Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations
Catalytic hydrogenation of carbon dioxide to methanol offers a promising avenue for recycling CO2, enhancing environmental sustainability. Cu/ZnO has long been identified as one of the most effective heterogeneous catalysts for this reaction, yet the detailed understanding of its reaction mechanism...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2025-01-01
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| Series: | Small Structures |
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| Online Access: | https://doi.org/10.1002/sstr.202400345 |
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| author | Cong Xi Yixin Nie Hongjuan Wang Cunku Dong Jiuhui Han Xi‐Wen Du |
| author_facet | Cong Xi Yixin Nie Hongjuan Wang Cunku Dong Jiuhui Han Xi‐Wen Du |
| author_sort | Cong Xi |
| collection | DOAJ |
| description | Catalytic hydrogenation of carbon dioxide to methanol offers a promising avenue for recycling CO2, enhancing environmental sustainability. Cu/ZnO has long been identified as one of the most effective heterogeneous catalysts for this reaction, yet the detailed understanding of its reaction mechanism and active sites remains incomplete. Recent advances have highlighted the critical role of defects, such as ZnCu steps and stacking faults on Cu surfaces, in enhancing catalyst performance. Here this concept is explored through first‐principles surface simulations of six models, featuring diverse Cu–Zn combinations and specific coordination environments under realistic conditions. It is revealed that Cu/ZnO catalysts with kink defects, rather than surface ZnCu alloys, exhibit optimal activity for methanol synthesis. Specifically, the findings demonstrate how intermediate configurations and rate‐determining steps vary with changes in surface structure and reveal the role of the kink in promoting CO2 reduction to methanol through electronic structure calculation. Moreover, it is found that the predominant synthetic pathway for CH3OH from CO2 involves the reverse water gas shift and CO hydrogenation, rather than the formate route, on Cu/ZnO surfaces with kinks. |
| format | Article |
| id | doaj-art-9c3fe4e49b8241fc81796ed85cc65028 |
| institution | Kabale University |
| issn | 2688-4062 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Small Structures |
| spelling | doaj-art-9c3fe4e49b8241fc81796ed85cc650282025-01-10T17:54:14ZengWiley-VCHSmall Structures2688-40622025-01-0161n/an/a10.1002/sstr.202400345Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles CalculationsCong Xi0Yixin Nie1Hongjuan Wang2Cunku Dong3Jiuhui Han4Xi‐Wen Du5Tianjin Key Laboratory of Advanced Functional Porous Materials Institute of New Energy Materials and Low‐Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 ChinaTianjin Key Laboratory of Advanced Functional Porous Materials Institute of New Energy Materials and Low‐Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 ChinaTianjin Key Laboratory of Advanced Functional Porous Materials Institute of New Energy Materials and Low‐Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 ChinaInstitute of New Energy Materials, School of Materials Science and Engineering Tianjin University Tianjin 300072 ChinaTianjin Key Laboratory of Advanced Functional Porous Materials Institute of New Energy Materials and Low‐Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 ChinaInstitute of New Energy Materials, School of Materials Science and Engineering Tianjin University Tianjin 300072 ChinaCatalytic hydrogenation of carbon dioxide to methanol offers a promising avenue for recycling CO2, enhancing environmental sustainability. Cu/ZnO has long been identified as one of the most effective heterogeneous catalysts for this reaction, yet the detailed understanding of its reaction mechanism and active sites remains incomplete. Recent advances have highlighted the critical role of defects, such as ZnCu steps and stacking faults on Cu surfaces, in enhancing catalyst performance. Here this concept is explored through first‐principles surface simulations of six models, featuring diverse Cu–Zn combinations and specific coordination environments under realistic conditions. It is revealed that Cu/ZnO catalysts with kink defects, rather than surface ZnCu alloys, exhibit optimal activity for methanol synthesis. Specifically, the findings demonstrate how intermediate configurations and rate‐determining steps vary with changes in surface structure and reveal the role of the kink in promoting CO2 reduction to methanol through electronic structure calculation. Moreover, it is found that the predominant synthetic pathway for CH3OH from CO2 involves the reverse water gas shift and CO hydrogenation, rather than the formate route, on Cu/ZnO surfaces with kinks.https://doi.org/10.1002/sstr.202400345coordination environmentsCu/ZnOfirst‐principles calculationmethanol synthesis |
| spellingShingle | Cong Xi Yixin Nie Hongjuan Wang Cunku Dong Jiuhui Han Xi‐Wen Du Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations Small Structures coordination environments Cu/ZnO first‐principles calculation methanol synthesis |
| title | Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations |
| title_full | Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations |
| title_fullStr | Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations |
| title_full_unstemmed | Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations |
| title_short | Thermal Methanol Synthesis from CO2 Using Cu/ZnO Catalysts: Insights from First‐Principles Calculations |
| title_sort | thermal methanol synthesis from co2 using cu zno catalysts insights from first principles calculations |
| topic | coordination environments Cu/ZnO first‐principles calculation methanol synthesis |
| url | https://doi.org/10.1002/sstr.202400345 |
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