/j.catcom.2012.03.001
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Facile synthesis of BiOCl nano-flowers of narrow band gap and their visible-light-induced photocatalytic property
Chen, Lang; Yin, Shuang-Feng; Huang, Rui; Zhou, Yan; Luo, Sheng-Lian; Au, Chak-Tong
Catalysis Communications (2012), 23 (), 54-57CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
Novel nanostructured flower-like bismuth oxychloride (BiOCl) has been fast synthesized by a simple method in the presence of nitric acid and L-Lysine. The BiOCl nano-flowers, with a narrow band gap (2.87 eV), show excellent photocatalytic activity in the degrdn. of Rh-B dye under visible light (λ ≥ 435 nm), much higher than those of the photocatalysts ever reported in the literatures.
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Su, W.; Wang, J.; Huang, Y.; Wang, W.; Wu, L.; Wang, X.; Liu, P. Synthesis and Catalytic Performances of a Novel Photocatalyst BiOF Scr. Mater. 2010, 62, 345– 348 DOI: 10.1016/j.scriptamat.2009.10.039
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Synthesis and catalytic performances of a novel photocatalyst BiOF
Su, Wenyue; Wang, Jian; Huang, Yingxing; Wang, Wanjun; Wu, Ling; Wang, Xu Xu; Liu, Ping
Scripta Materialia (2010), 62 (6), 345-348CODEN: SCMAF7; ISSN:1359-6462. (Elsevier Ltd.)
A novel oxyhalide photocatalyst BiOF was prepd. by pptn. and subsequent heat treatment. The influence of calcination temp. on the synthesis of BiOF was investigated. Interestingly, the as-prepd. BiOF exhibits high photocatalytic performance in the degrdn. of universal org. pollutants. The high photocatalytic activity is closely related to the internal elec. fields between [Bi2O2] slabs and fluorine anionic slabs.
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Deng, H.; Wang, J.; Peng, Q.; Wang, X.; Li, Y. Controlled Hydrothermal Synthesis of Bismuth Oxyhalide Nanobelts and Nanotubes Chem. - Eur. J. 2005, 11, 6519– 6524 DOI: 10.1002/chem.200500540
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Controlled hydrothermal synthesis of bismuth oxyhalide nanobelts and nanotubes
Deng, Hong; Wang, Junwei; Peng, Qing; Wang, Xun; Li, Yadong
Chemistry - A European Journal (2005), 11 (22), 6519-6524CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
Ternary Bi oxyhalide cryst. nanobelts (such as Bi24O31Br10, Bi3O4Br, Bi12O17Br2, BiOCl, and Bi24O31Cl10) and nanotubes (such as Bi24O31Br10) were synthesized by using convenient hydrothermal methods. The compn. and morphologies of the Bi oxyhalides could be controlled by adjusting some growth parameters, including reaction pH, time, and temp. All the nanostructures were characterized by using various methods including x-ray diffraction, TEM, high-resoln. TEM, electron diffraction, and energy-dispersive x-ray anal. The possible reaction mechanism and growth of the crystals are discussed based on the exptl. results.
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Heyd, S.; Scuseria, G. E.; Ernzerhof, M. Hybrid Functionals Based on a Screened Coulomb Potential J. Chem. Phys. 2003, 118, 8207– 8215 DOI: 10.1063/1.1564060
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Hybrid functionals based on a screened Coulomb potential
Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
Journal of Chemical Physics (2003), 118 (18), 8207-8215CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
Hybrid d. functionals are very successful in describing a wide range of mol. properties accurately. In large mols. and solids, however, calcg. the exact (Hartree-Fock) exchange is computationally expensive, esp. for systems with metallic characteristics. In the present work, we develop a new hybrid d. functional based on a screened Coulomb potential for the exchange interaction which circumvents this bottleneck. The results obtained for structural and thermodn. properties of mols. are comparable in quality to the most widely used hybrid functionals. In addn., we present results of periodic boundary condition calcns. for both semiconducting and metallic single wall carbon nanotubes. Using a screened Coulomb potential for Hartree-Fock exchange enables fast and accurate hybrid calcns., even of usually difficult metallic systems. The high accuracy of the new screened Coulomb potential hybrid, combined with its computational advantages, makes it widely applicable to large mols. and periodic systems.
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Krukau, A. V.; Vydrov, O. A.; Izmaylov, A. F.; Scuseria, G. E. Influence of the Exchange Screening Parameter on the Performance Of Screened Hybrid Functionals J. Chem. Phys. 2006, 125, 224106 DOI: 10.1063/1.2404663
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Influence of the exchange screening parameter on the performance of screened hybrid functionals
Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.; Scuseria, Gustavo E.
Journal of Chemical Physics (2006), 125 (22), 224106/1-224106/5CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
This work reexamines the effect of the exchange screening parameter ω on the performance of the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional. We show that variation of the screening parameter influences solid band gaps the most. Other properties such as mol. thermochem. or lattice consts. of solids change little with ω. We recommend a new version of HSE with the screening parameter ω = 0.11 bohr-1 for further use. Compared to the original implementation, the new parametrization yields better thermochem. results and preserves the good accuracy for band gaps and lattice consts. in solids.
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Blöchl, P. E. Projector Augmented-Wave Method Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 50, 17953 DOI: 10.1103/PhysRevB.50.17953
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Projector augmented-wave method
Blochl
Physical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.
There is no expanded citation for this reference.
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Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented Wave Method Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 1758– 1775 DOI: 10.1103/PhysRevB.59.1758
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From ultrasoft pseudopotentials to the projector augmented-wave method
Kresse, G.; Joubert, D.
Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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Grimme, S. Accurate Description of van der Waals Complexes by Density Funcitonal Theory Including Empirical Corrections J. Comput. Chem. 2004, 25, 1463– 1473 DOI: 10.1002/jcc.20078
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Savory, C. N.; Palgrave, R. G.; Bronstein, H.; Scanlon, D. O. Spatial Electron-hole Separation in a One Dimensional Hybrid Organic–Inorganic Lead Iodide Sci. Rep. 2016, 6, 20626 DOI: 10.1038/srep20626
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Spatial Electron-hole Separation in a One Dimensional Hybrid Organic-Inorganic Lead Iodide
Savory, Christopher N.; Palgrave, Robert G.; Bronstein, Hugo; Scanlon, David O.
Scientific Reports (2016), 6 (), 20626CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
The increasing efficiency of the inorg.-org. hybrid halides has revolutionised photovoltaic research. Despite this rapid progress, the significant issues of poor stability and toxicity have yet to be suitably overcome. In this article, we use D. Functional Theory to examine (Pb2I6)·(H2DPNDI)·(H2O)·(NMP), an alternative lead-based hybrid inorg.-org. solar absorber based on a photoactive org. cation. Our results demonstrate that optical properties suitable for photovoltaic applications, in addn. to spatial electron-hole sepn., are possible but efficient charge transport may be a limiting factor.
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Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for ab initio Total-Energy Calculations Using a Plane-wave Basis Set Phys. Rev. B: Condens. Matter Mater. Phys. 1996, 54, 11169– 11186 DOI: 10.1103/PhysRevB.54.11169
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Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
Kresse, G.; Furthmueller, J.
Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
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Kresse, G.; Hafner, J. Ab Initio Molecular-Dynamics Simulation of the Liquid-Metal–Amorphous-Semiconductor Transition in Germanium Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 49, 14251– 14271 DOI: 10.1103/PhysRevB.49.14251
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Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium
Kresse, G.; Hafner, J.
Physical Review B: Condensed Matter and Materials Physics (1994), 49 (20), 14251-69CODEN: PRBMDO; ISSN:0163-1829.
The authors present ab initio quantum-mech. mol.-dynamics simulations of the liq.-metal-amorphous-semiconductor transition in Ge. The simulations are based on (a) finite-temp. d.-functional theory of the 1-electron states, (b) exact energy minimization and hence calcn. of the exact Hellmann-Feynman forces after each mol.-dynamics step using preconditioned conjugate-gradient techniques, (c) accurate nonlocal pseudopotentials, and (d) Nose' dynamics for generating a canonical ensemble. This method gives perfect control of the adiabaticity of the electron-ion ensemble and allows the authors to perform simulations over >30 ps. The computer-generated ensemble describes the structural, dynamic, and electronic properties of liq. and amorphous Ge in very good agreement with expt.. The simulation allows the authors to study in detail the changes in the structure-property relation through the metal-semiconductor transition. The authors report a detailed anal. of the local structural properties and their changes induced by an annealing process. The geometrical, bounding, and spectral properties of defects in the disordered tetrahedral network are studied and compared with expt.
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Walsh, A.; Butler, K. T. Prediction of Electron Energies in Metal Oxides Acc. Chem. Res. 2014, 47, 364– 372 DOI: 10.1021/ar400115x
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Prediction of Electron Energies in Metal Oxides
Walsh, Aron; Butler, Keith T.
Accounts of Chemical Research (2014), 47 (2), 364-372CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
A review. The ability to predict energy levels in metal oxides is paramount to developing useful materials, such as in the development of water photolysis catalysts and efficient photovoltaic cells. The binding energy of electrons in materials encompasses a wealth of information concerning their physicochem. The energies control the optical and elec. properties, dictating for which kinds of chem. and physics a particular material is useful. Scientists have developed theories and models for electron energies in a variety of chem. systems over the past century. However, the prediction of quant. energy levels in new materials remains a major challenge. This issue is of particular importance in metal oxide research, where novel chemistries have opened the possibility of a wide range of tailored systems with applications in important fields including light-emitting diodes, energy efficient glasses, and solar cells. In this Account, we discuss the application of atomistic modeling techniques, covering the spectrum from classical to quantum descriptions, to explore the alignment of electron energies between materials. We present a no. of paradigmatic examples, including a series of oxides (ZnO, In2O3, and Cu2O). Such calcns. allow the detn. of a "band alignment diagram" between different materials and can facilitate the prediction of the optimal chem. compn. of an oxide for use in a given application. Throughout this Account, we consider direct computational solns. in the context of heuristic models, which are used to relate the fundamental theory to exptl. observations. We review a no. of techniques that have been commonly applied in the study of electron energies in solids. These models have arisen from different answers to the same basic question, coming from solid-state chem. and physics perspectives. We highlight common factors, as well as providing a crit. appraisal of the strengths and weaknesses of each, emphasizing the difficulties in translating concepts from mol. to solid-state systems. Finally, we stress the need for a universal description of the alignment of band energies for materials design from first-principles. By demonstrating the applicability and challenges of using theory to calc. the relevant quantities, as well as impressing the necessity of a clarification and unification of the descriptions, we hope to provide a stimulus for the continued development of this field.
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Ganose, A. M.; Butler, K. T.; Walsh, A.; Scanlon, D. O. Relativistic Electronic Struc-ture and Band Alignment of BiSI and BiSeI: Candidate Photovoltaic Materials J. Mater. Chem. A 2016, 4, 2060– 2068 DOI: 10.1039/C5TA09612J
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Relativistic electronic structure and band alignment of BiSI and BiSeI: candidate photovoltaic materials
Ganose, Alex M.; Butler, Keith T.; Walsh, Aron; Scanlon, David O.
Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (6), 2060-2068CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
Bi-based solar absorbers are of interest due to similarities in the chem. properties of Bi halides and the exceptionally efficient Pb halide hybrid perovskites. While they both experience the same beneficial relativistic effects acting to increase the width of the conduction band, Bi is non-toxic and non-bioaccumulating, meaning the impact of environmental contamination is greatly reduced. We use hybrid d. functional theory, with the addn. of spin orbit coupling, to examine 2 candidate bismuth contg. photovoltaic absorbers, BiSI and BiSeI, and show that they possess electronic structures suitable for photovoltaic applications. We calc. band alignments against commonly used hole transporting and buffer layers, which indicate band misalignments are likely to be the source of the poor efficiencies reported for devices contg. these materials. We suggest alternative device architectures expected to result in improved power conversion efficiencies.
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Brgoch, J.; Lehner, A. J.; Chabinyc, M.; Seshadri, R. Ab Initio Calculations of Band Gaps and Absolute Band Positions of Polymorphs of RbPbI₃ and CsPbI₃: Implications for Main-Group Halide Perovskite Photovoltaics J. Phys. Chem. C 2014, 118, 27721– 27727 DOI: 10.1021/jp508880y
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Ab Initio Calculations of Band Gaps and Absolute Band Positions of Polymorphs of RbPbI3 and CsPbI3: Implications for Main-Group Halide Perovskite Photovoltaics
Brgoch, Jakoah; Lehner, Anna J.; Chabinyc, Michael; Seshadri, Ram
Journal of Physical Chemistry C (2014), 118 (48), 27721-27727CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
Lead halide perovskites have attracted great interest because of rapid improvements in the efficiency of photovoltaics based on these materials. To predict new related functional materials, a good understanding of the correlations between crystal chem., electronic structure, and optoelectronic properties is required. Describing the electronic structure of these materials using d. functional theory provides a choice of exchange-correlation functionals, including hybrid functionals, and inclusion of spin-orbit coupling, which is crit. for the correct description of band gap and abs. band positions (ionization energy). Here, various computational schemes that employ different choices of exchange-correlation and hybrid functionals, and include or exclude spin-orbit coupling were implemented to examine these effects. Using PbI2 as an initial structural model, it is found that std. exchange correlation functionals (PBE) in conjunction with spin-orbit coupling suffice to locate ionization energies efficiently through the use of slab calcns. Band gaps require the use of hybrid functionals carried out on single unit cells and spin-orbit coupling. Polymorphs of alkali metal lead halides, APbI3 (A = Rb, Cs) are examd. in the cubic perovskite structure and the reduced dimensional NH4CdCl3/Sn2S3 structure with quasi-two-dimensional connectivity. The somewhat elevated Born effective charges computed for these structures suggest that while the Pb2+ 6s lone-pairs are stereochem. inert, the presence of proximal instabilities could have implications for the functional properties of these materials.
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Brivio, F.; Butler, K. T.; Walsh, A.; Van Schilfgaarde, M. Relativistic Quasiparticle Self-Consistent Electronic Structure of Hybrid Halide Perovskite Photovoltaic Absorbers Phys. Rev. B: Condens. Matter Mater. Phys. 2014, 89, 155204 DOI: 10.1103/PhysRevB.89.155204
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Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers
Brivio, Federico; Butler, Keith T.; Walsh, Aron; van Schilfgaarde, Mark
Physical Review B: Condensed Matter and Materials Physics (2014), 89 (15), 155204/1-155204/6CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
Solar cells based on a light absorbing layer of the organometal halide perovskite CH3NH3PbI3 have recently surpassed 15% conversion efficiency, though how these materials work remains largely unknown. We analyze the electronic structure and optical properties within the quasiparticle self-consistent GW approxn. While this compd. bears some similarity to conventional sp semiconductors, it also displays unique features. Quasiparticle self-consistency is essential for an accurate description of the band structure: Band gaps are much larger than what is predicted by the local-d. approxn. (LDA) or GW based on the LDA. Valence band dispersions are modified in a very unusual manner. In addn., spin-orbit coupling strongly modifies the band structure and gives rise to unconventional dispersion relations and a Dresselhaus splitting at the band edges. The av. hole mass is small, which partially accounts for the long diffusion lengths obsd. The surface ionization potential (work function) is calcd. to be 5.7 eV with respect to the vacuum level, explaining efficient carrier transfer to TiO2 and Au elec. contacts.
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Even, J.; Pedesseau, L.; Jancu, J.-M.; Katan, C. Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications J. Phys. Chem. Lett. 2013, 4, 2999– 3005 DOI: 10.1021/jz401532q
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Importance of Spin-Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc; Katan, Claudine
Journal of Physical Chemistry Letters (2013), 4 (17), 2999-3005CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
Three-dimensional (3D) hybrid perovskites MeNH3PbX3 (X = Br, I) have recently been suggested as new key materials for dye-sensitized solar cells (DSSC) leading to a new class of hybrid semiconductor photovoltaic cells (HSPC). Thanks to d. functional theory calcns., the band gap of these compds. is dominated by a giant spin-orbit coupling (SOC) in the conduction-band (CB). At room temp., direct and isotropic optical transitions are assocd. to a spin-orbit split-off band related to the triply degenerated CB of the cubic lattice without SOC. Due to the strong SOC, the electronic states involved in the optical absorption are only slightly perturbed by local distortions of the lattice. Band offset calcns. confirm that MeNH3PbX3/TiO2 is a ref. material for driving electrons toward the electrode in HSPC. Two-dimensional (2D) hybrids also probably have flexibility for light conversion efficiency. The study affords the basic concepts to reach the level of knowledge already attained for optoelectronic properties of conventional semiconductors.
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Ganose, A. M.; Savory, C. N.; Scanlon, D. O. (CH₃NH₃)₂Pb(SCN)₂I₂: A More Stable Structural Motif for Hybrid Halide Photovoltaics? J. Phys. Chem. Lett. 2015, 6, 4594– 4598 DOI: 10.1021/acs.jpclett.5b02177
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(CH3NH3)2Pb(SCN)2I2: A New More Stable Structural Motif for Hybrid Halide Photovoltaics?
Ganose, Alex M.; Savory, Christopher N.; Scanlon, David O.
Journal of Physical Chemistry Letters (2015), 6 (22), 4594-4598CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
Hybrid halide perovskites have recently emerged as a highly efficient class of light absorbers; however, there are increasing concerns over their long-term stability. Recently, incorporation of SCN- was suggested as a novel route to improving stability without neg. impacting performance. Intriguingly, despite crystg. in a 2-dimensional layered structure, (CH3NH3)2Pb(SCN)2I2 (MAPSI) possesses an ideal band gap of 1.53 eV, close to that of the 3-dimensional connected champion hybrid perovskite absorber, CH3NH3PbI3 (MAPI). Here, the authors identify, using hybrid d. functional theory, the origin of the smaller than expected band gap of MAPSI through a detailed comparison with the electronic structure of MAPI. Also, assessment of the MAPSI structure reveals that it is thermodynamically stable with respect to phase sepn., a likely source of the increased stability reported in expt.
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Zhang, H.; Liu, C.-X.; Qi, X.-L.; Dai, X.; Fang, Z.; Zhang, S.-C. Topological Insulators in Bi₂Se₃, Bi₂Te₃ and Sb₂Te₃ with a Single Dirac Cone on the Surface Nat. Phys. 2009, 5, 438– 442 DOI: 10.1038/nphys1270
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Topological insulators in Bi2Se3, Bi2Te3 and Sb2Te3 with a single Dirac cone on the surface
Zhang, Haijun; Liu, Chao-Xing; Qi, Xiao-Liang; Dai, Xi; Fang, Zhong; Zhang, Shou-Cheng
Nature Physics (2009), 5 (6), 438-442CODEN: NPAHAX; ISSN:1745-2473. (Nature Publishing Group)
Topol. insulators are new states of quantum matter in which surface states residing in the bulk insulating gap of such systems are protected by time-reversal symmetry. The study of such states was originally inspired by the robustness to scattering of conducting edge states in quantum Hall systems. Recently, such analogies resulted in the discovery of topol. protected states in two-dimensional and three-dimensional band insulators with large spin-orbit coupling. So far, the only known three-dimensional topol. insulator is BixSb1-x, which is an alloy with complex surface states. Here, the authors present the results of 1st-principles electronic structure calcns. of the layered, stoichiometric crystals Sb2Te3, Sb2Se3, Bi2Te3 and Bi2Se3. The authors' calcns. predict that Sb2Te3, Bi2Te3 and Bi2Se3 are topol. insulators, whereas Sb2Se3 is not. These topol. insulators have robust and simple surface states consisting of a single Dirac cone at the Γ point. The authors predict that Bi2Se3 has a topol. nontrivial energy gap of 0.3 eV, which is larger than the energy scale of room temp. The authors further present a simple and unified continuum model that captures the salient topol. features of this class of materials.
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Scanlon, D.; King, P.; Singh, R.; De La Torre, A.; Walker, S. M.; Balakrishnan, G.; Baumberger, F.; Catlow, C. Controlling Bulk Conductivity in Topological Insulators:Key Role of Anti-Site Defects Adv. Mater. 2012, 24, 2154– 2158 DOI: 10.1002/adma.201200187
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Waghmare, U.; Spaldin, N.; Kandpal, H.; Seshadri, R. First-Principles Indicators of Metallicity and Cation Off-Centricity in rhe IV-VI Rocksalt Chalcogenides of Divalent Ge, Sn, and Pb Phys. Rev. B: Condens. Matter Mater. Phys. 2003, 67, 125111 DOI: 10.1103/PhysRevB.67.125111
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There is no corresponding record for this reference.
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Raulot, J.-M.; Baldinozzi, G.; Seshadri, R.; Cortona, P. An Ab-Initio Study of the rôle of Lone Pairs in the Structure and Insulator–Metal Transition in SnO and PbO Solid State Sci. 2002, 4, 467– 474 DOI: 10.1016/S1293-2558(02)01280-3
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An ab-initio study of the role of lone pairs in the structure and insulator-metal transition in SnO and PbO
Raulot, Jean-Marc; Baldinozzi, Gianguido; Seshadri, Ram; Cortona, Pietro
Solid State Sciences (2002), 4 (4), 467-474CODEN: SSSCFJ; ISSN:1293-2558. (Editions Scientifiques et Medicales Elsevier)
We performed d. functional calcns. on tetragonal SnO and PbO (litharge) in the space group P4/nmm with the specific intention of examg. the role played by Sn 5s and Pb 6s lone pairs in stabilizing the structure and in giving rise to semi-metallic behavior (of SnO at ambient pressure and of PbO in the γ phase). Use of the electron localization function permitted real-space visualization of the lone pair in these structures. We also discussed the electronic structure of the orthorhombic PbO (massicot, space group Pbma) which again has localized lone pairs, contrary to some earlier expectation.
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Walsh, A.; Watson, G. W. The Origin of the Stereochemically Active Pb(II) Lone Pair: DFT Calculations on PbO And PbS J. Solid State Chem. 2005, 178, 1422– 1428 DOI: 10.1016/j.jssc.2005.01.030
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The origin of the stereochemically active Pb(II) lone pair: DFT calculations on PbO and PbS
Walsh, Aron; Watson, Graeme W.
Journal of Solid State Chemistry (2005), 178 (5), 1422-1428CODEN: JSSCBI; ISSN:0022-4596. (Elsevier)
The concept of a chem. inert but stereochem. active 6s2 lone pair is commonly assocd. with Pb(II). We have performed d. functional theory calcns. on PbO and PbS in both the rocksalt and litharge structures which show anion dependence of the stereochem. active lone pair. PbO is more stable in litharge while PbS is not, and adopts the sym. rocksalt structure showing no lone pair activity. Anal. of the electron d., d. of states and crystal orbital overlap populations shows that the asym. electron d. formed by Pb(II) is a direct result of anion-cation interactions. The formation has a strong dependence on the electronic states of the anion and while oxygen has the states required for interaction with Pb 6s, sulfur does not. This explains for the first time why PbO forms distorted structures and possesses an asym. d. and PbS forms sym. structures with no lone pair activity. This anal. shows that distorted Pb(II) structures are not the result of chem. inert, sterically active lone pairs, but instead result from asym. electron densities that rely on direct electronic interaction with the coordinated anions.
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Burton, L. A.; Walsh, A. Band Alignment in SnS Thin-Film Solar Cells: Possible Origin of the Low Conversion Efficiency Appl. Phys. Lett. 2013, 102, 132111 DOI: 10.1063/1.4801313
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Band alignment in SnS thin-film solar cells: Possible origin of the low conversion efficiency
Burton, Lee A.; Walsh, Aron
Applied Physics Letters (2013), 102 (13), 132111/1-132111/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
Tin sulfide is an attractive absorber material for low-cost thin-film solar cells. Despite the ideal phys. properties of bulk SnS, the photovoltaic conversion efficiencies achieved in devices to date have been no greater than 2%. Assessment of the valence band energy of the stable orthorhombic phase of SnS reveals a low ionization potential (4.7 eV) in comparison to typical absorber materials (CdTe, CuInSe2, and Cu2ZnSnS4). A band mis-alignment is therefore predicted with commonly used back contact and buffer layers. Alternative configurations are proposed that should improve device performance. (c) 2013 American Institute of Physics.
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Butler, K. T.; Hendon, C. H.; Walsh, A. Electronic Chemical Potentials of Porous Metal–Organic Frameworks J. Am. Chem. Soc. 2014, 136, 2703– 2706 DOI: 10.1021/ja4110073
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Electronic Chemical Potentials of Porous Metal-Organic Frameworks
Butler, Keith T.; Hendon, Christopher H.; Walsh, Aron
Journal of the American Chemical Society (2014), 136 (7), 2703-2706CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
The binding energy of an electron in a material is a fundamental characteristic, which dets. a wealth of important chem. and phys. properties. For metal-org. frameworks this quantity is hitherto unknown. We present a general approach for detg. the vacuum level of porous metal-org. frameworks and apply it to obtain the first ionization energy for six prototype materials including zeolitic, covalent, and ionic frameworks. This approach for valence band alignment can explain observations relating to the electrochem., optical, and elec. properties of porous frameworks.
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Hahn, N. T.; Hoang, S.; Self, J. L.; Mullins, C. B. Spray Pyrolysis Deposition and Photoelectrochemical Properties of n-Type BiOI Nanoplatelet Thin Films ACS Nano 2012, 6, 7712– 7722 DOI: 10.1021/nn3031063
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Spray pyrolysis deposition and photoelectrochemical properties of n-type BiOI nanoplatelet thin films
Hahn, Nathan T.; Hoang, Son; Self, Jeffrey L.; Mullins, C. Buddie
ACS Nano (2012), 6 (9), 7712-7722CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
Bismuth oxy-iodide is a potentially interesting visible-light-active photocatalyst; yet there is little research regarding its photoelectrochem. properties. Herein we report the synthesis of BiOI nanoplatelet photoelectrodes by spray pyrolysis on fluorine-doped tin oxide substrates at various temps. The films exhibited n-type cond., most likely due to the presence of anion vacancies, and optimized films possessed incident photon conversion efficiencies of over 20% in the visible range for the oxidn. of I- to I3- at 0.4 V vs Ag/AgCl in acetonitrile. Visible-light photons (λ > 420 nm) contributed approx. 75% of the overall photocurrent under AM1.5G illumination, illustrating their usefulness under solar light illumination. A deposition temp. of 260 °C was found to result in the best performance due to the balance of morphol., crystallinity, impurity levels, and optical absorption, leading to photocurrents of roughly 0.9 mA/cm2 at 0.4 V vs Ag/AgCl. Although the films performed stably in acetonitrile, their performance decreased significantly upon extended exposure to water, which was apparently caused by a loss of surface iodine and subsequent formation of an insulating bismuth hydroxide layer.
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Scanlon, D. O.; Watson, G. W. On the Possibility of p-Type SnO₂ J. Mater. Chem. 2012, 22, 25236– 25245 DOI: 10.1039/c2jm34352e
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On the possibility of p-type SnO2
Scanlon, David O.; Watson, Graeme W.
Journal of Materials Chemistry (2012), 22 (48), 25236-25245CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
SnO2 is an abundant, low cost, natively n-type, wide band gap oxide, which can achieve high conductivities due to facile donor doping. Realization of a p-type SnO2 would, however, open up many new avenues in device applications, and has become a major research goal. Previous exptl. and theor. studies have proved inconclusive, with the p-type ability of SnO2 being both supported and questioned in equal measure. We use state of the art hybrid d. functional theory to investigate the nature of intrinsic and extrinsic p-type defects in SnO2. All the p-type defects considered in SnO2 produce localized hole polarons centered on anion sites. We calc. the thermodn. ionization energies of these defects, and demonstrate that an efficient p-type SnO2 is not achievable.
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Frost, J. M.; Butler, K. T.; Brivio, F.; Hendon, C. H.; Van Schilfgaarde, M.; Walsh, A. Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells Nano Lett. 2014, 14, 2584– 2590 DOI: 10.1021/nl500390f
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Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico; Hendon, Christopher H.; van Schilfgaarde, Mark; Walsh, Aron
Nano Letters (2014), 14 (5), 2584-2590CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
The performance of organometallic perovskite solar cells has rapidly surpassed that of both conventional dye-sensitized and org. photovoltaics. High-power conversion efficiency can be realized in both mesoporous and thin-film device architectures. The authors address the origin of this success in the context of the materials chem. and physics of the bulk perovskite as described by electronic structure calcns. In addn. to the basic optoelectronic properties essential for an efficient photovoltaic device (spectrally suitable band gap, high optical absorption, low carrier effective masses), the materials are structurally and compositionally flexible. As the authors show, hybrid perovskites exhibit spontaneous elec. polarization; the authors also suggest ways in which this can be tuned through judicious choice of the org. cation. The presence of ferroelec. domains will result in internal junctions that may aid sepn. of photoexcited electron and hole pairs, and redn. of recombination through segregation of charge carriers. The combination of high dielec. const. and low effective mass promotes both Wannier-Mott exciton sepn. and effective ionization of donor and acceptor defects. The photoferroic effect could be exploited in nanostructured films to generate a higher open circuit voltage and may contribute to the current-voltage hysteresis obsd. in perovskite solar cells.
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Ganose, A. M.; Scanlon, D. O. Band Gap and Work Function Tailoring of SnO₂ for Improved Transparent Conducting Ability in Photovoltaics J. Mater. Chem. C 2016, 4, 1467– 1475 DOI: 10.1039/C5TC04089B
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Band gap and work function tailoring of SnO2 for improved transparent conducting ability in photovoltaics
Ganose, Alex M.; Scanlon, David O.
Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2016), 4 (7), 1467-1475CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)
Transparent conducting oxides (TCOs) are an essential component in modern optoelectronic devices, such as solar panels and touch screens. Their ability to combine transparency and cond., two properties that are normally mutually exclusive, have made them the subject of intense research over the last 50 years. SnO2, doped with F or Sb, is a widely used and relatively inexpensive transparent conducting material, however, its electronic structure leaves scope for improving its properties for use in many TCO applications, esp. in solar cell devices. Here we show using d. functional theory that incorporation of Pb into SnO2 reduces the band gap through lowering of the conduction band min., thereby increasing the electron affinity. The electron effective mass at the conduction band min. decreases alongside the band gap, indicating improved charge carrier mobilities. Furthermore, the calcd. optical absorption properties show the alloys retain their transparency in the visible spectrum. Our results suggest that alloying of PbO2 with SnO2 will enable improved electronic properties, including a highly tuneable workfunction, which will open up the material for other applications, such as hole injection layers in org. photovoltaics.
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Chang, X.; Gondal, M.; Al-Saadi, A.; Ali, M.; Shen, H.; Zhou, Q.; Zhang, J.; Du, M.; Liu, Y.; Ji, G. Photodegradation of Rhodamine B Over Unexcited Semiconductor Compounds of BiOCl and BiOBr J. Colloid Interface Sci. 2012, 377, 291– 298 DOI: 10.1016/j.jcis.2012.03.021
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Photodegradation of Rhodamine B over unexcited semiconductor compounds of BiOCl and BiOBr
Chang, Xiaofeng; Gondal, M. A.; Al-Saadi, A. A.; Ali, M. A.; Shen, Hefei; Zhou, Qin; Zhang, Jun; Du, Mengping; Liu, Yousong; Ji, Guangbin
Journal of Colloid and Interface Science (2012), 377 (1), 291-298CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
Reported is the photodegrdn. of Rhodamine B (RhB) in aq. soln. over BiOCl and BiOBr semiconductors. Under visible light irradn. (>400, >420, and 550 nm), RhB adsorbed on the surface of BiOCl and BiOBr was photosensitized and decompd. effectively over unexcited BiOCl and BiOBr. The degrdn. of Methyl orange (MO) and Methylene Blue (MB) over BiOCl and BiOBr was investigated as well, and the results were compared with RhB photodegrdn. MB mols. having the lowest LUMO could not be degraded by this process. Utilizing the quantum chem. calcn. (Gaussian 03 program), the relationship between frontier orbital energy of selected dye mols. and photodegrdn. rate was established.
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Zhang, J.; Xia, J.; Yin, S.; Li, H.; Xu, H.; He, M.; Huang, L.; Zhang, Q. Improvement of Visible Light Photocatalytic Activity Over Flower-Like BiOCl/BiOBr Microspheres Synthesized by Reactable Ionic Liquids Colloids Surf., A 2013, 420, 89– 95 DOI: 10.1016/j.colsurfa.2012.11.054
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Improvement of visible light photocatalytic activity over flower-like BiOCl/BiOBr microspheres synthesized by reactable ionic liquids
Zhang, Jing; Xia, Jiexiang; Yin, Sheng; Li, Huaming; Xu, Hui; He, Minqiang; Huang, Liying; Zhang, Qi
Colloids and Surfaces, A: Physicochemical and Engineering Aspects (2013), 420 (), 89-95CODEN: CPEAEH; ISSN:0927-7757. (Elsevier B.V.)
BiOCl/BiOBr uniform flower-like composite photocatalysts had been successfully synthesized through a one-pot ethylene glycol (EG)-assisted solvothermal process in the presence of 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl) and 1-hexadecyl-3-methylimidazolium bromide ([C16mim]Br) reactable ionic liqs. Their structures, morphol., and optical properties were characterized by x-ray diffraction (XRD), XPS, SEM, energy-dispersive x-ray spectroscopy (EDS) and UV-vis diffuse reflectance spectroscopy (DRS). The DRS anal. and high photocurrent suggested that BiOCl/BiOBr possessed absorption under visible light and was a benefit for the efficient generation and sepn. of the electron-hole pairs. Photocatalytic activity expt. proved that BiOCl/BiOBr composites exhibited higher photocatalytic activity than single BiOCl and BiOBr for the degrdn. of Rhodamine B (RhB) under visible light (λ > 400 nm). A possible photocatalytic mechanism based on the relative band positions of BiOCl and BiOBr had been proposed.
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Cao, J.; Xu, B.; Luo, B.; Lin, H.; Chen, S. Novel BiOI/BiOBr Heterojunction Photocatalysts with Enhanced Visible Light Photocatalytic Properties Catal. Commun. 2011, 13, 63– 68 DOI: 10.1016/j.catcom.2011.06.019
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Novel BiOI/BiOBr heterojunction photocatalysts with enhanced visible light photocatalytic properties
Cao, Jing; Xu, Benyan; Luo, Bangde; Lin, Haili; Chen, Shifu
Catalysis Communications (2011), 13 (1), 63-68CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
A novel heterojunction photocatalyst BiOI/BiOBr was synthesized by a simple modified deposition-pptn. method. Several characterization tools including XRD, SEM, HRTEM and UV-visible DRS were employed to study the phase structures, morphologies and optical properties of the samples. BiOI/BiOBr exhibited higher photocatalytic activity than single BiOI and BiOBr for the degrdn. of methyl orange (MO) under visible light (λ > 420 nm). This result can be due to the formation of the heterojunction between BiOI and BiOBr, which can sep. photogenerated carriers efficiently. The photocatalytic mechanism study demonstrates that [rad]O2 - and H+ are the main reactive species while [rad]OH can be negligible.

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Rui Zhao, Juexiu Li, Maiqi Sun, Qixu Shi, Mingzhu Zhao, Miaomiao Li, Zixuan Bi, Xinrui Lei, Jinping Jia. Enhanced photocatalytic degradation by higher exposure of {110} facet and surface oxygen vacancies of BiOBr through cobalt doping strategy. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2024, 687 , 133402. https://doi.org/10.1016/j.colsurfa.2024.133402
Longqiang He, Yongjun Wang, Yanmei Li, Xiaohua Wang, Lianwei Shan. Research Progress of and Perspectives of BiOCl Photocatalytic Materials. Ferroelectrics 2024, 618 (4) , 983-998. https://doi.org/10.1080/00150193.2023.2300609
Zaichun Sun, Tahta Amrillah. Potential application of bismuth oxyiodide (BiOI) when it meets light. Nanoscale 2024, 16 (10) , 5079-5106. https://doi.org/10.1039/D3NR06559F
Vinoth S, Pandikumar A. Recent advances in bismuth oxyfluoride-based photocatalysts for energy and environmental remediation. Materials Today Chemistry 2024, 36 , 101924. https://doi.org/10.1016/j.mtchem.2024.101924
Ivan Caño, Jonathan W. Turnley, Pol Benítez, Cibrán López-Álvarez, José-Miguel Asensi, David Payno, Joaquim Puigdollers, Marcel Placidi, Claudio Cazorla, Rakesh Agrawal, Edgardo Saucedo. Novel synthesis of semiconductor chalcohalide anti-perovskites by low-temperature molecular precursor ink deposition methodologies. Journal of Materials Chemistry C 2024, 12 (9) , 3154-3163. https://doi.org/10.1039/D3TC04410F
Mauro Mato, Josep Cornella. Bismuth in Radical Chemistry and Catalysis. Angewandte Chemie 2024, 136 (8) https://doi.org/10.1002/ange.202315046
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Xujun Liu, Hang Zhang, Xianhua Qiu, Hao Ye, Yu Xie, Yun Ling. Construction of BiOCl/In2O3 heterojunction for effective photocatalytic reduction of CO2. Applied Catalysis A: General 2024, 671 , 119574. https://doi.org/10.1016/j.apcata.2024.119574
Huijun Guo, Xin Wang, Shihao Wang, Hanyu Ma, Jianzhi Liu. A signal “switch-on” photoelectrochemical sensor based on a 3D-FM/BiOI heterostructure for the sensitive detection of l -ascorbic acid. RSC Advances 2024, 14 (7) , 4556-4567. https://doi.org/10.1039/D3RA08288A
Lei Yue, Dandan Cui, Fubo Tian, Shuang Liu, Zonglun Li, Ran Liu, Zhen Yao, Yanchun Li, Dongliang Yang, Xiaodong Li, Quanjun Li, Yi Du, Bingbing Liu. Synchronous pressure-induced enhancement in the photoresponsivity and response speed of BiOBr. Acta Materialia 2024, 263 , 119529. https://doi.org/10.1016/j.actamat.2023.119529
Zhen-Long Lv, Shi-Jie Lv, Xiao-Fei Wang, Hong-Ling Cui. Electronic, Mechanical, and Infrared Properties of BiOX (X = Cl, Br, I) Monolayers. physica status solidi (b) 2023, https://doi.org/10.1002/pssb.202300415

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Cite this: Chem. Mater. 2016, 28, 7, 1980–1984

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https://doi.org/10.1021/acs.chemmater.6b00349

Published March 10, 2016

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Abstract
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Figure 1
Figure 1. Crystal structure of the BiOX systems (space group P4/nmm, D_4h symmetry) with stoichiometric X–Bi–O–Bi–X bilayers stacked along the c axis.
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Figure 2
Figure 2. Scalar relativistic (dashed lines) and fully relativistic (black lines) electronic band structures of the BiOX series with the hybrid HSE06 functional. The highest occupied state (including spin–orbit coupling) is set to 0 eV.
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Figure 3
Figure 3. Fully relativistic (HSE06+SOC) electronic density of states (DOS), including projections onto ion-centered atomic orbitals (PEDOS). The highest occupied state is set to 0 eV.
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Figure 4
Figure 4. Calculated valence band alignment of the BiOX series (HSE including spin–orbit coupling). The vacuum level was aligned to the (001) surface in a slab calculation with a vacuum thickness of 15 Å. The electrostatic potentials were aligned and checked using the package MacroDensity. (53)
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References
This article references 60 other publications.
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  Pfaff, G.; Reynders, P. Angle-Dependent Optical Effects Deriving from Submicron Structures of Films and Pigments Chem. Rev. 1999, 99, 1963– 1982 DOI: 10.1021/cr970075u
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  Angle-Dependent Optical Effects Deriving from Submicron Structures of Films and Pigments
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  A review with 142 refs. Topics include: theory of angle-dependent optical effects; extended interference films; pearlescent pigments; pigments and films based on dichroism; pigments and films based on holog. and gratings; pigments formed by grinding a film.
3. 3
  Rotmensch, J.; Whitlock, J.; Dietz, M.; Hines, J.; Reba, R.; Horwitz, E.; Harper, P. Development of 212-BiOCl as a new therapeutic modality against microscopic carcinoma Abstr. Pap. Am. Chem. Soc. 1998, U926– U926
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  Bismuth Compounds and Preparations with Biological or Medicinal Relevance
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  Chemical Reviews (Washington, D. C.) (1999), 99 (9), 2601-2657CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
  A review, with 996 refs. Bi compds. in medicine, microbiol., and pharmacol., inorg. salts of Bi, Bi complexes with amino- and hydroxycarboxylic acids, colloidal Bi subcitrate, discovery and design of bioactive Bi compds., and interactions of Bi compds. with biomols. and pharmaceutical agents are discussed.
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  Michel, C. R.; Contreras, N. L. L.; Martínez-Preciado, A. H. Gas Sensing Properties of Nanostructured Bismuth Oxychloride Sens. Actuators, B 2011, 160, 271– 277 DOI: 10.1016/j.snb.2011.07.047
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  Gas sensing properties of nanostructured bismuth oxychloride
  Michel, Carlos R.; Contreras, Narda L. Lopez; Martinez-Preciado, Alma H.
  Sensors and Actuators, B: Chemical (2011), 160 (1), 271-277CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)
  Nanostructured bismuth oxychloride (BiOCl) was prepd. by a surfactant-assisted method. BiCl3 and dioctyl sulfosuccinate (AOT) were dissolved in non-aq. media, producing a fine ppt. Calcination of the pptd. particles at 180° produced 3D hierarchical BiOCl semi-spherical architectures, assembled by microplates. The increase of the calcination temp. to 600° produced nanostructured ribbons, which are formed by the stacking of several BiOCl layers. Other microstructures can be formed at different calcination temps. or by other surfactants. Thick-films of the as-prepd. BiOCl ribbons were made by its direct deposition on alumina substrates. The gas sensing characterization was performed at 300 and 400° using a.c. (AC). The tests gases were compressed air, CO, CO2, and O2. Humidity effects were discarded by the extra dry version of these gases. At 300°, reproducible CO gas sensing patterns were obtained; however, the detection of CO2 and O2 produced unreliable results. At 400°, reliable gas sensing patterns were obtained in CO, CO2, and O2. According to its gas response, BiOCl behaved as a p-type semiconductor material.
7. 7
  Kijima, N.; Matano, K.; Saito, M.; Oikawa, T.; Konishi, T.; Yasuda, H.; Sato, T.; Yoshimura, Y. Oxidative Catalytic Cracking of N-Butane to Lower Alkenes over Layered BiOCl Catalyst Appl. Catal., A 2001, 206, 237– 244 DOI: 10.1016/S0926-860X(00)00598-6
  7
  Oxidative catalytic cracking of n-butane to lower alkenes over layered BiOCl catalyst
  Kijima, Norihito; Matano, Koichi; Saito, Masao; Oikawa, Tomo; Konishi, Tomohiro; Yasuda, Hiroyuki; Sato, Toshio; Yoshimura, Yuji
  Applied Catalysis, A: General (2001), 206 (2), 237-244CODEN: ACAGE4; ISSN:0926-860X. (Elsevier Science B.V.)
  The catalytic performance of BiOCl in oxidative cracking of n-butane to lower alkenes was studied and compared with that of isostructural LaOCl and SmOCl catalysts. On the BiOCl catalyst, oxidative dehydrogenation and combustion were major reactions at ∼500°; above ∼600°, oxidative cracking reaction to produce ethylene and propylene began to be significant. At temp. as low as 625°, a 52% yield of overall C2-C4 alkenes was achieved, and then decreased above this temp. The conversion of n-butane and oxygen were const. within 6 h periods at 550 and 600°, however, both decreased slightly with time-onstream at 650°. The BiOCl catalyst shows rather high alkene selectivity and suppresses deep oxidn. reactions for the oxidative cracking of n-butane, as compared to the LaOCl and SmOCl catalysts. The overall yield of C2-C4 alkenes for the BiOCl catalyst is higher than that from LaOCl and SmOCl catalysts at 500-600°.
8. 8
  Ghosh, R.; Maiti, S.; Chakraborty, A. Facile Catalyzed Acylation of Heteroatoms Using BiCl₃ Generated in situ From the Procatalyst BiOCl and Acetyl Chloride Tetrahedron Lett. 2004, 45, 6775– 6778 DOI: 10.1016/j.tetlet.2004.07.044
  There is no corresponding record for this reference.
9. 9
  Zhang, K.-L.; Liu, C.-M.; Huang, F.-Q.; Zheng, C.; Wang, W.-D. Study of the Electronic Structure and Photocatalytic Activity of the BiOCl Photocatalyst Appl. Catal., B 2006, 68, 125– 129 DOI: 10.1016/j.apcatb.2006.08.002
  9
  Study of the electronic structure and photocatalytic activity of the BiOCl photocatalyst
  Zhang, Ke-Lei; Liu, Cun-Ming; Huang, Fu-Qiang; Zheng, Chong; Wang, Wen-Deng
  Applied Catalysis, B: Environmental (2006), 68 (3-4), 125-129CODEN: ACBEE3; ISSN:0926-3373. (Elsevier B.V.)
  A novel bismuth oxychloride (BiOCl) was synthesized by a hydrolysis method. The powder sample was characterized by x-ray diffraction, field emission scanning electron microscope and UV-vis spectrophotometer. The layered compd. BiOCl was the first oxyhalide to be used as a photocatalyst. The prepd. material has an optical indirect band-gap of 3.46 eV. For its photocatalytic reactivity, the Methyl orange (MO) dye degrdn. was chosen to be investigated. In a comparison of a three-cycle measurement of BiOCl with that of TiO2 (P25, Degussa), it was found that BiOCl had better performance than P25 at every recycle. The calcd. electronic structure of BiOCl confirms that it has an indirect band-gap, and the Cl 3p and Bi 6p states dominate the highest occupied MOs (HOMO) and the lowest unoccupied orbitals (LUMO), resp. The open crystal structure and indirect optical transitions of BiOCl play important roles in its excellent photocatalytic activity.
10. 10
  Zhang, J.; Shi, F.; Lin, J.; Chen, D.; Gao, J.; Huang, Z.; Ding, X.; Tang, C. Self-Assembled 3-D Architectures of BiOBr as a Visible Light-Driven Photocatalyst Chem. Mater. 2008, 20, 2937– 2941 DOI: 10.1021/cm7031898
  10
  Self-Assembled 3-D Architectures of BiOBr as a Visible Light-Driven Photocatalyst
  Zhang, Jun; Shi, Fengjun; Lin, Jing; Chen, Dongfeng; Gao, Jianming; Huang, Zhixin; Ding, Xiaoxia; Tang, Chengcun
  Chemistry of Materials (2008), 20 (9), 2937-2941CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  In this work, the authors demonstrated the ethylene glycol-assisted solvothermal synthesis of 3-D microspherical BiOBr architectures assembled by nanosheets. The morphol. and compositional characteristics of the 3-D architectures were investigated by various microscopy techniques. The possible formation mechanism for the architectures was discussed. The band gap of the obtained BiOBr materials was estd. to be 2.54 eV by UV-vis. The sp. surface area and porosity of the BiOBr 3-D architectures also were investigated by using nitrogen adsorption and desorption isotherms. Because of the narrow band gap and the novel 3-D micro-/nanostructure, the BiOBr architectures show a more excellent photocatalytic activity under visible light irradn. than the BiOBr bulk plates. Several possible reasons for the higher photocatalytic activity have been taken into consideration. In addn., the photocatalyst is stable during the reaction and can be used repeatedly.
11. 11
  Zhang, X.; Ai, Z.; Jia, F.; Zhang, L. Generalized One-Pot Synthesis, Characterization,and Photocatalytic Activity of Hierarchical BiOX (x= Cl, Br, I) Nanoplate Microspheres J. Phys. Chem. C 2008, 112, 747– 753 DOI: 10.1021/jp077471t
  There is no corresponding record for this reference.
12. 12
  An, H.; Du, Y.; Wang, T.; Wang, C.; Hao, W.; Zhang, J. Photocatalytic Properties of BiOX (X= Cl, Br, and I) Rare Met. 2008, 27, 243– 250 DOI: 10.1016/S1001-0521(08)60123-0
  12
  Photocatalytic properties of BiOX (X = Cl, Br, and I)
  An, Huizhong; Du, Yi; Wang, Tianmin; Wang, Cong; Hao, Weichang; Zhang, Junying
  Rare Metals (Beijing, China) (2008), 27 (3), 243-250CODEN: RARME8; ISSN:1001-0521. (Rare Metals)
  A novel series of photocatalysts, bismuth oxyhalide (BiOX, X = Cl, Br, and I), were synthesized by a hydrolysis method. The powder samples were characterized by the use of x-ray diffraction (XRD), scanning electron microscope, and UV-Vis spectrophotometer. The XRD pattern showed that all the BiOX were well crystd. in the tetragonal structure. The band gaps of the sheet-shaped compds. BiOX (X = Cl, Br, and I) were 3.44, 2.76, and 1.85 eV, resp. BiOBr showed the highest photocatalytic activity in degrading Rhodamine B (RhB) and evolving O2 for its proper valence band (VB). BiOI has no photocatalytic activity. BiOCl showed the highest activity in decompg. isopropanol because of electron-hole pair sepn. through trapping electrons by oxygen vacancies.
13. 13
  Chai, S. Y.; Kim, Y. J.; Jung, M. H.; Chakraborty, A. K.; Jung, D.; Lee, W. I. Het-erojunctioned BiOCl/Bi₂O₃, a New Visible Light Photocatalyst J. Catal. 2009, 262, 144– 149 DOI: 10.1016/j.jcat.2008.12.020
  There is no corresponding record for this reference.
14. 14
  Chang, X.; Huang, J.; Cheng, C.; Sui, Q.; Sha, W.; Ji, G.; Deng, S.; Yu, G. BiOX (X = Cl, Br, I) Photocatalysts Prepared Using NaBiO₃ as the Bi Source: Characterization and Catalytic Performance Catal. Commun. 2010, 11, 460– 464 DOI: 10.1016/j.catcom.2009.11.023
  14
  BiOX (X = Cl, Br, I) photocatalysts prepared using NaBiO3 as the Bi source: Characterization and catalytic performance
  Chang, Xiaofeng; Huang, Jun; Cheng, Cheng; Sui, Qian; Sha, Wei; Ji, Guangbin; Deng, Shubo; Yu, Gang
  Catalysis Communications (2010), 11 (5), 460-464CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
  The Bismuth oxyhalides, cryst. BiOX (X = Cl, Br, I) were prepd. via a facile method, using NaBiO3 and HX aq. solns. as the raw materials for the first time. The systematic microstructure and optical property characterizations of the BiOX photocatalysts demonstrated the reliability of this new and facile prepn. approach. The photocatalytic activity on the degrdn. of typical phenolic endocrine disrupting chems. over BiOX and P25 were evaluated under Xenon-light irradn. and the initial photocatalytic mechanism was discussed based on the band edge potential anal.
15. 15
  Cheng, H.; Huang, B.; Dai, Y. Engineering BiOX (X= Cl, Br, I) Nanostructures for Highly Efficient Photocatalytic Applications Nanoscale 2014, 6, 2009– 2026 DOI: 10.1039/c3nr05529a
  15
  Engineering BiOX (X = Cl, Br, I) nanostructures for highly efficient photocatalytic applications
  Cheng, Hefeng; Huang, Baibiao; Dai, Ying
  Nanoscale (2014), 6 (4), 2009-2026CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
  A review. Heterogeneous photocatalysis that employs photo-excited semiconductor materials to reduce water and oxidize toxic pollutants upon solar light irradn. holds great prospects for renewable energy substitutes and environmental protection. To utilize solar light effectively, the quest for highly active photocatalysts working under visible light has always been the research focus. Layered BiOX (X = Cl, Br, I) are a kind of newly exploited efficient photocatalysts, and their light response can be tuned from UV to visible light range. The properties of semiconductors are dependent on their morphologies and compns. as well as structures, and this also offers the guidelines for design of highly-efficient photocatalysts. In this review, recent advances and emerging strategies in tailoring BiOX (X = Cl, Br, I) nanostructures to boost their photocatalytic properties are surveyed.
16. 16
  Bhachu, D. S.; Moniz, S. J. A.; Sathasivam, S.; Scanlon, D. O.; Walsh, A.; Bawaked, S. M.; Mokhtar, M.; Obaid, A. Y.; Parkin, I. P.; Tang, J.; Carmalt, C. J. Bismuth Oxyhalides: Synthesis, Structure and Photoelectrochemical Activity Chem. Sci. 2016, DOI: 10.1039/C6SC00389C
  There is no corresponding record for this reference.
17. 17
  Zhang, H.; Liu, L.; Zhou, Z. First-Principles Studies on Facet-Dependent Photocatalytic Properties of Bismuth Oxyhalides (BiOXs) RSC Adv. 2012, 2, 9224– 9229 DOI: 10.1039/c2ra20881d
  17
  First-principles studies on facet-dependent photocatalytic properties of bismuth oxyhalides (BiOXs)
  Zhang, Haijun; Liu, Lu; Zhou, Zhen
  RSC Advances (2012), 2 (24), 9224-9229CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
  The photocatalytic properties were compared for the {001}, {110} and {010} facets of bismuth oxyhalides (BiOXs) through d. functional theory (DFT) computations. X-terminated bulk-like {001} facets with clear boundary of [Bi2O2] and halogen slabs result in high thermodn. stability and efficient sepn. of photo-induced e--h+ pairs. Moreover, surface O vacancies, which act as e--h+ recombination centers, are energetically unfavorable within {001} facets. BiX-terminated {110} and other facets with surface O vacancies introduce deep defect levels to the band gap, which are detrimental to the sepn. of e--h+ pairs. These findings can better understand the origin of facet-dependent photocatalytic activities in BiOXs, and provide guidance for the design of high-efficiency photocatalysts.
18. 18
  Gnayem, H.; Sasson, Y. Hierarchical Nanostructured 3D Flowerlike BiOCl_xBr_1–x Semi- conductors with Exceptional Visible Light Photocatalytic Activity ACS Catal. 2013, 3, 186– 191 DOI: 10.1021/cs3005133
  18
  Hierarchical Nanostructured 3D Flowerlike BiOClxBr1-x Semiconductors with Exceptional Visible Light Photocatalytic Activity
  Gnayem, Hani; Sasson, Yoel
  ACS Catalysis (2013), 3 (2), 186-191CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
  With careful rational optimization and substantial simplification of the syntheses of the recently reported alloys BiO(ClxBr1-x), the authors fabricated, via a very simple procedure and at room temp., a unique visible-light-driven photocatalyst with excellent activity. The alloy BiOCl0.875Br0.125 totally decompd. 15 mg/L aq. Rhodamine B soln. within 120 s upon irradn. with visible light (λ > 422 nm). The transparent substrate acetophenone was also swiftly destroyed under the above conditions. The catalyst maintained partial activity even after switching off the light source. Initial mechanistic studies clearly suggest that the mode of action of these materials is fundamentally different from previously reported photocatalytic mechanisms. Evidently, the putative mol. mechanism does not engage dye photosensitization or oxygen radicals.
19. 19
  Zhang, H.; Liu, L.; Zhou, Z. Towards Better Photocatalysts: First-Principles Studies of the Alloying Effects on the Photocatalytic Activities of Bismuth Oxyhalides Under Visible Light Phys. Chem. Chem. Phys. 2012, 14, 1286– 1292 DOI: 10.1039/C1CP23516H
  19
  Towards better photocatalysts: first-principles studies of the alloying effects on the photocatalytic activities of bismuth oxyhalides under visible light
  Zhang, Haijun; Liu, Lu; Zhou, Zhen
  Physical Chemistry Chemical Physics (2012), 14 (3), 1286-1292CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  Via d. functional theory computations, we studied the photocatalytic activities of pure and alloyed Bi oxyhalides (BiOXs). The dipole moments of the majority of pure and alloyed BiOXs are larger than 2.00 Debye, which can ensure their high photocatalytic efficiencies. Both the redox potentials of the photon-induced holes and the band gaps increase with an increasing content of lighter halogen atoms in the BiOXs, which competitively affects the photocatalytic efficiency. The hole mobility decreases a lot due to the hybridization of the halogen np states, while the electron mobility is not affected by such hybridization. Therefore, the alloying effect in BiOXs brings about a substantially lower electron-hole recombination rate and, accordingly, a much higher photocatalytic efficiency. Also probably O vacancies, which are energetically more favorable in alloyed BiOXs, could act as capture centers for excited electrons and, consequently, improve the sepn. of the electron-hole pairs. The findings present a reasonable explanation for the recent exptl. reports and provide some guidance for the design of alloyed BiOX photocatalysts.
20. 20
  Li, J.; Yu, Y.; Zhang, L. Bismuth Oxyhalide Nanomaterials: Layered Structures Meet Photocatalysis Nanoscale 2014, 6, 8473– 8488 DOI: 10.1039/C4NR02553A
  20
  Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis
  Li, Jie; Yu, Ying; Zhang, Lizhi
  Nanoscale (2014), 6 (15), 8473-8488CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
  A review. In recent years, layered bismuth oxyhalide nanomaterials have received more and more interest as promising photocatalysts because their unique layered structures endow them with fascinating physicochem. properties; thus, they have great potential photocatalytic applications for environment remediation and energy harvesting. In this article, we explore the synthesis strategies and growth mechanisms of layered bismuth oxyhalide nanomaterials, and propose design principles of tailoring a layered configuration to control the nanoarchitectures for high efficient photocatalysis. Subsequently, we focus on their layered structure dependent properties, including pH-related crystal facet exposure and phase transformation, facet-dependent photoactivity and mol. oxygen activation pathways, so as to clarify the origin of the layered structure dependent photoreactivity. Furthermore, we summarize various strategies for modulating the compn. and arrangement of layered structures to enhance the photoactivity of nanostructured bismuth oxyhalides via internal elec. field tuning, dehalogenation effect, surface functionalization, doping, plasmon modification, and heterojunction construction, which may offer efficient guidance for the design and construction of high-performance bismuth oxyhalide-based photocatalysis systems. Finally, we highlight some crucial issues in engineering the layered-structure mediated properties of bismuth oxyhalide photocatalysts and provide tentative suggestions for future research on increasing their photocatalytic performance.
21. 21
  Shamaila, S.; Sajjad, A. K. L.; Chen, F.; Zhang, J. WO₃ /BiOCl, a novel heterojunction as visible light photocatalyst J. Colloid Interface Sci. 2011, 356, 465– 472 DOI: 10.1016/j.jcis.2011.01.015
  There is no corresponding record for this reference.
22. 22
  Shenawi-Khalil, S.; Uvarov, V.; Fronton, S.; Popov, I.; Sasson, Y. A Novel Heterojunc-tion BiOBr/Bismuth Oxyhydrate Photocatalyst with Highly Enhanced Visible Light Photocatalytic Properties J. Phys. Chem. C 2012, 116, 11004– 11012 DOI: 10.1021/jp3009964
  There is no corresponding record for this reference.
23. 23
  Keramidas, K.; Voutsas, G.; Rentzeperis, P. The Crystal Structure of BiOCl Z. Kristallogr. - Cryst. Mater. 1993, 205, 35– 40 DOI: 10.1524/zkri.1993.205.12.35
  23
  The crystal structure of bismuth oxychloride (BiOCl)
  Keramidas, K. G.; Voutsas, G. P.; Rentzeperis, P. I.
  Zeitschrift fuer Kristallographie (1993), 205 (1), 35-40CODEN: ZEKRDZ; ISSN:0044-2968.
  The crystal structure of prepd. BiOCl was redetd. with 3570 obsd. reflections of which 174 were unique measured on a computer controlled Philips PW 1100 single crystal diffractometer. The structure belongs to the tetragonal space group P4/nmm and the cell consts., obtained by a least-squares calcn. from direct Θ-value measurements on the diffractometer, are a 3.8870(5) and c 7.3540(5) Å. The positional and thermal parameters, with anisotropic temp. factors, were refined by full-matrix least-squares calcns. to a final R = 9.17%. Each Bi atom is 8-coordinate by 4 O and 4 Cl atoms at distances of 2.316 Å and 3.059 Å, resp., thus forming a decahedron. The faces of the decahedron are 2 rectangles (O-O-O-O and Cl-Cl-Cl-Cl) with sides 3.487 Å and 8 isosceles triangles (4 O-Cl-O and 4 Cl-O-Cl) with side O-Cl 3.249 Å and O-O or Cl-Cl 3.487 Å. The decahedra are linked to each other by a common O-Cl edge along the a and b axes in infinite layers.
24. 24
  Bannister, F.; Hey, M. The Crystal Structure Of The Bismuth Oxyhalides Mineral. Mag. 1935, 24, 49– 58 DOI: 10.1180/minmag.1935.024.149.01
  24
  The crystal structure of the bismuth oxyhalides
  Bannister, F. A.
  Mineralogical Magazine and Journal of the Mineralogical Society (1876-1968) (1935), 24 (), 49-58CODEN: MIASA6; ISSN:0369-0148.
  BiOCl, BiOBr and BiOI were prepd. by diffusion methods. Laue photographs indicate true tetragonal symmetry. Rotation and powder x-ray photographs indicate crystal structures of the matlockite type. The at. positions are Bi, 00u, 1/2 1/2‾u; X(Cl, Br, I), 00v, 1/2 1/2 ‾v; 0 1/2 00, 0 1/2 0. Unit cell dimensions are, BiOCl a = 3.89, c = 7.37 A.; BiOBr, a = 3.92, c = 8.11 A.; BiOI, a = 4.01, c = 9.14 A. The x-ray data for bismoclite and daubreeite are discussed.
25. 25
  Kusainova, A. M.; Zhou, W.; Irvine, J. T.; Lightfoot, P. Layered Intergrowth Phases Bi₄MO₈X (X= Cl, M= Ta and X= Br, M= Ta or Nb): Structural and Electrophysical Characterization J. Solid State Chem. 2002, 166, 148– 157 DOI: 10.1006/jssc.2002.9572
  25
  Layered intergrowth phases Bi4MO8X (X = Cl, M = Ta, and X = Br, M = Ta or Nb): structural and electrophysical characterization
  Kusainova, Ardak M.; Zhou, Wuzong; Irvine, John T. S.; Lightfoot, Philip
  Journal of Solid State Chemistry (2002), 166 (1), 148-157CODEN: JSSCBI; ISSN:0022-4596. (Elsevier Science)
  The high-temp. structural behavior of the layered inter-growth phase Bi4TaO8Cl, belonging to the Sillen-Aurivillius family, has been studied by powder neutron diffraction. This material is ferroelec., space group P21cn, at TC < 640 K. An order-disorder transition to centrosym. space group Pmcn is found around 640 K, which involves disordering of TaO6 octahedral tilts. A second phase transition, of a first-order nature, to space group P4/mmm occurs at a temp. of ∼1038 K. The crystal structures of the bromide analogs Bi4MO8Br (M = Nb, Ta) have also been detd. at room temp.; both are isomorphous with Bi4TaO8Cl and exhibit maxima in dielec. const. at temps. of approx. 588 and 450 K, resp.
26. 26
  Ai, Z.; Ho, W.; Lee, S.; Zhang, L. Efficient Photocatalytic Removal of NO in Indoor Air with Hierarchical Bismuth Oxybromide Nanoplate Microspheres Under Visible Light Environ. Sci. Technol. 2009, 43, 4143– 4150 DOI: 10.1021/es9004366
  26
  Efficient Photocatalytic Removal of NO in Indoor Air with Hierarchical Bismuth Oxybromide Nanoplate Microspheres under Visible Light
  Ai, Zhihui; Ho, Wingkei; Lee, Shuncheng; Zhang, Lizhi
  Environmental Science & Technology (2009), 43 (11), 4143-4150CODEN: ESTHAG; ISSN:0013-936X. (American Chemical Society)
  Hierarchical bismuth oxybromide (BiOBr) nano-plate micro-spheres were used to remove NO from indoor air under visible light irradn. BiOBr micro-spheres were synthesized with a non-aq., sol-gel method using bismuth nitrate and cetyltrimethyl ammonium bromide as precursors. For the NO degrdn. under visible light irradn. (λ >420 nm) at 400 part-per-billion concn., a typical concn. for indoor air, these non-aq., sol-gel synthesized hierarchical BiOBr micro-spheres exhibited superior photocatalytic activity to chem. pptn.-synthesized counterpart BiOBr bulk powder and Degussa TiO2 P25 and C-doped TiO2. The excellent catalytic activity and long-term activity of non-aq., sol-gel synthesized BiOBr micro-spheres were attributed to their special hierarchical structure, favorable for diffusion of NO oxidn. intermediate compds. and final products. Ion chromatog. results confirmed HNO3 was produced on the BiOBr micro-sphere surface during gas-phase NO photooxidn. Results suggested that non-aq., sol-gel synthesized BiOBr nano-plate micro-spheres are promising photocatalytic material for indoor air purifn.
27. 27
  Henle, J.; Simon, P.; Frenzel, A.; Scholz, S.; Kaskel, S. Nanosized BiOX (X= Cl, Br, I) Particles Synthesized in Reverse Microemulsions Chem. Mater. 2007, 19, 366– 373 DOI: 10.1021/cm061671k
  There is no corresponding record for this reference.
28. 28
  Wang, W.; Huang, F.; Lin, X. xBiOI—(1–x)BiOCl as efficient visible-light-driven photocatalysts Scr. Mater. 2007, 56, 669– 672 DOI: 10.1016/j.scriptamat.2006.12.023
  28
  xBiOI-(1 - x)BiOCl as efficient visible-light-driven photocatalysts
  Wang, Wendeng; Huang, Fuqiang; Lin, Xinping
  Scripta Materialia (2007), 56 (8), 669-672CODEN: SCMAF7; ISSN:1359-6462. (Elsevier Ltd.)
  A new class of oxyhalide photocatalysts, xBiOI-(1 - x)BiOCl, were prepd. by a soft chem. method. The samples with x = 0.2-1.0 have intense absorptions in the visible light region and the optical band gaps are in the range 1.92-2.31 eV. They possess high photocatalytic activities under visible light irradn. for the degrdn. of methyl orange. This high photocatalytic activity is in close relation with the deep valance band edge position and the internal elec. fields between [Bi2O2] slabs and halogen anionic slabs.
29. 29
  Wang, W.; Huang, F.; Lin, X.; Yang, J. Visible-Light-Responsive Photocatalysts xBiOBr—(1–x)BiOI Catal. Commun. 2008, 9, 8– 12 DOI: 10.1016/j.catcom.2007.05.014
  29
  Visible-light-responsive photocatalysts xBiOBr-(1-x)BiOI
  Wang, Wendeng; Huang, Fuqiang; Lin, Xinping; Yang, Jianhua
  Catalysis Communications (2007), 9 (1), 8-12CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
  A new class of oxyhalide photocatalysts xBiOBr-(1-x)BiOI prepd. by a soft chem. method were characterized by X-ray diffraction and UV-Vis diffuse reflectance spectra. They are all visible-light-responsive materials with the bandgaps ranging from 1.92 to 2.91 eV. Methyl orange (MO) photocatalytic degrdn. expts. showed that BiOBr possessed a higher photocatalytic activity than P25 (TiO2) under UV illumination and iodine-modified BiOBr exhibited high photocatalytic activities under visible-light irradn. The high photocatalytic activity is in close relation with the deep valance band edge position and the internal elec. fields between [Bi2O2] slabs and halogen anionic slabs.
30. 30
  Chen, L.; Yin, S.-F.; Huang, R.; Zhou, Y.; Luo, S.-L.; Au, C.-T. Facile Synthesis of BiOCl Nano-Flowers of Narrow Band Gap and their Visible-Light-Induced Photocatalytic Property Catal. Commun. 2012, 23, 54– 57 DOI: 10.1016/j.catcom.2012.03.001
  30
  Facile synthesis of BiOCl nano-flowers of narrow band gap and their visible-light-induced photocatalytic property
  Chen, Lang; Yin, Shuang-Feng; Huang, Rui; Zhou, Yan; Luo, Sheng-Lian; Au, Chak-Tong
  Catalysis Communications (2012), 23 (), 54-57CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
  Novel nanostructured flower-like bismuth oxychloride (BiOCl) has been fast synthesized by a simple method in the presence of nitric acid and L-Lysine. The BiOCl nano-flowers, with a narrow band gap (2.87 eV), show excellent photocatalytic activity in the degrdn. of Rh-B dye under visible light (λ ≥ 435 nm), much higher than those of the photocatalysts ever reported in the literatures.
31. 31
  Su, W.; Wang, J.; Huang, Y.; Wang, W.; Wu, L.; Wang, X.; Liu, P. Synthesis and Catalytic Performances of a Novel Photocatalyst BiOF Scr. Mater. 2010, 62, 345– 348 DOI: 10.1016/j.scriptamat.2009.10.039
  31
  Synthesis and catalytic performances of a novel photocatalyst BiOF
  Su, Wenyue; Wang, Jian; Huang, Yingxing; Wang, Wanjun; Wu, Ling; Wang, Xu Xu; Liu, Ping
  Scripta Materialia (2010), 62 (6), 345-348CODEN: SCMAF7; ISSN:1359-6462. (Elsevier Ltd.)
  A novel oxyhalide photocatalyst BiOF was prepd. by pptn. and subsequent heat treatment. The influence of calcination temp. on the synthesis of BiOF was investigated. Interestingly, the as-prepd. BiOF exhibits high photocatalytic performance in the degrdn. of universal org. pollutants. The high photocatalytic activity is closely related to the internal elec. fields between [Bi2O2] slabs and fluorine anionic slabs.
32. 32
  Deng, H.; Wang, J.; Peng, Q.; Wang, X.; Li, Y. Controlled Hydrothermal Synthesis of Bismuth Oxyhalide Nanobelts and Nanotubes Chem. - Eur. J. 2005, 11, 6519– 6524 DOI: 10.1002/chem.200500540
  32
  Controlled hydrothermal synthesis of bismuth oxyhalide nanobelts and nanotubes
  Deng, Hong; Wang, Junwei; Peng, Qing; Wang, Xun; Li, Yadong
  Chemistry - A European Journal (2005), 11 (22), 6519-6524CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Ternary Bi oxyhalide cryst. nanobelts (such as Bi24O31Br10, Bi3O4Br, Bi12O17Br2, BiOCl, and Bi24O31Cl10) and nanotubes (such as Bi24O31Br10) were synthesized by using convenient hydrothermal methods. The compn. and morphologies of the Bi oxyhalides could be controlled by adjusting some growth parameters, including reaction pH, time, and temp. All the nanostructures were characterized by using various methods including x-ray diffraction, TEM, high-resoln. TEM, electron diffraction, and energy-dispersive x-ray anal. The possible reaction mechanism and growth of the crystals are discussed based on the exptl. results.
33. 33
  Heyd, S.; Scuseria, G. E.; Ernzerhof, M. Hybrid Functionals Based on a Screened Coulomb Potential J. Chem. Phys. 2003, 118, 8207– 8215 DOI: 10.1063/1.1564060
  33
  Hybrid functionals based on a screened Coulomb potential
  Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  Journal of Chemical Physics (2003), 118 (18), 8207-8215CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
  Hybrid d. functionals are very successful in describing a wide range of mol. properties accurately. In large mols. and solids, however, calcg. the exact (Hartree-Fock) exchange is computationally expensive, esp. for systems with metallic characteristics. In the present work, we develop a new hybrid d. functional based on a screened Coulomb potential for the exchange interaction which circumvents this bottleneck. The results obtained for structural and thermodn. properties of mols. are comparable in quality to the most widely used hybrid functionals. In addn., we present results of periodic boundary condition calcns. for both semiconducting and metallic single wall carbon nanotubes. Using a screened Coulomb potential for Hartree-Fock exchange enables fast and accurate hybrid calcns., even of usually difficult metallic systems. The high accuracy of the new screened Coulomb potential hybrid, combined with its computational advantages, makes it widely applicable to large mols. and periodic systems.
34. 34
  Krukau, A. V.; Vydrov, O. A.; Izmaylov, A. F.; Scuseria, G. E. Influence of the Exchange Screening Parameter on the Performance Of Screened Hybrid Functionals J. Chem. Phys. 2006, 125, 224106 DOI: 10.1063/1.2404663
  34
  Influence of the exchange screening parameter on the performance of screened hybrid functionals
  Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.; Scuseria, Gustavo E.
  Journal of Chemical Physics (2006), 125 (22), 224106/1-224106/5CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
  This work reexamines the effect of the exchange screening parameter ω on the performance of the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional. We show that variation of the screening parameter influences solid band gaps the most. Other properties such as mol. thermochem. or lattice consts. of solids change little with ω. We recommend a new version of HSE with the screening parameter ω = 0.11 bohr-1 for further use. Compared to the original implementation, the new parametrization yields better thermochem. results and preserves the good accuracy for band gaps and lattice consts. in solids.
35. 35
  Blöchl, P. E. Projector Augmented-Wave Method Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 50, 17953 DOI: 10.1103/PhysRevB.50.17953
  35
  Projector augmented-wave method
  Blochl
  Physical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.
  There is no expanded citation for this reference.
36. 36
  Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented Wave Method Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 1758– 1775 DOI: 10.1103/PhysRevB.59.1758
  36
  From ultrasoft pseudopotentials to the projector augmented-wave method
  Kresse, G.; Joubert, D.
  Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
  The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
37. 37
  Grimme, S. Accurate Description of van der Waals Complexes by Density Funcitonal Theory Including Empirical Corrections J. Comput. Chem. 2004, 25, 1463– 1473 DOI: 10.1002/jcc.20078
  There is no corresponding record for this reference.
38. 38
  Savory, C. N.; Palgrave, R. G.; Bronstein, H.; Scanlon, D. O. Spatial Electron-hole Separation in a One Dimensional Hybrid Organic–Inorganic Lead Iodide Sci. Rep. 2016, 6, 20626 DOI: 10.1038/srep20626
  38
  Spatial Electron-hole Separation in a One Dimensional Hybrid Organic-Inorganic Lead Iodide
  Savory, Christopher N.; Palgrave, Robert G.; Bronstein, Hugo; Scanlon, David O.
  Scientific Reports (2016), 6 (), 20626CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
  The increasing efficiency of the inorg.-org. hybrid halides has revolutionised photovoltaic research. Despite this rapid progress, the significant issues of poor stability and toxicity have yet to be suitably overcome. In this article, we use D. Functional Theory to examine (Pb2I6)·(H2DPNDI)·(H2O)·(NMP), an alternative lead-based hybrid inorg.-org. solar absorber based on a photoactive org. cation. Our results demonstrate that optical properties suitable for photovoltaic applications, in addn. to spatial electron-hole sepn., are possible but efficient charge transport may be a limiting factor.
39. 39
  Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for ab initio Total-Energy Calculations Using a Plane-wave Basis Set Phys. Rev. B: Condens. Matter Mater. Phys. 1996, 54, 11169– 11186 DOI: 10.1103/PhysRevB.54.11169
  39
  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
  Kresse, G.; Furthmueller, J.
  Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
  The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
40. 40
  Kresse, G.; Hafner, J. Ab Initio Molecular-Dynamics Simulation of the Liquid-Metal–Amorphous-Semiconductor Transition in Germanium Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 49, 14251– 14271 DOI: 10.1103/PhysRevB.49.14251
  40
  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium
  Kresse, G.; Hafner, J.
  Physical Review B: Condensed Matter and Materials Physics (1994), 49 (20), 14251-69CODEN: PRBMDO; ISSN:0163-1829.
  The authors present ab initio quantum-mech. mol.-dynamics simulations of the liq.-metal-amorphous-semiconductor transition in Ge. The simulations are based on (a) finite-temp. d.-functional theory of the 1-electron states, (b) exact energy minimization and hence calcn. of the exact Hellmann-Feynman forces after each mol.-dynamics step using preconditioned conjugate-gradient techniques, (c) accurate nonlocal pseudopotentials, and (d) Nose' dynamics for generating a canonical ensemble. This method gives perfect control of the adiabaticity of the electron-ion ensemble and allows the authors to perform simulations over >30 ps. The computer-generated ensemble describes the structural, dynamic, and electronic properties of liq. and amorphous Ge in very good agreement with expt.. The simulation allows the authors to study in detail the changes in the structure-property relation through the metal-semiconductor transition. The authors report a detailed anal. of the local structural properties and their changes induced by an annealing process. The geometrical, bounding, and spectral properties of defects in the disordered tetrahedral network are studied and compared with expt.
41. 41
  Walsh, A.; Butler, K. T. Prediction of Electron Energies in Metal Oxides Acc. Chem. Res. 2014, 47, 364– 372 DOI: 10.1021/ar400115x
  41
  Prediction of Electron Energies in Metal Oxides
  Walsh, Aron; Butler, Keith T.
  Accounts of Chemical Research (2014), 47 (2), 364-372CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
  A review. The ability to predict energy levels in metal oxides is paramount to developing useful materials, such as in the development of water photolysis catalysts and efficient photovoltaic cells. The binding energy of electrons in materials encompasses a wealth of information concerning their physicochem. The energies control the optical and elec. properties, dictating for which kinds of chem. and physics a particular material is useful. Scientists have developed theories and models for electron energies in a variety of chem. systems over the past century. However, the prediction of quant. energy levels in new materials remains a major challenge. This issue is of particular importance in metal oxide research, where novel chemistries have opened the possibility of a wide range of tailored systems with applications in important fields including light-emitting diodes, energy efficient glasses, and solar cells. In this Account, we discuss the application of atomistic modeling techniques, covering the spectrum from classical to quantum descriptions, to explore the alignment of electron energies between materials. We present a no. of paradigmatic examples, including a series of oxides (ZnO, In2O3, and Cu2O). Such calcns. allow the detn. of a "band alignment diagram" between different materials and can facilitate the prediction of the optimal chem. compn. of an oxide for use in a given application. Throughout this Account, we consider direct computational solns. in the context of heuristic models, which are used to relate the fundamental theory to exptl. observations. We review a no. of techniques that have been commonly applied in the study of electron energies in solids. These models have arisen from different answers to the same basic question, coming from solid-state chem. and physics perspectives. We highlight common factors, as well as providing a crit. appraisal of the strengths and weaknesses of each, emphasizing the difficulties in translating concepts from mol. to solid-state systems. Finally, we stress the need for a universal description of the alignment of band energies for materials design from first-principles. By demonstrating the applicability and challenges of using theory to calc. the relevant quantities, as well as impressing the necessity of a clarification and unification of the descriptions, we hope to provide a stimulus for the continued development of this field.
42. 42
  Ganose, A. M.; Butler, K. T.; Walsh, A.; Scanlon, D. O. Relativistic Electronic Struc-ture and Band Alignment of BiSI and BiSeI: Candidate Photovoltaic Materials J. Mater. Chem. A 2016, 4, 2060– 2068 DOI: 10.1039/C5TA09612J
  42
  Relativistic electronic structure and band alignment of BiSI and BiSeI: candidate photovoltaic materials
  Ganose, Alex M.; Butler, Keith T.; Walsh, Aron; Scanlon, David O.
  Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (6), 2060-2068CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
  Bi-based solar absorbers are of interest due to similarities in the chem. properties of Bi halides and the exceptionally efficient Pb halide hybrid perovskites. While they both experience the same beneficial relativistic effects acting to increase the width of the conduction band, Bi is non-toxic and non-bioaccumulating, meaning the impact of environmental contamination is greatly reduced. We use hybrid d. functional theory, with the addn. of spin orbit coupling, to examine 2 candidate bismuth contg. photovoltaic absorbers, BiSI and BiSeI, and show that they possess electronic structures suitable for photovoltaic applications. We calc. band alignments against commonly used hole transporting and buffer layers, which indicate band misalignments are likely to be the source of the poor efficiencies reported for devices contg. these materials. We suggest alternative device architectures expected to result in improved power conversion efficiencies.
43. 43
  Brgoch, J.; Lehner, A. J.; Chabinyc, M.; Seshadri, R. Ab Initio Calculations of Band Gaps and Absolute Band Positions of Polymorphs of RbPbI₃ and CsPbI₃: Implications for Main-Group Halide Perovskite Photovoltaics J. Phys. Chem. C 2014, 118, 27721– 27727 DOI: 10.1021/jp508880y
  43
  Ab Initio Calculations of Band Gaps and Absolute Band Positions of Polymorphs of RbPbI3 and CsPbI3: Implications for Main-Group Halide Perovskite Photovoltaics
  Brgoch, Jakoah; Lehner, Anna J.; Chabinyc, Michael; Seshadri, Ram
  Journal of Physical Chemistry C (2014), 118 (48), 27721-27727CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
  Lead halide perovskites have attracted great interest because of rapid improvements in the efficiency of photovoltaics based on these materials. To predict new related functional materials, a good understanding of the correlations between crystal chem., electronic structure, and optoelectronic properties is required. Describing the electronic structure of these materials using d. functional theory provides a choice of exchange-correlation functionals, including hybrid functionals, and inclusion of spin-orbit coupling, which is crit. for the correct description of band gap and abs. band positions (ionization energy). Here, various computational schemes that employ different choices of exchange-correlation and hybrid functionals, and include or exclude spin-orbit coupling were implemented to examine these effects. Using PbI2 as an initial structural model, it is found that std. exchange correlation functionals (PBE) in conjunction with spin-orbit coupling suffice to locate ionization energies efficiently through the use of slab calcns. Band gaps require the use of hybrid functionals carried out on single unit cells and spin-orbit coupling. Polymorphs of alkali metal lead halides, APbI3 (A = Rb, Cs) are examd. in the cubic perovskite structure and the reduced dimensional NH4CdCl3/Sn2S3 structure with quasi-two-dimensional connectivity. The somewhat elevated Born effective charges computed for these structures suggest that while the Pb2+ 6s lone-pairs are stereochem. inert, the presence of proximal instabilities could have implications for the functional properties of these materials.
44. 44
  Brivio, F.; Butler, K. T.; Walsh, A.; Van Schilfgaarde, M. Relativistic Quasiparticle Self-Consistent Electronic Structure of Hybrid Halide Perovskite Photovoltaic Absorbers Phys. Rev. B: Condens. Matter Mater. Phys. 2014, 89, 155204 DOI: 10.1103/PhysRevB.89.155204
  44
  Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers
  Brivio, Federico; Butler, Keith T.; Walsh, Aron; van Schilfgaarde, Mark
  Physical Review B: Condensed Matter and Materials Physics (2014), 89 (15), 155204/1-155204/6CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
  Solar cells based on a light absorbing layer of the organometal halide perovskite CH3NH3PbI3 have recently surpassed 15% conversion efficiency, though how these materials work remains largely unknown. We analyze the electronic structure and optical properties within the quasiparticle self-consistent GW approxn. While this compd. bears some similarity to conventional sp semiconductors, it also displays unique features. Quasiparticle self-consistency is essential for an accurate description of the band structure: Band gaps are much larger than what is predicted by the local-d. approxn. (LDA) or GW based on the LDA. Valence band dispersions are modified in a very unusual manner. In addn., spin-orbit coupling strongly modifies the band structure and gives rise to unconventional dispersion relations and a Dresselhaus splitting at the band edges. The av. hole mass is small, which partially accounts for the long diffusion lengths obsd. The surface ionization potential (work function) is calcd. to be 5.7 eV with respect to the vacuum level, explaining efficient carrier transfer to TiO2 and Au elec. contacts.
45. 45
  Even, J.; Pedesseau, L.; Jancu, J.-M.; Katan, C. Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications J. Phys. Chem. Lett. 2013, 4, 2999– 3005 DOI: 10.1021/jz401532q
  45
  Importance of Spin-Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
  Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc; Katan, Claudine
  Journal of Physical Chemistry Letters (2013), 4 (17), 2999-3005CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
  Three-dimensional (3D) hybrid perovskites MeNH3PbX3 (X = Br, I) have recently been suggested as new key materials for dye-sensitized solar cells (DSSC) leading to a new class of hybrid semiconductor photovoltaic cells (HSPC). Thanks to d. functional theory calcns., the band gap of these compds. is dominated by a giant spin-orbit coupling (SOC) in the conduction-band (CB). At room temp., direct and isotropic optical transitions are assocd. to a spin-orbit split-off band related to the triply degenerated CB of the cubic lattice without SOC. Due to the strong SOC, the electronic states involved in the optical absorption are only slightly perturbed by local distortions of the lattice. Band offset calcns. confirm that MeNH3PbX3/TiO2 is a ref. material for driving electrons toward the electrode in HSPC. Two-dimensional (2D) hybrids also probably have flexibility for light conversion efficiency. The study affords the basic concepts to reach the level of knowledge already attained for optoelectronic properties of conventional semiconductors.
46. 46
  Ganose, A. M.; Savory, C. N.; Scanlon, D. O. (CH₃NH₃)₂Pb(SCN)₂I₂: A More Stable Structural Motif for Hybrid Halide Photovoltaics? J. Phys. Chem. Lett. 2015, 6, 4594– 4598 DOI: 10.1021/acs.jpclett.5b02177
  46
  (CH3NH3)2Pb(SCN)2I2: A New More Stable Structural Motif for Hybrid Halide Photovoltaics?
  Ganose, Alex M.; Savory, Christopher N.; Scanlon, David O.
  Journal of Physical Chemistry Letters (2015), 6 (22), 4594-4598CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
  Hybrid halide perovskites have recently emerged as a highly efficient class of light absorbers; however, there are increasing concerns over their long-term stability. Recently, incorporation of SCN- was suggested as a novel route to improving stability without neg. impacting performance. Intriguingly, despite crystg. in a 2-dimensional layered structure, (CH3NH3)2Pb(SCN)2I2 (MAPSI) possesses an ideal band gap of 1.53 eV, close to that of the 3-dimensional connected champion hybrid perovskite absorber, CH3NH3PbI3 (MAPI). Here, the authors identify, using hybrid d. functional theory, the origin of the smaller than expected band gap of MAPSI through a detailed comparison with the electronic structure of MAPI. Also, assessment of the MAPSI structure reveals that it is thermodynamically stable with respect to phase sepn., a likely source of the increased stability reported in expt.
47. 47
  Zhang, H.; Liu, C.-X.; Qi, X.-L.; Dai, X.; Fang, Z.; Zhang, S.-C. Topological Insulators in Bi₂Se₃, Bi₂Te₃ and Sb₂Te₃ with a Single Dirac Cone on the Surface Nat. Phys. 2009, 5, 438– 442 DOI: 10.1038/nphys1270
  47
  Topological insulators in Bi2Se3, Bi2Te3 and Sb2Te3 with a single Dirac cone on the surface
  Zhang, Haijun; Liu, Chao-Xing; Qi, Xiao-Liang; Dai, Xi; Fang, Zhong; Zhang, Shou-Cheng
  Nature Physics (2009), 5 (6), 438-442CODEN: NPAHAX; ISSN:1745-2473. (Nature Publishing Group)
  Topol. insulators are new states of quantum matter in which surface states residing in the bulk insulating gap of such systems are protected by time-reversal symmetry. The study of such states was originally inspired by the robustness to scattering of conducting edge states in quantum Hall systems. Recently, such analogies resulted in the discovery of topol. protected states in two-dimensional and three-dimensional band insulators with large spin-orbit coupling. So far, the only known three-dimensional topol. insulator is BixSb1-x, which is an alloy with complex surface states. Here, the authors present the results of 1st-principles electronic structure calcns. of the layered, stoichiometric crystals Sb2Te3, Sb2Se3, Bi2Te3 and Bi2Se3. The authors' calcns. predict that Sb2Te3, Bi2Te3 and Bi2Se3 are topol. insulators, whereas Sb2Se3 is not. These topol. insulators have robust and simple surface states consisting of a single Dirac cone at the Γ point. The authors predict that Bi2Se3 has a topol. nontrivial energy gap of 0.3 eV, which is larger than the energy scale of room temp. The authors further present a simple and unified continuum model that captures the salient topol. features of this class of materials.
48. 48
  Scanlon, D.; King, P.; Singh, R.; De La Torre, A.; Walker, S. M.; Balakrishnan, G.; Baumberger, F.; Catlow, C. Controlling Bulk Conductivity in Topological Insulators:Key Role of Anti-Site Defects Adv. Mater. 2012, 24, 2154– 2158 DOI: 10.1002/adma.201200187
  There is no corresponding record for this reference.
49. 49
  Waghmare, U.; Spaldin, N.; Kandpal, H.; Seshadri, R. First-Principles Indicators of Metallicity and Cation Off-Centricity in rhe IV-VI Rocksalt Chalcogenides of Divalent Ge, Sn, and Pb Phys. Rev. B: Condens. Matter Mater. Phys. 2003, 67, 125111 DOI: 10.1103/PhysRevB.67.125111
  There is no corresponding record for this reference.
50. 50
  Raulot, J.-M.; Baldinozzi, G.; Seshadri, R.; Cortona, P. An Ab-Initio Study of the rôle of Lone Pairs in the Structure and Insulator–Metal Transition in SnO and PbO Solid State Sci. 2002, 4, 467– 474 DOI: 10.1016/S1293-2558(02)01280-3
  50
  An ab-initio study of the role of lone pairs in the structure and insulator-metal transition in SnO and PbO
  Raulot, Jean-Marc; Baldinozzi, Gianguido; Seshadri, Ram; Cortona, Pietro
  Solid State Sciences (2002), 4 (4), 467-474CODEN: SSSCFJ; ISSN:1293-2558. (Editions Scientifiques et Medicales Elsevier)
  We performed d. functional calcns. on tetragonal SnO and PbO (litharge) in the space group P4/nmm with the specific intention of examg. the role played by Sn 5s and Pb 6s lone pairs in stabilizing the structure and in giving rise to semi-metallic behavior (of SnO at ambient pressure and of PbO in the γ phase). Use of the electron localization function permitted real-space visualization of the lone pair in these structures. We also discussed the electronic structure of the orthorhombic PbO (massicot, space group Pbma) which again has localized lone pairs, contrary to some earlier expectation.
51. 51
  Walsh, A.; Watson, G. W. The Origin of the Stereochemically Active Pb(II) Lone Pair: DFT Calculations on PbO And PbS J. Solid State Chem. 2005, 178, 1422– 1428 DOI: 10.1016/j.jssc.2005.01.030
  51
  The origin of the stereochemically active Pb(II) lone pair: DFT calculations on PbO and PbS
  Walsh, Aron; Watson, Graeme W.
  Journal of Solid State Chemistry (2005), 178 (5), 1422-1428CODEN: JSSCBI; ISSN:0022-4596. (Elsevier)
  The concept of a chem. inert but stereochem. active 6s2 lone pair is commonly assocd. with Pb(II). We have performed d. functional theory calcns. on PbO and PbS in both the rocksalt and litharge structures which show anion dependence of the stereochem. active lone pair. PbO is more stable in litharge while PbS is not, and adopts the sym. rocksalt structure showing no lone pair activity. Anal. of the electron d., d. of states and crystal orbital overlap populations shows that the asym. electron d. formed by Pb(II) is a direct result of anion-cation interactions. The formation has a strong dependence on the electronic states of the anion and while oxygen has the states required for interaction with Pb 6s, sulfur does not. This explains for the first time why PbO forms distorted structures and possesses an asym. d. and PbS forms sym. structures with no lone pair activity. This anal. shows that distorted Pb(II) structures are not the result of chem. inert, sterically active lone pairs, but instead result from asym. electron densities that rely on direct electronic interaction with the coordinated anions.
52. 52
  Burton, L. A.; Walsh, A. Band Alignment in SnS Thin-Film Solar Cells: Possible Origin of the Low Conversion Efficiency Appl. Phys. Lett. 2013, 102, 132111 DOI: 10.1063/1.4801313
  52
  Band alignment in SnS thin-film solar cells: Possible origin of the low conversion efficiency
  Burton, Lee A.; Walsh, Aron
  Applied Physics Letters (2013), 102 (13), 132111/1-132111/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
  Tin sulfide is an attractive absorber material for low-cost thin-film solar cells. Despite the ideal phys. properties of bulk SnS, the photovoltaic conversion efficiencies achieved in devices to date have been no greater than 2%. Assessment of the valence band energy of the stable orthorhombic phase of SnS reveals a low ionization potential (4.7 eV) in comparison to typical absorber materials (CdTe, CuInSe2, and Cu2ZnSnS4). A band mis-alignment is therefore predicted with commonly used back contact and buffer layers. Alternative configurations are proposed that should improve device performance. (c) 2013 American Institute of Physics.
53. 53
  Butler, K. T.; Hendon, C. H.; Walsh, A. Electronic Chemical Potentials of Porous Metal–Organic Frameworks J. Am. Chem. Soc. 2014, 136, 2703– 2706 DOI: 10.1021/ja4110073
  53
  Electronic Chemical Potentials of Porous Metal-Organic Frameworks
  Butler, Keith T.; Hendon, Christopher H.; Walsh, Aron
  Journal of the American Chemical Society (2014), 136 (7), 2703-2706CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  The binding energy of an electron in a material is a fundamental characteristic, which dets. a wealth of important chem. and phys. properties. For metal-org. frameworks this quantity is hitherto unknown. We present a general approach for detg. the vacuum level of porous metal-org. frameworks and apply it to obtain the first ionization energy for six prototype materials including zeolitic, covalent, and ionic frameworks. This approach for valence band alignment can explain observations relating to the electrochem., optical, and elec. properties of porous frameworks.
54. 54
  Hahn, N. T.; Hoang, S.; Self, J. L.; Mullins, C. B. Spray Pyrolysis Deposition and Photoelectrochemical Properties of n-Type BiOI Nanoplatelet Thin Films ACS Nano 2012, 6, 7712– 7722 DOI: 10.1021/nn3031063
  54
  Spray pyrolysis deposition and photoelectrochemical properties of n-type BiOI nanoplatelet thin films
  Hahn, Nathan T.; Hoang, Son; Self, Jeffrey L.; Mullins, C. Buddie
  ACS Nano (2012), 6 (9), 7712-7722CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
  Bismuth oxy-iodide is a potentially interesting visible-light-active photocatalyst; yet there is little research regarding its photoelectrochem. properties. Herein we report the synthesis of BiOI nanoplatelet photoelectrodes by spray pyrolysis on fluorine-doped tin oxide substrates at various temps. The films exhibited n-type cond., most likely due to the presence of anion vacancies, and optimized films possessed incident photon conversion efficiencies of over 20% in the visible range for the oxidn. of I- to I3- at 0.4 V vs Ag/AgCl in acetonitrile. Visible-light photons (λ > 420 nm) contributed approx. 75% of the overall photocurrent under AM1.5G illumination, illustrating their usefulness under solar light illumination. A deposition temp. of 260 °C was found to result in the best performance due to the balance of morphol., crystallinity, impurity levels, and optical absorption, leading to photocurrents of roughly 0.9 mA/cm2 at 0.4 V vs Ag/AgCl. Although the films performed stably in acetonitrile, their performance decreased significantly upon extended exposure to water, which was apparently caused by a loss of surface iodine and subsequent formation of an insulating bismuth hydroxide layer.
55. 55
  Scanlon, D. O.; Watson, G. W. On the Possibility of p-Type SnO₂ J. Mater. Chem. 2012, 22, 25236– 25245 DOI: 10.1039/c2jm34352e
  55
  On the possibility of p-type SnO2
  Scanlon, David O.; Watson, Graeme W.
  Journal of Materials Chemistry (2012), 22 (48), 25236-25245CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
  SnO2 is an abundant, low cost, natively n-type, wide band gap oxide, which can achieve high conductivities due to facile donor doping. Realization of a p-type SnO2 would, however, open up many new avenues in device applications, and has become a major research goal. Previous exptl. and theor. studies have proved inconclusive, with the p-type ability of SnO2 being both supported and questioned in equal measure. We use state of the art hybrid d. functional theory to investigate the nature of intrinsic and extrinsic p-type defects in SnO2. All the p-type defects considered in SnO2 produce localized hole polarons centered on anion sites. We calc. the thermodn. ionization energies of these defects, and demonstrate that an efficient p-type SnO2 is not achievable.
56. 56
  Frost, J. M.; Butler, K. T.; Brivio, F.; Hendon, C. H.; Van Schilfgaarde, M.; Walsh, A. Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells Nano Lett. 2014, 14, 2584– 2590 DOI: 10.1021/nl500390f
  56
  Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
  Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico; Hendon, Christopher H.; van Schilfgaarde, Mark; Walsh, Aron
  Nano Letters (2014), 14 (5), 2584-2590CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
  The performance of organometallic perovskite solar cells has rapidly surpassed that of both conventional dye-sensitized and org. photovoltaics. High-power conversion efficiency can be realized in both mesoporous and thin-film device architectures. The authors address the origin of this success in the context of the materials chem. and physics of the bulk perovskite as described by electronic structure calcns. In addn. to the basic optoelectronic properties essential for an efficient photovoltaic device (spectrally suitable band gap, high optical absorption, low carrier effective masses), the materials are structurally and compositionally flexible. As the authors show, hybrid perovskites exhibit spontaneous elec. polarization; the authors also suggest ways in which this can be tuned through judicious choice of the org. cation. The presence of ferroelec. domains will result in internal junctions that may aid sepn. of photoexcited electron and hole pairs, and redn. of recombination through segregation of charge carriers. The combination of high dielec. const. and low effective mass promotes both Wannier-Mott exciton sepn. and effective ionization of donor and acceptor defects. The photoferroic effect could be exploited in nanostructured films to generate a higher open circuit voltage and may contribute to the current-voltage hysteresis obsd. in perovskite solar cells.
57. 57
  Ganose, A. M.; Scanlon, D. O. Band Gap and Work Function Tailoring of SnO₂ for Improved Transparent Conducting Ability in Photovoltaics J. Mater. Chem. C 2016, 4, 1467– 1475 DOI: 10.1039/C5TC04089B
  57
  Band gap and work function tailoring of SnO2 for improved transparent conducting ability in photovoltaics
  Ganose, Alex M.; Scanlon, David O.
  Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2016), 4 (7), 1467-1475CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)
  Transparent conducting oxides (TCOs) are an essential component in modern optoelectronic devices, such as solar panels and touch screens. Their ability to combine transparency and cond., two properties that are normally mutually exclusive, have made them the subject of intense research over the last 50 years. SnO2, doped with F or Sb, is a widely used and relatively inexpensive transparent conducting material, however, its electronic structure leaves scope for improving its properties for use in many TCO applications, esp. in solar cell devices. Here we show using d. functional theory that incorporation of Pb into SnO2 reduces the band gap through lowering of the conduction band min., thereby increasing the electron affinity. The electron effective mass at the conduction band min. decreases alongside the band gap, indicating improved charge carrier mobilities. Furthermore, the calcd. optical absorption properties show the alloys retain their transparency in the visible spectrum. Our results suggest that alloying of PbO2 with SnO2 will enable improved electronic properties, including a highly tuneable workfunction, which will open up the material for other applications, such as hole injection layers in org. photovoltaics.
58. 58
  Chang, X.; Gondal, M.; Al-Saadi, A.; Ali, M.; Shen, H.; Zhou, Q.; Zhang, J.; Du, M.; Liu, Y.; Ji, G. Photodegradation of Rhodamine B Over Unexcited Semiconductor Compounds of BiOCl and BiOBr J. Colloid Interface Sci. 2012, 377, 291– 298 DOI: 10.1016/j.jcis.2012.03.021
  58
  Photodegradation of Rhodamine B over unexcited semiconductor compounds of BiOCl and BiOBr
  Chang, Xiaofeng; Gondal, M. A.; Al-Saadi, A. A.; Ali, M. A.; Shen, Hefei; Zhou, Qin; Zhang, Jun; Du, Mengping; Liu, Yousong; Ji, Guangbin
  Journal of Colloid and Interface Science (2012), 377 (1), 291-298CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
  Reported is the photodegrdn. of Rhodamine B (RhB) in aq. soln. over BiOCl and BiOBr semiconductors. Under visible light irradn. (>400, >420, and 550 nm), RhB adsorbed on the surface of BiOCl and BiOBr was photosensitized and decompd. effectively over unexcited BiOCl and BiOBr. The degrdn. of Methyl orange (MO) and Methylene Blue (MB) over BiOCl and BiOBr was investigated as well, and the results were compared with RhB photodegrdn. MB mols. having the lowest LUMO could not be degraded by this process. Utilizing the quantum chem. calcn. (Gaussian 03 program), the relationship between frontier orbital energy of selected dye mols. and photodegrdn. rate was established.
59. 59
  Zhang, J.; Xia, J.; Yin, S.; Li, H.; Xu, H.; He, M.; Huang, L.; Zhang, Q. Improvement of Visible Light Photocatalytic Activity Over Flower-Like BiOCl/BiOBr Microspheres Synthesized by Reactable Ionic Liquids Colloids Surf., A 2013, 420, 89– 95 DOI: 10.1016/j.colsurfa.2012.11.054
  59
  Improvement of visible light photocatalytic activity over flower-like BiOCl/BiOBr microspheres synthesized by reactable ionic liquids
  Zhang, Jing; Xia, Jiexiang; Yin, Sheng; Li, Huaming; Xu, Hui; He, Minqiang; Huang, Liying; Zhang, Qi
  Colloids and Surfaces, A: Physicochemical and Engineering Aspects (2013), 420 (), 89-95CODEN: CPEAEH; ISSN:0927-7757. (Elsevier B.V.)
  BiOCl/BiOBr uniform flower-like composite photocatalysts had been successfully synthesized through a one-pot ethylene glycol (EG)-assisted solvothermal process in the presence of 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl) and 1-hexadecyl-3-methylimidazolium bromide ([C16mim]Br) reactable ionic liqs. Their structures, morphol., and optical properties were characterized by x-ray diffraction (XRD), XPS, SEM, energy-dispersive x-ray spectroscopy (EDS) and UV-vis diffuse reflectance spectroscopy (DRS). The DRS anal. and high photocurrent suggested that BiOCl/BiOBr possessed absorption under visible light and was a benefit for the efficient generation and sepn. of the electron-hole pairs. Photocatalytic activity expt. proved that BiOCl/BiOBr composites exhibited higher photocatalytic activity than single BiOCl and BiOBr for the degrdn. of Rhodamine B (RhB) under visible light (λ > 400 nm). A possible photocatalytic mechanism based on the relative band positions of BiOCl and BiOBr had been proposed.
60. 60
  Cao, J.; Xu, B.; Luo, B.; Lin, H.; Chen, S. Novel BiOI/BiOBr Heterojunction Photocatalysts with Enhanced Visible Light Photocatalytic Properties Catal. Commun. 2011, 13, 63– 68 DOI: 10.1016/j.catcom.2011.06.019
  60
  Novel BiOI/BiOBr heterojunction photocatalysts with enhanced visible light photocatalytic properties
  Cao, Jing; Xu, Benyan; Luo, Bangde; Lin, Haili; Chen, Shifu
  Catalysis Communications (2011), 13 (1), 63-68CODEN: CCAOAC; ISSN:1566-7367. (Elsevier B.V.)
  A novel heterojunction photocatalyst BiOI/BiOBr was synthesized by a simple modified deposition-pptn. method. Several characterization tools including XRD, SEM, HRTEM and UV-visible DRS were employed to study the phase structures, morphologies and optical properties of the samples. BiOI/BiOBr exhibited higher photocatalytic activity than single BiOI and BiOBr for the degrdn. of methyl orange (MO) under visible light (λ > 420 nm). This result can be due to the formation of the heterojunction between BiOI and BiOBr, which can sep. photogenerated carriers efficiently. The photocatalytic mechanism study demonstrates that [rad]O2 - and H+ are the main reactive species while [rad]OH can be negligible.
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Interplay of Orbital and Relativistic Effects in Bismuth Oxyhalides: BiOF, BiOCl, BiOBr, and BiOI
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Interplay of Orbital and Relativistic Effects in Bismuth Oxyhalides: BiOF, BiOCl, BiOBr, and BiOI
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