Lin Xuliang, Liu Jianglin, Qiu Xueqing, Liu Bowen, Wang Xiaofei, Chen Liheng, Qin Yanlin
Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, School of Chemical Engineering and Light Industry, Guangdong University of Technology, 510006, Guangzhou, P. R. China.
Angew Chem Int Ed Engl. 2023 Aug 14;62(33):e202306333. doi: 10.1002/anie.202306333. Epub 2023 Jul 7.
Rational design of efficient, stable, and inexpensive bifunctional electrocatalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) is a key challenge to realize green hydrogen production via electrolytic water splitting. Herein, Ru nanoparticles and FeNi alloy heterojunction catalyst (Ru-FeNi@NLC) encapsulated via lignin-derived carbon was prepared by self-assembly precipitation and in situ pyrolysis. The designed catalyst displays excellent performance at 10 mA cm with low overpotentials of 36 mV for HER and 198 mV for OER, and only needs 1.48 V for overall water splitting. Results and DFT calculations show the unique N-doped lignin-derived carbon layer and Ru-FeNi heterojunction contribute to optimized electronic structure for enhancing electron transfer, balanced free energy of reactants and intermediates in the sorption/desorption process, and significantly reduced reaction energy barrier for the HER and OER rate-determining steps, thus improved reaction kinetics. This work provides a new in situ pyrolysis doping strategy based on renewable biomass for the construction of highly active, stable and cost-effective catalysts.
设计高效、稳定且廉价的用于析氧反应（OER）和析氢反应（HER）的双功能电催化剂是通过电解水分解实现绿色制氢的关键挑战。在此，通过自组装沉淀和原位热解制备了由木质素衍生碳包裹的钌纳米颗粒和铁镍合金异质结催化剂（Ru-FeNi@NLC）。所设计的催化剂在10 mA cm⁻²时表现出优异的性能，HER的过电位低至36 mV，OER的过电位为198 mV，全水解仅需1.48 V。结果和密度泛函理论（DFT）计算表明，独特的氮掺杂木质素衍生碳层和Ru-FeNi异质结有助于优化电子结构，从而增强电子转移，平衡吸附/解吸过程中反应物和中间体的自由能，并显著降低HER和OER速率决定步骤的反应能垒，进而改善反应动力学。这项工作基于可再生生物质提供了一种新的原位热解掺杂策略，用于构建高活性、稳定且具有成本效益的催化剂。
