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Breaking Surface Atomic Monogeneity of Rh2P Nanocatalysts by Defect-Derived Phosphorus Vacancies for Efficient Alkaline Hydrogen Oxidation |
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| Authors: | Hongpu Huang Dr. Kai Liu Dr. Fulin Yang Junlin Cai Shupeng Wang Weizhen Chen Dr. Qiuxiang Wang Dr. Luhong Fu Prof. Zhaoxiong Xie Prof. Shuifen Xie |
| Affiliation: | 1. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021 China These authors contributed equally to this work. Contribution: Investigation (lead), Writing - original draft (equal), Writing - review & editing (supporting);2. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021 China These authors contributed equally to this work. Contribution: Investigation (equal), Writing - original draft (equal), Writing - review & editing (equal);3. School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002 China;4. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021 China Contribution: Investigation (supporting), Writing - review & editing (supporting);5. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021 China Contribution: Investigation (supporting);6. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021 China Contribution: Investigation (supporting), Writing - original draft (supporting);7. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China Contribution: Supervision (supporting), Writing - review & editing (supporting);8. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021 China |
| Abstract: | Breaking atomic monogeneity of catalyst surfaces is promising for constructing synergistic active centers to cope with complex multi-step catalytic reactions. Here, we report a defect-derived strategy for creating surface phosphorous vacancies (P-vacancies) on nanometric Rh2P electrocatalysts toward drastically boosted electrocatalysis for alkaline hydrogen oxidation reaction (HOR). This strategy disrupts the monogeneity and atomic regularity of the thermodynamically stable P-terminated surfaces. Density functional theory calculations initially verify that the competitive adsorption behavior of Had and OHad on perfect P-terminated Rh2P{200} facets (p-Rh2P) can be bypassed on defective Rh2P{200} surfaces (d-Rh2P). The P-vacancies enable the exposure of sub-surface Rh atoms to act as exclusive H adsorption sites. Therein, the Had cooperates with the OHad on the peripheral P-sites to effectively accelerate the alkaline HOR. Defective Rh2P nanowires (d-Rh2P NWs) and perfect Rh2P nanocubes (p-Rh2P NCs) are then elaborately synthesized to experimentally represent the d-Rh2P and p-Rh2P catalytic surfaces. As expected, the P-vacancy-enriched d-Rh2P NWs catalyst exhibits extremely high catalytic activity and outstanding CO tolerance for alkaline HOR electrocatalysis, attaining 5.7 and 14.3 times mass activity that of p-Rh2P NCs and commercial Pt/C, respectively. This work sheds light on breaking the surface atomic monogeneity for the development of efficient heterogeneous catalysts. |
| Keywords: | Alkaline Hydrogen Oxidation Reaction Defect Engineering Phosphorus Vacancy Rhodium Phosphide Ultrathin Nanowires |