DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon
The catalytic conversion of CO<sub>2</sub> to C<sub>2</sub> products through the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) offers the possibility of preparing carbon-based fuels and valuable chemicals in a sustainable way. Herein, various Fe...
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MDPI AG
2022-06-01
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| Online Access: | https://www.mdpi.com/2079-4991/12/13/2239 |
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| author | Qian Xue Xueqiang Qi Tingting Yang Jinxia Jiang Qi Zhou Chuang Fu Na Yang |
| author_facet | Qian Xue Xueqiang Qi Tingting Yang Jinxia Jiang Qi Zhou Chuang Fu Na Yang |
| author_sort | Qian Xue |
| collection | DOAJ |
| description | The catalytic conversion of CO<sub>2</sub> to C<sub>2</sub> products through the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) offers the possibility of preparing carbon-based fuels and valuable chemicals in a sustainable way. Herein, various Fe<sub>n</sub> and Co<sub>5</sub> clusters are designed to screen out the good catalysts with reasonable stability, as well as high activity and selectivity for either C<sub>2</sub>H<sub>4</sub> or CH<sub>3</sub>CH<sub>2</sub>OH generation through density functional theory (DFT) calculations. The binding energy and cohesive energy calculations show that both Fe<sub>5</sub> and Co<sub>5</sub> clusters can adsorb stably on the N-doped carbon (NC) with one metal atom anchored at the center of the defected hole via a classical MN<sub>4</sub> structure. The proposed reaction pathway demonstrates that the Fe<sub>5</sub>-NC cluster has better activity than Co<sub>5</sub>-NC, since the carbon–carbon coupling reaction is the potential determining step (PDS), and the free energy change is 0.22 eV lower in the Fe<sub>5</sub>-NC cluster than that in Co<sub>5</sub>-NC. However, Co<sub>5</sub>-NC shows a better selectivity towards C<sub>2</sub>H<sub>4</sub> since the hydrogenation of CH<sub>2</sub>CHO to CH<sub>3</sub>CHO becomes the PDS, and the free energy change is 1.08 eV, which is 0.07 eV higher than that in the C-C coupling step. The larger discrepancy of d band center and density of states (DOS) between the topmost Fe and sub-layer Fe may account for the lower free energy change in the C-C coupling reaction. Our theoretical insights propose an explicit indication for designing new catalysts based on the transition metal (TM) clusters supported on N-doped carbon for multi-hydrocarbon synthesis through systematically analyzing the stability of the metal clusters, the electronic structure of the critical intermediates and the energy profiles during the CO<sub>2</sub>RR. |
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| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T03:59:51Z |
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| spelling | doaj.art-cf1fafc449c147deaef4b23528651d072023-12-03T14:15:05ZengMDPI AGNanomaterials2079-49912022-06-011213223910.3390/nano12132239DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped CarbonQian Xue0Xueqiang Qi1Tingting Yang2Jinxia Jiang3Qi Zhou4Chuang Fu5Na Yang6School of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, ChinaSchool of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, ChinaSchool of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, ChinaChongqing Medical and Pharmaceutical College, Chongqing 400020, ChinaSchool of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, ChinaSchool of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, ChinaChongqing Key Laboratory of Chemical Process for Clean Energy and Resource Utilization, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, ChinaThe catalytic conversion of CO<sub>2</sub> to C<sub>2</sub> products through the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) offers the possibility of preparing carbon-based fuels and valuable chemicals in a sustainable way. Herein, various Fe<sub>n</sub> and Co<sub>5</sub> clusters are designed to screen out the good catalysts with reasonable stability, as well as high activity and selectivity for either C<sub>2</sub>H<sub>4</sub> or CH<sub>3</sub>CH<sub>2</sub>OH generation through density functional theory (DFT) calculations. The binding energy and cohesive energy calculations show that both Fe<sub>5</sub> and Co<sub>5</sub> clusters can adsorb stably on the N-doped carbon (NC) with one metal atom anchored at the center of the defected hole via a classical MN<sub>4</sub> structure. The proposed reaction pathway demonstrates that the Fe<sub>5</sub>-NC cluster has better activity than Co<sub>5</sub>-NC, since the carbon–carbon coupling reaction is the potential determining step (PDS), and the free energy change is 0.22 eV lower in the Fe<sub>5</sub>-NC cluster than that in Co<sub>5</sub>-NC. However, Co<sub>5</sub>-NC shows a better selectivity towards C<sub>2</sub>H<sub>4</sub> since the hydrogenation of CH<sub>2</sub>CHO to CH<sub>3</sub>CHO becomes the PDS, and the free energy change is 1.08 eV, which is 0.07 eV higher than that in the C-C coupling step. The larger discrepancy of d band center and density of states (DOS) between the topmost Fe and sub-layer Fe may account for the lower free energy change in the C-C coupling reaction. Our theoretical insights propose an explicit indication for designing new catalysts based on the transition metal (TM) clusters supported on N-doped carbon for multi-hydrocarbon synthesis through systematically analyzing the stability of the metal clusters, the electronic structure of the critical intermediates and the energy profiles during the CO<sub>2</sub>RR.https://www.mdpi.com/2079-4991/12/13/2239DFTCO<sub>2</sub>RRclustersselectivity and activity |
| spellingShingle | Qian Xue Xueqiang Qi Tingting Yang Jinxia Jiang Qi Zhou Chuang Fu Na Yang DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon Nanomaterials DFT CO<sub>2</sub>RR clusters selectivity and activity |
| title | DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon |
| title_full | DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon |
| title_fullStr | DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon |
| title_full_unstemmed | DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon |
| title_short | DFT Study on the CO<sub>2</sub> Reduction to C<sub>2</sub> Chemicals Catalyzed by Fe and Co Clusters Supported on N-Doped Carbon |
| title_sort | dft study on the co sub 2 sub reduction to c sub 2 sub chemicals catalyzed by fe and co clusters supported on n doped carbon |
| topic | DFT CO<sub>2</sub>RR clusters selectivity and activity |
| url | https://www.mdpi.com/2079-4991/12/13/2239 |
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