There has been a direct correlation between the rate of industrial development and the spread of pollution on Earth, particularly in the last century. The organic and inorganic pollutants generated from industrial activities have created serious risks to human life and the environment. The concept of sustainability has emerged to tackle the environmental issues in developing chemical-based industries. However, pollutants have continued to be discharged to water resources, and finding appropriate techniques for the removal and remedy of wastewater is in high demand. Chromium is one of the high-risk heavy metals in industrial wastewaters that should be removed via physical adsorption and/or transformed into less hazardous chemicals. Photocatalysis as a sustainable process has received considerable attention as it utilizes sunlight irradiation to remedy Cr^(VI) via a cost-effective process. Numerous photocatalytic systems have been developed up to now, but metal–organic frameworks (MOFs) have gained growing attention because of their unique versatilities and facile structural modulations. A variety of MOF-based photocatalysts have been widely employed for the photoreduction of Cr^(VI). Here, we review the recent progress in the design of MOF photocatalysts and summarize their performance in photoreduction reactions.

Antibiotic resistance in bacteria, especially Gram-positive bacteria like Staphylococcus aureus, is gaining considerable momentum worldwide and unless checked will pose a global health crisis. With few new antibiotics coming on the market, there is a need for novel antimicrobial materials that target and kill multi-drug-resistant (MDR) Gram-positive pathogens like methicillin-resistant Staphylococcus aureus (MRSA). In this study, using a novel mixed-bacteria antimicrobial assay, we show that the star-peptide polymers preferentially target and kill Gram-positive pathogens including MRSA. A major effect on the activity of the star-peptide polymer was structure, with an eight-armed structure inducing the greatest bactericidal activity. The different star-peptide polymer structures were found to induce different mechanisms of bacterial death both in vitro and in vivo. These results highlight the potential utility of peptide/polymers to fabricate materials for therapeutic development against MDR Gram-positive bacterial infections.

Bacterial infection is still a thorny problem threatening human health, and nanozymes offer a promising alternative strategy to combat the health threat posed by bacterial infection. However, the antibacterial efficacies of nanozymes are unsatisfactory because of low catalytic activity of nanozymes and their inability to trap bacteria. Herein, a multifunctional nanozyme, polydopamine (PDA)-modified copper oxide (Cu_xO-PDA) is designed to overcome this challenge. Cu_xO-PDA showed peroxidase-mimicking activity and the catalytic activity was enhanced upon near-infrared (NIR) irradiation. Cu_xO-PDA was negatively charged under neutral or alkaline condition and showed no obvious peroxidase-mimicking activity. On the contrary, the surface charge of Cu_xO-PDA can be switched to positive under acidic conditions, which can target negatively charged bacteria. More interestingly, well-dispersed Cu_xO-PDA can aggregate rapidly under NIR irradiation, which trapped the bacteria and nanozymes together. It was found that shortening the distance between nanozyme and bacteria could improve the antibacterial effect. The obtained Cu_xO-PDA can cause DNA degradation, lipid peroxidation, and biofilm eradication. Cu_xO-PDA showed good antibacterial effect against two kinds of representative bacteria, Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). The experiment in vivo further proved favorable antibacterial activity of Cu_xO-PDA nanozyme.

A key challenge for nanomedicines in clinical application is to reduce the dose while achieving excellent efficacy, which has attracted extensive attention in dose toxicity and potential risks. It is thus necessary to reasonably design nanomedicine with high-efficiency targeting and accumulation. Here, we designed and synthesized a tetragonal bismuthene-based “all-in-one” composite nanosystem (TPP-Bi@PDA@CP) with two-stage targeting, multimodal imaging, photothermal therapy, and immune enhancement functions. Through the elaborate design of its structure, the composite nanosystem possesses multiple properties including (i) two-stage targeting function of hepatoma cells and mitochondria [the aggregation at the tumor site is 2.63-fold higher than that of traditional enhanced permeability and retention (EPR) effect]; (ii) computed tomography (CT) contrast-enhancement efficiency as high as ∼51.8 HU mL mg^–1 (3.16-fold that of the clinically available iopromide); (iii) ultrahigh photothermal conversion efficiency (52.3%, 808 nm), promising photothermal therapy (PTT), and high-contrast infrared thermal (IRT)/photoacoustic (PA) imaging of tumor; (iv) benefitting from the two-stage targeting function and excellent photothermal conversion ability, the dose used in this strategy is one of the lowest doses in hyperthermia (the inhibition rate of tumor cells was 50% at a dose of 15 μg mL^–1 and 75% at a dose of 25 μg mL^–1); (v) the compound polysaccharide (CP) shell with hepatoma cell targeting and immune enhancement functions effectively inhibited the recurrence of tumor. Therefore, our work reduces the dose toxicity and potential risk of nanomedicines and highlights the great potential as an all-in-one theranostic nanoplatform for two-stage targeting, integrated diagnostic imaging, photothermal therapy, and inhibition of tumor recurrence.

The design of metal nanoparticle-modified polymer surfaces in a green and scalable way is both desirable and highly challenging. Herein, a new green low-temperature plasma-based in situ surface reduction strategy termed plasma electroless reduction (PER) is reported for achieving in situ metallic nanostructuring on polymer surfaces. Proof of concept for this new method was first demonstrated on hydrophilic cellulose papers. Cellulose papers were dip-coated with different metal ion (Ag⁺ and Au³⁺) solutions and then subjected to hydrogen plasma treatment for this PER process. Transmission electron microscopy (TEM) analysis has revealed that this PER process caused anisotropic growth of either gold or silver nanoparticles, resulting in the time-dependent formation of both distinct spherical nanoparticles (∼20 nm) and anisotropic 2D nanosheets. Furthermore, we have demonstrated the adaptability of this process by applying it to hydrophobic fibrous and 3D printed polymeric materials such as surgical face masks and 3D printed polylactic acid scaffolds. The PER process on these hydrophobic polymer surfaces was accomplished via a sequential combination of air plasma and hydrogen plasma treatment. The metallic nanostructuring caused by the PER process on these hydrophobic surfaces was systematically studied using different surface imaging techniques including 3D confocal laser surface scanning microscopy and scanning electron microscopy. We have also systematically optimized the PER process on the surface of 3D scaffolds via varying the concentration of the silver ion precursor and by different postprocessing methods such as sonication and medium soaking. These optimization processes were found to be very important in generating uniform metallic nanoparticle-modified 3D printed scaffolds while simultaneously improving cytocompatibility. Through joint disk diffusion and inhibitory concentration testing, the antibacterial efficacy of silver coatings on face masks and 3D scaffolds was established. Altogether, these results clearly suggest the excellent futuristic potential of this new PER method for designing metallic nanostructured interfaces for different biomedical applications.

Nanoprodrugs with responsive release properties integrate the advantages of stimuli-responsive prodrugs and nanotechnology. They would provide ultimate opportunity in fighting atherosclerosis. In this study, we synthesized a redox-responsive nanoprodrug of simvastatin (TPTS) by conjugating α-tocopherol polyethylene glycol derivative to the pharmacophore of simvastatin with a thioketal linker. TPTS formed nanoparticles and released parent simvastatin in the presence of hydrogen peroxide. Moreover, by taking advantage of the self-assembly behavior of TPTS, we developed a fibronectin-targeted delivery system (TPTS/C/T) to codelivery simvastatin prodrug and ticagrelor. In vitro and in vivo experiments indicated that TPTS and TPTS/C/T had good stability, which could reduce off-target leakage of drugs. They greatly inhibited the M1-type polarization of macrophages; reduced intracellular reactive oxygen species level and inflammatory cytokine; and TNF-α, MCP-1, and IL-1β were secreted by macrophage cells, thus providing enhanced anti-inflammatory and antioxidant effects compared with free simvastatin. TPTS/C/T realized targeted drug release to plaques and synergistic therapeutic effects of simvastatin and ticagrelor on atherosclerosis treatment in an ApoE–/– mouse model, resulting in excellent atherosclerosis therapeutic efficacy and a promising biosafety profile. Therefore, this study provides a new method for manufacturing statin nanodrugs and a new design idea for related responsive drug release nanosystems for atherosclerosis.

Articular cartilage, which exhibits toughness and ultralow friction even under high squeezing pressures, plays an important role in the daily movement of joints. However, joint soft tissue lesions or injuries caused by diseases, trauma, or human functional decline are inevitable. Poly(vinyl alcohol) (PVA) hydrogels, which have a water content and compressive strength similar to those of many tissues and organs, have the potential to replace tough connective tissues, including cartilage. However, currently, PVA hydrogels are not suitable for complex dynamic environments and lack rebound resilience, especially under long-term or multicycle mechanical loads. Inspired by biological tissues that exhibit increased mechanical strength after swelling, we report a tough engineered hydrogel (TEHy) fabricated by swelling and freeze–thaw methods with a high compressive strength (31 MPa), high toughness (1.17 MJ m^–3), a low friction coefficient (0.01), and a low energy loss factor (0.22). Notably, the TEHy remained remarkably resilient after 100 000 cycles of contact extrusion and remains intact after being compressed by an automobile with a weight of approximately 1600 kg. The TEHy also exhibited excellent water swelling resistance (volume and weight changes less than 5%). Moreover, skeletal muscle cells were able to readily attach and proliferate on the surface of TEHy-6, suggesting its outstanding biocompatibility. Overall, this swelling and freeze–thaw strategy solves the antifatigue and stability problems of PVA hydrogels under large static loads (>10 000 N) and provides an avenue to fabricate engineering hydrogels with strong antifatigue and antiswelling properties and ultralow friction for potential use as biomaterials in tissue engineering.

This study describes the preparation, characterization, and antimicrobial properties of novel hybrid biopolymer materials doped with bioactive silver(I) coordination polymers (bioCPs). Two new bioCPs, [Ag₂(μ₆-hfa)]_n (1) and [Ag₂(μ₄-nda)(H₂O)₂]_n (2), were assembled from Ag₂O and homophthalic (H₂hfa) or 2,6-naphthalenedicarboxylic (H₂nda) acids as unexplored building blocks. Their structures feature 2D metal–organic and supramolecular networks with 3,6L64 or sql topology. Both compounds act as active antimicrobial agents for producing bioCP-doped biopolymer films based on epoxidized soybean oil acrylate (SBO) or potato starch (PS) as model biopolymer materials with a different rate of degradability and silver release. BioCPs and their hybrid biopolymer films (1@[SBO]_n, 2@[SBO]_n, 1@[PS]_n, and 2@[PS]_n) with a very low loading of coordination polymer (0.05–0.5 wt %) show remarkable antimicrobial activity against Staphylococcus aureus and Staphylococcus epidermidis (Gram-positive) and Escherichia coli and Pseudomonas aeruginosa (Gram-negative) bacteria. Biopolymer films also effectively impair the formation of bacterial biofilms, allowing total biofilm inhibition in several cases. By reporting on new bioCPs and biopolymer films obtained from renewable biofeedstocks (soybean oil and PS), this study blends highly important research directions and widens a limited antimicrobial application of bioCPs and derived functional materials. This research thus opens up the perspectives for designing hybrid biopolymer films with outstanding bioactivity against bacterial biofilms.

For rapid and effective hemostasis of uncontrollable bleeding, versatile hemostatic agents have been emerging. Among them, polyphenol-derived adhesives have attracted those hemostatic materials due to instantaneous formation of sticky barriers by robust interactions between the material and the serum proteins from wound. However, a critical challenge in such phenolic materials lies in long-term storage due to spontaneous oxidation under humid environments, leading to changes in hemostatic capability and adhesive strength. Here, we report a transparent hemostatic film consisting of gallol-conjugated chitosan (CHI–G) for minimizing the phenolic oxidation even for 3 months and maintaining strong tissue adhesiveness and its hemostatic ability. The film undergoes a phase transition from solid to injectable hydrogels at physiological pH for efficiently stopping internal and external hemorrhage. Interestingly, the hemostatic capability of the CHI–G hydrogels after 3 month storage depends on (i) the folded microstructure of the polymer with optimal gallol modification and (ii) an initial phase of either a solution state or a solid film. When the hydrogels are originated from the dehydrated film, their successful hemostasis is observed in a liver bleeding model. Our finding would provide an insight for design rationale of hemostatic formulations with long shelf-life.

Liposomal spherical nucleic acids possess a high density of nucleic acids, e.g., DNA, on a liposomal core. There are two approaches to conjugate DNA onto the zwitterionic liposomes, i.e., covalent and noncovalent conjugation, otherwise using cationic liposomes. However, complex and expensive DNA chemical modification methods need to seek a novel and easy-operating approach to decorating DNA onto liposomes. Inspired by the nanoparticle solution as nanoglues for gels and biological tissues, we use MnO₂ nanosheets to “glue” DNA onto liposomes without DNA modification. In tumor cells with a high glutathione concentration, MnO₂-based nanoglues are degraded, generating water-soluble Mn²⁺ ions, further “unglue” DNA (i.e., DNAzyme), and liposomes. Using the intelligent liposomal nanoglue (DNAzyme/MnO₂/Lip) combining glutathione-sensitive MnO₂ nanosheets, gene silencing agent DNAzyme, and photosensitizer Chlorin e6 (Ce6) in liposomes, effective photo-gene therapy was demonstrated.

N95 respirator face masks serve as effective physical barriers against airborne virus transmission, especially in a hospital setting. However, conventional filtration materials, such as nonwoven polypropylene fibers, have no inherent virucidal activity, and thus, the risk of surface contamination increases with wear time. The ability of face masks to protect against infection can be likely improved by incorporating components that deactivate viruses on contact. We present a facile method for covalently attaching antiviral quaternary ammonium polymers to the fiber surfaces of nonwoven polypropylene fabrics that are commonly used as filtration materials in N95 respirators via ultraviolet (UV)-initiated grafting of biocidal agents. Here, C₁₂-quaternized benzophenone is simultaneously polymerized and grafted onto melt-blown or spunbond polypropylene fabric using 254 nm UV light. This grafting method generated ultrathin polymer coatings which imparted a permanent cationic charge without grossly changing fiber morphology or air resistance across the filter. For melt-blown polypropylene, which comprises the active filtration layer of N95 respirator masks, filtration efficiency was negatively impacted from 72.5 to 51.3% for uncoated and coated single-ply samples, respectively. Similarly, directly applying the antiviral polymer to full N95 masks decreased the filtration efficiency from 90.4 to 79.8%. This effect was due to the exposure of melt-blown polypropylene to organic solvents used in the coating process. However, N95-level filtration efficiency could be achieved by wearing coated spunbond polypropylene over an N95 mask or by fabricating N95 masks with coated spunbond as the exterior layer. Coated materials demonstrated broad-spectrum antimicrobial activity against several lipid-enveloped viruses, as well as Staphylococcus aureus and Escherichia coli bacteria. For example, a 4.3-log reduction in infectious MHV-A59 virus and a 3.3-log reduction in infectious SuHV-1 virus after contact with coated filters were observed, although the level of viral deactivation varied significantly depending on the virus strain and protocol for assaying infectivity.

Current developments in precision medicine require the simultaneous detection of an increasing number of biomarkers in heterogeneous, complex solutions, such as blood samples. To meet this need, immunoassays on barcoded hydrogel beads have been proposed, although the encoding and decoding of these barcodes is usually complex and/or resource-intensive. Herein, an efficient method for the fabrication of barcoded, functionalized hydrogel beads is presented. The hydrogel beads are generated using droplet-based microfluidics in combination with photochemically induced C–H insertion reactions, allowing photo-crosslinking, (bio-) functionalization, and barcode integration to be performed in a single step. The generated functionalized beads carry single-color barcodes consisting of green-fluorescent particles of different sizes and concentrations, allowing simple and simultaneous readout with a standard plate reader. As a test example, the performance of barcoded hydrogel beads (3 × 3 matrix) functionalized with capture molecules of interest (e.g., antigens) is investigated for the detection of Lyme-disease-specific antibodies in patient sera. The described barcoding strategy for hydrogel beads does not interfere with the bioanalytical process and captivates by its simplicity and versatility, making it an attractive candidate for multiplex bioanalytical processes.

The repair of spinal cord injury (SCI) is still a tough clinical challenge and needs innovative therapies. Mitochondrial function is significantly compromised after SCI and has emerged as an important factor causing neuronal apoptosis and hindering functional recovery. In this study, umbilical cord mesenchymal stem cells (UCMSC), which are promising seed cells for nerve regeneration, and basic fibroblast growth factor (bFGF) that have been demonstrated to have a variety of effects on neural regeneration were jointly immobilized in extracellular matrix (ECM) and heparin-poloxamer (HP) to create a polymer bioactive system that brings more hope and possibility for the treatment of SCI. Our results in vitro and in vivo showed that the UCMSC-bFGF-ECM-HP thermosensitive hydrogel has good therapeutic effects, mainly in reducing apoptosis and improving the mitochondrial function. It showed promising utility for the functional recovery of impaired mitochondrial function by promoting mitochondrial fusion, reducing pathological mitochondrial fragmentation, increasing mitochondrial energy supply, and improving the metabolism of MDA, LDH, and ROS. In addition, we uncovered a distinct molecular mechanism underlying the protective effects associated with activating p21-activated kinase 1 (PAK1) and mitochondrial sirtuin 4 (SIRT4) by the UCMSC-bFGF-ECM-HP hydrogel. The expansion of new insights into the molecular relationships between PAK1 and SIRT4, which links the mitochondrial function in SCI, can lay the foundation for future applications and help to provide promising interventions of stem-cell-based biological scaffold therapies and potential therapeutic targets for the clinical formulation of SCI treatment strategies.

The development of a biodegradable and shape-adaptable bioscaffold that can enhance local cytokine retention and bioactivity is essential for the application of immunotherapy in periodontal diseases. Here, we report a biodegradable, anti-inflammatory, and osteogenic ILGel that uses a physically cross-linked DNA hydrogel as a soft bioscaffold for the long-term sustained release of cytokine interleukin-10 (IL-10) to accelerate diabetic alveolar bone rebuilding. Porous microstructures of ILGel favored the encapsulation of IL-10 and maintained IL-10 bioactivity for at least 7 days. ILGel can be gradually degraded or hydrolyzed under physiological conditions, avoiding the potential undesired side effects on dental tissues. Long-term sustained release of bioactive IL-10 from ILGel not only promoted M2 macrophage polarization and attenuated periodontal inflammation but also triggered osteogenesis of mesenchymal stem cells (MSCs), leading to accelerated alveolar bone formation and healing of alveolar bone defects under diabetic conditions in vivo. ILGel treatment significantly accelerated the defect healing rate of diabetic alveolar injury up to 93.42 ± 4.6% on day 21 post treatment compared to that of free IL-10 treatment (63.30 ± 7.39%), with improved trabecular architectures. Our findings imply the potential application of the DNA hydrogel as the bioscaffold for cytokine-based immunotherapy in diabetic alveolar bone injury and other periodontal diseases.

Chemodynamic therapy (CDT), as a powerful tumor therapeutic approach with low side effects and selective therapeutic efficiency, has gained much attention. However, the low intracellular content of H₂O₂ and the cellular bottleneck of low intracellular oxidative reaction rates at tumor sites have limited the antitumor efficacy of CDT. Herein, a series of sulfur-deficient engineered biodegradable cobalt sulfide quantum dots (CoS_x QDs) were constructed for improved synergistic photothermal- and hyperthermal-enhanced CDT of tumors through regulating the photothermal conversion efficiency (PCE) and Fenton-like activity. Through defect engineering, we modulated the PCE and promoted the Fenton catalytic capability of CoS_x QDs. With increasing defect sites, the Fenton-like activity improved to generate more toxic ^•OH, while the photothermal effect declined slightly. In light of above unique superiorities, the best synergistic effects of CoS_x QDs were obtained through comparing their PCE and catalytic activity by regulating the sulfur defect fraction degree in these QDs during the synthetic process. In addition, the ultrasmall size and biodegradation endowed QDs with the ability to be rapidly decomposed to ions that were easily excreted after therapy, thus reducing biogenic accumulation in the body with lowered systemic side effects. The in vitro/vivo results demonstrated that the photothermal- and hyperthermal-enhanced chemodynamic effect of CoS_x QDs can enable remarkable anticancer properties with favorable biocompatibility. In this study, the defect-driven mechanism for the photothermal-enhanced Fenton-like reaction provides a flexible strategy to deal with different treatment environments, holding great promise in developing a multifunctional platform for cancer treatment in the future.

Hypoxic tumor microenvironment and nonspecific accumulation of photosensitizers are two key factors that limit the efficacy of photodynamic therapy (PDT). Herein, a strategy of oxygen microbubbles (MBs) boosting photosensitizer micelles is developed to enhance PDT efficacy and inhibit tumor metastasis by self-assembling renal-clearable ultrasmall poly(ethylene glycol)-modified protoporphyrin IX micelles (PPM) and perfluoropentane (PFP)-doped oxygen microbubbles (OPMBs), followed by ultrasound imaging-guided OPMB destruction to realize the tumor-targeted delivery of PPM and oxygen in tumor. Doping PFP into oxygen MBs increases the production of MBs and stability of oxygen MBs, allowing for persistent circulation in blood. Following co-injection, destruction of OPMBs with ultrasound leads to ∼2.2-fold increase of tumor-specific PPM accumulation. Furthermore, the burst release of oxygen by MB destruction improves tumor oxygenation from 22 to 50%, which not only raises the production of singlet oxygen but also significantly reduces the expression of hypoxia-inducible factor-1 alpha and related genes, thus preventing angiogenesis and epithelial–mesenchymal transition. It is verified that this strategy effectively eradicates orthotopic breast cancer and inhibits lung metastasis. Furthermore, the survival rate of mice bearing orthotopic pancreatic tumor is significantly extended by such interventional PDT strategy. Therefore, the combination of ultrasmall PPM and OPMBs represents a simple but effective strategy in overcoming the limitations of PDT.

Microfluidic devices are widely used in many fields of biology, but a key limitation is that cells are typically surrounded by solid walls, making it hard to access those that exhibit a specific phenotype for further study. Here, we provide a general and flexible solution to this problem that exploits the remarkable properties of microfluidic circuits with fluid walls─transparent interfaces between culture media and an immiscible fluorocarbon that are easily pierced with pipets. We provide two proofs of concept in which specific cell subpopulations are isolated and recovered: (i) murine macrophages chemotaxing toward complement component 5a and (ii) bacteria (Pseudomonas aeruginosa) in developing biofilms that migrate toward antibiotics. We build circuits in minutes on standard Petri dishes, add cells, pump in laminar streams so molecular diffusion creates attractant gradients, acquire time-lapse images, and isolate desired subpopulations in real time by building fluid walls around migrating cells with an accuracy of tens of micrometers using 3D printed adaptors that convert conventional microscopes into wall-building machines. Our method allows live cells of interest to be easily extracted from microfluidic devices for downstream analyses.

Insights into developing innovative routes for the stabilization of photogenerated charge-separated states by suppressing charge recombination in photocatalysts is a topic of immense importance. Herein, we report the synthesis of a metal–organic framework (MOF)-based composite where CdS nanoparticles (NPs) are confined inside the nanosized pores of Zr⁴⁺-based MOF-808, namely, CdS@MOF-808. Anchoring l-cysteine into the nanospace of MOF-808 via postsynthetic ligand exchange allows the capture of Cd²⁺ ions from their aqueous solution, which are further utilized for in situ growth of CdS NPs inside the nanosized MOF pores. The formation of CdS@MOF-808 opens up a possibility for visible-light photocatalysis as CdS NPs (1–2 nm) are a well-studied semiconductor system with a band gap of ∼2.6 eV. The confinement of the CdS NPs inside the MOF pores, close to the Zr⁴⁺ cluster, opens up a shorter electron transfer route from CdS to the catalytic Zr⁴⁺ cluster and shows a high rate of H₂ evolution (10.41 mmol g^–1 h^–1) from water with a loading of 3.56 wt % CdS. In contrast, a similar composite in which CdS NPs are stabilized on the external surface of MOF-808 reveals poor activity (0.15 mmol g^–1 h^–1). CdS NPs stabilized on the MOF-808 surface show slower and inefficient electron transfer kinetics compared to CdS stabilized inside the nanospace of the MOF, as realized by the transient absorption measurements. Therefore, this work unveils the critical role of stabilizing the photosensitizer NPs in close proximity of the catalytic sites in MOF systems towards developing highly efficient H₂ evolution photocatalysts.

Aqueous rechargeable batteries based on aluminum chemistry have become the focus of immense research interest owing to their earth abundance, low cost, and the higher theoretical volumetric energy density of this element compared to lithium-ion batteries. Efforts to harness this huge potential have been hindered by the narrow potential window of water and by passivating effects of the high-electrical band-gap aluminum oxide film. Herein, we report a high-performing aqueous aluminum-ion battery (AIB), which is constructed using a Zn-supported Al alloy, an aluminum bis(trifluoromethanesulfonyl)imide (Al[TFSI]₃) electrolyte, and a MnO₂ cathode. The use of Al[TFSI]₃ significantly extends the voltage window of the electrolyte and enables the cell to access Al³⁺/Al electrochemistry, while the use of Zn–Al alloy mitigates the issue of surface passivation. The Zn–Al alloy, which is produced by in situ electrochemical deposition, obtained from Al[TFSI]₃ showed excellent long-term reversibility for Al electrochemistry and displays the highest performance in AIB when compared to the response obtained in Al₂(SO₄)₃ or aluminum trifluoromethanesulfonate electrolyte. AIB cells constructed using the Zn–Al|Al[TFSI]₃|MnO₂ combination achieved a record discharge voltage plateau of 1.75 V and a specific capacity of 450 mAh g^–1 without significant capacity fade after 400 cycles. These findings will promote the development of energy-dense aqueous AIBs.

Over the last years, the development of highly active and durable Pt-based electrocatalysts has been identified as the main target for a large-scale industrial application of fuel cells. In this work, we make a significant step ahead in this direction by preparing a high-performance electrocatalyst and suggesting new structure–activity design concepts which could shape the future of oxygen reduction reaction (ORR) catalyst design. For this, we present a new one-dimensional nanowire catalyst consisting of a L1₀ ordered intermetallic PtCo alloy core and compressively strained high-index facets in the Pt-rich shell. We find the nanoscale PtCo catalyst to provide an excellent turnover for the ORR and hydrogen evolution reaction (HER), which we explain from high-resolution transmission electron microscopy and density functional theory calculations to be due to the high ratio of Pt(221) facets. These facets include highly active ORR and HER sites surprisingly on the terraces which are activated by a combination of sub-surface Co-induced high Miller index-related strain and oxygen coverage on the step sites. The low dimensionality of the catalyst provides a cost-efficient use of Pt. In addition, the high catalytic activity and durability are found during both half-cell and proton exchange membrane fuel cell (PEMFC) operations for both ORR and HER. We believe the revealed design concepts for generating active sites on the Pt-based catalyst can open up a new pathway toward the development of high-performance cathode catalysts for PEMFCs and other catalytic systems.

Electrochemical CO₂ reduction technology can combine renewable energy sources with carbon capture and storage to convert CO₂ into industrial chemicals. However, the catalytic activity under high current density and long-term electrocatalysis process may deteriorate due to agglomeration, catalytic polymerization, element dissolution, and phase change of active substances. Here, we report a scalable and facile method to fabricate aligned InS nanorods by chemical dealloying. The resulting aligned InS nanorods exhibit a remarkable CO₂RR activity for selective formate production at a wide potential window, achieving over 90% faradic efficiencies from −0.5 to −1.0 V vs reversible hydrogen electrode (RHE) under gas diffusion cell, as well as continuously long-term operation without deterioration. In situ electrochemical Raman spectroscopy measurements reveal that the *OCHO* species (Bidentate adsorption) are the intermediates that occurred in the reaction of CO₂ reduction to formate. Meanwhile, the presence of sulfur can accelerate the activation of H₂O to react with CO₂, promoting the formation of *OCHO* intermediates on the catalyst surface. Significantly, through additional coupling anodic methanol oxidation reaction (MOR), the unusual two-electrode electrolytic system allows highly energy-efficient and value-added formate manufacturing, thereby reducing energy consumption.

Despite that the practical gravimetric energy density of lithium sulfur batteries has exceeded that of the traditional lithium-ion battery, the volumetric energy density still pales due to the low density of carbonaceous materials. Herein, hollow polar nickel selenide (Ni₃Se₄) with various architectures was designed and employed as a carbon-free sulfur immobilizer. Among them, hollow sea urchins like Ni₃Se₄ with high porosity (0.39 cm³ g^–1) and large specific surface area (82.7 m² g^–1) exhibit abundant adsorptive and electrocatalytic sites, which pledge excellent electrochemical performances of the Li–S battery. Correspondingly, the Ni₃Se₄-based sulfur electrode presents excellent rate endurability (581 mAh g^–1_–composite at 2.0 C) and superior cycle stability (ultralow fading rate of 0.042% per cycle during the 1000 cycles at 1.0 C). More importantly, thanks to the higher tap density (Ni₃Se₄/S: 1.57 g cm^–3 vs super P/S: 0.7 g cm^–3), the volumetric specific capacity of Ni₃Se₄-based cathodes is as high as 1699 mAh cm^–3_–composite at 0.1 C, which is almost 2.8 times that of the carbonaceous electrode. Hence, rational transition metal selenide architecture design with synergistic function of good conductivity, well-defined catalyst and adsorption, as well as high tap density provide a promising route toward high gravimetric and volumetric energy density of Li–S batteries.

Construction of heterostructures is one of the most promising strategies for designing photocatalysts for highly efficient solar hydrogen (H₂) production because the introduction of an electron-donating counterpart contributes to more effective photon absorption, while the heterostructures benefit spatial carrier separation. However, the hole-transfer rate is usually 2–3 orders of magnitude slower than that of the electron-transfer rate within the heterostructures, ensuing serious charge recombination. Here, we find the energy band offset-driven charge-transfer behavior in a donor–acceptor (D–A)-conjugated polymer/CdS organic/inorganic heterostructure and realize hole-transfer improvement in cooperation with a further hole removal motif of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. The photocatalytic H₂ production activity is increased by nearly 2 orders of magnitude with the apparent quantum yield hitting ca. 80% at 450 nm without co-catalysts. Ultrafast transient absorption together with surface photovoltage characterizations consolidates the hole extraction mechanism. The intimate bond formed at the interface between the polymer and the inorganic semiconductor acts as an interpenetrating network at the nanoscale level, thus providing a charge-transfer freeway for boosting charge separation.

Selective semihydrogenation of acetylene for the production of polymer-grade ethylene is a significant chemical industrial process. Facile activization of acetylene and weak adsorption of ethylene are critical requirements for high-performance catalysis. Single-atom alloys (SAAs) have strong binding effect on acetylene and weak effect on ethylene, which have been regarded as the superior catalysts for acetylene semihydrogenation. Herein, we established a pioneering machine learning (ML) assisted approach to investigate the reaction activity and selectivity of 70 SAA catalysts for acetylene semihydrogenation. As the most desirable ML model, the gradient boosting regression (GBR) algorithm has been extended to predict the energy barrier of *C₂H_n (n = 2–4) hydrogenation with a root-mean-square error (RMSE) of only 0.02 eV. Notably, five candidate SAAs with excellent activity and selectivity for acetylene semihydrogenation are screened out via accessible descriptors. These data of ML prediction have been verified by DFT calculation with a high-accuracy (error less than 0.07 eV). This work demonstrates the potential of ML-assisted approach for predicting the energy barrier of transition state and simultaneously provides a convenient approach for the rational design of efficient catalysts.

Photocatalytic H₂ evolution coupled with organic transformation provides a new avenue to cooperatively produce clean fuels and fine chemicals, enabling a more efficient conversion of solar energy. Here, a novel two-dimensional (2D) heterostructure of ultrathin ZnIn₂S₄ nanosheets decorated with amorphous nickel boride (Ni_x-B) is prepared for simultaneous photocatalytic anaerobic H₂ generation and aromatic aldehydes production. This ZnIn₂S₄/Ni_x-B catalyst elaborately combines the ultrathin structure advantage of the ZnIn₂S₄ semiconductor and the cocatalytic function of Ni_x-B. A high H₂ production rate of 8.9 mmol h^–1 g^–1 is delivered over the optimal ZnIn₂S₄/Ni_x-B with a stoichiometric production of benzaldehyde, which is about 22 times higher than ZnIn₂S₄. Especially, the H₂ evolution rate is much higher than the value (2.8 mmol h^–1 g^–1) of the traditional photocatalytic half reaction of H₂ production with triethanolamine as a sacrificial agent. The apparent quantum yield reaches 24% at 420 nm, representing an advanced photocatalyst system. Moreover, compared with traditional sulfide, hydroxide, and even noble metal modified ZnIn₂S₄/M counterparts (M = NiS, Ni(OH)₂, Pt), the ZnIn₂S₄/Ni_x-B also maintains markedly higher photocatalytic activity, showing a highly efficient and economical advantage of the Ni_x-B cocatalyst. This work sheds light on the exploration of 2D ultrathin semiconductors decorated with novel transition metal boride cocatalyst for efficient photocatalytic organic transformation integrated with solar fuel production.

A dual-mode self-powered aptasensing platform of photoelectrochemical (PEC) and photofuel cell (PFC) was constructed for Microcystin-LR (MC-LR) detection. Specifically, the In₂O₃–In₂S₃–Ti₃C₂ (IO–IS–TC) composite was facilely assembled on the base of MOF-derived In₂O₃ hollow tubulars, and the integrated mechanism and photoconversion efficiency are proposed and discussed in detail. Herein, a promising dual-mode sensing platform was constructed using the IO–IS–TC composite as a photoanode matrix with higher output power and obvious photocurrent response. Moreover, the dual-mode sensing platform did not require external bias and the addition of sacrificial agents under visible light irradiation. The enhanced PEC properties can be attributed to the matched energy level of ternary components and the improved separation of photogenerated carriers. Moreover, aptamer-based recognition was adopted to catch MC-LR molecules, which realized the highly sensitive and selective detection. The PFC aptasensor was exhibited at 50–5 × 10⁵ pmol/L with a detection limit of 17.4 pmol/L, and the PEC aptasensor was realized from 0.5 to 4 × 10⁵ pmol/L with a detection limit of 0.169 pmol/L. The proposed aptasensing platform showed good specificity, reproducibility, and stability, which paved the way for the construction of a fast and ultrasensitive PEC sensing methodology for environmental analysis.

The combination of transition metal (TM) atoms and high electron affinity organic framework tetrafluorotetracyanoquinodimethanes (F₄TCNQs) makes the TM-embedded two-dimensional (2D) square F₄TCNQ monolayers (TM-sF₄TCNQ) possible to have excellent characteristics of single-atom catalysts and 2D materials. For the first time, the TM-sF₄TCNQ monolayers have been considered for application in the electrocatalytic nitrogen reduction reaction (eNRR) field. Through high-throughput screening, the catalytic performance of 30 TM-sF₄TCNQ (TM = 3d∼5d TMs) monolayers for eNRR was comprehensively evaluated. The Mo-, Nb-, and Tc-sF₄TCNQ catalysts stand out with the onset potentials of −0.18, −0.44, and −0.54 V, respectively, through the optimal reaction paths. Our work will provide guidance for the green and sustainable development of electrocatalytic nitrogen fixation.

In 2017, we reported a dye-sensitized, photoelectrolysis cell consisting of fluorine-doped tin oxide (FTO)-coated glass covered by SnO₂ nanoparticles coated with N,N′-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) dye and then a photoelectrochemically deposited CoO_x water oxidation catalyst (WOCatalyst), FTO/nano-SnO₂/PMPDI/CoO_x. This system employed nanostructured SnO₂ stabilized by a polyethyleneglycol bisphenol A epichlorohydrin (PEG-BAE) copolymer and other C-containing additives based on a literature synthesis to achieve a higher surface area and thus greater PMPDI dye absorption and resultant light collection. Surprisingly, the addition of the well-established WOCatalyst CoO_x resulted in a decrease in the photocurrent, an unexpected “anti-catalyst” effect. Two primary questions addressed in the present study are (1) what is the source of this “anti-catalyst” effect? and (2) are the findings of broader interest? Reflection on the synthesis of nano-SnO₂ stabilized by PEG-BAE, and the large, ca. 10:1 ratio of C to Sn in synthesis, led to the hypothesis that even the annealing step at 450 °C in of the FTO/SnO₂ anode precursors was unlikely to remove all the carbon initially present. Indeed, residual carbon impurities are shown to be the culprit in the presently observed “anti-catalyst” effect. The implication and anticipated broader impact of the results of answering the two abovementioned questions are also presented and discussed along with a section entitled “Perspective and Suggestions for the Field Going Forward.”

Single-atom catalysts (SACs) have demonstrated catalytic efficacy toward lithium polysulfide conversion in Li–S batteries. However, achieving high-density M–N_x sites with rational design by a simple method is still challenging to date. Herein, an ultrathin porous 3D carbon-supported single-atom catalyst (SACo/NDC) is synthesized with a salt-template strategy via a facile freeze-drying and one-step pyrolysis procedure and serves well as a sulfur host. The well-defined 3D carbon structure can effectively alleviate volume stress and confine polysulfides inside. Moreover, the dispersed Co–N_x sites exhibit strong chemical adsorption function and valid catalytic efficiency to LiPSs redox conversion. As a result, the SACo/NDC cathodes display enhanced long-term cycling stability and better rate capability.

P2 and O3 structures are two important sodium manganese oxide phases for sodium-ion batteries; however, encounter Na-deficient and poor rate performance, respectively. Herein, a systematic study of Na_xMn_0.85Al_0.1Fe_0.05O₂ (0.7 ≤ x ≤ 1.0) materials is performed by employing solid-state NMR, X-ray diffraction, and electrochemical analysis, to provide an in-depth understanding on the structure and the correlated performance for the rational design. The interlayer spacing of α-NaMnO₂ broadens, and the content of distorted O3 structures (α- and β-NaMnO₂) increases with raising Na content. It is exhibited that the NaMn_0.85Al_0.1Fe_0.05O₂ composite material presents better rate and cycling performance than P2-type Na_0.7Mn_0.85Al_0.1Fe_0.05O₂, delivering a capacity of 87 mAh g^–1 at 5 C. Significantly, the determinants of performance are further discussed, which reveal that diffusion coefficient is probably not the decisive factor restricts the rate performance of O3 and composite materials. The phase transition relaxation and the interfacial charge transfer resistance should be seriously addressed for further improvement.

Triplet excitons are generally confined within a semiconductor. Hence, solar energy utilization via direct triplet energy transfer (TET) from semiconductors is challenging. TET from lead halide perovskite semiconductors to nearby organic molecules has been illustrated with ultrafast spectroscopy. Direct utilization of solar energy, i.e., visible light, via TET for photocatalysis is an important route but has not yet been demonstrated with lead halide perovskite semiconductors. Here, we show that a photocatalytic reaction, focusing on a 2 + 2 cycloaddition reaction, can been successfully demonstrated via TET from lead halide perovskite nanocrystals (PNCs). The triplet excitons are shown to induce a highly diastereomeric syn-selective 2 + 2 cycloaddition starting from olefins. Such photocatalytic reactions probe the TET process previously only observed spectroscopically. Moreover, our observation demonstrates that bulk-like PNCs (size, >10 nm; PL = 530 nm), in addition to quantum-confined smaller PNCs, are also effective for TET. Our findings may render a new energy conversion pathway to employ PNCs via direct TET for photocatalytic organic synthesis.

Probing porosity evolution is essential to understand the degradation mechanism of electrocatalytic activity. However, spatially dependent degradation pathways for porous catalysts remain elusive. Here, we reveal the multiple degradation behaviors of individual PtCu₃ nanocatalysts spatially by three-dimensional (3D) electron tomography. We demonstrate that the surface area–volume ratio (SVR) of cycled porous particles decreases linearly rather than reciprocally with particle size. Additionally, an improved SVR (about 3-fold enhancement) results in increased oxygen reduction reaction (ORR) efficiency at the early stage. However, in the subsequent cycles, the degradation of catalytic activity is due to the excessive growth of pores, the reduction of reaction sites, and the chemical segregation of Cu atoms. The spatial porosity evolution model of nanocatalysts is applicable for a wide range of catalytic reactions, providing a critical insight into the degradation of catalyst activity.

Efficient separation of the CH₄/N₂ mixture is of great significance for coalbed methane purification. It is an effective strategy to separate this mixture by tuning the van der Waals interaction due to the nonpolar properties of CH₄ and N₂ molecules. Herein, we prepared several isoreticular Al-based metal–organic frameworks (MOFs) with different ligand sizes and polarities because of their high structural stability and low cost/toxicity feature of Al metal. Adsorption experiments indicated that the CH₄ uptake, Q_st of CH₄, and CH₄/N₂ selectivity are in the order of Al-FUM-Me (27.19 cm³(STP) g^–1, 24.06 kJ mol^–1 and 8.6) > Al-FUM (20.44 cm³(STP) g^–1, 20.60 kJ mol^–1 and 5.1) > Al-BDC (15.98 cm³(STP) g^–1, 18.81 kJ mol^–1 and 3.4) > Al-NDC (10.86 cm³(STP) g^–1, 14.89 kJ mol^–1 and 3.1) > Al-BPDC (5.90 cm³(STP) g^–1, 11.75 kJ mol^–1 and 2.2), confirming the synergetic effects of pore sizes and pore surface polarities. Exhilaratingly, the ideal adsorbed solution theory selectivity of Al-FUM-Me is higher than those of all zeolites, carbon materials, and most water-stable MOF materials (except Al-CDC and Co₃(C₄O₄)₂(OH)₂), which is comparable to MIL-160. Breakthrough results demonstrate its excellent separation performance for the CH₄/N₂ mixture with good regenerability. The separation mechanism of Al-FUM-Me for the CH₄/N₂ mixture was elucidated by theoretical calculations, showing that the stronger affinity of CH₄ can be attributed to its relatively shorter interaction distance with adsorption binding sites. Therefore, this work not only offers a promising candidate for CH₄/N₂ separation but also provides valuable guidance for the design of high-performance adsorbents.

In view of the serious perniciousness and complex diversity of actual wastewater systems, exploiting a robust and multifunctional adsorbent material featuring high sorption efficiency, broad-spectrum applicability, and excellent recyclability in treating multifarious pollutants in water (such as oils and fluoride ions) is highly required; however, it is still a daunting goal to pursue to date. In this work, novel mechanically robust and exceptional graphene oxide/hydroxyapatite nanowire (GO/HAPNW) aerogels (RGHAs/polydopamine (PDA)@RGHAs) with adjustable surface wettability were developed through a facile sol–gel self-assembly technology and subsequently optional bioinspired hydrophilic modification. Thanks to the reinforcing effect of HAPNWs with higher aspect ratio, a remarkably improved mechanical robustness (including superior compressibility and superelasticity) was acquired for the resulting aerogels. Based on the cooperative effect of the favorable selective wetting properties (i.e., hydrophobic/oleophilic for RGHAs) and the excellent mechanic stability, the aerogels displayed an outstanding sorption performance for diverse oils/organic solvents accompanied with a prominent recyclability. Specifically, a fairly high adsorption capacity of as high as 191 times of its own mass (for pump oil) was achieved based on a fast adsorption kinetic process. More importantly, superamphiphilic three-dimensional (3D) PDA@RGHAs revealed an extraordinary removal capability for water-soluble fluoride ions, exhibiting a superior equilibrium adsorption capacity (q_e, 9.93 mg/g), which is distinctly superior to those of low-dimensional fluorine adsorbent materials recently reported. Accordingly, the as-prepared 3D aerogels combining both superior oil/organic solvent adsorption and excellent defluorination capability reveal a competitive application prospect toward effective intricate oily wastewater purification.

Due to adverse health effects and the broad sources of per- and polyfluoroakyl substances (PFAS), PFAS removal is a critical research area in water purification. We demonstrate the functionalization of thin-film composite (TFC) hollow fiber nanofiltration (HFN) membranes by MXene nanosheets during the interfacial polymerization (IP) process for enhanced removal of perfluorooctane sulfonic acid (PFOS) from water. A MXene-polyamide (PA) selective layer was fabricated on top of a polysulfone (PSF) hollow fiber support via IP of trimesoyl chloride (TMC) and a mixture of piperazine (PIP) and MXene nanosheets to form MXene-PA thin-film nanocomposite (TFN) membranes. Incorporating MXene nanosheets during the IP process tuned the morphology and negative surface charge of the selective layer, resulting in enhanced PFOS rejection from 72% (bare TFC) to more than 96% (0.025 wt % MXene TFN), while the water permeability was also increased from 13.19 (bare TFC) to 29.26 LMH/bar (0.025 wt % MXene TFN). Our results demonstrate that both electrostatic interaction and size exclusion are the main factors governing the PFOS rejection, and both are determined by PA selective layer structural and chemical properties. The lamella structure and interlayer of MXene nanosheets inside the PA layer provided different transport mechanisms for water, ions, and PFAS molecules, resulting in enhanced water permeability and PFAS rejection due to traveling through the membrane by both diffusions through the PA layer and the MXene intralayer channels. MXene nanosheets showed very promising capability as a 2D additive for tuning the structural and chemical properties of the PA layer at the permeability-rejection tradeoff.

Gold nanoclusters (NCs) can be used as sensitizers to extend the absorption capabilities of TiO₂ as photoelectrodes. However, the adsorption of NCs also creates additional surface states on the TiO₂ surface, which gives rise to intricacies in the understanding of various interfacial phenomena occurring in NC-sensitized TiO₂. One of the complexities that have recently been discovered is the size-dependent hole-transfer mechanism. In this work, we reveal another anomalous behavior in the hole-transfer process that the hole scavenging ability of the electrolyte also plays a role in determining the hole-transfer mechanism in the NC-TiO₂ system, which is unprecedented in other photoelectrode systems. In the presence of an efficient hole scavenger (Na₂SO₃), the hole transfer in Au₁₈–TiO₂ occurs directly through the highest occupied molecular orbital (HOMO) of Au₁₈ NCs. However, in the presence of a less efficient hole scavenger (ethylenediaminetetraacetic acid), hole transfer in Au₁₈–TiO₂ does not occur through the HOMO and shifts to surface state-assisted hole transfer. Due to surface state charging, this surface state-assisted hole-transfer mechanism results in delayed photocurrent response in Au₁₈–TiO₂. Evidence for this exotic hole-transfer mechanism shift is provided by photoelectrochemical electrochemical impedance spectroscopy, and its implications are discussed.

Realizing the high selectivity of CH₄ from the photocatalytic CO₂ reduction reaction (CO₂ RR) remains a great challenge owing to the lower efficiency of multi-electron transfer and the similar thermodynamic properties of CH₄ and CO. Herein, nitrogen-deficient carbon nitride two-dimensional (2D) nanosheets were prepared via the high-temperature crystalline phase transformation process. Optimizing crystallinity enhances the in-plane polarization along the a-axis. Owing to the increased electron density of the N defect, the kinetic possibilities of CH₄ production have increased. Furthermore, the potential energy of the mid-gap states introduced by the N defect favors the thermodynamics of CH₄ production. The selectivity values of CH₄ based on yield and electrons are 87.1 and 96.4%. This work unravels the mechanism to selectively produce CH₄ from CO₂ photoreduction through the crystalline phase and defect regulation and provides significant guidance for the rational design of CO₂ reduction photocatalysts for selective CH₄ production.

Rechargeable Zn–air batteries have received extensive attention due to their use of nontoxic materials, safety, and high energy density. However, the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air electrode of Zn–air batteries both suffer from slow kinetics, limiting their commercialization development. Herein, we prepared Co, N, and S co-doped hollow carbon nanoboxes (Co–N/S-CNBs) rich in topological defects using polyphenylene sulfide (PPS) as a sulfur-rich carbon source. Critically, by utilizing the self-propagating high-temperature synthesis (SHS), PPS can avoid melting, while simultaneously enabling the catalyst to take on a unique hollow structure. Additional post-treatment to introduce Co and N atoms as active centers further increases the defect sites and microporous structures of the catalyst. Under alkaline electrolytes, the Co–N/S-CNBs enabled Zn–air batteries to exhibit excellent bifunctional catalytic activity for both ORR and OER, surpassing commercial catalysts. Chemical analysis showed that the cracking loss of small molecules from PPS during pyrolysis is the main reason for the formation of topological defects, where the defect sites act as active centers to enhance the catalytic performance. Overall, this work provides new insights into the mechanism of how defects are formed in such a catalyst, as well as shows how a high-performance bifunctional electrocatalyst can be utilized for practical Zn–air batteries.

Methane dry reforming (MDR) has attracted significant attention for effectively consuming greenhouse gases and producing valuable syngas. The development of coking- and sintering-resistant catalysts is still a challenge. Herein, highly active Ni nanocatalysts confined by the active edges of boron nitride have been originally developed, and the coking- and sintering-resistant MDR mechanism has also been unraveled. The active edges of boron nitride consisted of boundary BO_x species interact with Ni nanoparticles (NPs), which can contribute to the activation of both CH₄ and CO₂. The etching of BN is restrained under the buffer of boundary BO_x species. Operando spectra reveal that the formation and conversion of active bicarbonate species is accelerated by the boundary BO_x species. The complete decomposition of CH₄ is suppressed, and thus the coke formation is restricted. The functional groups of active BN edges are confirmed to stabilize the Ni NPs and facilitate the MDR reaction. This work provides a novel approach for the development of coking- and sintering-resistant catalysts for MDR.

Li⁺ conducting halide solid-state electrolytes (SEs) are developing as an alternative to contemporary oxide and sulfide SEs for all-solid-state batteries (ASSBs) due to their high ionic conductivity, excellent chemical and electrochemical oxidation stability, and good deformability. However, the instability of halide SEs against the Li anode is still one of the key challenges that need to be addressed. Among halides, fluorides have shown a wider electrochemical stability window due to fluoride’s high electronegativity and smaller ionic radius. However, the ionic conductivity of fluoride-based SEs is lower compared to other halide-based SEs. To achieve better interface stability with the Li anode, the presence of fluoride is not only advantageous for a wider potential window but also forms a stable passivation layer at the Li/SEs interface. Therefore, developing mixed halogen-based solid electrolytes, particularly fluorine and chlorine-based SEs are promising in ASSBs. Herein, we report dual halogen-based SEs, Li₂ZrF_6–xCl_x (0 ≤ x ≤ 2), synthesized via ball-milling. The X-ray diffraction results revealed that Li₂ZrF_6–xCl_x compounds crystallize in the trigonal phase (P3̅1m). Using impedance spectroscopy, an increase in Li⁺ conductivity with the increase in Cl content was observed for Li₂ZrF_6–xCl_x. Compared with x = 0, Li⁺ conductivity for the sample with x = 1 improved by ∼5 orders of magnitude. The Li⁺ conductivities for Li₂ZrF₅Cl₁ at 25 and 100 °C are 5.5 × 10^–7 and 2.1 × 10^–5 S/cm, respectively. Moreover, Li₂ZrF₅Cl₁ exhibits the widest electrochemical stability window and excellent Li interface stability. Our work indicates Li₂ZrF_6–xCl_x as an attractive material for optimization in the class of halide-based solid-state Li-ion conductors.

The combination of energy and chemical conversion can be achieved by designing glycerol fuel cells. However, the anode must promote the reaction at onset potentials low enough to allow a spontaneous reaction, when coupled to the cathodic reaction, and must be selective. Here, we build a three-dimensional (3D)-printed glycerol microfluidic fuel cell that produces power concomitantly to glycolate and formate at zero bias. The balance between energy and the two carbonyl compounds is tuned by decorating the Pt/C/CP anode in situ (before feeding the cell reactants) or in operando (while feeding the cell with reactants) with Bi. The Bi-modified anodes improve glycerol conversion and output power while decreasing the formation of the carbonyl compounds. The in operando method builds dendrites of rodlike Bi oxides that are inactive for the anodic reaction and cover active sites. The in situ strategy promotes homogeneous Bi decoration, decreasing activation losses, increasing the open-circuit voltage to 1.0 V, and augmenting maximum power density 6.5 times and the glycerol conversion to 72% at 25 °C while producing 0.2 mmoL L^–1 of glycolate and formate (each) at 100 μL min^–1. Such a performance is attributed to the low CO poisoning of the anode, which leads the glycerol electrooxidation toward a more complete reaction, harvesting more electrons at the device. Printing the microfluidic fuel cell takes 23 min and costs ∼US$1.85 and can be used for other coupled reactions since the methods of modification presented here are applied to any existing and assembled systems.

Covalent organic frameworks (COFs) are of great interest in the energy and optoelectronic fields due to their high porosity, superior thermal stability, and highly ordered conjugated architecture, which are beneficial for charge migration, charge separation, and light harvesting. In this study, polyimide COFs (PI-COFs) are synthesized through the condensation reaction of pyromellitic dianhydride (PMDA) with tris(4-aminophenyl) amine (TAPA) and then doped in the TiO₂ photoelectrode of a dye-sensitized solar cell (DSSC) to co-work with N719 dye to explore their functionality. As a benchmark, the pristine DSSC without the doping of PI-COFs exhibits a power conversion efficiency of 9.05% under simulated one sun illumination. The doping of 0.04 wt % PI-COFs contributes an enhanced short-circuit current density (J_SC) from 17.43 to 19.03 mA/cm², and therefore, the cell efficiency is enhanced to 9.93%. The enhancement of J_SC is attributed to the bifunctionality of PI-COFs, which enhances the charge transfer/injection and suppresses the charge recombination through the host (PI-COF)–guest (N719 dye) interaction. In addition, the PI-COFs also function as a cosensitizer and contribute a small quantity of photoinduced electrons upon sunlight illumination. Surface modification of oxygen plasma improves the hydrophilicity of PI-COF particles and reinforces the heterogeneous linkage between PI-COF and TiO₂ nanoparticles, giving rise to more efficient charge injection. As a result, the champion cell exhibits a high power conversion efficiency of 10.46% with an enhanced J_SC of 19.43 mA/cm². This methodology of increasing solar efficiency by modification of the photoelectrode with the doping of PI-COFs in the TiO₂ nanoparticles is promising in the development of DSSCs.

The electrocatalytic reduction of nitrobenzene to aniline normally faces high overpotential and poor selectivity because of its six-electron redox nature. Herein, a Ag nanoparticles/laser-induced-graphene (LIG) heterointerface was fabricated on polyimide films and employed as an electrode material for an efficient nitrobenzene reduction reaction (NBRR) via a one-step laser direct writing technology. The first-principles calculations reveal that Ag/LIG shows the lowest activation barriers for the NBRR, which could be attributed to the optimum adsorption of the H atom realized by the appropriate interaction between Ag/LIG heterointerfaces and nitrobenzene. As a result, the overpotential of the NBRR is reduced by 217 mV after silver loading, and Ag/LIG shows a high aniline selectivity of 93%. Furthermore, an electrochemical reduction of nitrobenzene in tandem with an electrochemical oxidative polymerization of aniline was designed to serve as an alternative method to remove nitrobenzene from the aqueous solution. This strategy highlights the significance of heterointerfaces for efficient electrocatalysts, which may stimulate the development of novel electrocatalysts to boost the electrocatalytic activity.

Nickel-rich layered cathode LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) is the most promising cathode material due to its high specific capacity and lower cost than lithium cobalt oxides. However, NCM811 suffers from structural instability and capacity degradation during charge–discharge cycles. Herein, we report a strategy to construct a conductive network by employing a holistic Ge coating, which interconnects Mg-doped NCM811 particles. Dopant Mg ions, serving as a “pillar” in the Li slab of NCM811, substantially enhance the structural reversibility. The Ge particles are not only coated on the electrode surface but also enter into the electrode pores to form a multidimensional conductive structure, which improves the conductivity of the electrode and slows down the interface side reaction, thus minimizing the irreversible loss of NCM811 upon long cycling. The modified NCM811 electrode delivers a high discharge capacity (∼204 mAh g^–1 at 0.1C), excellent rate performance (∼155 mAh g^–1 at 10C), and high capacity retention (83% after 200 cycles) even at 4.4 V. Additionally, a cylindrical full battery with graphite/modified NCM811 undergoes 1000 cycles with 86% capacity retention at 2C.

The narrow electrochemical stability window (1.23 V) of an aqueous electrolyte hinders the practical realization of calcium-ion chemistries of high-energy-density and long-cycle-life batteries. Furthermore, developing an aqueous electrolyte that is low cost, is environmentally friendly, and has a wide voltage window is essential to designing safe, high-energy-density, and sustainable calcium-ion batteries. A calcium-based water-in-salt (WISE) aqueous electrolyte surpasses the narrow stability window by offering a 2.12 V wide window by suppressing the hydrogen evolution at the anode and minimizing the overall water activity at the cathode. A comprehensive theoretical study predicts the preferential reduction of salt aggregates over water to form a passivation layer at the electrode–electrolyte interface and enhance the electrolyte stability window. Additionally, Raman spectroscopy reveals that the calcium ion coordination number, which is the number of nitrate ions surrounding the calcium ions in the aqueous electrolyte, gradually increases with an increase in the electrolyte concentration, leading to a gradual decrease in the hydration number of the calcium ions. A full cell in WISE was demonstrated to exhibit an excellent rate capability and cycling stability with negligible capacity loss (0.01 per cycle), maintaining 80% capacity retention over 1800 cycles with ∼99.99% Coulombic efficiency. The full cell provides an energy density of 232 Wh kg^–1 at a power density of 69 W kg^–1 and a current rate of 0.15 A g^–1. Even at a higher current rate of 5 A g^–1, the battery delivers an energy density of 182 Wh kg^–1 (based on the active mass of the anode). This is one of the best performances to date of all previously reported full-cell aqueous calcium-ion batteries. A fundamental understanding of the storage mechanism and a electrode degradation study was achieved. This work suggests and expands new avenues for the practical realization of low-cost, safe, eco-friendly, and high-performance aqueous calcium-ion batteries for future large storage applications.

The development of intercalation anodes with high capacity is key to promote the progress of “rocking-chair” Zn-ion batteries (ZIBs). Here, layered BiOI is considered as a promising electrode in ZIBs due to its large interlayer distance (0.976 nm) and low Zn²⁺ diffusion barrier (0.57 eV) obtained by density functional theory, and a free-standing BiOI nanopaper is designed. The process and mechanism of Zn(H₂O)_n²⁺ insertion in BiOI are proved by ex situ X-ray diffraction, Raman, and X-ray photoelectron spectroscopy. The suitable potential (0.6 V vs Zn/Zn²⁺), high reversible capacity (253 mAh g^–1), good rate performance (171 mAh g^–1 at 10 A g^–1), long cyclic life (113 mAh g^–1 after 5000 cycles at 5 A g^–1), and dendrite-free operation of BiOI nanopaper prove its potential as a superior anode. When it is coupled with Mn₃O₄ cathode, the quasi-solid-state battery exhibits a high initial capacity of 149 mAh g^–1 (for anode) and a good capacity retention of 70 mAh g^–1 after 400 cycles. The self-assembled flexible battery also shows stable charge–discharge during the cyclic test. This work shows the feasibility of BiOX anode for dendrite-free ZIBs.

Although the rapid development of electrical energy storage devices has slowed down environmental pollution, their large-scale application has posed huge challenges to battery-related mineral resources; thus, extending the lifespan of high-voltage lithium cobalt oxide (LCO) is of great importance. Surface oxide coating is considered as the most common low-cost modification method for addressing unstable cycling performance. However, studies have shown that the oxide layer would further react with an electrolyte, while the investigation on the corresponding component evolution is lacking. Herein, a typical example utilizing the above reaction to realize surface reconstruction is presented. Applying atomic layer deposition (ALD), originally, an ultrathin Al₂O₃ layer is coated on the LCO surface; however, this coating layer has undergone reconstruction after reacting with electrolyte decomposition products during the cycling. Compared with simple coating, the in situ formed Li₃AlF₆ layer has a tighter binding to the LCO surface while possessing good Li⁺ conductivity and electrochemical stability. In addition, the unique properties of the ALD technology allow us to achieve ultrathin (1 nm) and conformal coating, which is beneficial for electronic conductivity and cycling stability. Furthermore, the surface phase transition layer stripping failure mechanism has first been revealed to explain the loss of Co and O, while the reconstructed Li₃AlF₆ effectively suppresses the surface stripping. Thus, excellent high-voltage performance has been realized (an 89% capacity retention after 1000 cycles at 4.5 V and an 88% capacity retention after 200 cycles at 4.6 V). This work casts a new understanding on the surface reconstruction of the oxide coating layer, which is also significant for other electrode materials’ modification.

We present a novel anode interface modification on the β″-alumina solid-state electrolyte that improves the wetting behavior of molten sodium in battery applications. Heat treating a simple slurry, composed only of water, acetone, carbon black, and lead acetate, formed a porous carbon network decorated with PbO_x (0 ≤ x ≤ 2) nanoparticles between 10 and 50 nm. Extensive performance analysis, through impedance spectroscopy and symmetric cycling, shows a stable, low-resistance interface for close to 6000 cycles. Furthermore, an intermediate temperature Na–S cell with a modified β″-alumina solid-state electrolyte could achieve an average stable cycling capacity as high as 509 mA h/g. This modification drastically decreases the amount of Pb content to approximately 3% in the anode interface (6 wt % or 0.4 mol %) and could further eliminate the need for toxic Pb altogether by replacing it with environmentally benign Sn. Overall, in situ reduction of oxide nanoparticles created a high-performance anode interface, further enabling large-scale applications of liquid metal anodes with solid-state electrolytes.

The direct growth of sub-100 nm thin-film metal oxides has witnessed a sustained interest as a superlative approach for the fabrication of smart energy storage platforms. Herein, sub-100 nm Zr-doped orthorhombic Nb₂O₅ nanotube films are synthesized directly on the Nb-Zr substrate and tested as negative supercapacitor electrode materials. To boost the pseudocapacitive performance of the fabricated films, supplement Nb⁴⁺ active sites (defects) are subtly induced into the metal oxide lattice, resulting in 13% improvement in the diffusion current at 100 m V/s over that of the defect-free counterpart. The defective sub-100 nm film (H-NbZr) exhibits areal and volumetric capacitances of 6.8 mF/cm² and 758.3 F/cm³, respectively. The presence of oxygen-deficient states enhances the intrinsic conductivity of the thin film, resulting in a reduction in the band gap energy from 3.25 to 2.5 eV. The assembled supercapacitor device made of nitrogen-doped activated carbon (N-AC) and H-NbZr (N-AC//H-NbZr) is able to retain 93, 83, 78, and 66% of its first cycle capacitance after 1000, 2000, 3000, and 4500 successive charge/discharge cycles, respectively. An eminent energy record of approximately 0.77 μW h/cm² at a power of 0.9 mW/cm² is achieved at 1 mA/cm² with superb capability.

All-solid-state lithium batteries (ASSLBs) with high volumetric energy density and enhanced safety are considered one of the most promising next-generation batteries. Elucidating the capacity-fading mechanism caused by the space-charge layer (SCL) and the interfacial side reaction (ISR) is crucial for the future development of high-energy-density ASSLBs with a longer cycle life. Here, a systematic study to probe the electrochemical performance of Li₁₀GeP₂S₁₂-based ASSLBs with stoichiometric-controlled Li_xCoO₂ was performed with the aid of density functional theory (DFT) calculations, X-ray photoelectron spectroscopy (XPS), focused ion beam-field emission scanning electron microscopy (FIB-SEM), and solid-state nuclear magnetic resonance (NMR) spectroscopy. We discovered that the overstoichiometric Li_1.042CoO₂ shows a high capacity at first cycle with the smallest overpotential, but the capacity gradually decreases, which is ascribed to the weak SCL effect and strong interfacial side reactions. On the contrary, the lithium-deficient Li_0.945CoO₂ achieves the best cycling stability with a very low capacity associated with the strongest SCL effect and weak interfacial side reactions. The SCL effect is indeed coupled with ISR, which eventually leads to capacity fading in long-term operation. We believe that the new insights gained from this work will accelerate the future development of LiCoO₂/LGPS-based ASSLBs with both a mitigated SCL effect and a longer cycle life.

Organic cathode materials (OCMs) for rechargeable Li and Na batteries show great advantages in resource sustainability and huge potential in electrochemical performance but suffer from dissolution problems and costly synthesis. Herein, for the first time, we investigated the copolymer of benzoquinone (BQ) and pyrrole (Py), namely, poly(benzoquinone-pyrrole) (PBQPy), as an OCM for Li batteries. The low-cost raw materials and solvent-free synthesis provide PBQPy much brighter prospects in large-scale production compared to other carbonyl-based polymer cathode materials. Nevertheless, PBQPy showed one of the best electrochemical performances among all OCMs, including excellent energy density (2.32 V × 255 mAh g^–1 = 592 Wh kg^–1), rate capability (79%@2000 mA g^–1), and cycling stability (81%@1000th cycle). By introducing poly(benzoquinone-methyl pyrrole) for comparison, as well as employing density functional theory calculations and various characterizations for in-depth understanding, the synthesis mechanism, polymer structure, electrochemical behavior, and redox mechanism were clearly clarified. It is believed that this work will encourage more efforts to develop cost-effective OCMs toward practical organic batteries.

Obtaining good-quality perovskite thin films is a fundamental facet that contributes to efficient inorganic perovskite solar cells. Herein, we successfully deposited ethylammonium bromide (EABr) additive-assisted high quality γ-CsPbI₂Br perovskite films under ambient conditions. Detailed morphological, structural, optical, charge transport, photovoltaic performance, and stability properties have been studied. It is observed that the EABr additive helps to retard the crystal growth of perovskite films to produce a highly crystalline perovskite film with microsized grains (>1 μm) and with reduced grain boundaries. The fabricated devices based on an optimum amount of EABr (4 mg mL^–1) exhibited the highest 14.47 % power conversion efficiency. Moreover, the EABr-4 mg mL^–1-assisted γ-CsPbI₂Br-based devices achieved a high thermal long-term stability and maintained ∼75% of their initial efficiency over 180 h at 85 °C thermal stress under ambient conditions (relative humidity: ∼35%) without encapsulation. This additive-assisted method suggests a new pathway to achieve high-quality perovskite films with a stabilized photoactive black phase and efficient devices.

Polymer-based materials with the incorporation of redox-active dopants serve as promising electrodes for Li-ion batteries but their use is restricted by the limited doping level and inevitable dissolution behavior of the dopants. Here, we proposed a conjugated polymer-based electrode with an assistant dopant to realize the reversible capacity contribution of a redox-active dopant. By employing phosphate anion (PO) as the assistant dopant to stable the polymer matrix, the reversible capacity was improved by introducing indigo carmine (IC) into the polymer electrode. Based on the real-time monitoring of the electrochemical quartz crystal microbalance toward the mass change, the charge storage behavior of the redox-active dopant IC was observed and the stabilizing effect of the assistant dopant PO was revealed. The modified electrode delivered an increased capacity of 191 mA h g^–1, and the reversible capacity remained 56% higher than that of the PO-undoped electrode after 200 cycles. The dual-doping strategy with the assistant dopant and the redox-active dopant is used to develop advanced polymer-based electrodes for high-capacity and long-cycling batteries.

Single atom (SA)- and monolayer (ML)-supported catalysts are two main technical routines to increase electrochemical catalytic performance and reduce cost. To date, it is still a debate which one is better for catalysis in experiments as both routines face a puzzling problem of searching for balance between stability and catalytic activity. Here, hydrogen evolution on two-dimensional 2H-MoS₂ with SA- and ML-adsorbed metal atoms (23 kinds in total) is taken as an example to solve this question by first-principles calculations. The thermodynamic stability during synthesis, in vacuum, and in electrochemical reaction conditions is determined to access the stability of MoS₂ loaded with single (M_S@MoS₂) and monolayer metal atoms (M_M@MoS₂). The realistic catalytic surfaces determined by surface Pourbaix diagrams, the free energy changes of hydrogen atoms at different coverages, and the exchange current densities are applied to determine hydrogen evolution reaction (HER) activity. The results show that all M_M@MoS₂ are much more stable than the corresponding M_S@MoS₂ as the metal–metal interaction in MLs could make the former structures more stable. In general, M_M@MoS₂ show higher hydrogen evolution activities than those of M_S@MoS₂. In detail, the exchange current densities of MoS₂ loaded by Pd ML and Au ML are 6.208, and 1.109 mA/cm^–2, respectively, which are comparable to Pt(111). Combining with small binding energies, the Pd and Au MLs are the most promising catalysts for hydrogen evolution. The purpose of this work is to highlight the advantages and disadvantages of SA- and ML-supported surfaces as HER catalysts and provide a fundamental standard for studying them.

Extraction of valuable metals such as gold from electronic wastes (e-waste) is regarded as a promising way of environmental remediation; however, this process is still confronted with the cost-ineffective product for normal usages like electronic devices or jewelry. Therefore, there would be merits in directly converting gold from e-waste to materials of higher value, for example, catalysts for pollutant treatment. Herein, a porous aromatic framework (PAF) with cationic sites, named iPAF-7, was synthesized and exhibited rapid extraction of gold from e-waste. Au@iPAF-7 completely converted nitroarenes to arylamines within 10 s at a rate constant of 7.8 × 10^–2 s^–1, which is much higher than that of any other gold nanoparticle (AuNP) catalysts with solid supports reported so far. Furthermore, considering the limitations and difficulties of operating powder materials, the aerogel monolith incorporating iPAF-7 was successfully fabricated, which retained the excellent gold extraction ability and catalytic activity of its powder form, thus exhibiting its potential application for continuous-flow catalysis of nitroarene reduction.

Passive electronic components are an indispensable part of integrated circuits, which are key to the miniaturization and integration of electronic components. As an important branch of passive devices, the relatively low energy-storage capacity of ceramic capacitors limits their miniaturization. To solve this problem, this study adopts the strategy of doping linear materials, specifically CT, into 0.95NaNbO₃–0.05Bi(Mg_0.5Sn_0.5)O₃ (0.95NN–0.05BMS) ceramics to increase the disorder of the system through the nonequivalent substitution of A and B sites to achieve the sintering temperature and the residual polarization. Meanwhile, the breakdown electric field strength (E_b) is improved by adjusting the activation energy of the material and the relative density of the sample. Thus, an ultrahigh W_rec of 6.35 J/cm³ and a η of 80% are obtained at an E_b of 646 kV/cm. Additionally, through the analysis of the dielectric temperature spectrum, it is found that the 0.88(0.95NN–0.05BMS)–0.12CT sample can satisfy the technical standards of general ceramic Z5U and patch ceramic X6R. The performance of the ceramics also remains stable within a temperature range of 20–200 °C, a frequency range of 1–100 Hz, and 10⁴ cycles. The charge and discharge tests of the ceramics show that the t_0.9 of the sample floats between 1.02 and 1.04 μs, which illustrates its potential application in the field of pulsed power components.

The polyhedra unit structure (MO_x) in an amorphous metal oxide network has more freedom and flexibility than the same unit structure in a crystalline phase. Consequently, a mild external stimulus (e.g., instant photonic and acoustic energy) could affect and change this network parameter, thereby enhancing and modulating the electrical properties. However, it is difficult to tune these atomic parameters solely while maintaining the metal oxide’s initial global amorphous phase and thereby preventing mechanical instability at the film–substrate interface (i.e., cracking or distortion). Here, we report local disordering in an amorphous network of a solution-processable indium tin oxide (ITO) film, where the disordering is triggered by mild-light irradiation (<0.1 mJ/cm²). Through a combination of systematic characterizations of the global structural and chemical compositional changes in conjunction with extended X-ray absorption fine structure analyses, we revealed the distortion of the atomic structure in the amorphous network of the ITO film led to the formation of additional structural oxygen vacancies. Our findings enabled us to fabricate mechanical-instability-free, perfect amorphous-phase ITO thin films on plastic substrates, where the sheet resistance substantially decreased to ∼ 2 × 10³ Ω/□. Furthermore, this sheet resistance did not vary when the film and substrate were bent to a radius of 2 mm and could operate at low temperatures. This work can pave the novel way to fabricate high-quality flexible transparent electrodes suitable for rapid, cost-effective, and patternable processing on plastic substrates, and the domain can be extended to flexible electronics.

A multifunctional wearable tactile sensor assisted by deep learning algorithms is developed, which can realize the functions of gesture recognition and interaction. This tactile sensor is the fusion of a triboelectric nanogenerator and piezoelectric nanogenerator to construct a hybrid self-powered sensor with a higher power density and sensibility. The power generation performance is characterized with an open-circuit voltage V_OC of 200 V, a short-circuit current I_SC of 8 μA, and a power density of 0.35 mW cm^–2 under a matching load. It also has an excellent sensibility, including a response time of 5 ms, a signal-to-noise ratio of 22.5 dB, and a pressure resolution of 1% (1–10 kPa). The sensor is successfully integrated on a glove to collect the electrical signal output generated by the gesture. Using deep learning algorithms, the functions of gesture recognition and control can be realized in real time. The combination of tactile sensor and deep learning algorithms provides ideas and guidance for its applications in the field of artificial intelligence, such as human–computer interaction, signal monitoring, and smart sensing.

Perovskite oxides are an important class of oxygen evolution reaction (OER) catalysts offering an ordered atomic arrangement and a highly flexible electronic structure. Currently, understanding and adjusting the dynamic reconstruction of perovskite during the OER process remains a formidable challenge. Here, we report the artificial construction of a heterostructure by the cation exsolution of perovskite to control the active site formation and reconstruction. The deliberately made La deficiency in LaNiO₃ perovskite facilitates the original segregation of NiO from the parent matrix and forms a well-defined interface between perovskite parent and NiO exsolution phase. The dynamic formation process of such heterojunction was studied by density functional theory computation and high quality imaging characterization. Due to the valence redistribution of Ni ions caused by the interfacial electron transfer, the in situ formed LaNiO₃/NiO heterostructure displays high electroactivity. Therefore, the LaNiO₃/NiO heterostructure exhibits a dynamic surface evolution feature with the generation of the highly active NiOOH layer under a low anodic potential (∼1.35 V vs RHE) during the OER process, which is very different from the conventional LaNiO₃ with a stoichiometry and NiO catalysts. With the newly formed heterostructure, the reconstructed catalysts impart a 4.5-fold increase in OER activity and a 3-fold improvement in stability against La and Ni dissolution during the OER process. This work provides a feasible interface engineering strategy for artificially controlling the reconstruction of the active phase in high-performance perovskite-based electrocatalytic materials.

Self-powered deep-ultraviolet photodetectors have received considerable attention in recent years because of their efficiency, reliability, and various applications in civilian and military fields. Herein, a Ag/Ag₂O layer is continuously deposited on a β-Ga₂O₃ epitaxial layer by a facing target sputtering system without opening the chamber, which has an advantage in time and cost. A p–n junction photodetector was constructed through the Ag₂O/β-Ga₂O₃ heterojunction and by varying the thickness of the Ag film, which was controlled by the sputtering time. The effect of top electrode thickness on the photoresponse characteristics of photodetectors was studied. Because thin Ag films have low surface roughness, indicating low optical loss and good interfacial conditions, photodetectors using a thin Ag film as the top electrode exhibit high photoresponsivity. However, Ag films that were thinner than the threshold thickness, which is the minimum thickness required to form a continuous, homogeneous surface film, exhibited rather low performance owing to the high reflection and scattering caused by the inhomogeneous surface morphology. The as-fabricated photodetector with a 20 nm Ag film presents a high on/off ratio of 3.43 × 10⁸, responsivity and detectivity of 25.65 mA/W and 6.10 × 10¹¹ Jones, respectively, and comparable rise and decay times of 108 and 80 ms, respectively. Additionally, even after three months of storage in an ambient environment, the photoresponse of the photodetector was maintained, indicating good stability in air. These results suggest that Ag₂O/β-Ga₂O₃ heterojunction-based photodetectors with thin Ag films can be used in various applications requiring deep-ultraviolet detection without an external power supply.

Recently, the ultrafast operation (∼20 ns) of a two-dimensional (2D) heterostructured nonvolatile memory (NVM) device was demonstrated, attracting considerable attention. However, there is no consensus on its physical origin. In this study, various 2D NVM device structures are compared. First, we reveal that the hole injection at the metal/MoS₂ interface is the speed-limiting path in the NVM device with the access region. Therefore, MoS₂ NVM devices with a direct tunneling path between source/drain electrodes and the floating gate are fabricated by removing the access region. Indeed, a 50 ns program/erase operation is successfully achieved for devices with metal source/drain electrodes as well as graphite source/drain electrodes. This controlled experiment proves that an atomically sharp interface is not necessary for ultrafast operation, which is contrary to the previous literature. Finally, the dielectric breakdown strength (E_BD) of h-BN under short voltage pulses is examined. Since a high dielectric breakdown strength allows a large tunneling current, ultrafast operations can be achieved. Surprisingly, an E_BD = 26.1 MV/cm for h-BN is realized under short voltage pulses, largely exceeding the E_BD = ∼12 MV/cm from the direct current (DC) measurement. This suggests that the high E_BD of h-BN can be the physical origin of the ultrafast operation.

The development of high-performance p-type oxides with wide band gap and high hole mobility is critical for the application of oxide semiconductors in back-end-of-line (BEOL) complementary metal-oxide-semiconductor (CMOS) devices. SnO has been intensively studied as a high-mobility p-type oxide due to its low effective hole mass resulting from the hybridized O-2p/Sn-5s orbital character at the valence band edge. However, SnO has a very small band gap (∼0.7 eV) for practical p-type oxide devices. In this work, we report an engineering method to enhance the band gap and hole mobility in SnO. It is found that both the band gap and the hole mobility of a layer-structured SnO increase with the interlayer stacking spacing change. By exploiting this unique electronic structure feature, we propose expanding the interlayer spacing by interlayer intercalation to engineer the band gap and p-type mobility in SnO. Small molecules like NH₃ and CH₄ are shown to be capable of expanding the interlayer spacing and of increasing the band gap and hole mobility in SnO and thus could potentially serve as the interlayer intercalants. The results provide a viable way for the experimental realization of wide-band-gap and high hole-mobility p-type SnO for BEOL vertical CMOS device applications.

The accelerated evolution of the Internet of Things has brought new challenges to the gas sensors, which are required to work persistently under harsh conditions, like high humidity. However, currently, it is quite challenging to solve the hindrance of the trade-off between gas-sensing performance and anti-humidity ability of the chemiresistive gas sensors. Herein, hydrophobic inorganic CeO₂/SnO₂ heterostructure films were prepared by depositing the CeO₂ layers with a thickness of a few nanometers onto the SnO₂ film via a magnetron sputtering method. The sensors based on the CeO₂/SnO₂ heterostructure films demonstrated excellent gas-sensing performance toward trimethylamine (TEA) with high response, wide detection range (0.04–500 ppm), low record detection limit (0.04 ppm), ideal reproducibility, and long-term stability, while concurrently possessing promising anti-humidity ability. A portable, wireless TEA-sensing system containing the CeO₂/SnO₂ sensor was constructed to realize the real-time monitoring of trace concentration of the volatiles released from a fish. This work provides a novel strategy to prepare advanced chemiresistive gas sensors for humidity-independent detection of harmful gases and vapors and will accelerate their commercialization process in the field of food safety and public health.

The electric dipole locking effect observed in van der Waals (vdW) ferroelectric α-In₂Se₃ has resulted in a surge of applied research in electronics with nonvolatile functionality. However, ferroelectric tunnel junctions with advantages of lower power consumption and faster writing/reading operations have not been realized in α-In₂Se₃. Here, we demonstrate the tunneling electroresistance effect in a lateral β/α/β In₂Se₃ heterojunction built by local laser irradiation. Switchable in-plane polarizations of the vdW ferroelectric control the tunneling conductance of the heterojunction device by 4000% of magnitude. The electronic logic bit can be represented and stored with different orientations of electric dipoles. This prototype enables a new approach to rewritable nonvolatile memory with in-plane ferroelectricity in vdW 2D materials.

Magnetoelectric materials present a unique opportunity for electric field-controlled magnetism. Even though strain-mediated multiferroic heterostructures have shown unprecedented increase in magnetoelectric coupling compared to single-phase materials, further improvements must be made before ultra-low power memory, logic, magnetic sensors, and wide spectrum antennas can be realized. This work presents how magnetoelectric coupling can be enhanced by simultaneously exploiting multiple strain engineering approaches in heterostructures composed of Fe_0.5Co_0.5/Ag multilayers on (011) Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ piezoelectric crystals. When grown and measured under strain, these heterostructures exhibit an effective converse magnetoelectric coefficient in the order of 10^–5 s m^–1: the highest directly measured, non-resonant value to-date. This response occurred at room temperature and at low electric fields (<2 kV cm^–1). This large effect is enabled by magnetization reorientation caused by changing the magnetic anisotropy with strain from the substrate and the use of multilayered magnetic materials to minimize the internal stress from deposition. Additionally, the coercive field dependence of the magnetoelectric response under strain suggests contributions from domain-mediated magnetization switching modified by voltage-induced magnetoelastic anisotropy. This work highlights how multicomponent strain engineering enables enhanced magnetoelectric coupling in heterostructures and provides an approach to realize energy-efficient magnetoelectric applications.

Resistive random-access memory (RRAM) has been extensively investigated for 20 years due to its excellent advantages, including scalability, switching speed, compatibility with the complementary metal oxide semiconductor process, and neuromorphic computing application. However, the issue of memristor reliability for cycle to cycle and device to device resulting from the random ion drift and diffusion in solid-state thin films is still a great challenge for commercialization. Therefore, controlling the internal ionic process to improve the memristor performance and reliability is a primary and urgent task. Here, a Ni nanocone array prepared by an electrodeposition method is integrated with an Ag/Al₂O₃/Pt resistive switching device. The nanocone-array-based memristor yields superior switching performance, including an ultralow set voltage (−0.37 V), a concentrated voltage/resistance distribution (C_V 14.8%/32.7%), robust endurance (>10⁵ cycles), and multilevel storage capability. A finite element analysis, transmission electron microscope observation, and current mapping test indicate that the local enhancement of the electric field confines the ionic migration process and yields a predictable formation and dissolution process of the conductive filament. The nanocone-array-based RRAM device provides a new and feasible method to control the conductive filament growth reliably, which paves the way for memristor development.

The potential of Fe₂TiSn full-Heusler compounds for thermoelectric applications has been suggested theoretically, but not yet proven experimentally, due to the difficulty in obtaining reproducible, homogeneous, phase-pure and defect-free samples. In this work, we studied Fe₂TiSn_1–xSb_x polycrystals (x from 0 to 0.6), fabricated by high-frequency melting and long-time high-temperature annealing. We obtained fairly good phase purity, a homogeneous microstructure, and good matrix stoichiometry. Although the intrinsic p-type transport behavior is dominant, n-type charge compensation by Sb-doping is demonstrated. Calculations of the formation energy of defects and electronic properties carried out using the density functional theory formalism reveal that charged iron vacancies V_Fe^2– are the dominant defects responsible for the intrinsic p-type doping of Fe₂TiSn under all types of (except Fe-rich) growing conditions. In addition, Sb substitutions at the Sn site give rise either to Sb_Sn, Sb_Sn¹⁺, which are responsible for n-type doping and magnetism (Sb_Sn) or to magnetic Sb_Sn^1–, which act as additional p-type dopants. Our experimental data highlight good thermoelectric properties close to room temperature, with Seebeck coefficients up to 56 μV/K in the x = 0.2 sample and power factors up to 4.8 × 10^–4 W m^–1 K^–2 in the x = 0.1 sample. Our calculations indicate the appearance of a pseudogap under Ti-rich conditions and a large Sb-doping level, possibly improving further the thermoelectric properties.

The difficulty of current injection into single-crystalline hexagonal boron nitride (h-BN) has long hindered the realization of h-BN-based high-performance electronic and optoelectronic devices. Here, with the contact formed by Ar plasma treatment, Ni/Au metal deposition, and subsequent high-temperature annealing, we demonstrate current injection into single-crystalline h-BN with a C doping level of ∼1.5 × 10¹⁹ atoms/cm³. A comparison to the current flow during the dielectric breakdown of h-BN clearly verifies our current injection. The devices show non-Ohmic conduction for all measured temperatures (20–598 K). Analysis of activation energies for carrier transport suggests nearest-neighbor-hopping-assisted Poole–Frenkel (PF) conduction in the highly defective h-BN at the contact region. The estimated dominant defect level with the range of 240–720 meV is much smaller than the Schottky barrier height at the metal/h-BN interface, supporting the effective contact formation for current injection. Moreover, structural and chemical characterizations at the contact suggest that an interaction between Ni and defective h-BN introduces defect states in the gap, assisting the current injection. In contrast, the characterizations confirm the well-retained high crystallinity of h-BN in the channel, indicating the potential of the present contact formation method for the future development of high-performance h-BN-based devices.

Among transition metal oxides, MoO₃ is a promising material due to its layered structure and different oxidation states, making it suitable for different device applications. One of the methods used to grow MoO₃ is radio frequency magnetron sputtering (RFMS), which is the most compatible method in industry. However, obtaining nanostructures by RFMS for metal oxides is challenging because of compact morphology film formation. In this study, α-MoO₃ with vertical nanowalls is obtained by a two-step process; deposition of magnetron-sputtered MoS₂ vertical nanowalls and postoxidation of these structures without changing the morphology. In situ transmittance and electrical measurements are performed to control the oxidation process, which shed light on understanding the oxidation of MoS₂ nanowalls. The transition from MoS₂ to α-MoO₃ is investigated with partially oxidized MoS₂/MoO₃ samples with different thicknesses. It is also concluded that oxidation starts from nanowalls perpendicular to the substrate and lasts with oxidation of basal planes. Four different thicknesses of α-MoO₃ nanowall samples are fabricated for H₂ gas sensors. Also, the effect of Pd deposition on the H₂-sensing properties of sensors is deeply investigated. An outstanding response of 3.3 × 10⁵ as well as the response and recovery times of 379 and 304 s, respectively, are achieved from the thinnest Pd-loaded sample. Also, the gas-sensing mechanism is explored by gasochromic measurements to investigate the sensor behaviors under the conditions of dry air and N₂ gas as the carrier gas.

Flexible strain-sensitive sensors have been receiving intensive attention in many aspects ranging from human motion capture to health-related signal monitoring. However, the fabric strain sensor with multi-directional sensing capability, besides having a wide strain range and high response sensitivity, is still very challenging and deserves further exploration. Here, we have prepared a wearable cotton fabric strain sensor uniformly decorated with single-walled carbon nanotubes through a facile solution process. The unique hierarchical architecture of the cotton fabric woven from twisted yarns combined with the conductive carbon nanotube network endows the fabric strain sensors with attractive performance, including low detection limit, large workable strain range, fascinating stability and durability, excellent direction-dependent strain response, and good air permeability. The strain sensor without polymer encapsulation can not only monitor subtle and large multi-directional motions but also fit well to the human body with satisfactory comfort, demonstrating its potential application in wearable electronics and intelligent clothing.

Two-dimensional transition-metal dichalcogenide (TMD) materials have attracted increasing attention in efforts to overcome fundamental issues faced by the complementary metal-oxide-semiconductor industry. Multilayer TMD materials such as MoS₂ can be used for high-performance transistor-based applications; the drive currents are high and the materials handle low-frequency (LF) noise well. We fabricated double-gated multilayer MoS₂ transistors using the h-BN dielectric for the top gate and silicon dioxide for the bottom gate. We systemically investigated the bottom gate voltage (V_b)-controlled electrical characteristics and the top/bottom interface-coupling effects. The effective thickness of the MoS₂ channel (t_{MoS2_eff}) was well modulated by V_b, and t_{MoS2_eff} reduction by negative V_b dramatically improved the I_on/I_off ratio. Numerical simulation and analytical modeling with a variation of the depletion depth under different bias conditions verified the experimental results. We were also the first to observe V_b-tuned LF noise characteristics. Here, we discuss the V_b-affected series resistance and carrier mobility in detail. Our findings greatly enhance the understanding of how double-gated multilayer MoS₂ transistors operate and will facilitate performance optimization in the real world.

Antiferroelectric materials have shown potential applications in energy storage. However, controlling and improving the energy-storage performance in antiferroelectric remain challenging. Here, a domain structure and energy-storage performance diagram for Pb(Zr_1–xTi_x)O₃ (x ≤ 0.1) single crystal are investigated via phase-field simulations. Controlling the ratio of domain wall coefficients λ and g can tune the periodicities of the antiferroelectric stripe domain and generate a complicated topological domain. By decreasing the antiferroelectric domain periodicity, one can achieve high recoverable energy-storage density (W_rec = 30.24 J/cm³) with an efficiency of 80.9%. In addition, Pb(Zr_1–xTi_x)O₃ (x ≤ 0.1) thin-film system has also been investigated. Positive equiaxial misfit strain significantly enhances recoverable energy-storage density up to 21.96 J/cm³ with an efficiency of 84.9%. Our results offer another train of thought to tune antiferroelectric domain structure, which provides the idea to design high-energy-density materials in experiments.

Microlight-emitting diode (Micro-LED) is the only display production technology capable of meeting the high-performance requirements of future screens. However, it has significant obstacles in commercialization due to etching loss and efficiency reduction caused by the singulation process, in addition to expensive costs and a significant amount of time spent on transfer. Herein, multiple-sapphire nanomembrane (MSNM) technology has been developed that enables the rapid transfer of arrays while producing micro-LEDs without the need for any singulation procedure. Individual micro-LEDs of tens of μm size were formed by the pendeo-epitaxy and coalescence of GaN grown on 2 μm width SNMs spaced with regular intervals. We have successfully fabricated micro-LEDs of different sizes including 20 × 20 μm², 40 × 40 μm², and 100 × 100 μm², utilizing the membrane design. It was confirmed that the 100 × 100 μm² micro-LED manufactured with MSNM technology not only relieved stress by 80.6% but also reduced threading dislocation density by 58.7% compared to the reference sample. It was proven that micro-LED arrays of varied chip sizes using MSNM were all transferred to the backplane. A vertical structure LED device could be fabricated using a 100 × 100 μm² micro-LED chip, and it was confirmed to have a low operation voltage. Our work suggests that the development of the MSNM technology is promising for the commercialization of micro-LED technology.

Photomechanical effect in semiconductors refers to a phenomenon that plastic deformation is influenced by light-induced electron–hole (e-h) excitation. To date, increasing amounts of theoretical and experimental studies have been performed to illustrate the physical origin of this phenomenon. In contrast, there has been little discussion about this effect in superhard materials. Here, we adopted constrained density functional theory simulations to assess how e-h excitation influences two boron-based superhard materials: boron carbide (B₄C) and boron subphosphide (B₁₂P₂). We found that the ideal shear strengths of both systems decrease under e-h excited states. Under e-h excitation, the redistribution of electrons and holes contributes to the decreased strength, weakening the bonds initially broken under the shear deformation. The simulation results provide a fundamental explanation for the softening effects of superhard materials under e-h excitation. This study also provides a basis to tune the mechanical properties of superhard materials via light irradiation.

Recently, rock-salt lead-free chalcogenide SnTe-based thermoelectric (TE) materials have been considered an alternative to PbTe because of the nontoxic properties of Sn as compared to Pb. However, high carrier concentration that originated from intrinsic Sn vacancies and relatively high thermal conductivity of pristine SnTe lead to poor TE efficiency, which makes room for improving its TE properties. In this study, we present that the Na incorporation into the SnTe matrix is helpful for modifying the electronic band structure, optimization of carrier concentration, introducing dislocations, and kink planes; benefiting from these synergistic effects obviates the disadvantages of SnTe and makes a significant improvement in TE performance. We reveal that Na favorably impacts the structure of electronic bands by valence, conduction band engineering, leading to a nice enhancement in the Seebeck coefficient, which exhibits the highest power factor value of 37.93 μWcm^–1 K^–2 at 898 K, representing the best result for the SnTe material system. Moreover, a broader phonon spectrum is introduced by new phonon-scattering centers, scattered by dislocations and kink planes which suppressed lattice thermal conductivity to 0.57 Wm^–1 K^–1 at 898 K, which is much lower than that of pristine SnTe. Ultimately, a maximum ZT of 1.26 at 898 K is achieved in the Sn_1.03Te + 3% Na sample, which is 97% higher than that of the pristine SnTe, suggesting that SnTe-based materials are a robust candidate for TE applications specifically, an ideal alternative of lead chalcogenides for TE power generation at high temperatures.

Lead sulfide colloidal quantum dots (PbS CQDs) have shown great potential in photodetectors owing to their promising optical properties, especially their strong and tunable absorption. However, the limitation of the specific detectivity (D*) in CQD near-infrared (NIR) photodetectors remains unknown due to the ambiguous noise analysis. Therefore, a clear understanding of the noise current is critically demanded. Here, we elucidate that the noise current is the predominant factor limiting D*, and the noise is highly dependent on the trap densities in halide-passivated PbS films and the carriers injected from the Schottky contact (EDT-passivated PbS films/metal). It is found that the thickness of CQDs is proportional to their interface trap density, while it is inversely proportional to their minimal bulk trap density. A balance point can be reached at a certain thickness (136 nm) to minimize the trap density, giving rise to the improvement of D*. Utilizing thicker PbS-EDT films broadens the width of the tunneling barrier and thereby reduces the carrier injection, contributing to a further enhancement of D*. The limiting factors of D* determined in this work not only explain the physical mechanism of the influence on detection sensitivity but also give guidance to the design of high-performance CQD photodetectors.