Engineering the electronic properties of catalysts to target intermediate adsorption energy as well as harvest high selectivity represents a promising strategy to design advanced electrocatalysts for efficient CO_(2) ...Engineering the electronic properties of catalysts to target intermediate adsorption energy as well as harvest high selectivity represents a promising strategy to design advanced electrocatalysts for efficient CO_(2) electroreduction.Herein,a synergistical tuning on the electronic structure of the Cd Se nanorods is proposed for boosting electrochemical reduction of CO_(2) .The synergy of Ag doping coupled with Se vacancies tuned the electronic structure of the CdSe nanorods,which shows the metalloid characterization and thereby the accelerated electron transfer of CO_(2) electroreduction.Operando synchrotron radiation Fourier transform infrared spectroscopy and theoretical simulation revealed that the Ag doping and Se vacancies accelerated the CO_(2) activation process and lowered the energy barrier for the conversion from CO_(2) to;COOH;as a result,the performance of CO_(2) electroreduction was enhanced.The as-obtained metalloid Ag-doped CdSe nanorods exhibited a 2.7-fold increment in current density and 1.9-fold Faradaic efficiency of CO compared with the pristine CdSe nanorod.展开更多
Actinide-based catalysts have been regarded as promising candidates for N_(2) fixation owing to their unique 5f orbital with flexible oxidation states.Herein,we report for the first time the dispersion of uranium(U)si...Actinide-based catalysts have been regarded as promising candidates for N_(2) fixation owing to their unique 5f orbital with flexible oxidation states.Herein,we report for the first time the dispersion of uranium(U)single atoms on TiO_(2) nanosheets via oxygen vacancy confinement for N_(2) electroreduction.The single-atom U catalyst exhibited a high NH_(3) yield of 40.57μg h^(-1) mg^(-1),with a reasonably high Faraday efficiency of 25.77%,ranking first among the reported nitrogen-free catalysts.Isotope-labeling operando synchrotron infrared spectroscopy verifies that the key*N_(2)H_(y) intermediate species was derived from the N_(2) gas of the feed.By using operando X-ray absorption spectroscopy,we found enhanced metal-support interaction between U single atoms and TiO_(2) lattice with more U-O_(latt) coordination under working conditions.Theoretical simulations suggest that the evolved 1O_(ads)-U-4O_(latt) moieties act as a critical electronfeedback center,lowering the thermodynamic energy barrier for the N_(2) dissociation and the first hydrogenation step.This work provides the possibility of tailoring the interaction between metal active sites and supports for designing high-performance actinide-based single-atom catalysts.展开更多
基金supported by the National Natural Science Foundation of China(12025505 and 21873050)China Ministry of Science and Technology(2017YFA0208300)+1 种基金the Open Fund Project of State Key Laboratory of Environmentally Friendly Energy Materials(20KFHG08)the Youth Innovation Promotion Association CAS(CX2310007007 and CX2310000091)。
文摘Engineering the electronic properties of catalysts to target intermediate adsorption energy as well as harvest high selectivity represents a promising strategy to design advanced electrocatalysts for efficient CO_(2) electroreduction.Herein,a synergistical tuning on the electronic structure of the Cd Se nanorods is proposed for boosting electrochemical reduction of CO_(2) .The synergy of Ag doping coupled with Se vacancies tuned the electronic structure of the CdSe nanorods,which shows the metalloid characterization and thereby the accelerated electron transfer of CO_(2) electroreduction.Operando synchrotron radiation Fourier transform infrared spectroscopy and theoretical simulation revealed that the Ag doping and Se vacancies accelerated the CO_(2) activation process and lowered the energy barrier for the conversion from CO_(2) to;COOH;as a result,the performance of CO_(2) electroreduction was enhanced.The as-obtained metalloid Ag-doped CdSe nanorods exhibited a 2.7-fold increment in current density and 1.9-fold Faradaic efficiency of CO compared with the pristine CdSe nanorod.
基金supported by the National Key R&D Program of China(2021YFA1600800)the National Natural Science Foundation of China(12025505,21976147,and 22106126)+3 种基金the University of China Innovation Program of Anhui Province(GXXT-2020-053)the Youth Innovation Promotion Association CAS(2015366)Open Fund Project of State Key Laboratory of Environmentally Friendly Energy Materials(20kfhg08)Collaborative Innovation Program of Hefei Science Center(2021HSC-CIP006)。
文摘Actinide-based catalysts have been regarded as promising candidates for N_(2) fixation owing to their unique 5f orbital with flexible oxidation states.Herein,we report for the first time the dispersion of uranium(U)single atoms on TiO_(2) nanosheets via oxygen vacancy confinement for N_(2) electroreduction.The single-atom U catalyst exhibited a high NH_(3) yield of 40.57μg h^(-1) mg^(-1),with a reasonably high Faraday efficiency of 25.77%,ranking first among the reported nitrogen-free catalysts.Isotope-labeling operando synchrotron infrared spectroscopy verifies that the key*N_(2)H_(y) intermediate species was derived from the N_(2) gas of the feed.By using operando X-ray absorption spectroscopy,we found enhanced metal-support interaction between U single atoms and TiO_(2) lattice with more U-O_(latt) coordination under working conditions.Theoretical simulations suggest that the evolved 1O_(ads)-U-4O_(latt) moieties act as a critical electronfeedback center,lowering the thermodynamic energy barrier for the N_(2) dissociation and the first hydrogenation step.This work provides the possibility of tailoring the interaction between metal active sites and supports for designing high-performance actinide-based single-atom catalysts.
