Strategies for Developing Transition Metal Phosphides in Electrochemical Water Splitting

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Abstract

Electrochemical water splitting involving hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is a greatly promising technology to generate sustainable and renewable energy resources, which relies on the exploration regarding the design of electrocatalysts with high efficiency, high stability, and low cost. Transition metal phosphides (TMPs), as nonprecious metallic electrocatalysts, have been extensively investigated and proved to be high-efficient electrocatalysts in both HER and OER. In this minireview, a general overview of recent progress in developing high-performance TMP electrocatalysts for electrochemical water splitting has been presented. Design strategies including composition engineering by element doping, hybridization, and tuning the molar ratio, structure engineering by porous structures, nanoarray structures, and amorphous structures, and surface/interface engineering by tuning surface wetting states, facet control, and novel substrate are summarized. Key scientific problems and prospective research directions are also briefly discussed.

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Phosphorene: an unexplored 2D semiconductor with a high hole mobility.

Han Liu, Adam T. Neal, Zhen Zhu … (2014)

We introduce the 2D counterpart of layered black phosphorus, which we call phosphorene, as an unexplored p-type semiconducting material. Same as graphene and MoS2, single-layer phosphorene is flexible and can be mechanically exfoliated. We find phosphorene to be stable and, unlike graphene, to have an inherent, direct, and appreciable band gap. Our ab initio calculations indicate that the band gap is direct, depends on the number of layers and the in-layer strain, and is significantly larger than the bulk value of 0.31-0.36 eV. The observed photoluminescence peak of single-layer phosphorene in the visible optical range confirms that the band gap is larger than that of the bulk system. Our transport studies indicate a hole mobility that reflects the structural anisotropy of phosphorene and complements n-type MoS2. At room temperature, our few-layer phosphorene field-effect transistors with 1.0 μm channel length display a high on-current of 194 mA/mm, a high hole field-effect mobility of 286 cm(2)/V·s, and an on/off ratio of up to 10(4). We demonstrate the possibility of phosphorene integration by constructing a 2D CMOS inverter consisting of phosphorene PMOS and MoS2 NMOS transistors.

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High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting.

Liang-Liang Feng, Guangtao Yu, Yuanyuan Wu … (2015)

Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {2̅10} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.

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Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies.

Hong Li, Charlie Tsai, Ai Leen Koh … (2016)

As a promising non-precious catalyst for the hydrogen evolution reaction (HER; refs ,,,,), molybdenum disulphide (MoS2) is known to contain active edge sites and an inert basal plane. Activating the MoS2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bind directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔGH) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Proper combinations of S-vacancy and strain yield the optimal ΔGH = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.

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Author and article information

Contributors

Jie Ying: URI : https://loop.frontiersin.org/people/1305064/overview

Huan Wang: URI : https://loop.frontiersin.org/people/1363690/overview

Journal

Journal ID (nlm-ta): Front Chem

Journal ID (iso-abbrev): Front Chem

Journal ID (publisher-id): Front. Chem.

Title: Frontiers in Chemistry

Publisher: Frontiers Media S.A.

ISSN (Electronic): 2296-2646

Publication date (Electronic): 03 November 2021

Publication date Collection: 2021

Volume: 9

Electronic Location Identifier: 700020

Affiliations

School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, China

Author notes

Edited by: Hyun-Seok Cho, Korea Institute of Energy Research, South Korea

Reviewed by: Shengjie Peng, Nanjing University of Aeronautics and Astronautics, China

Taekeun Kim, Chungnam National University, South Korea

*Correspondence: Jie Ying, whutyingjie@ 123456gmail.com

This article was submitted to Electrochemistry, a section of the journal Frontiers in Chemistry

Article

Publisher ID: 700020

DOI: 10.3389/fchem.2021.700020

PMC ID: 8595924

PubMed ID: 34805087

SO-VID: a1829bbe-ac03-4c65-8639-87e4e9f5d372

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This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

History

Date received : 25 April 2021

Date accepted : 20 August 2021

Funding

Funded by: Fundamental Research Funds for the Central Universities , doi 10.13039/501100012226;

Strategies for Developing Transition Metal Phosphides in Electrochemical Water Splitting

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Most cited references 100

Phosphorene: an unexplored 2D semiconductor with a high hole mobility.

High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting.

Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies.

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