Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution

Cai，Chao1; Liu，Kang1; Zhu，Yuanmin2; Li，Pengcheng1; Wang，Qiyou1; Liu，Bao1; Chen，Shanyong1; Li，Huangjingwei1; Zhu，Li1,3; Li，Hongmei1; Fu，Junwei1; Chen，Yu1; Pensa，Evangelina3; Hu，Junhua4; Lu，Ying Rui5; Chan，Ting Shan5; Cortés，Emiliano3; Liu，Min1

2021

10.1002/anie.202113664

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Ruthenium (Ru)-based catalysts, with considerable performance and desirable cost, are becoming highly interesting candidates to replace platinum (Pt) in the alkaline hydrogen evolution reaction (HER). The hydrogen binding at Ru sites (Ru−H) is an important factor limiting the HER activity. Herein, density functional theory (DFT) simulations show that the essence of Ru−H binding energy is the strong interaction between the (Formula presented.) orbital of Ru and the 1s orbital of H. The charge transfer between Ru sites and substrates (Co and Ni) causes the appropriate downward shift of the (Formula presented.) -band center of Ru, which results in a Gibbs free energy of 0.022 eV for H* in the RuCo system, much lower than the 0.133 eV in the pure Ru system. This theoretical prediction has been experimentally confirmed using RuCo alloy-nanosheets (RuCo ANSs). They were prepared via a fast co-precipitation method followed with a mild electrochemical reduction. Structure characterizations reveal that the Ru atoms are embedded into the Co substrate as isolated active sites with a planar symmetric and Z-direction asymmetric coordination structure, obtaining an optimal (Formula presented.) modulated electronic structure. Hydrogen sensor and temperature program desorption (TPD) tests demonstrate the enhanced Ru−H interactions in RuCo ANSs compared to those in pure Ru nanoparticles. As a result, the RuCo ANSs reach an ultra-low overpotential of 10 mV at 10 mA cm and a Tafel slope of 20.6 mV dec in 1 M KOH, outperforming that of the commercial Pt/C. This holistic work provides a new insight to promote alkaline HER by optimizing the metal-H binding energy of active sites.

Alkaline HER Cobalt nanosheet Hydrogen adsorption/desorption Orbital modulation Ruthenium

SCI ; EI

英语

NI论文 ; ESI热点 ; ESI高被引

其他

WOS:000727437100001

20214911294728

Binary alloys ; Binding energy ; Binding sites ; Carbon ; Cobalt ; Cobalt alloys ; Density functional theory ; Design for testability ; Electrolytic reduction ; Electronic structure ; Free energy ; Gas adsorption ; Gibbs free energy ; Nanosheets ; Platinum alloys ; Potassium hydroxide ; Precipitation (chemical) ; Substrates

Ore Treatment:533.1 ; Precious Metals:547.1 ; Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Thermodynamics:641.1 ; Nanotechnology:761 ; Biochemistry:801.2 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4 ; Solid State Physics:933

CHEMISTRY

2-s2.0-85120642799

Scopus

1.School of Physics and Electronics,Central South University,Changsha,410083,China
2.Department of Materials Science and Engineering,Southern University of Science and Technology,Shenzhen,518055,China
3.Nanoinstitut München,Fakultät für Physik,Ludwig-Maximilians-Universität München,München,80539,Germany
4.School of Materials Science and Engineering,Zhengzhou University,Zhengzhou,450001,China
5.National Synchrotron Radiation Research Center,Hsinchu,300,Taiwan

Cai，Chao,Liu，Kang,Zhu，Yuanmin,et al. Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2021,61.

Cai，Chao.,Liu，Kang.,Zhu，Yuanmin.,Li，Pengcheng.,Wang，Qiyou.,...&Liu，Min.(2021).Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,61.

Cai，Chao,et al."Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61(2021).