Choi Jounghwan, Chiu Shawn, Banerjee Avishek, Sacci Robert L, Veith Gabriel M, Stieber Chantal, Hahn Christopher, Alexandrova Anastassia N, Morales-Guio Carlos G
Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, California 90095, United States.
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States.
J Phys Chem Lett. 2024 Aug 8;15(31):8007-8017. doi: 10.1021/acs.jpclett.4c01638. Epub 2024 Jul 31.
Experiments and theory are combined to search for catalyst activity and stability descriptors for the direct reactive capture and conversion (RCC) of CO in ammonia capture solutions using Cu, Ag, Au, Sn, and Ti electrodes. Two major phenomena emerge in RCC that are not predominant in the electrochemical CO reduction (COR) reaction, namely, the rapid corrosion and restructuring of the catalyst in the presence of the CO-ammonia adducts and the promotion of the competing hydrogen evolution reaction (HER). The prevalence of HER in RCC is correlated to the electrostatic attraction of the protonated amine to the electrode and the repulsion of the captured CO, using the potential of zero charge (PZC). The stability of catalysts under RCC conditions is a function of the applied potential and cannot be readily predicted using binding energy descriptors commonly used in the prediction of COR activity. A direct correlation between calculated binding energies of COR intermediates, atomic oxygen, hydrogen, and ammonia and the activity and stability of transition metals for RCC cannot be found, highlighting the need for descriptors beyond those known for COR.
通过实验与理论相结合，寻找使用铜、银、金、锡和钛电极在氨捕获溶液中直接进行一氧化碳反应性捕获和转化（RCC）时的催化剂活性和稳定性描述符。RCC中出现了两种在电化学一氧化碳还原（COR）反应中不占主导地位的主要现象，即在一氧化碳 - 氨加合物存在下催化剂的快速腐蚀和重构，以及竞争性析氢反应（HER）的促进。利用零电荷电位（PZC），RCC中HER的普遍性与质子化胺对电极的静电吸引以及捕获的一氧化碳的排斥相关。RCC条件下催化剂的稳定性是施加电位的函数，不能使用预测COR活性时常用的结合能描述符轻易预测。在COR中间体、原子氧、氢和氨的计算结合能与RCC过渡金属的活性和稳定性之间未发现直接相关性，这突出表明需要超越COR已知描述符的描述符。
