Highly efficient catalytic transfer hydrogenation for the conversion of nitrobenzene to aniline over PdO/TiO_(2):The key role of in situ switching from PdO to Pd  

作　　者：Anqi Lu Xiaokang Xiang Ming Lei Shuangshuang Huang Bingbing Liang Siyu Zhao Lihua Zhu Heqing Tang 

机构地区：[1]College of Resources and Environmental Science,South-Central Minzu University,Wuhan 430074,China [2]School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074,China [3]School of Physics and Technology,Center for Electron Microscopy,MOE Key Laboratory of Artificial Micro-and Nano-Structures,and Institute for Advance Studies,Wuhan University,Wuhan 430072,China

出　　处：《Journal of Environmental Sciences》2025年第2期515-528,共14页环境科学学报(英文版)

基　　金：supported by the National Natural Science Foundation of China (No.22076052);the Natural Science Foundation of Hubei Province (Nos.2021CFB535 and 2020CFB437);the Knowledge Innovation Program of Wuhan-Basic Research (No.SZY23005);the Fundamental Research Funds for the Central Universities,South-Central Minzu University (No.CZQ22002);Wuhan University (No.2042020kf0036).

摘　　要：The reduction of nitrobenzene to aniline is very important for both pollution control and chemical synthesis.Nevertheless,difficulties still remain in developing a catalytic system having high efficiency and selectivity for the production of aniline.Herein,it was found that PdO nanoparticles highly dispersed on TiO_(2)support(PdO/TiO_(2))functioned as a highly efficient catalyst for the reduction of nitrobenzene in the presence of NaBH4.Under favorable conditions,95%of the added nitrobenzene(1 mmol/L)was reduced within 1 min with an ultra-low apparent activation energy of 10.8 kJ/mol by using 0.5%PdO/TiO_(2)as catalysts and 2 mmol/L of NaBH4 as reductants,and the selectivity to aniline even reached up to 98%.The active hydrogen specieswere perceived as dominant species during the hydrogenation of nitrobenzene by the results of isotope labeling experiments and ESR spectroscopic.A mechanismwas proposed as follows:PdO activates the nitro groups and leads to in-situ generation of Pd,and the generated Pd acts as the reduction sites to produce active hydrogen species.In this catalytic system,nitrobenzene prefers to be adsorbed on the PdO nanoparticles of the PdO/TiO_(2)composite.Subsequently,the addition of NaBH_(4) results in in-situ generation of a Pd/PdO/TiO_(2)composite from the PdO/TiO_(2)composite,and the Pd nanoclusters would activate NaBH_(4) to generate active hydrogen species to attack the adsorbed nitro groups.This work will open up a new approach for the catalytic transfer hydrogenation of nitrobenzene to aniline in green chemistry.

关 键 词：Catalytic transfer hydrogenation Reduction PD NITROBENZENE ANILINE 

分 类 号：X773[环境科学与工程—环境工程]