Kuang Panyong, Wang Yaru, Zhu Bicheng, Xia Fanjie, Tung Ching-Wei, Wu Jinsong, Chen Hao Ming, Yu Jiaguo
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, P. R. China.
Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Xianhu Hydrogen Valley, Foshan, 528200, P. R. China.
Adv Mater. 2021 May;33(18):e2008599. doi: 10.1002/adma.202008599. Epub 2021 Apr 1.
The electronic metal-support interaction (EMSI) plays a crucial role in catalysis as it can induce electron transfer between metal and support, modulate the electronic state of the supported metal, and optimize the reduction of intermediate species. In this work, the tailoring of electronic structure of Pt single atoms supported on N-doped mesoporous hollow carbon spheres (Pt /NMHCS) via strong EMSI engineering is reported. The Pt /NMHCS composite is much more active and stable than the nanoparticle (Pt ) counterpart and commercial 20 wt% Pt/C for catalyzing the electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 40 mV at a current density of 10 mA cm , a high mass activity of 2.07 A mg at 50 mV overpotential, a large turnover frequency of 20.18 s at 300 mV overpotential, and outstanding durability in acidic electrolyte. Detailed spectroscopic characterizations and theoretical simulations reveal that the strong EMSI effect in a unique N -Pt -C coordination structure significantly tailors the electronic structure of Pt 5d states, resulting in promoted reduction of adsorbed proton, facilitated H-H coupling, and thus Pt-like HER activity. This work provides a constructive route for precisely designing single-Pt-atom-based robust electrocatalysts with high HER activity and durability.
电子金属-载体相互作用（EMSI）在催化过程中起着至关重要的作用，因为它可以诱导金属与载体之间的电子转移，调节负载金属的电子态，并优化中间物种的还原。在这项工作中，报道了通过强EMSI工程对负载在氮掺杂介孔空心碳球（Pt/NMHCS）上的铂单原子的电子结构进行剪裁。在催化电催化析氢反应（HER）时，Pt/NMHCS复合材料比纳米颗粒（Pt）对应物和商业20 wt% Pt/C更具活性和稳定性，在电流密度为10 mA cm时具有40 mV的低过电位，在50 mV过电位下具有2.07 A mg的高质量活性，在300 mV过电位下具有20.18 s的大周转频率，并且在酸性电解质中具有出色的耐久性。详细的光谱表征和理论模拟表明，独特的N-Pt-C配位结构中的强EMSI效应显著地剪裁了Pt 5d态的电子结构，导致吸附质子的还原促进，H-H耦合促进，从而具有类铂的HER活性。这项工作为精确设计具有高HER活性和耐久性的基于单铂原子的稳健电催化剂提供了一条建设性途径。
