Xiao Gang, Wang Zishuai, Jin Yu, Wang Fengping
Beijing Key Laboratory of Bioprocess, College of Life Science and Technology, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
College of Pharmacy, Hebei North University, Zhangjiakou 075100, People's Republic of China.
Nanotechnology. 2024 Sep 24;35(49). doi: 10.1088/1361-6528/ad7b3f.
The selective cleavage of lignin C-C bonds is a highly sought-after process with the goal of obtaining low-molecular-weight aromatic chemicals from renewable resources. However, it remains a challenging task to achieve under mild conditions. Photocatalysis is a potentially promising approach to address this issue, but the development of efficient photocatalysts is still in progress. In this study, we introduce the heterostructured TiO@g-CNphotocatalyst for the development of a visible light photocatalytic procedure for the selective cleavage of lignin C-C bonds under mild conditions. The photocatalyst displays favourable visible light absorption, efficient charge separation efficiency, and promising reusability. A typical-O-4 dimer model, 2-phenoxy-1-phenylethanol, was effectively (96.0% conversion) and selectively (95.0 selectivity) cleaved under visible light at ambient conditions. This photocatalytic procedure was also effective when subjected to solar irradiation or other lignin dimer models with-O-4 or-1 linkages. This reaction occurred through a C-centred radical intermediate and a six-membered transition state with photogenerated holes as the primary active species. The C-OH oxidative dehydrogenation of the substrate could also take place but was a relatively minor route. This study provides a new photocatalytic procedure for visible-light-driven lignin valorisation and sheds light on the design of high-performance nanocomposite photocatalysts for C-C bond cleavage.
木质素碳 - 碳键的选择性断裂是一个备受关注的过程,其目标是从可再生资源中获取低分子量的芳香族化学品。然而,在温和条件下实现这一过程仍然是一项具有挑战性的任务。光催化是解决这一问题的一种潜在有前景的方法,但高效光催化剂的开发仍在进行中。在本研究中,我们引入了异质结构的TiO@g-CN光催化剂,用于开发一种在温和条件下选择性断裂木质素碳 - 碳键的可见光光催化方法。该光催化剂具有良好的可见光吸收性能、高效的电荷分离效率和良好的可重复使用性。典型的β-O-4二聚体模型2-苯氧基-1-苯基乙醇在可见光和环境条件下被有效(转化率96.0%)且选择性地(选择性95.0%)断裂。当受到太阳辐射或其他具有β-O-4或β-1键的木质素二聚体模型时,这种光催化过程也有效。该反应通过以碳为中心的自由基中间体和六元过渡态发生,光生空穴是主要活性物种。底物的C-OH氧化脱氢也可能发生,但这是一条相对次要的途径。本研究为可见光驱动的木质素增值提供了一种新的光催化方法,并为用于碳 - 碳键断裂的高性能纳米复合光催化剂的设计提供了思路。