催化学报

催化学报 ›› 2020, Vol. 41 ›› Issue (1): 31-40.DOI: 10.1016/S1872-2067(19)63467-4

• 光催化产氢 • 上一篇    下一篇

2D-2D CdS/Cu7S4层状异质结高效可见光光催化产氢

任豆豆a,b, 沈荣晨a,b, 姜志民a,b, 鲁信勇a,b, 李鑫a,b   

  1. a 华南农业大学林学与风景园林学院, 农业部能源植物资源与利用重点实验室, 广东广州 510642;
    b 华南农业大学材料与能源学院, 广东广州 510642
  • 收稿日期:2019-06-01 修回日期:2019-07-03 出版日期:2020-01-18 发布日期:2019-10-22
  • 通讯作者: 李鑫
  • 基金资助:
    X. Li would like to thank the National Natural Science Foundation of China (21975084, 51672089), Special Funding on Applied Science and Technology in Guangdong (2017B020238005), the State Key Laboratory of Advanced Technology for Material Synthesis and Processing (Wuhan University of Technology) (2015-KF-7), State Scholarship Fund of China Scholarship Council (200808440114), and the Ding Ying Talent Project of South China Agricultural University for their support.

Highly efficient visible-light photocatalytic H2 evolution over 2D-2D CdS/Cu7S4 layered heterojunctions

Doudou Rena,b, Rongchen Shena,b, Zhimin Jianga,b, Xinyong Lua,b, Xin Lia,b   

  1. a College of Forestry and Landscape Architecture, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture, South China Agricultural University, Guangzhou 510642, Guangdong, China;
    b College of Materials and Energy, South China Agricultural University, Guangzhou 510642, Guangdong, China
  • Received:2019-06-01 Revised:2019-07-03 Online:2020-01-18 Published:2019-10-22
  • Supported by:
    X. Li would like to thank the National Natural Science Foundation of China (21975084, 51672089), Special Funding on Applied Science and Technology in Guangdong (2017B020238005), the State Key Laboratory of Advanced Technology for Material Synthesis and Processing (Wuhan University of Technology) (2015-KF-7), State Scholarship Fund of China Scholarship Council (200808440114), and the Ding Ying Talent Project of South China Agricultural University for their support.

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摘要： 利用太阳能将水转化为清洁可持续的化学燃料是一种很有前途的策略.光催化水分解制氢技术是有效解决能源可持续发展和环境保护问题的重要技术.CdS由于具有较窄的带隙（2.4eV）和合适的能带位置而被认为是最有潜力的光催化水产氢催化剂之一.然而，CdS强光的腐蚀性和快速的电子空穴复合导致光催化剂活性低、稳定性差，严重阻碍了CdS光催化剂的广泛应用.为了有效提高光催化产氢活性及稳定性，人们对CdS光催化剂进行了大量改性研究.其中，合理巧妙地加载助催化剂和构造纳米结构CdS被认为是两种极为重要的改性策略，两种策略的有效耦合可以更有效地利用太阳能，实现清洁氢燃料的生成.一方面，各种形貌的CdS光催化剂均已被开发，例如纳米线、纳米棒、纳米片和量子点等.然而，由于制备工艺复杂，在以往的报道中很少有超薄2D CdS纳米片用于光催化产氢.另一方面，由于贵金属（Ag，Pt，Au）的稀缺性和高成本阻碍了其修饰光催化剂的实际应用，所以利用非贵金属助催化剂（MoSx，CuS，Ni3C，WS2，NiS，MXene，CoxP和MoP）修饰CdS提高光催化产氢活性近年来备受关注.对于地球丰富的2D层状助催化剂Cu7S4而言，具有优异的光电催化产氢活性和简单制备方法，但是在光催化产氢领域的应用上未引起足够重视.因此，本文充分利用超薄CdS纳米片以及Cu7S4纳米片各自的独特优势，构建了独特的2D-2D层状异质结，实现了高效协同光催化产氢.
我们首先以乙酸镉和硫脲为原料通过一步水热法合成了超薄2D CdS纳米片，并用静电自组装方法制备了CdS/Cu7S4.在可见光下进行了产氢测试，实验结果证实了优化的2D CdS/2% Cu7S4层状异质结在含有Na2S·9H2O和Na2SO3的水溶液中光催化析氢活性最高（27.8 mmol g-1 h-1），是原始CdS纳米片（2.6 mmol g-1 h-1）的10.69倍.经过4次连续循环反应，CdS/Cu7S4二元复合体系展现出良好的稳定性.
为深入探讨高效产氢机制，对纳米级CdS复合材料的光催化物化性能及载流子分离机制进行了表征.通过X射线衍射确定了CdS和CdS/Cu7S4的晶体结构.用高分辨电子显微镜和X射线光电子能谱证实合成了CdS催化剂和Cu7S4助催化剂的超薄纳米片结构且成功复合.用紫外-可见漫反射光谱法对制备的纯CdS和CdS/Cu7S4复合样品的光吸收特性进行了表征.结果表明，在CdS上负载Cu7S4以后，可以明显观察到样品对可见光的吸收能力明显增强.对CdS/Cu7S4进行XPS测试分析，进一步证明了样品中S、Cd和Cu的化学成分和状态.利用PL发射光谱研究了CdS/Cu7S4光催化剂的电荷载流子复合和转移行为.进一步对纯CdS和CdS/Cu7S4复合光催化剂的瞬态光电流响应（I-t曲线）进行了研究，确定了光生载体的分离效率.阻抗是深入研究电荷载流子迁移和界面转移的最有力技术，利用阻抗技术证实CdS/Cu7S4界面高效的载流子分离性能.极化曲线结果表明，加入Cu7S4可以降低CdS的产氢过电势，因此加速表面产氢动力学.
由此可见，本文所构建的2D-2D CdS/Cu7S4二元层状异质结可以同时实现光生电子空穴对的快速分离、电子的转移和增加光生电子在表面利用效率，从而最大幅度地提高其光催化水分解产氢活性.本文所采用基于CdS纳米片的2D-2D界面耦合策略可以作为一种通用策略扩展到各种传统半导体纳米片的改性，从而极大地推进高效光催化产氢材料的持续进步.

关键词: 可见光光催化产氢, CdS纳米片, Cu7S4助催化剂, 层状异质结, 载流子分离

Abstract: Converting solar energy into clean and sustainable chemical fuels is a promising strategy for exploiting renewable energy. The application of photocatalytic water splitting technology in hydrogen production is important for sustainable energy development and environmental protection. In this study, for the first time, 2D Cu7S4 co-catalysts were coupled on the surface of a CdS nanosheet photocatalyst by a one-step ultrasonic-assisted electrostatic self-assembly method at room temperature. The as-fabricated 2D-2D CdS/Cu7S4 layered heterojunctions were demonstrated to be advanced composite photocatalysts that enhance the water splitting efficiency toward hydrogen production. The highest hydrogen evolution rate of the 2D-2D CdS/2%Cu7S4 binary heterojunction photocatalyst was up to 27.8 mmol g-1 h-1 under visible light irradiation, with an apparent quantum efficiency of 14.7% at 420 nm, which was almost 10.69 times and 2.65 times higher than those of pure CdS nanosheets (2.6 mmol g-1 h-1) and CdS-2%CuS (10.5 mmol g-1 h-1), respectively. The establishment of the CdS/Cu7S4 binary-layered heterojunction could not only enhance the separation of photogenerated electron-hole (e--h+) pairs, improve the transfer of photo-excited electrons, and prolong the life-span of photo-generated electrons, but also enhance the light absorption and hydrogen-evolution kinetics. All these factors are important for the enhancement of the photocatalytic activity. Expectedly, the 2D-2D interface coupling strategy based on CdS NSs can be extensively exploited to improve the hydrogen-evolution activity over various kinds of conventional semiconductor NSs.

Key words: Visible-light photocatalytic H2 evolution, CdS nanosheet, Cu7S4 cocatalysts, Layered heterojunction, Charge separation