华南师范大学兰亚乾团队报道了通过钛氧团簇的功能改造实现4-氯苯酚的高效光电催化降解。相关研究成果发表在2023年3月8日出版的国际学术期刊《美国化学会杂志》。

合理设计具有优异光吸收和电荷转移的晶体催化剂，以实现高效光电催化（PEC）反应和能量回收仍然是一个巨大的挑战。

该文中，研究人员精心构建了用单官能配体（9-蒽羧酸（Ac）或二茂铁羧酸（Fc））和双官能配体（Ac和Fc）修饰的三种稳定的钛氧代簇（TOCs、Ti10Ac6、Ti10Fc8和Ti12Fc2Ac4）。它们具有可调的光收集和电荷转移能力，因此可以作为出色的结晶催化剂，以实现高效的PEC整体反应，即阳极有机污染物4-氯苯酚（4-CP）降解和阴极废水转化为H₂。这些TOCs均表现出非常高的PEC活性和4-CP的降解效率。特别是，与用单官能化配体修饰的Ti10Ac6和Ti10Fc8相比，用双官能化配体装饰的Ti12Fc2Ac4表现出更好的PEC降解效率（超过99%）和H₂产率。对4-CP降解途径和机制的研究表明，Ti12Fc2Ac4的这种更好的PEC性能可能是由于其与4-CP分子更强的相互作用和更好的OH自由基产生。

该项工作不仅提出了使用晶体配位簇作为阳极和阴极催化剂的有机污染物降解和同时H₂释放反应的有效组合，而且还开发了晶体配位化合物的PEC新应用。

附：英文原文

Title: Achieving High-Efficient Photoelectrocatalytic Degradation of 4-Chlorophenol via Functional Reformation of Titanium-Oxo Clusters

Author: Jing-Jing Liu, Sheng-Nan Sun, Jiang Liu, Yi Kuang, Jing-Wen Shi, Long-Zhang Dong, Ning Li, Jia-Ni Lu, Jiao-Min Lin, Shun-Li Li, Ya-Qian Lan

Issue&Volume: March 8, 2023

Abstract: Rational design of crystalline catalysts with superior light absorption and charge transfer for efficient photoelectrocatalytic (PEC) reaction coupled with energy recovery remains a great challenge. In this work, we elaborately construct three stable titanium-oxo clusters (TOCs, Ti10Ac6, Ti10Fc8, and Ti12Fc2Ac4) modified with a monofunctionalized ligand (9-anthracenecarboxylic acid (Ac) or ferrocenecarboxylic acid (Fc)) and bifunctionalized ligands (Ac and Fc). They have tunable light-harvesting and charge transfer capacities and thus can serve as outstanding crystalline catalysts to achieve efficient PEC overall reaction, that is, the integration of anodic organic pollutant 4-chlorophenol (4-CP) degradation and cathodic wastewater-to-H2 conversion. These TOCs can all exhibit very high PEC activity and degradation efficiency of 4-CP. Especially, Ti12Fc2Ac4 decorated with bifunctionalized ligands exhibits better PEC degradation efficiency (over 99%) and H2 generation than Ti10Ac6 and Ti10Fc8 modified with a monofunctionalized ligand. The study of the 4-CP degradation pathway and mechanism revealed that such better PEC performance of Ti12Fc2Ac4 is probably due to its stronger interactions with the 4-CP molecule and better OH radical production. This work not only presents the effective combination of organic pollutant degradation and simultaneously H2 evolution reaction using crystalline coordination clusters as both anodic and cathodic catalyst but also develops a new PEC application for crystalline coordination compounds.

DOI: 10.1021/jacs.2c11509

Source: https://pubs.acs.org/doi/10.1021/jacs.2c11509