Exploitation of the Large‐Area Basal Plane of MoS₂ and Preparation of Bifunctional Catalysts through On‐Surface Self‐Assembly

Abstract

The development of nonprecious electrochemical catalysts for water splitting is a key step to achieve a sustainable energy supply for the future. Molybdenum disulfide (MoS2) has been extensively studied as a promising low‐cost catalyst for hydrogen evolution reaction (HER), whereas HER is only catalyzed at the edge for pristine MoS2, leaving a large area of basal plane useless. Herein, on‐surface self‐assembly is demonstrated to be an effective, facile, and damage‐free method to take full advantage of the large ratio surface of MoS2 for HER by using multiscale simulations. It is found that as supplement of edge sites of MoS2, on‐MoS2 M(abt)2 (M = Ni, Co; abt = 2‐aminobenzenethiolate) owns high HER activity, and the self‐assembled M(abt)2 monolayers on MoS2 can be obtained through a simple liquid‐deposition method. More importantly, on‐surface self‐assembly provides potential application for overall water splitting once the self‐assembled systems prove to be of both HER and oxygen evolution reaction activities, for example, on‐MoS2 Co(abt)2. This work opens up a new and promising avenue (on‐surface self‐assembly) toward the full exploitation of the basal plane of MoS2 for HER and the preparation of bifunctional catalysts for overall water splitting.

Nanoarchitectonics for Transition‐Metal‐Sulfide‐Based Electrocatalysts for Water Splitting

“…Therefore, the exposed { ̅ onto MoS 2 using a liquid-deposition method. [254] Based on DFT calculations and classical molecular dynamics (MD), it was found that on-surface self-assembly of M(abt) 2 onto the MoS 2 can maximally activate the large-area basal plane of MoS 2 for HER, and made it possible for MoS 2 to catalyze OER.…”

“…Meanwhile, the required overpotential values on the (10) surface were smaller than the (001) surface, indicating the better catalytic activity of (10) surface toward OER. Therefore, the exposed {10} high‐index facets together with the synergistic effects between Ni 3 S 2 nanosheet and NF contributed to the efficient catalytic activity of Ni 3 S 2 /NF toward catalysis of water splitting, with ≈100% Faradaic efficiency and remarkable catalytic stability over 200 h. Later, MoS 2 was activated to catalyze both HER and OER by depositing the self‐assembled M(abt) 2 (M = Ni, Co, abt = 2‐amin‐obenzenethiolate) monolayer onto MoS 2 using a liquid‐deposition method . Based on DFT calculations and classical molecular dynamics, it was found that on‐surface self‐assembly of M(abt) 2 on the MoS 2 can maximally activate the large‐area basal plane of MoS 2 to enable it to catalyze both HER and OER.…”

“…Copyright 2017, American Chemical Society. Right part: Reproduced under the terms of the CC‐BY Creative Commons Attribution 4.0 International License ( http://creativecommons.org/licenses/by/4.0/) . Copyright 2017, The Authors, published by Wiley‐VCH.…”

Oxygen Dissociation on the C3n Monolayer: A First-Principles Study

“…The emergence of a wide variety of two-dimensional (2D) materials and the advancement of their promising applications in electronics [1][2][3], catalysis [4][5][6], gas sensors [7][8][9], energy conversion and storage [10][11][12] inspired by the great success of graphene [13,14], has been accompanied by an increasing attention on their chemical stability under ambient conditions. Especially, the O2 dissociation involved in the oxidation of 2D materials when exposed to air is the inevitably critical issue in nanomaterial manipulation and device engineering.…”