增强光催化H2O2生产的S型异质结In2S3/HOF

doi:10.1016/S1872-2067(26)65018-8

摘要/Abstract

摘要： 作为一种多功能的绿色氧化剂, 过氧化氢广泛应用于有机合成、消毒、废水处理等众多领域. 工业上大规模制备过氧化氢采用的是能耗高和污染大的蒽醌氧化法, 不符合当前倡导的绿色化工生产理念. 半导体光催化过氧化氢生产是一种绿色和可持续的技术, 对其进行开发具有重要的环境、经济与能源战略意义. 氢键有机框架(HOF)是一种新兴的多孔有机晶体材料, 被认为是光催化产过氧化氢的理想候选催化剂之一. 然而, 由于氢键等分子间作用力较弱, 导致大多数HOF稳定性性欠佳, 且单组分HOF存在光生载流子快速复合等弊端, 严重限制了它在光催化产过氧化氢领域中的应用. 选用高稳定性的HOF材料与无机物复合, 构建S型异质结光催化剂, 可有效解决上述问题.
本文采用湿化学方法在高度稳定的HOF(PFC-1)纳米棒表面原位生长了In₂S₃纳米片, 得到了一种新型的无机/有机S型异质结In₂S₃/PFC-1(IP). 在可见光照射下, 以苯甲醇为牺牲剂, 最优复合材料IP-40实现了3.78 mmol g^‒1 h^‒1的光催化产过氧化氢速率, 分别是In₂S₃和PFC-1性能的2.9倍和3.7倍. S型异质结IP-40不仅具有较高的热稳定性，而且在光催化循环测试中表现出良好的化学稳定性. IP-40还具有增强的可见光吸收能力、丰富的活性位点和高效的电荷分离和转移效率，这使得其获得了显著提升的光催化性能. 此外, IP-40的优异氧气吸附能力、适中的的质子亲和力和疏水性协同优化了表面反应动力学, 这也有助于提高其光催化产过氧化氢的性能. 通过原位辐照X射线光电子能谱和飞秒瞬态吸收光谱阐明了S型异质结IP的电荷转移机理. 电子顺磁共振光谱和原位红外光谱光谱均检测到了IP-40在光催化过程中的超氧阴离子自由基的信号, 旋转圆盘电极实验测得其电子转移数约为2.11, 这证实了S型异质结IP-40在光催化产过氧化氢过程中经历了两步单电子氧气还原路径. IP-40在不同条件下光催化产过氧化氢的对比实验表明, 氧气在光催化产过氧化氢的过程中是不可或缺的, 光生电子和超氧阴离子自由基在光催化过程中起着至关重要的作用, 它们是参与过氧化氢生成的主要活性物种. 密度泛函理论计算揭示, 在光催化产过氧化氢的反应路径中, 氧气吸附和两步质子化过程在热力学上是有利的, 而过氧化氢在IP-40催化剂表面上的解吸是光催化反应中的决速步骤.
综上, 合理构建S型异质结是提高其光催化性能的行之有效策略. 本文详细研究了一种增强光催化过氧化氢生产的无机/有机S型异质结IP, 这项工作为设计高效稳定的HOF基光催化剂提供了一种重要的参考.

关键词: 氢键有机框架, 三硫化二铟, S型光催化剂, 氧气还原, 光催化产过氧化氢

Abstract: As an emerging crystalline porous material, hydrogen bonded organic frameworks (HOFs) have enormous potential in photocatalytic field. However, poor stability and rapid recombination of photogenerated charges hinder their practical application in photocatalytic H₂O₂ production. To address the above challenges, this work employs a wet chemical method to grow In₂S₃ nanosheets in situ on the surface of highly stable HOF nanorods (PFC-1), resulting in a novel inorganic/organic In₂S₃/PFC-1 (IP) S-scheme heterojunction. The optimal IP composite achieves a significantly improved photocatalytic H₂O₂ evolution rate of 3.78 mmol g^‒1 h^‒1, which is 2.9- and 3.7-fold than that of In₂S₃ and PFC-1, respectively. The elevated visible-light absorption, abundant active sites, and effective charge separation of IP S-scheme heterojunction result in the improvement in photocatalytic performance. Additionally, photocatalytic H₂O₂ production of IP goes through a two-electron O₂ reduction reaction pathway. This work offers a novel strategy for the fabrication of efficient HOF-based S-scheme heterostructures and their application in photocatalytic field.

Key words: Hydrogen-bonded organic frameworks, In₂S₃, S-scheme photocatalyst, O₂ reduction, Photocatalytic H₂O₂ production

张勇, 朱文君, 赵艳艳, 张淑敏. 增强光催化H₂O₂生产的S型异质结In₂S₃/HOF[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65018-8.

Yong Zhang, Wenjun Zhu, Yanyan Zhao, Shumin Zhang. In₂S₃/HOF S-scheme heterojunction for enhanced photocatalytic H₂O₂ production[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65018-8.

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增强光催化H₂O₂生产的S型异质结In₂S₃/HOF

In₂S₃/HOF S-scheme heterojunction for enhanced photocatalytic H₂O₂ production

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