title: Enhancing the Hydrogen Activation Reactivity of Nonprecious Metal Substrates via Confined Catalysis Underneath Graphene.
abstract: In the hydrogen evolution reaction (HER), the reactivity as a function of the hydrogen adsorption energy on different metal substrates follows a well-known volcano curve, peaked at the precious metal Pt. The goal of turning nonprecious metals into efficient catalysts for HER and other important chemical reactions is a fundamental challenge; it is also of technological significance. Here, we present results toward achieving this goal by exploiting the synergistic power of marginal catalysis and confined catalysis. Using density functional theory calculations, we first show that the volcano curve stays qualitatively intact when van der Waals attractions between a hydrogen adatom and different metal (111) surfaces are included. We further show that the hydrogen adsorption energy on the metal surfaces is weakened by 0.12-0.23 eV when hydrogen is confined between graphene and the metal surfaces, with Ni exhibiting the largest change. In particular, we find that the graphene-modified volcano curve peaks around Ni, whose bare surface already possesses moderate (or marginal) reactivity, and the corresponding HER rate of graphene-covered Ni is comparable to that of bare Pt. A hydrogen adatom has high mobility within the confined geometry. These findings demonstrate that graphene-covered Ni is an appealing effective, stable, and economical catalytic platform for HER.
authors: International Center for Quantum Design of Functional Materials (ICQD), Hefei National Laboratory for Physical Sciences at the Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors: Yinong
authors: Y
authors: Zhou
authors: International Center for Quantum Design of Functional Materials (ICQD), Hefei National Laboratory for Physical Sciences at the Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.|Department of Physics and School of Engineering and Applied Sciences, Harvard University , Cambridge, Massachusetts 02138, United States.
authors: Wei
authors: W
authors: Chen
authors: International Center for Quantum Design of Functional Materials (ICQD), Hefei National Laboratory for Physical Sciences at the Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors: Ping
authors: P
authors: Cui
authors: International Center for Quantum Design of Functional Materials (ICQD), Hefei National Laboratory for Physical Sciences at the Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.|Beijing Computational Science Research Center, Beijing 100094, China.
authors: Jiang
authors: J
authors: Zeng
authors: International Center for Quantum Design of Functional Materials (ICQD), Hefei National Laboratory for Physical Sciences at the Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.|School of Physics and Technology, Wuhan University , Wuhan 430072, China.
authors: Zhuonan
authors: Z
authors: Lin
authors: Department of Physics and School of Engineering and Applied Sciences, Harvard University , Cambridge, Massachusetts 02138, United States.
authors: Efthimios
authors: E
authors: Kaxiras
authors: International Center for Quantum Design of Functional Materials (ICQD), Hefei National Laboratory for Physical Sciences at the Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors: Zhenyu
authors: Z
authors: Zhang
keywords: confined catalysis; density functional calculations; graphene; heterogeneous catalysis; hydrogen evolution reaction