Zhang Dan, Zhao Huan, Huang Bolong, Li Bin, Li Hongdong, Han Yi, Wang Zuochao, Wu Xueke, Pan Yue, Sun Yingjun, Sun Xuemei, Lai Jianping, Wang Lei
Key Laboratory of Eco-Chemical Engineering, Taishan Scholar Advantage and Characteristic Discipline Team of Eco-Chemical Process and Technology, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, P. R. China.
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, P. R. China.
ACS Cent Sci. 2019 Dec 26;5(12):1991-1997. doi: 10.1021/acscentsci.9b01110. Epub 2019 Dec 9.
The hydrogen evolution reaction (HER) is one of the most significant reactions in the electrolysis water process, and electrocatalysts which possess high mass activity and excellent stability are the most important driving factors to improve the efficiency of HER. As for the efficient commercially electrocatalyst, Pt/C is limited in development because of its high cost. Therefore, the study of non-Pt high-efficiency catalysts is particularly important at this moment. Here, we creatively report for the first time a kind of RuPdM (M= Ni, Co, Fe) ultrathin nanosheets (NSs), which exhibit extraordinary electrochemical properties for HER under alkaline conditions. The overpotential of optimized trimetallic RuPdNi ultrathin NSs is only 20 mV (10 mA cm), and the mass activity reaches 6.15 A mg at -0.07 V vs RHE. It can be compared to Pt-based electrocatalysts, which have the highest mass activity currently reported. The durability tests also prove that the stability of the electrocatalyst is outstanding. DFT calculations disclose that the flexible modulation of electronic structures of RuPd ultrathin NSs is achieved by utilizing the additional 3d transition metals Fe, Co, and Ni. In particular, the Ni-3d bands act as the continuous electron-supply center for Ru to ensure an efficient electron transfer toward the adsorbates. Meanwhile, the stable Pd sites are critical for coupling the O-2pπ orbital in the initial HO splitting with a facile barrier. This work will open up a new era of non-Pt materials for alkaline hydrogen evolution toward practical application.
析氢反应(HER)是电解水过程中最重要的反应之一,具有高质量活性和优异稳定性的电催化剂是提高析氢反应效率的最重要驱动因素。至于高效的商业电催化剂,Pt/C由于成本高昂,其发展受到限制。因此,目前对非Pt高效催化剂的研究尤为重要。在此,我们首次创新性地报道了一种RuPdM(M = Ni、Co、Fe)超薄纳米片(NSs),其在碱性条件下对析氢反应表现出非凡的电化学性能。优化后的三金属RuPdNi超薄纳米片的过电位仅为20 mV(10 mA cm),在相对于可逆氢电极(RHE)为 -0.07 V时质量活性达到6.15 A mg 。它可与目前报道的具有最高质量活性的Pt基电催化剂相媲美。耐久性测试也证明该电催化剂的稳定性出色。密度泛函理论(DFT)计算表明,通过利用额外的3d过渡金属Fe、Co和Ni实现了RuPd超薄纳米片电子结构的灵活调制。特别是,Ni-3d能带充当Ru的连续电子供应中心,以确保向吸附质的高效电子转移。同时,稳定的Pd位点对于在初始水分解中耦合O-2pπ轨道并具有较低能垒至关重要。这项工作将开启非Pt材料用于碱性析氢实际应用的新时代。