文献类型：期刊文献

英文题名：Reduction of the Photogenerated Electron Transport Path by Modulating the Conduction Band Region to Achieve the Highest Lignin Β–O–4 Bond Photocleavage Efficiency Under Xenon Excitation

作者：Li, Xiang[1,2,3] Wu, Ting[1,2,3] Zhu, Yawei[1,2,3] Tian, Qingwen[1,2,3] Yang, Qiang[1,2,3] Fang, Guigan[1,2,3,4]

第一作者：Li, Xiang

机构：[1] Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Lab. Of Biomass Energy and Material, Jiangsu Province, China; [2] Co-Innovation Center of Efficient Processing, Utilization of Forest Resource, Jiangsu Province, China; [3] Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration, National Engineering Lab. for Biomass Chemical Utilization, Nanjing, 210042, China; [4] Shandong Huatai Paper Co., Ltd., Shandong Province, Dongying, 257335, China

年份：2024

外文期刊名：SSRN

收录：EI(收录号：20240246431)

语种：英文

外文关键词：Carbon nitride - Conduction bands - Conversion efficiency - Electron transport properties - Electron tunneling - Etching - Gas adsorption - Metal ions - Reaction intermediates - Sulfur compounds

摘要：Photocracking of lignin β–O–4 bonds is a green approach for the high-value modification of lignin. Graphitic carbon nitride (g-C3N4) that can photocleave the β–O–4 bond is presently the only stable, metal-free photocatalyst owing to the residual metal ions generated due to photocorrosion of metal sulfides. However, the catalytic efficiency of g-C3N4 is constrained owing to the critical complexation of the photogenerated electron–hole pairs. Herein, g-C3N4 with a N–C3 vacancy structure is prepared by etching site–engineering strategy in an argon atmosphere. The N–C3 vacancy structure can reduce the transport path of the photogenerated electrons by tuning the conduction band (CB) region to the edge of the photocatalyst, which impedes the complexation of the photogenerated electron–hole pairs and enhances the photoelectric conversion efficiency five-fold. The lignin β–O–4 bond photocleavage efficiency of g-C3N4 with N–C3 vacancy structure is increased by 13 times compared with that of g-C3N4. In addition, based on the reaction enthalpy changes and free energies investigated through simulations, the existing photocleavage reaction route is optimized. Hence, the reaction intermediates should be reoxidized and dehydrogenated by photogenerated holes to cleave the Cα–Cβ bonds spontaneously. ? 2024, The Authors. All rights reserved.