Wei Yang, Xu Xin, Shi Dehuan, Jiang Yaming, Zheng Chaoyang, Tan Li, Liu Zheyuan, Zhong Shenghong, Yu Yan
Key Laboratory of Advanced Materials Technologies, International (HongKong Macao and Taiwan) Joint Laboratory on Advanced Materials Technologies, College of Materials Science and Engineering, Fuzhou University, Fuzhou, 350108, China.
College of Chemistry, Fuzhou University, Fuzhou, 350108, China.
Small. 2024 Aug;20(34):e2401017. doi: 10.1002/smll.202401017. Epub 2024 Apr 9.
Doping is a recognized method for enhancing catalytic performance. The introduction of strains is a common consequence of doping, although it is often overlooked. Differentiating the impact of doping and strain on catalytic performance poses a significant challenge. In this study, Cu-doped Bi catalysts with substantial tensile strain are synthesized. The synergistic effects of doping and strain in bismuth result in a remarkable CORR performance. Under optimized conditions, Cu-Bi demonstrates exceptional formate Faradaic efficiency (>95%) and maintains over 90% across a wide potential window of 900 mV. Furthermore, it delivers an industrial-relevant partial current density of -317 mA cm at -1.2 V in a flow cell, while maintaining its selectivity. Additionally, it exhibits exceptional long-term stability, surpassing 120 h at -200 mA cm. Through experimental and theoretical mechanistic investigations, it has been determined that the introduction of tensile strain facilitates the adsorption of *CO, thereby enhancing the reaction kinetics. Moreover, the presence of Cu dopants and tensile strain further diminishes the energy barrier for the formation of *OCHO intermediate. This study not only offers valuable insights for the development of effective catalysts for CORR through doping, but also establishes correlations between doping, lattice strains, and catalytic properties of bismuth catalysts.
掺杂是一种公认的提高催化性能的方法。引入应变是掺杂的常见结果，尽管它常常被忽视。区分掺杂和应变对催化性能的影响是一项重大挑战。在本研究中，合成了具有大量拉伸应变的铜掺杂铋催化剂。铋中掺杂和应变的协同效应导致了卓越的CO₂RR性能。在优化条件下，Cu-Bi表现出优异的甲酸盐法拉第效率（>95%），并在900 mV的宽电位窗口内保持超过90%。此外，在流动池中，它在-1.2 V时提供了与工业相关的-317 mA cm⁻²的部分电流密度，同时保持其选择性。此外，它还表现出卓越的长期稳定性，在-200 mA cm⁻²下超过120小时。通过实验和理论机理研究，已确定引入拉伸应变促进了CO的吸附，从而增强了反应动力学。此外，Cu掺杂剂和拉伸应变的存在进一步降低了形成OCHO中间体的能垒。本研究不仅为通过掺杂开发有效的CO₂RR催化剂提供了有价值的见解，还建立了铋催化剂的掺杂、晶格应变和催化性能之间的关联。
