No Access Submitted: 16 November 2020 Accepted: 09 February 2021 Published Online: 09 March 2021
Chem. Phys. Rev. 2, 011401 (2021);
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  • Abhishek Parija
  • Wasif Zaheer
  • Junsang Cho
  • Theodore E. G. Alivio
  • Sirine C. Fakra
  • Mohammed Al-Hashimi
  • David Prendergast
  • Sarbajit Banerjee
The design of earth-abundant electrocatalysts that can facilitate water splitting at low overpotentials, provide high current densities, and enable prolonged operational lifetimes is central to the production of sustainable fuels. The distinctive atomistic and electronic structure characteristics of the edges of MoS2 imbue high reactivity toward the hydrogen evolution reaction. MoS2 is nevertheless characterized by significantly high overpotentials as compared to platinum. Here, we demonstrate that modulation of the electronic structure of MoS2 through interfacial hybridization with MoO3 and alloying of selenium on the anion sublattice allows for systematic lowering of the conduction band edge and raising of the valence band edge, respectively. The former promotes enhanced electrocatalytic activity toward hydrogen evolution, whereas the latter promotes enhanced activity toward the oxygen evolution reaction. Such alloyed heterostructures prepared by sol-gel reactions and hydrothermal selenization expose a high density of edge sites. The alloyed heterostructures exhibit low overpotential, high current density, high turnover frequency, and prolonged operational lifetime. The mechanistic origins of catalytic activity have been established based on electronic structure calculations and x-ray absorption and emission spectroscopy probes of electronic structure, which suggest that interfacial hybridization at the MoO3 interface yields low-lying conduction band states that facilitate hydrogen adsorption. In contrast, shallow Se 4p-derived states give rise to a raised effective valence band maximum, which facilitates adsorption of oxygen intermediates and engenders a low overpotential for the oxygen evolution reaction. The findings illustrate the use of electronic structure modulation through interfacial hybridization and alloying to systematically improve electrocatalytic activity.
This work was supported primarily by the National Science Foundation under DMR 1627197. We also acknowledge support from the Qatar National Research Fund (QNRF) and the National Priorities Research Program (Project No. NPRP 10-0111-170152). We acknowledge the Texas A&M University (TAMU) Supercomputing Facility for computational resources. DFT simulations were performed as part of a User Project with D.P. at The Molecular Foundry (TMF), Lawrence Berkeley National Laboratory. T.M.F. is supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy (Contract No. DE-AC02-05CH11231). A.P. and W.Z. acknowledge support from the Advanced Light Source (ALS) doctoral fellowship in residence. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy, (Contract No. DE-AC02-05CH11231). Use of the TAMU Materials Characterization Facility is acknowledged. Use of the TAMU Microscopy and Imaging Center is acknowledged. Portions of this research were conducted with the advanced computing resources provided by TAMU High Performance Research Computing (HPRC).
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