Integrating Pd(I)Atoms in Schottky Junctions for Visible-Light-Driven Urea Production from Ambient Nitrogenous Species and CO_(2)  

作　　者：Wei-Yao Hu Qi-Yuan Li Dong Xu Peng Gao Pan-Zhe Qiao Dong Li Si-Yuan Xia Xiu Lin Jie-Sheng Chen Xin-Hao Li 

机构地区：[1]School of Chemistry and Chemical Engineering,Frontiers Science Center for Transformative Molecules,Shanghai Jiao Tong University,Shanghai 200240 [2]Shanghai Synchrotron Radiation Facility,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201210 [3]State Key Laboratory of Precision Spectroscopy,East China Normal University,Shanghai 200241

出　　处：《CCS Chemistry》2024年第12期3008-3017,共10页中国化学会会刊(英文)

基　　金：supported by the National Natural Science Foundation of China(grant nos.22071146 and 21931005);the Shanghai Science and Technology Committee(grant no.23XD1421800);the Shanghai Shuguang Program(grant no.21SG12);the Shanghai Municipal Science and Technology Major Project.

摘　　要：The mass production of urea,the most widely used agricultural fertilizer,usually relies on energy-and carbon-intensive processes.The light-driven synthesis path has great potential for more sustainable techniques to produce urea from abundant naturally occurring resources,but this method suffers fromthe use of pure CO_(2)and high-energy-driven forces(high temperature or ultraviolet light).Herein,we present a mild photocatalytic pathway for urea production from diverse nitrogenous species(such as NO3-,NH3,and N2)and diluted CO_(2)using visible light.We designed a palladium(Pd)-doped Schottky heterojunction,composed of graphene and titanium dioxide,as an effective photocatalyst to achieve on-farm urea generation.With the injection of visible-lightgenerated hot electrons from graphene to TiO_(2),the as-integrated Pd(I)centers with a special oxidation state of+1.36 in the TiO_(2)lattice can initiate the universal reaction path of cascade reduction of NO3-/N2 to NH3 and resulting C-N coupling of CO_(2)with as-formed or added NH3 to transform diverse nitrogenous species and CO_(2)into urea.The urea yield over the at.-Pd@TiO_(2)/Gr photocatalyst is 1.62 mmol g-1 h-1 under visible-light irradiation with an apparent quantum yield of 1.05%at 400 nm and 0.39%even at 700 nm.

关 键 词：urea production visible-light-driven Schottky heterojunction hot electron C-N coupling 

分 类 号：TQ113.24[化学工程—无机化工]