物理化学学报 >> 2024, Vol. 40 >> Issue (11): 2311001.doi: 10.3866/PKU.WHXB202311001

所属专题： 太阳燃料光催化剂

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引入内建电场增强光载流子分离以促进H2的生产

孙培培1, 张锦源1, 宋艳华2,*(), 莫曌1,*(), 陈志刚1, 许晖1,*()   

  1. 1 江苏大学环境与安全工程学院, 京江学院, 江苏 镇江 212013
    2 江苏科技大学环境与化学工程学院, 江苏 镇江 212003
  • 收稿日期:2023-11-01 修回日期:2023-12-13 录用日期:2023-12-14 发布日期:2023-12-25
  • 通讯作者: Email: songyh@just.edu.cn (宋艳华)zhaomo@ujs.edu.cn (莫曌)xh@ujs.edu.cn; Tel.: +86-15896387738 (许晖)
  • 基金资助:
    国家自然科学基金(国家自然科学基金); 国家自然科学基金(21878134); 国家自然科学基金(22208129); 国家自然科学基金(22108110)

Built-in Electric Fields Enhancing Photocarrier Separation and H2 Evolution

Peipei Sun1, Jinyuan Zhang1, Yanhua Song2,*(), Zhao Mo1,*(), Zhigang Chen1, Hui Xu1,*()   

  1. 1 School of the Environment and Safety Engineering, Jingjiang College, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China
    2 School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, Jiangsu Province, China
  • Received:2023-11-01 Revised:2023-12-13 Accepted:2023-12-14 Published:2023-12-25
  • Contact: Email: songyh@just.edu.cn (Yanhua Song)zhaomo@ujs.edu.cn (Zhao Mo)xh@ujs.edu.cn; Tel.: +86-15896387738 (Hui Xu)
  • Supported by:
    the National Natural Science Foundation of China(国家自然科学基金); the National Natural Science Foundation of China(21878134); the National Natural Science Foundation of China(22208129); the National Natural Science Foundation of China(22108110)

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摘要：

内建电场被认为是促进电荷迁移和分离，以提高光催化性能的有效驱动因素。本工作通过一步溶剂热法合成了间隙氯和取代氯共掺杂的一维纳米棒Mn0.2Cd0.8S (MCS)。间隙氯和取代氯的掺杂导致MCS纳米棒中的电荷分布不平衡，形成内建电场，有利于提高光生载流子动力学。通过密度泛函理论计算，本研究通过对电子结构、电荷分布和H2吸附/解吸平衡差异的研究，直观地描述了间隙氯和取代氯的掺杂对MCS活性的影响。有趣的是，MCS能带结构的调控主要源于间隙氯的贡献，而取代氯无贡献。同时，取代氯可以进一步促进间隙氯对MCS的H2吸附-脱附吉布斯自由能的优化。最终，0.9 Cl-MCS的H2吸附-脱附吉布斯自由能更有利于H2的产生(1.14 vs. 0.17 eV)，光催化产H2活性提高了9倍。本研究为在双金属硫化物光催化剂中构建内建电场提供了有价值的途径。

关键词: 光催化, 产氢, 双金属硫化物, 内建电场, 吉布斯自由能

Abstract:

The construct of the internal electric field (IEF) is recognized as an effective driver for promoting charge migration and separation to enhance photocatalytic performance. In this study, one-dimensional nanorods of Mn0.2Cd0.8S (MCS) co-doped with interstitial chlorine (Clint) and substitutional chlorine (Clsub) were designed and synthesized using a one-step solvothermal method. The incorporation of Clint and Clsub led to an unbalanced charge distribution and the formation of IEF in the MCS nanorods, contributing to the improvement of photogenerated carrier kinetic behavior. Through density functional theory (DFT) calculations, the effect of Clint and Clsub doping on the activity of the MCS was visually explained by examining differences in electronic structure, charge distribution and H2 adsorption/desorption balance. Interestingly, the modulation of the energy band structure of MCS primarily resulted from the contribution of Clint, while Clsub playing a negligible role. Moreover, the Clsub further facilitated the optimization of Clint concerning the H2 adsorption-desorption Gibbs free energy (ΔGH*) of MCS. Ultimately, the ΔGH* of 0.9 Cl-MCS favored H2 production (1.14 vs. 0.17 eV), leading to a 9 times increase in photocatalytic H2 production activity compared to MCS. This investigation presents a valuable approach for constructing IEF in bimetallic sulfide photocatalysts.

Key words: Photocatalysis, H2 production, Bimetallic sulfides, Internal electric fields, Gibbs free energy