Yue Zongyang, Shao Shibo, Yu Jialin, Lu Guanchu, Wei Wenjing, Huang Yi, Zhang Kai, Wang Ke, Fan Xianfeng
Institute for Materials and Processes, School of Engineering, The University of Edinburgh, Edinburgh EH9 3BF, U.K.
Petrochemical Research Institute, PetroChina Company Limited, Beijing 102206, China.
ACS Appl Mater Interfaces. 2024 Jun 12;16(23):29991-30009. doi: 10.1021/acsami.4c02315. Epub 2024 Jun 3.
Photocatalysis has the potential for lignin valorization to generate functionalized aromatic monomers, but its application has been limited by the slow conversion rate and the low selectivity to desirable aromatic products. In this work, we designed the phase junction CdS with coexposed hexagonal (100) and cubic (220) facets to improve the photogenerated charge carriers' transfer efficiency from (100) facet to (220) facet and the hydrogen transfer efficiency for an enhanced conversion rate of lignin to aromatic monomers. Water is found as a sufficient external hydrogen supplier to increase the yields of aromatic monomers. These innovative designs in the reaction system promoted complete conversion of PP-ol to around 94% of aromatic monomers after 1 h of visible light irradiation, which shows the highest reaction rate and selectivity of target products in comparison with previous works. PP-one is a byproduct from the overoxidation of PP-ol and is usually difficult to be further cleaved to acetophenone and phenol as the desirable aromatic monomers. TEA was first identified in this study as a sacrificial electron donor, a hydrogen source, and a mediator to enhance the cleavage of the C-O bonds in PP-one. With the assistance of TEA, PP-one can be completely cleaved to desirable aromatic monomer products, and the reaction time is reduced from several hours to 10 min of visible light irradiation.
光催化具有将木质素转化为功能化芳香单体的潜力,但其应用受到转化率低和对所需芳香产物选择性低的限制。在这项工作中,我们设计了具有共暴露的六方(100)和立方(220)面的相结硫化镉,以提高光生电荷载流子从(100)面到(220)面的转移效率以及氢转移效率,从而提高木质素向芳香单体的转化率。发现水是一种充足的外部氢供体,可提高芳香单体的产率。反应体系中的这些创新设计在可见光照射1小时后促进了PP-ol完全转化为约94%的芳香单体,与先前的工作相比,这显示出最高的反应速率和目标产物选择性。PP-one是PP-ol过度氧化的副产物,通常难以进一步裂解为所需的芳香单体苯乙酮和苯酚。在本研究中,TEA首次被确定为牺牲电子供体、氢源和促进PP-one中C-O键裂解的介质。在TEA的协助下,PP-one可以完全裂解为所需的芳香单体产物,反应时间从几小时减少到可见光照射10分钟。