Zhao WLuo CLin YWang G.-BHAO MING CHENKuang PYu J.2022-12-142022-12-14202221555435https://www.scopus.com/inward/record.uri?eid=2-s2.0-85129277698&doi=10.1021%2facscatal.2c00851&partnerID=40&md5=137f47949987daf9333720414657ec45https://scholars.lib.ntu.edu.tw/handle/123456789/626337Dual-atom catalysts (DACs) have attracted considerable interest since they utilize adjacent metal centers in the metal(I)-metal(II) dimer structure to achieve functionality complementarity and more flexible active sites compared to single-atom catalysts (SACs). Herein, we report that the synergistic effect and electron redistribution effect in the Pt1Ru1dimer can simultaneously accelerate the H2generation and improve the catalyst's activity. The as-developed Pt1Ru1/NMHCS-A exhibits a quite low overpotential (η10) of 22 mV to drive a current density of 10 mA cm-2, a large mass activity of 3.49 A mg-1at 50 mV overpotential, a high turnover frequency (TOF) of 74.14 H2s-1at 200 mV overpotential, and a slight increment of 3 mV for η10after 10,000 consecutive cyclic voltammetry (CV) cycles in 0.5 M H2SO4solution, greatly outperforming the commercial 20 wt % Pt/C benchmark and nanoparticle counterparts. The detailed spectroscopic investigations and theoretical calculations confirm the formation of a C1-Pt-Ru-N2coordination structure in Pt1Ru1/NMHCS-A and reveal the electron redistribution effect of Ru on the Pt atom. With the Ru atom tuning the electron redistribution, the Pt atom acting as the active site shows strong abilities to adsorb and reduce the proton, thus leading to the optimal HER activity. Our work provides constructive guidance for the fabrication of metal(I)-metal(II) dimers and the precise regulation of their electronic structures to achieve excellent catalytic activities. © 2022 American Chemical Society. All rights reserved.coordination structure; dual-atom catalysts; electron redistribution effect; hydrogen evolution reaction; Pt-Ru dimer[SDGs]SDG7Binary alloys; Catalyst activity; Coordination reactions; Cyclic voltammetry; Electrocatalysts; Electronic structure; Electrons; Hydrogen; Platinum; Ruthenium; Active site; Coordination structures; Dual-atom catalyst; Electron redistribution effect; Hydrogen evolution reactions; Metal centres; Overpotential; Pt atoms; Pt-ru dimer; ]+ catalyst; Atomsjournal article10.1021/acscatal.2c008512-s2.0-85129277698