ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES
RETURN TO ISSUEPREVResearch ArticleNEXT

Combined EXAFS, XRD, DRIFTS, and DFT Study of Nano Copper-Based Catalysts for CO2 Hydrogenation

View Author Information
Department of Chemistry, Christopher Ingold Laboratories, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom
Department of Chemical Engineering and Technology, KTH-Royal Institute of Technology, Teknikringen 42, 100 44 Stockholm, Sweden
§ School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, U.K.
*J.A.D.: e-mail, [email protected]; tel, +44 (0)20 7679 4345.
Cite this: ACS Catal. 2016, 6, 9, 5823–5833
Publication Date (Web):July 21, 2016
https://doi.org/10.1021/acscatal.6b01529
Copyright © 2016 American Chemical Society

    Article Views

    5774

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    Highly monodispersed CuO nanoparticles (NPs) were synthesized via continuous hydrothermal flow synthesis (CHFS) and then tested as catalysts for CO2 hydrogenation. The catalytic behavior of unsupported 11 nm sized nanoparticles from the same batch was characterized by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS), extended X-ray absorption fine structure (EXAFS), X-ray diffraction (XRD), and catalytic testing, under CO2/H2 in the temperature range 25–500 °C in consistent experimental conditions. This was done to highlight the relationship among structural evolution, surface products, and reaction yields; the experimental results were compared with modeling predictions based on density functional theory (DFT) simulations of the CuO system. In situ DRIFTS revealed the formation of surface formate species at temperatures as low as 70 °C. DFT calculations of CO2 hydrogenation on the CuO surface suggested that hydrogenation reduced the CuO surface to Cu2O, which facilitated the formation of formate. In situ EXAFS supported a strong correlation between the Cu2O phase fraction and the formate peak intensity, with the maxima corresponding to where Cu2O was the only detectable phase at 170 °C, before the onset of reduction to Cu at 190 °C. The concurrent phase and crystallite size evolution were monitored by in situ XRD, which suggested that the CuO NPs were stable in size before the onset of reduction, with smaller Cu2O crystallites being observed from 130 °C. Further reduction to Cu from 190 °C was followed by a rapid decrease of surface formate and the detection of adsorbed CO from 250 °C; these results are in agreement with heterogeneous catalytic tests where surface CO was observed over the same temperature range. Furthermore, CH4 was detected in correspondence with the decomposition of formate and formation of the Cu phase, with a maximum conversion rate of 2.8% measured at 470 °C (on completely reduced copper), supporting the indication of independent reaction pathways for the conversion of CO2 to CH4 and CO that was suggested by catalytic tests. The resulting Cu NPs had a final crystallite size of ca. 44 nm at 500 °C and retained a significantly active surface.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.6b01529.

    • Schematic representation of the continuous hydrothermal flow synthesis (CHFS) process, DFT model surfaces, and heterogeneous test results for WHSV = 4900 mL h–1 g–1 (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 48 publications.

    1. Jie Hu, He Zheng, Lei Li, Guoxujia Chen, Kaixuan Li, Meng Qi, Ying Zhang, Peili Zhao, Weiwei Meng, Shuangfeng Jia, Jianbo Wang. Probing the Atomistic Reaction Pathways in CuO/C Catalysts. Nano Letters 2023, 23 (20) , 9367-9374. https://doi.org/10.1021/acs.nanolett.3c02651
    2. Rekha Yadav, D. P. Goyal, Vijay Kumar, Pawan Kumar, Ramcharan Meena, Abhishek Kumar Mishra, Asokan Kandasami. Defect-Induced Phase Transformations in CuO Thin Films by Ag Ion Implantation and Their Gas-Sensing Applications. The Journal of Physical Chemistry C 2023, 127 (24) , 11438-11447. https://doi.org/10.1021/acs.jpcc.3c01917
    3. Anna Strijevskaya, Akira Yamaguchi, Shusaku Shoji, Shigenori Ueda, Ayako Hashimoto, Yu Wen, Aufandra Cakra Wardhana, Ji-Eun Lee, Min Liu, Hideki Abe, Masahiro Miyauchi. Nanophase-Separated Copper–Zirconia Composites for Bifunctional Electrochemical CO2 Conversion to Formic Acid. ACS Applied Materials & Interfaces 2023, 15 (19) , 23299-23305. https://doi.org/10.1021/acsami.3c02874
    4. Xiwen Song, Chengsheng Yang, Xianghong Li, Zhongyan Wang, Chunlei Pei, Zhi-Jian Zhao, Jinlong Gong. On the Role of Hydroxyl Groups on Cu/Al2O3 in CO2 Hydrogenation. ACS Catalysis 2022, 12 (22) , 14162-14172. https://doi.org/10.1021/acscatal.2c03591
    5. Ergys Pahija, Christopher Panaritis, Sergey Gusarov, Jalil Shadbahr, Farid Bensebaa, Gregory Patience, Daria Camilla Boffito. Experimental and Computational Synergistic Design of Cu and Fe Catalysts for the Reverse Water–Gas Shift: A Review. ACS Catalysis 2022, 12 (12) , 6887-6905. https://doi.org/10.1021/acscatal.2c01099
    6. Wei Wang, Chaoyuan Deng, Shijie Xie, Yangfan Li, Wanyi Zhang, Hua Sheng, Chuncheng Chen, Jincai Zhao. Photocatalytic C–C Coupling from Carbon Dioxide Reduction on Copper Oxide with Mixed-Valence Copper(I)/Copper(II). Journal of the American Chemical Society 2021, 143 (7) , 2984-2993. https://doi.org/10.1021/jacs.1c00206
    7. Zhao Luo, Shoushuai Tian, Zhao Wang. Enhanced Activity of Cu/ZnO/C Catalysts Prepared by Cold Plasma for CO2 Hydrogenation to Methanol. Industrial & Engineering Chemistry Research 2020, 59 (13) , 5657-5663. https://doi.org/10.1021/acs.iecr.9b06996
    8. Wen Li, Kuncan Wang, Junjie Huang, Xiao Liu, Dun Fu, Jiale Huang, Qingbiao Li, Guowu Zhan. MxOy–ZrO2 (M = Zn, Co, Cu) Solid Solutions Derived from Schiff Base-Bridged UiO-66 Composites as High-Performance Catalysts for CO2 Hydrogenation. ACS Applied Materials & Interfaces 2019, 11 (36) , 33263-33272. https://doi.org/10.1021/acsami.9b11547
    9. Wenhui Li, Guanghui Zhang, Xiao Jiang, Yi Liu, Jie Zhu, Fanshu Ding, Zhongmin Liu, Xinwen Guo, Chunshan Song. CO2 Hydrogenation on Unpromoted and M-Promoted Co/TiO2 Catalysts (M = Zr, K, Cs): Effects of Crystal Phase of Supports and Metal–Support Interaction on Tuning Product Distribution. ACS Catalysis 2019, 9 (4) , 2739-2751. https://doi.org/10.1021/acscatal.8b04720
    10. Kartavya Bhola, Jithin John Varghese, Liu Dapeng, Yan Liu, and Samir H. Mushrif . Influence of Hubbard U Parameter in Simulating Adsorption and Reactivity on CuO: Combined Theoretical and Experimental Study. The Journal of Physical Chemistry C 2017, 121 (39) , 21343-21353. https://doi.org/10.1021/acs.jpcc.7b05385
    11. Jawwad A. Darr, Jingyi Zhang, Neel M. Makwana, and Xiaole Weng . Continuous Hydrothermal Synthesis of Inorganic Nanoparticles: Applications and Future Directions. Chemical Reviews 2017, 117 (17) , 11125-11238. https://doi.org/10.1021/acs.chemrev.6b00417
    12. Xiaorui Chen, Tongming Su, Xuan Luo, Xinling Xie, Zuzeng Qin, Hongbing Ji. Catalytic hydrogenation of CO2 to DME on surface Cu via highly efficient electron redistribution at the Cu0/Cu+ interface. Surfaces and Interfaces 2024, 48 , 104346. https://doi.org/10.1016/j.surfin.2024.104346
    13. Baoyong 保勇 REN 任, Shiyu 世玉 FANG 方, Tiantian 甜甜 ZHANG 张, Yan 燕 SUN 孙, Erhao 尔豪 GAO 高, Jing 晶 LI 李, Zuliang 祖良 WU 吴, Jiali 佳丽 ZHU 朱, Wei 伟 WANG 王, Shuiliang 水良 YAO 姚. Efficient simultaneous removal of diesel particulate matter and hydrocarbons from diesel exhaust gas at low temperatures over Cu–CeO 2 /Al 2 O 3 coupling with dielectric barrier discharge plasma. Plasma Science and Technology 2024, 26 (5) , 055503. https://doi.org/10.1088/2058-6272/ad1572
    14. Kankan Bu, Yikun Kang, Yefei Li, Yahong Zhang, Yi Tang, Zhen Huang, Wei Shen, Hualong Xu. CO2-assisted propane dehydrogenation to aromatics over copper modified Ga-MFI catalysts. Applied Catalysis B: Environmental 2024, 343 , 123528. https://doi.org/10.1016/j.apcatb.2023.123528
    15. Chen Wang, Xinhua Gao, Jianli Zhang, Qingxiang Ma, Subing Fan, Tian-Sheng Zhao. Effects of surface groups on Fe/ZnO catalysts for CO2 hydrogenation to olefin. Applied Surface Science 2024, 47 , 159820. https://doi.org/10.1016/j.apsusc.2024.159820
    16. Jian Han, Jun Yu, Zhaoteng Xue, Guisheng Wu, Dongsen Mao. Highly efficient CO2 hydrogenation to methanol over Cu–Ce1-xZrxO2 catalysts prepared by an eco-friendly and facile solid-phase grinding method. Renewable Energy 2024, 222 , 119951. https://doi.org/10.1016/j.renene.2024.119951
    17. Tomáš Stryšovský, Martina Kajabová, Robert Prucek, Aleš Panáček, Karolína Simkovičová, Štefan Vajda, Zdeněk Bastl, Libor Kvítek. Temperature switching of product selectivity in CO2 reduction on Cu/In2O3 catalysts. Journal of CO2 Utilization 2023, 77 , 102617. https://doi.org/10.1016/j.jcou.2023.102617
    18. Ming Yang, Yingying Li, Chung‐Li Dong, Shengkai Li, Leitao Xu, Wei Chen, Jingcheng Wu, Yuxuan Lu, Yuping Pan, Yandong Wu, Yongxiang Luo, Yu‐Cheng Huang, Shuangyin Wang, Yuqin Zou. Correlating the Valence State with the Adsorption Behavior of a Cu‐Based Electrocatalyst for Furfural Oxidation with Anodic Hydrogen Production Reaction. Advanced Materials 2023, 35 (39) https://doi.org/10.1002/adma.202304203
    19. Marco A. Rossi, Letícia F. Rasteiro, Luiz H. Vieira, Marco A. Fraga, José M. Assaf, Elisabete M. Assaf. Investigation of In Promotion on Cu/ZrO2 Catalysts and Application in CO2 Hydrogenation to Methanol. Catalysis Letters 2023, 153 (9) , 2728-2744. https://doi.org/10.1007/s10562-022-04191-0
    20. Lidan Deng, Zheng Wang, Xingmao Jiang, Jie Xu, Zijian Zhou, Xiaozhong Li, Zhixiong You, Mingyue Ding, Tetsuya Shishido, Xiaowei Liu, Minghou Xu. Catalytic aqueous CO2 reduction to formaldehyde at Ru surface on hydroxyl-groups-rich LDH under mild conditions. Applied Catalysis B: Environmental 2023, 322 , 122124. https://doi.org/10.1016/j.apcatb.2022.122124
    21. Kamila Mamat, Arzugul Muslim, Haidie Lan, Dilnur Malik, Aynur Musajan. Significantly improving the Cu 2+ removal performance of conducting polymer‐based adsorbent from aqueous solution through cross‐linking modification. Journal of Applied Polymer Science 2023, 140 (3) https://doi.org/10.1002/app.53176
    22. Ge Yang, Pei Qiu, Jinyan Xiong, Xueteng Zhu, Gang Cheng. Facilely anchoring Cu2O nanoparticles on mesoporous TiO2 nanorods for enhanced photocatalytic CO2 reduction through efficient charge transfer. Chinese Chemical Letters 2022, 33 (8) , 3709-3712. https://doi.org/10.1016/j.cclet.2021.10.047
    23. Marco A. Rossi, Luiz H. Vieira, Letícia F. Rasteiro, Marco A. Fraga, José M. Assaf, Elisabete M. Assaf. Promoting effects of indium doped Cu/CeO 2 catalysts on CO 2 hydrogenation to methanol. Reaction Chemistry & Engineering 2022, 7 (7) , 1589-1602. https://doi.org/10.1039/D2RE00033D
    24. Xuanbo Chen, Ping Li, Jiao Wang, Jiawei Wan, Nailiang Yang, Bo Xu, Lianming Tong, Lin Gu, Jiang Du, Jianjian Lin, Ranbo Yu, Dan Wang. Multishelled CuO/Cu2O induced fast photo-vapour generation for drinking water. Nano Research 2022, 15 (5) , 4117-4123. https://doi.org/10.1007/s12274-021-4063-y
    25. Anand Kumar, Ahmed A. A. Mohammed, Mohammed A. H. S. Saad, Mohammed J. Al‐Marri. Effect of nickel on combustion synthesized copper/ fumed‐SiO 2 catalyst for selective reduction of CO 2 to CO. International Journal of Energy Research 2022, 46 (1) , 441-451. https://doi.org/10.1002/er.6586
    26. Mona Saini, Nutan Rani, Asifa Mushtaq, Rini Singh, Seema Rawat, Manoj Kumar, Kalawati saini. Trisodium 2-Hydroxypropane-1,2,3-Tricarboxylate Encapsulated Nanocontainer-Based Template-Free Electrochemical Synthesis of Multidimensional Copper/Copper Oxide Nanoparticles. 2022, 193-205. https://doi.org/10.1007/978-981-16-7554-6_18
    27. M. Zwawi, A. Attar, A. F. Al-Hossainy, M. H. Abdel-Aziz, M. Sh. Zoromba. Polypyrrole/functionalized multi-walled carbon nanotube composite for optoelectronic device application. Chemical Papers 2021, 75 (12) , 6575-6589. https://doi.org/10.1007/s11696-021-01830-5
    28. I. Hussain, A.A. Jalil, N.S. Hassan, M.Y.S. Hamid. Recent advances in catalytic systems for CO2 conversion to substitute natural gas (SNG): Perspective and challenges. Journal of Energy Chemistry 2021, 62 , 377-407. https://doi.org/10.1016/j.jechem.2021.03.040
    29. Oleg Lupan, Nicolai Ababii, Abhishek Kumar Mishra, Mani Teja Bodduluri, Nicolae Magariu, Alexander Vahl, Helge Krüger, Bernhard Wagner, Franz Faupel, Rainer Adelung, Nora H. de Leeuw, Sandra Hansen. Heterostructure-based devices with enhanced humidity stability for H2 gas sensing applications in breath tests and portable batteries. Sensors and Actuators A: Physical 2021, 329 , 112804. https://doi.org/10.1016/j.sna.2021.112804
    30. Shanshan Xu, Huanhao Chen, Christopher Hardacre, Xiaolei Fan. Non-thermal plasma catalysis for CO 2 conversion and catalyst design for the process. Journal of Physics D: Applied Physics 2021, 54 (23) , 233001. https://doi.org/10.1088/1361-6463/abe9e1
    31. Yaning Wang, Lea R. Winter, Jingguang G. Chen, Binhang Yan. CO 2 hydrogenation over heterogeneous catalysts at atmospheric pressure: from electronic properties to product selectivity. Green Chemistry 2021, 23 (1) , 249-267. https://doi.org/10.1039/D0GC03506H
    32. Bingqiao Xie, Roong Jien Wong, Tze Hao Tan, Michael Higham, Emma K. Gibson, Donato Decarolis, June Callison, Kondo-Francois Aguey-Zinsou, Michael Bowker, C. Richard A. Catlow, Jason Scott, Rose Amal. Synergistic ultraviolet and visible light photo-activation enables intensified low-temperature methanol synthesis over copper/zinc oxide/alumina. Nature Communications 2020, 11 (1) https://doi.org/10.1038/s41467-020-15445-z
    33. Qian Zheng, Yi Wei, Xianghua Zeng, Weiwei Xia, Qihong Lu, Jiawei Sun, Zhihao Li, Wenjian Fang. Effect of bandgap alignment on the photoreduction of CO 2 into methane based on Cu 2 O-decorated CuO microspheres. Nanotechnology 2020, 31 (42) , 425402. https://doi.org/10.1088/1361-6528/ab9f74
    34. Liping Ding, Taotao Shi, Jing Gu, Yun Cui, Zhiyang Zhang, Changju Yang, Teng Chen, Ming Lin, Peng Wang, Nianhua Xue, Luming Peng, Xuefeng Guo, Yan Zhu, Zhaoxu Chen, Weiping Ding. CO2 Hydrogenation to Ethanol over Cu@Na-Beta. Chem 2020, 6 (10) , 2673-2689. https://doi.org/10.1016/j.chempr.2020.07.001
    35. Mausumi Mahapatra, Luis E. Betancourt, Zongyuan Liu, Dimitriy Vovchok, Juan P. Simonovis, José A. Rodriguez, Sanjaya D. Senanayake. In Situ Characterization of Metal/Oxide Catalysts for CO2 Conversion: From Fundamental Aspects to Real Catalyst Design. 2020, 431-458. https://doi.org/10.1039/9781788019576-00431
    36. Guangcheng Zhang, Guoli Fan, Lan Yang, Feng Li. Tuning surface-interface structures of ZrO2 supported copper catalysts by in situ introduction of indium to promote CO2 hydrogenation to methanol. Applied Catalysis A: General 2020, 605 , 117805. https://doi.org/10.1016/j.apcata.2020.117805
    37. Weiwei Wang, Zhenping Qu, Lixin Song, Qiang Fu. An investigation of Zr/Ce ratio influencing the catalytic performance of CuO/Ce1-Zr O2 catalyst for CO2 hydrogenation to CH3OH. Journal of Energy Chemistry 2020, 47 , 18-28. https://doi.org/10.1016/j.jechem.2019.11.021
    38. Jian Zhao, Song Xue, James Barber, Yiwei Zhou, Jie Meng, Xuebin Ke. An overview of Cu-based heterogeneous electrocatalysts for CO 2 reduction. Journal of Materials Chemistry A 2020, 8 (9) , 4700-4734. https://doi.org/10.1039/C9TA11778D
    39. Xinyue Wang, Qidong Zhao, Bin Yang, Zhongjian Li, Zheng Bo, Kwok Ho Lam, Nadia Mohd Adli, Lecheng Lei, Zhenhai Wen, Gang Wu, Yang Hou. Emerging nanostructured carbon-based non-precious metal electrocatalysts for selective electrochemical CO 2 reduction to CO. Journal of Materials Chemistry A 2019, 7 (44) , 25191-25202. https://doi.org/10.1039/C9TA09681G
    40. Haijun Guo, Qinglin Li, Hairong Zhang, Fen Peng, Lian Xiong, Shimiao Yao, Chao Huang, Xinde Chen. CO2 hydrogenation over acid-activated Attapulgite/Ce0.75Zr0.25O2 nanocomposite supported Cu-ZnO based catalysts. Molecular Catalysis 2019, 476 , 110499. https://doi.org/10.1016/j.mcat.2019.110499
    41. Xuanheng Zhu, Kalyani Gupta, Marco Bersani, Jawwad A. Darr, Paul R. Shearing, Dan J.L. Brett. Electrochemical reduction of carbon dioxide on copper-based nanocatalysts using the rotating ring-disc electrode. Electrochimica Acta 2018, 283 , 1037-1044. https://doi.org/10.1016/j.electacta.2018.07.025
    42. Haozhi Wang, Xiaowa Nie, Yonggang Chen, Xinwen Guo, Chunshan Song. Facet effect on CO2 adsorption, dissociation and hydrogenation over Fe catalysts: Insight from DFT. Journal of CO2 Utilization 2018, 26 , 160-170. https://doi.org/10.1016/j.jcou.2018.05.003
    43. Bin Li, Wenchao Niu, Yongwei Cheng, Junjie Gu, Ping Ning, Qingqing Guan. Preparation of Cu2O modified TiO2 nanopowder and its application to the visible light photoelectrocatalytic reduction of CO2 to CH3OH. Chemical Physics Letters 2018, 700 , 57-63. https://doi.org/10.1016/j.cplett.2018.03.049
    44. Rahele Rostamian, Hassan Behnejad. Insights into doxycycline adsorption onto graphene nanosheet: a combined quantum mechanics, thermodynamics, and kinetic study. Environmental Science and Pollution Research 2018, 25 (3) , 2528-2537. https://doi.org/10.1007/s11356-017-0687-6
    45. Wenhui Li, Haozhi Wang, Xiao Jiang, Jie Zhu, Zhongmin Liu, Xinwen Guo, Chunshan Song. A short review of recent advances in CO 2 hydrogenation to hydrocarbons over heterogeneous catalysts. RSC Advances 2018, 8 (14) , 7651-7669. https://doi.org/10.1039/C7RA13546G
    46. Run-Ping Ye, Ling Lin, Qiaohong Li, Zhangfeng Zhou, Tongtong Wang, Christopher K. Russell, Hertanto Adidharma, Zhenghe Xu, Yuan-Gen Yao, Maohong Fan. Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds. Catalysis Science & Technology 2018, 8 (14) , 3428-3449. https://doi.org/10.1039/C8CY00608C
    47. Ping Shao, Suqin Ci, Luocai Yi, Pingwei Cai, Peng Huang, Changsheng Cao, Zhenhai Wen. Hollow CuS Microcube Electrocatalysts for CO 2 Reduction Reaction. ChemElectroChem 2017, 4 (10) , 2593-2598. https://doi.org/10.1002/celc.201700517
    48. Jianfeng Wu, Tongming Su, Yuexiu Jiang, Xinling Xie, Zuzeng Qin, Hongbing Ji. In situ DRIFTS study of O 3 adsorption on CaO, γ-Al 2 O 3 , CuO, α-Fe 2 O 3 and ZnO at room temperature for the catalytic ozonation of cinnamaldehyde. Applied Surface Science 2017, 412 , 290-305. https://doi.org/10.1016/j.apsusc.2017.03.237

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect