TJU-NIMS International Collaboration Laboratory, School of Materials Science and Engineering, Key Lab of Advanced Ceramics and Machining Technology (Ministry of Education), Tianjin University, Tianjin, P. R. China.
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, P. R. China.
Nat Commun. 2023 Feb 10;14(1):751. doi: 10.1038/s41467-023-36263-z.
Exploring efficient electrocatalysts with fundamental understanding of the reaction mechanism is imperative in CO electroreduction. However, the impact of sluggish water dissociation as proton source and the surface species in reaction are still unclear. Herein, we report a strategy of promoting protonation in CO electroreduction by implementing oxygen vacancy engineering on BiOCO over which high Faradaic efficiency of formate (above 90%) and large partial current density (162 mA cm) are achieved. Systematic study reveals that the production rate of formate is mainly hampered by water dissociation, while the introduction of oxygen vacancy accelerates water dissociation kinetics by strengthening hydroxyl adsorption and reduces the energetic span of CO electroreduction. Moreover, CO* involved in formate formation as the key surface species is clearly identified by electron spin resonance measurements and designed in situ Raman spectroscopy study combined with isotopic labelling. Coupled with photovoltaic device, the solar to formate energy conversion efficiency reaches as high as 13.3%.
在 CO 电还原中，通过深入了解反应机理来探索高效电催化剂是至关重要的。然而，质子源水的解离缓慢以及反应中的表面物种的影响仍不清楚。在此，我们报告了一种通过在 BiOCO 上实施氧空位工程来促进 CO 电还原中质子化的策略，该策略实现了高甲酸（超过 90%）的法拉第效率和大的部分电流密度（162 mA cm）。系统研究表明，甲酸的生成速率主要受到水的解离的限制，而氧空位的引入通过增强羟基吸附加速了水的解离动力学，并降低了 CO 电还原的能量跨度。此外，通过电子自旋共振测量和结合同位素标记的原位拉曼光谱研究，明确了甲酸形成中涉及的 CO*作为关键表面物种。与光伏器件耦合后，太阳能到甲酸的能量转换效率高达 13.3%。
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