Li Weidong, Zhao Yunxuan, Liu Yuan, Sun Mingzi, Waterhouse Geoffrey I N, Huang Bolong, Zhang Kan, Zhang Tierui, Lu Siyu
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450000, China.
College of Materials Engineering, Henan International Joint Laboratory of Rare Earth Composite Material, Henan University of Engineering, Zhengzhou, 451191, China.
Angew Chem Int Ed Engl. 2021 Feb 8;60(6):3290-3298. doi: 10.1002/anie.202013985. Epub 2020 Dec 8.
Designing bifunctional catalysts capable of driving the electrochemical hydrogen evolution reaction (HER) and also H evolution via the hydrolysis of hydrogen storage materials such as ammonia borane (AB) is of considerable practical importance for future hydrogen economies. Herein, we systematically examined the effect of tensile lattice strain in CoRu nanoalloys supported on carbon quantum dots (CoRu/CQDs) on hydrogen generation by HER and AB hydrolysis. By varying the Ru content, the lattice parameters and Ru-induced lattice strain in the CoRu nanoalloys could be tuned. The CoRu /CQDs catalyst with an ultra-low Ru content (1.33 wt.%) exhibited excellent catalytic activity for HER (η=18 mV at 10 mA cm in 1 M KOH) and extraordinary activity for the hydrolysis of AB with a turnover frequency of 3255.4 mol mol min or 814.7 mol mol min at 298 K, respectively, representing one of the best activities yet reported for AB hydrolysis over a ruthenium alloy catalyst. Moreover, the CoRu /CQDs catalyst displayed excellent stability during each reaction, including seven alternating cycles of HER and AB hydrolysis. Theoretical calculations revealed that the remarkable catalytic performance of CoRu /CQDs resulted from the optimal alloy electronic structure realized by incorporating small amounts of Ru, which enabled fast interfacial electron transfer to intermediates, thus benefitting H evolution kinetics. Results support the development of new and improved catalysts HER and AB hydrolysis.
设计能够驱动电化学析氢反应（HER）以及通过水解储氢材料（如氨硼烷（AB））析氢的双功能催化剂，对于未来的氢能经济具有相当重要的实际意义。在此，我们系统地研究了负载在碳量子点上的CoRu纳米合金（CoRu/CQDs）中的拉伸晶格应变对HER和AB水解产氢的影响。通过改变Ru含量，可以调节CoRu纳米合金中的晶格参数和Ru诱导的晶格应变。超低Ru含量（1.33 wt.%）的CoRu/CQDs催化剂对HER表现出优异的催化活性（在1 M KOH中，10 mA cm时η = 18 mV），对AB水解具有非凡的活性，在298 K时的周转频率分别为3255.4 mol mol min或814.7 mol mol min，是迄今报道的钌合金催化剂上AB水解的最佳活性之一。此外，CoRu/CQDs催化剂在每个反应过程中都表现出优异的稳定性，包括HER和AB水解的七个交替循环。理论计算表明，CoRu/CQDs卓越的催化性能源于通过掺入少量Ru实现的最佳合金电子结构，这使得能够快速向中间体进行界面电子转移，从而有利于析氢动力学。研究结果支持开发新型且性能更优的HER和AB水解催化剂。
