Electroreduction of nitrate(NO_(3)-)to ammonia(NH_(3))is an environmentally friendly route for NH_(3)production,serving as an appealing alternative to the Haber-Bosch process.Recently,various noble metal-based electro...Electroreduction of nitrate(NO_(3)-)to ammonia(NH_(3))is an environmentally friendly route for NH_(3)production,serving as an appealing alternative to the Haber-Bosch process.Recently,various noble metal-based electrocatalysts have been reported for electroreduction of NO_(3)-.However,the application of pure metal electrocatalysts is still limited by unsatisfactory performance,owing to the weak adsorption of nitrogen-containing intermediates on the surface of pure metal electrocatalysts.In this work,we report thiol ligand-modified Au nanoparticles as the effective electrocatalysts toward electroreduction of NO_(3)-.Specifically,three mercaptobenzoic acid(MBA)isomers,thiosalicylic acid(ortho-MBA),3-mercaptobenzoic acid(meta-MBA),and 4-mercaptobenzoic acid(para-MBA),were employed to modify the surface of the Au nanocatalyst.During the NO_(3)-electroreduction,para-MBA modified Au(denoted as para-Au/C)displayed the highest catalytic activity among these Au-based catalysts.At-1.0 V versus reversible hydrogen electrode(vs RHE),para-Au/C exhibited a partial current density for NH_(3)of 472.2 mA cm^(-2),which was 1.7 times that of the pristine Au catalyst.Meanwhile,the Faradaic efficiency(FE)for NH_(3)reached 98.7%at-1.0 V vs RHE for para-Au/C.The modification of para-MBA significantly improved the intrinsic activity of the Au/C catalyst,thus accelerating the kinetics of NO_(3)-reduction and giving rise to a high NH_(3)yield rate of para-Au/C.展开更多
Using CdSe/CdS core/shell nanocrystals with 1-10 monolayers of CdS shell as the model system, we studied effects of thiol ligands on optical properties of the nanocrystals. The core/shell nanocrystals with original li...Using CdSe/CdS core/shell nanocrystals with 1-10 monolayers of CdS shell as the model system, we studied effects of thiol ligands on optical properties of the nanocrystals. The core/shell nanocrystals with original ligands possessed near unity photoluminescence （PL） quantum yield and single-exponential PL decay dynamics. The effects of thiol ligands on optical properties were found to depend on the shell thickness, environment （with/without oxygen）, and excitation power （single- or multi-exciton）. Systematic and quantitative results reported in this work should provide necessary information for fundamental understanding and technical applications of quantum dots （QDs） coated with thiol ligands.展开更多
基金This work was supported by Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450401)National Key Research and Development Program of China(2021YFA1500500 and 2019YFA0405600)+3 种基金NSFC(22209161,22209163,92061111,22322901,22221003,and 22250007)CAS Project for Young Scientists in Basic Research(YSBR-051 and YSBR-022)National Science Fund for Distinguished Young Scholars(21925204),China Postdoctoral Program for Innovative Talents(BX20200324)Fundamental Research Funds for the Central Universities.J.Z.acknowledges support from the Tencent Foundation through the XPLORER PRIZE.The authors acknowledge support from Prof.Chao Ma and Mr.Sunpei Hu in conducting the microscopic characterization,and Dr.Hong Wu in the DFT computations.This work was partially carried out at the Instruments Center for Physical Science,University of Science and Technology of China.This work was also partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication。
文摘Electroreduction of nitrate(NO_(3)-)to ammonia(NH_(3))is an environmentally friendly route for NH_(3)production,serving as an appealing alternative to the Haber-Bosch process.Recently,various noble metal-based electrocatalysts have been reported for electroreduction of NO_(3)-.However,the application of pure metal electrocatalysts is still limited by unsatisfactory performance,owing to the weak adsorption of nitrogen-containing intermediates on the surface of pure metal electrocatalysts.In this work,we report thiol ligand-modified Au nanoparticles as the effective electrocatalysts toward electroreduction of NO_(3)-.Specifically,three mercaptobenzoic acid(MBA)isomers,thiosalicylic acid(ortho-MBA),3-mercaptobenzoic acid(meta-MBA),and 4-mercaptobenzoic acid(para-MBA),were employed to modify the surface of the Au nanocatalyst.During the NO_(3)-electroreduction,para-MBA modified Au(denoted as para-Au/C)displayed the highest catalytic activity among these Au-based catalysts.At-1.0 V versus reversible hydrogen electrode(vs RHE),para-Au/C exhibited a partial current density for NH_(3)of 472.2 mA cm^(-2),which was 1.7 times that of the pristine Au catalyst.Meanwhile,the Faradaic efficiency(FE)for NH_(3)reached 98.7%at-1.0 V vs RHE for para-Au/C.The modification of para-MBA significantly improved the intrinsic activity of the Au/C catalyst,thus accelerating the kinetics of NO_(3)-reduction and giving rise to a high NH_(3)yield rate of para-Au/C.
基金This work was supported in part by the National Natural Science Foundation of China （NSFC） （Nos. 21233005 and 91433204） and Fundamental Research Funds for the Central Universities （No. 2014FZA3006）.
文摘Using CdSe/CdS core/shell nanocrystals with 1-10 monolayers of CdS shell as the model system, we studied effects of thiol ligands on optical properties of the nanocrystals. The core/shell nanocrystals with original ligands possessed near unity photoluminescence （PL） quantum yield and single-exponential PL decay dynamics. The effects of thiol ligands on optical properties were found to depend on the shell thickness, environment （with/without oxygen）, and excitation power （single- or multi-exciton）. Systematic and quantitative results reported in this work should provide necessary information for fundamental understanding and technical applications of quantum dots （QDs） coated with thiol ligands.
