Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn<sub>2</sub>S<sub>4</sub> Heterojunctions for Photocatalytic Hydrogen Evolution

Citation: Kezhen Lai, Fengyan Li, Ning Li, Yangqin Gao, Lei Ge. Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution[J]. Acta Physico-Chimica Sinica, 2024, 40(1): 230401. doi: 10.3866/PKU.WHXB202304018 shu

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

赖可溱 ^{1, 2,} ,
李丰彦 ^{1, 2,} ,
李宁 ^{1, 2,} ,
高旸钦 ^{1, 2,} ,
戈磊 ^{1, 2,
,}

1.
中国石油大学(北京)新能源与材料学院重质油国家重点实验室, 北京 102249
2.
中国石油大学(北京)新能源与材料学院材料科学与工程系, 北京 102249

通讯作者: 戈磊, gelei@cup.edu.cn

基金项目:
国家重点研发计划 2021YFA1501300

国家重点研发计划 2019YFC1907602

国家自然科学基金 51572295

国家自然科学基金 21273285

国家自然科学基金 21003157

摘要: 氢气是缓解环境污染和能源短缺的零污染绿色能源，利用太阳能诱导半导体裂解水制氢是最环保的方法之一。本文以MOFs衍生的Ni-CNT(Ni修饰的碳纳米管)作为非贵金属助催化剂，通过简单的油浴法原位生长ZnIn₂S₄纳米片合成了Ni-CNT/ZnIn₂S₄。在Ni-CNT/ZnIn₂S₄中，Ni纳米颗粒包裹在CNT的顶部和横截面上，有效地阻止了Ni纳米颗粒的团聚。Ni-CNT/ZnIn₂S₄异质结构具有紧密的接触界面，有利于电荷转移，可作为高效的析氢光催化剂。38Ni-CNT/ZnIn₂S₄样品具有最佳的产氢性能(12267 μmol·h⁻¹·g⁻¹)，约为纯ZnIn₂S₄的6.4倍，且在420 nm单色光下其表观量子效率达到11.3%。X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)结果证实了Ni-CNT/ZnIn₂S₄异质结构的存在。电化学测试表明，Ni-CNT与ZnIn₂S₄的结合促进了光生电荷的转移，有效地阻止了光生载流子的快速复合，从而增强了ZnIn₂S₄的析氢性能。电子自旋共振(ESR)结果进一步证明了Ni-CNT助催化剂的存在延长了ZnIn₂S₄光生电荷的寿命，促进了光生电荷和空穴的分离效率。通过密度泛函理论计算探索并确定了异质结界面中的电荷转移途径。Ni、CNT和ZnIn₂S₄费米能级的差异导致界面处电荷发生迁移从而形成内嵌电场，ZnIn₂S₄的能带向下弯曲，促进光生电子从ZnIn₂S₄流向Ni-CNT电子受体。平面平均电子密度差结果证实了热电子从Ni转移至CNT再转移至ZnIn₂S₄，表明光生电子转移途径为ZnIn₂S₄ → CNT → Ni。此外，吸附H*吉布斯自由能(ΔG_H*)和晶体轨道哈密顿布居(COHP)结果表明Ni纳米颗粒可作为析氢反应的活性位点，促进了产氢效率。本工作将为开发低成本、高效的非贵金属光催化制氢催化剂提供新的策略。

关键词:

Ni-CNT
/ 光催化
/ 析氢
/ ZnIn₂S₄
/ 助催化剂

English

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution

Kezhen Lai ^{1, 2,} ,
Fengyan Li ^{1, 2,} ,
Ning Li ^{1, 2,} ,
Yangqin Gao ^{1, 2,} ,
Lei Ge ^{1, 2,
,}

1.
State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China
2.
Department of Materials Science and Engineering, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China

Corresponding author: Lei Ge, gelei@cup.edu.cn

Received Date: 06 April 2023
Accepted Date: 22 May 2023
Revised Date: 20 May 2023
Available Online: 15 January 2024
Fund Project:

Abstract: Hydrogen is an important zero-pollution green energy source with potential for alleviating environmental contamination and energy shortages. Hydrogen evolution via solar-energy-induced semiconducting water splitting is among the most environmentally friendly methods available to date. In this study, a metal–organic-framework-derived, Ni-decorated carbon nanotube (Ni-CNT) is used as a non-noble co-catalyst. This Ni-CNT is grown in situ on ZnIn₂S₄ nanosheets using a simple one-step oil bath strategy, wherein Ni nanoparticles are wrapped around the top and cross sections of the nanotubes, preventing their agglomeration. Notably, Ni-CNT/ZnIn₂S₄ heterostructures feature intimate contact interfaces that promote charge transfer, facilitating their use as efficient photocatalysts for hydrogen evolution. The 38Ni-CNT/ZnIn₂S₄ sample exhibits a high H₂ production rate (12267 μmol·h⁻¹·g⁻¹), with an apparent quantum efficiency (AQE) of 11.3% under 420 nm monochromatic light irradiation, which is nearly 6.4 times that of pure ZnIn₂S₄. The results of X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) corroborate the observations on Ni-CNT/ZnIn₂S₄ heterostructures. Electrochemical measurements reveal that the combination of the Ni-CNT and ZnIn₂S₄ facilitates the transfer of photogenerated electrons and effectively prevents rapid recombination of photocarriers, thus improving the hydrogen evolution performance of ZnIn₂S₄. Electron spin resonance (ESR) results further prove that co-catalyst Ni-CNTs are beneficial for prolonging the lifetimes of ZnIn₂S₄ photogenerated electrons, thereby achieving effective charge separation. A charge transfer pathway in the heterojunction interfaces is further explored and confirmed by density functional theory (DFT) calculations. The difference in the Fermi level energy (E_f) contributes to both charge migration and the generation of a built-in electronic field (BEF), indicating that the energy band of ZnIn₂S₄ bends downward, which is favorable for photogenerated electron flow from ZnIn₂S₄ to the Ni-CNT electron acceptor. The results of planar-averaged electron density difference analysis confirm that the hot electrons are transferred from Ni nanoparticles to the CNT and then to the ZnIn₂S₄ nanosheets, indicating the formation of a photogenerated electron transfer pathway of ZnIn₂S₄ → CNT → Ni. Furthermore, Gibbs free energy of H* adsorption (ΔG_H*) and crystal orbital Hamilton population (COHP) analysis indicate that Ni nanoparticles can serve as active sites, promoting H₂ evolution. Thus, the present study formulates a new strategy for developing low-cost, high-efficiency, non-noble-metal co-catalysts for photocatalytic hydrogen production.

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

通讯作者: 戈磊, gelei@cup.edu.cn

English

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution

Corresponding author: Lei Ge, gelei@cup.edu.cn

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金属-有机骨架衍生的Ni-CNT/ZnIn2S4异质结用于光催化产氢及其电荷转移途径的确定

通讯作者: 戈磊, gelei@cup.edu.cn

English

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn2S4 Heterojunctions for Photocatalytic Hydrogen Evolution

Corresponding author: Lei Ge, gelei@cup.edu.cn

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CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

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中国化学会秘书处

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

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