A New Class of Molecular Electrocatalysts for Hydrogen Evolution: Catalytic Activity of M3N@C2 n (2 n = 68, 78, and 80) Fullerenes

Alain R Puente Santiago; Mohamed Fathi Sanad; Antonio Moreno-Vicente; Md Ariful Ahsan; Maira R Cerón; Yang-Rong Yao; Sreeprasad T Sreenivasan; Antonio Rodriguez-Fortea; Josep M Poblet; Luis Echegoyen

doi:10.1021/jacs.0c13002

A New Class of Molecular Electrocatalysts for Hydrogen Evolution: Catalytic Activity of M₃N@C_{2 n} (2 n = 68, 78, and 80) Fullerenes

J Am Chem Soc. 2021 Apr 28;143(16):6037-6042. doi: 10.1021/jacs.0c13002. Epub 2021 Apr 6.

Affiliations

¹ Department of Chemistry, University of Texas at El Paso, 500 West University Avenue, El Paso, Texas 79968, United States.
² Department of Environmental Sciences and Engineering, University of Texas at El Paso, 500 West University Avenue, El Paso, Texas 79968, United States.
³ Departmento de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcellí Domingo 1, 43007 Tarragona, Spain.
⁴ Lawrence Livermore National Laboratory 7000 East Ave, Livermore, California 94550, United States.

PMID: 33821637
DOI: 10.1021/jacs.0c13002

Abstract

The electrocatalytic properties of some endohedral fullerenes for hydrogen evolution reactions (HER) were recently predicted by DFT calculations. Nonetheless, the experimental catalytic performance under realistic electrochemical environments of these 0D-nanomaterials have not been explored. Here, for the first time, we disclose the HER electrocatalytic behavior of seven M₃N@2n (2n = 68, 78, and 80) fullerenes (Gd₃N@I_h(7)-C₈₀, Y₃N@I_h(7)-C₈₀, Lu₃N@I_h(7)-C₈₀, Sc₃N@I_h(7)-C₈₀, Sc₃N@D_5h(6)-C₈₀, Sc₃N@D_3h(5)-C₇₈, and Sc₃N@D₃(6140)-C₆₈) using a combination of experimental and theoretical techniques. The non-IPR Sc₃N@D₃(6140)-C₆₈ compound exhibited the best catalytic performance toward the generation of molecular hydrogen, exhibiting an onset potential of -38 mV vs RHE, a very high mass activity of 1.75 A·mg^-1 at -0.4 V vs RHE, and an excellent electrochemical stability, retaining 96% of the initial current after 24 h. The superior performance was explained on the basis of the fused pentagon rings, which represent a new and promising HER catalytic motif.

Publication types

Research Support, Non-U.S. Gov't