Enhancement of Photocatalytic H2-Evolution Kinetics through the Dual Cocatalyst Activity of Ni2P-NiS-Decorated g-C3N4 Heterojunctions

Citation: Zhuonan Lei, Xinyi Ma, Xiaoyun Hu, Jun Fan, Enzhou Liu. Enhancement of Photocatalytic H₂-Evolution Kinetics through the Dual Cocatalyst Activity of Ni₂P-NiS-Decorated g-C₃N₄ Heterojunctions[J]. Acta Physico-Chimica Sinica, 2022, 38(7): 211004. doi: 10.3866/PKU.WHXB202110049 shu

Ni₂P-NiS双助剂促进g-C₃N₄光催化产氢动力学

雷卓楠 ^1, ,
马心怡 ^1, ,
胡晓云 ^2, ,
樊君 ^{1,
,} ,
刘恩周 ^{1,
,}

1.
西北大学化学工程学院/西安特种能源材料重点实验室，西安 710069
2.
西北大学物理学院，西安 710069

通讯作者: 樊君, fanjun@nwu.edu.cn
刘恩周, liuenzhou@nwu.edu.cn

基金项目:
国家自然科学基金 21676213

国家自然科学基金 11974276

国家自然科学基金 22078261

陕西省自然科学基础研究计划项目 2020JM-422

摘要: 本文通过简单的一步水热法得到Ni₂P-NiS双助催化剂，之后采用溶剂蒸发法将Ni₂P-NiS与g-C₃N₄纳米片结合构建获得无贵金属的Ni₂P-NiS/g-C₃N₄异质结。研究结果表明，优化后的复合材料具有良好的光催化产氢活性，其产氢速率最高可到6892.7 μmol·g^-1·h^-1，分别为g-C₃N₄ (150 μmol·g^-1·h^-1)、15%NiS/g-C₃N₄ (914.5 μmol·g^-1·h^-1)和15%Ni₂P/g-C₃N₄ (1565.9 μmol·g^-1·h^-1)的46.1、7.5和4.4倍。这主要归因于Ni₂P-NiS相比Ni₂P和NiS单体具有更好的载流子转移能力，其与g-C₃N₄形成的肖特基势垒能有效促进光生载流子在二者界面上的分离，同时Ni₂P-NiS能进一步降低析氢过电势，进而显著增强了表面析氢反应动力学。本研究为开发稳定、高效的非贵金属产氢助剂提供了实验基础。

关键词:

English

Enhancement of Photocatalytic H₂-Evolution Kinetics through the Dual Cocatalyst Activity of Ni₂P-NiS-Decorated g-C₃N₄ Heterojunctions

Zhuonan Lei ^1, ,
Xinyi Ma ^1, ,
Xiaoyun Hu ^2, ,
Jun Fan ^{1,
,} ,
Enzhou Liu ^{1,
,}

1.
School of Chemical Engineering/Xi'an Key Laboratory of Special Energy Materials, Northwest University, Xi'an 710069, China
2.
School of Physics, Northwest University, Xi'an 710069, China

Corresponding author: Jun Fan, fanjun@nwu.edu.cn Enzhou Liu, liuenzhou@nwu.edu.cn

Received Date: 29 October 2021
Accepted Date: 22 November 2021
Revised Date: 12 November 2021
Available Online: 15 July 2022
Fund Project:

Abstract: With rapid industrialization, issues pertaining to the environment and energy have become an alarming concern. Photocatalytic water splitting is considered one of the most promising green technologies capable of resolving these issues, as it can convert solar energy into chemical energy and have a positive impact on the realization of "carbon neutrality". Current research focuses on the development of highly efficient catalysts to improve the photocatalytic H₂-production activity. Transition metal phosphides and sulfides are often used as photocatalysts owing to their low H₂-evolution overpotential and excellent electrical conductivity. Among them, Ni₂P and NiS have generally been used independently during photocatalytic H₂ production; however, it is necessary to study the synergistic effect when they are combined as a dual cocatalyst. In this work, we successfully prepared a Ni₂P-NiS dual cocatalyst for the first time via a simple hydrothermal method using red phosphorus (RP) and thioacetamide (C₂H₅NS) as the sources of P and S. Ni₂P-NiS was then introduced to the surface of g-C₃N₄ nanosheets through solvent evaporation to create a Ni₂P-NiS/g-C₃N₄ heterojunction. Furthermore, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), ultraviolet-visible spectrophotometry (UV-Vis), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), linear sweep voltammetry (LSV), Mott-Schottky (M-S), and electrochemical impedance spectroscopy (EIS) were used to reveal the crystal structures, morphologies, element compositions, and photoelectric characteristics of the samples; thus, it was demonstrated that Ni₂P-NiS was successfully deposited on the surface of g-C₃N₄ and that together they exhibited better activity than their monomers. Moreover, the optimized 15% Ni₂P-NiS/g-C₃N₄ composite exhibits a H₂ generation rate of 6892.7 μmol·g^-1·h^-1, which is about 46.1, 7.5 and 4.4 times higher than that of g-C₃N₄ (150 μmol·g^-1·h^-1), 15% NiS/g-C₃N₄ (914.5 μmol·g^-1·h^-1), and 15% Ni₂P/g-C₃N₄ (1565.9 μmol·g^-1·h^-1), respectively. In addition, photoelectric performance tests show that Ni₂P-NiS/g-C₃N₄ has a stronger photocurrent intensity, smaller charge-transfer resistance, more positive H₂-evolution overpotential, and better charge-separation ability than the individual components (i.e., Ni₂P and NiS), suggesting that the coexistence of Ni₂P and NiS can further boost the activity of g-C₃N₄ during H₂ evolution compared with their monomers. This is mainly due to the Schottky barrier effect between Ni₂P-NiS nanoparticles and g-C₃N₄ nanosheets, which can greatly promote charge separation and charge transfer at their interface. Additionally, Ni₂P-NiS can reduce the H₂-evolution overpotential, leading to the increased surface kinetics of H₂ evolution. This work offers a promising approach to obtaining a highly active and stable noble-metal-free dual cocatalyst for photocatalytic H₂ production.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ni₂P-NiS双助剂促进g-C₃N₄光催化产氢动力学

通讯作者: 樊君, fanjun@nwu.edu.cn
刘恩周, liuenzhou@nwu.edu.cn

English

Enhancement of Photocatalytic H₂-Evolution Kinetics through the Dual Cocatalyst Activity of Ni₂P-NiS-Decorated g-C₃N₄ Heterojunctions

Corresponding author: Jun Fan, fanjun@nwu.edu.cn Enzhou Liu, liuenzhou@nwu.edu.cn

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Ni2P-NiS双助剂促进g-C3N4光催化产氢动力学

通讯作者: 樊君, fanjun@nwu.edu.cn 刘恩周, liuenzhou@nwu.edu.cn

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