Buffering Donor Shuttles in Proton-Coupled Electron Transfer Kinetics for Electrochemical Hydrogenation of Hydroxyacetone to Propylene Glycol

化学 电解质 无机化学 质子 电化学 缓冲溶液 电催化剂 支撑电解质 有机化学 缓冲器(光纤) 法拉第效率 催化作用 电极 物理化学 物理 电信 量子力学 计算机科学
作者
Guoquan Ma,Na Jiang,Yu Zhang,Dandan Song,Bo Qiao,Zheng Xu,Suling Zhao,Zhiqin Liang
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:146 (33): 23194-23204
标识
DOI:10.1021/jacs.4c05446
摘要

Electrochemical hydrogenation reactions demand rapid proton-coupled electron transfer at the electrode surface, the kinetics of which depend closely on pH. Buffer electrolytes are extensively employed to regulate pH over a wide range. However, the specific role of buffer species should be taken into account when interpreting the intrinsic pH dependence, which is easily overlooked in the current research. Herein, we report the electrochemical hydrogenation of hydroxyacetone, derived from glycerol feedstock, to propylene glycol with a faradaic efficiency of 56 ± 5% on a polycrystalline Cu electrode. The reaction activities are comparable in citrate, phosphate, and borate buffer electrolytes, encompassing different buffer identities and pH. The electrokinetic profile reveals that citrate is a site-blocking adsorbate on the Cu surface, thereby decreasing buffer concentration and increasing pH will enhance the reaction rate; phosphate is an explicit proton donor, which promotes the interfacial rate by increasing buffer concentration and decreasing pH, while borate is an innocent buffer, which can be used to investigate the intrinsic pH effect. Combined with in situ SEIRAS, we demonstrate that water is the primary proton source in citrate and borate electrolytes, reiterating the rationality of the proposed mechanism based on the microkinetic modeling. Our results emphasize the intrinsic complexity of the buffer system on the kinetic activity for electrocatalysis. It calls for special care when we diagnose the mechanistic pathway in buffer electrolytes convoluted by different buffer identities and pH.
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