硫化镍修饰的硫化镉/硫化锌异质结复合光催化剂用于高效光催化产氢性质的研究

注册 English

硫化镍修饰的硫化镉/硫化锌异质结复合光催化剂用于高效光催化产氢性质的研究

江道传 , 祝亮 , Rana Muhammad Irfan , 张磊 , 杜平武

引用本文: 江道传, 祝亮, Rana Muhammad Irfan, 张磊, 杜平武. 硫化镍修饰的硫化镉/硫化锌异质结复合光催化剂用于高效光催化产氢性质的研究[J]. 催化学报, 2017, 38(12): 2102-2109. doi: 10.1016/S1872-2067(17)62956-5 shu

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Citation: Daochuan Jiang, Liang Zhu, Rana Muhammad Irfan, Lei Zhang, Pingwu Du. Integrating noble-metal-free NiS cocatalyst with a semiconductor heterojunction composite for efficient photocatalytic H₂ production in water under visible light[J]. Chinese Journal of Catalysis, 2017, 38(12): 2102-2109. doi: 10.1016/S1872-2067(17)62956-5 shu

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硫化镍修饰的硫化镉/硫化锌异质结复合光催化剂用于高效光催化产氢性质的研究

中国科学技术大学化学与材料科学学院材料科学与工程系, 中国科学院能量转换材料重点实验室, 能源材料化学协同创新中心, 安徽合肥 230026
基金项目:
国家重大研究计划（2017YFA0402800）；国家自然科学基金（51772285，21473170）.

摘要: 光催化水分解是一种经济而且可持续的利用太阳能来制备洁净能源氢气的方式，因此寻找和开发高效稳定的光催化剂已成为光催化产氢领域的研究热点.CdS因其具有高效、廉价、较负的导带位置等优点而引起人们的关注.然而，由于CdS镉本身光生电子/空穴对易复合，以及存在光腐蚀等不足，限制了其实际利用.为了提高CdS的光催化水分解产氢性质，人们开发了构建异质结和负载助催化剂等策略.近年来，ZnO，g-C₃N₄，TiO₂等半导体已被证实可以与CdS一起形成Ⅱ型异质结来促进光生电子和空穴的分离，进而提升光催化产氢性质.此外，传统的type I型CdS/ZnS异质结也被证实能提高光催化产氢速率.研究表明，ZnS一方面能够钝化CdS表面态，另一方面ZnS半导体中存在缺陷能（VZn，IS），有利于转移CdS价带的空穴，最终大幅度提高了整个体系的光催化活性.在适用于CdS的各种助催化剂中，由于常用的Pt，Pd和Ru等贵金属的高成本严重限制了它们的实际应用，所以近年来基于过渡金属的各种非贵金属助催化剂（包括MoS₂，Ni₂P，FeP，Ni₃N，NiS，Ni（OH）₂等）得到了广泛的研究.我们采用原位化学沉积法将无定型的NiS助催化剂修饰在CdS/ZnS异质结表面，开发出廉价高效的NiS-CdS/ZnS三元产氢光催化体系.在该三元体系中，NiS和ZnS分别用于促进CdS导带上光生电子和价带的光生空穴的分离及利用，从而使得高能的CdS的光生电子转移到NiS表面并应用于光催化产氢，而高能的CdS的光生空穴被应用于氧化牺牲剂Na₂S和Na₂SO₃，最终实现了整个体系的高效光催化产氢活性及稳定性.
我们首先利用水热合成法得到大量的CdS纳米棒，然后使用化学浴沉积法在CdS表面沉积一定量的ZnS壳层，制备出CdS/ZnS异质结.光照前，采用原位化学沉积法将NiS颗粒负载在CdS/ZnS表面.光催化产氢的性能测试表明，当初始加入镍盐（20 mmol/L）量为100 μL时，所得样品N2（NiS-CdS/ZnS）产氢效率最高（574 μmol·h^-1），分别是CdS/NiS，CdS/ZnS和CdS的16.2，5.6和38倍.复合材料的表观量子效率高达43.2%.由此可见，NiS助催化剂和CdS/ZnS异质结存在协同效应，实现了三元体系的高效的光催化产氢性能.瞬态光电流测试结果表明，ZnS和NiS的加入能有效地促进光生电子/空穴的分离和利用.X射线衍射结果表明，CdS以六方相的形式存在，负载ZnS和NiS之后没有明显变化.高分辨透射电子显微镜照片和元素分布证实了NiS-CdS/ZnS复合材料中ZnS和NiS富集在纳米棒表层，其中NiS没有明显晶格条纹.紫外-可见漫反射结果表明，NiS和ZnS的负载后，复合材料的吸收边和纯相的CdS相近，而加入NiS助催化剂使得复合催化剂的颜色变黑，进而增加了可见光的吸收.

关键词:

English

Integrating noble-metal-free NiS cocatalyst with a semiconductor heterojunction composite for efficient photocatalytic H₂ production in water under visible light

CAS Key Laboratory of Materials for Energy Conversion, Hefei National Laboratory for Physical Sciences at Microscale, Department of Materials Science and Engineering, iChEM(Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, Hefei 230026, Anhui, China
Received Date: 09 October 2017
Revised Date: 31 October 2017
Fund Project:
This work was supported by the National Key Research and Development Program of China (2017YFA0402800), the National Natural Science Foundation of China (51772285, 21473170).

Abstract: Photocatalytic water splitting is an economical and sustainable pathway to use solar energy for large-scale H₂ production. We report a highly efficient noble-metal-free photocatalyst formed by integrating amorphous NiS with a CdS nanorods (NRs)/ZnS heterojunction material for photocatalytic H₂ production in water under visible light irradiation (λ > 420 nm). The results show that the photocatalytic H₂ production rate reaches an optimal value of up to 574 μmol·h^-1 after the loading of NiS, which is more than 38 times higher than the catalytic activity of pure CdS NRs. The average apparent quantum yield is~43.2% during 5 h of irradiation by monochromatic 420 nm light. The present study demonstrates the advantage of integration strategies to form not only semiconductor heterojunctions but also photocatalyst-cocatalyst interfaces to enhance the catalytic activity for photocatalytic H₂ production.

Key words:

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