Document Type

Article

Publication Date

2020

Abstract

Recent developments in graphene related materials including molybdenum disulfide (MoS2) is gaining popularity as efficient and cost-effective nanoscale electrocatalyst essential for hydrogen production. These “clean” energy technologies require delicate control over geometric, morphological, chemical and electronic structure affecting physical and electrochemical catalytic properties. In this work, we prepared three-dimensional hierarchical mesoporous aerogels consisting of two-dimensional functionalized graphene and MoS2 nanosheets of varying ratio of components under hydrothermal–solvothermal conditions (P bar, T °C). We systematically characterized these hybrid aerogels in terms of surface morphology, microstructure, understand heterointerfaces interaction through electron microscopy, X-ray diffraction, optical absorption and emission and Raman spectroscopy, besides electrochemical properties prior to and post electrochemical desulfurization that induces finely controlled sulfur vacancies. They feature enhanced electrical conductivity by means of eliminating contact resistance and meso-/nanoporous structure facilitating faster ion diffusion (mass transport). We demonstrate that controlled defects density, edges plane sites (nanowalls), mesoscale porosity and topological interconnectedness (monolithic aerogel sheets) invoked can accelerate electrocatalytic hydrogen production. For instance, low over potential with Tafel slope ~77 mV·dec-1 for 60 wt.% MoS2, highcurrent density, and good stability was achieved with desulfurization. These results are compared with continuous multilayer MoS2 films highlighting the multiple role of tunable structure and electronic properties. The adjacent S-vacancy defectsinduced increase in density of states, dissociation and confinement of water molecules at the pore edge and planar S-vacancy sites calculated using density functional theory helped in establishing improved heterogeneous electrocatalytic rate. This is supported with combined measurements of diffusion coefficient and heterogeneous electron transfer rate via surface-sensitive scanning electrochemical microscopy (SECM) technique.

Comments

© 2020 American Scientific Publishers. Original published version available at https://doi.org/10.1166/jnn.2020.18573

First Page

6191

Last Page

6214

Publication Title

Journal of Nanoscience and Nanotechnology

DOI

10.1166/jnn.2020.18573

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