Sodium-carbon dioxide(Na-CO_(2))batteries are regarded as promising energy storage technologies because of their impressive theoretical energy density and CO_(2)reutilization,but their practical applications are restr...Sodium-carbon dioxide(Na-CO_(2))batteries are regarded as promising energy storage technologies because of their impressive theoretical energy density and CO_(2)reutilization,but their practical applications are restricted by uncontrollable sodium dendrite growth and poor electrochemical kinetics of CO_(2)cathode.Constructing suitable multifunctional electrodes for dendritefree anodes and kinetics-enhanced CO_(2)cathodes is considered one of the most important ways to advance the practical application of Na-CO_(2)batteries.Herein,RuO2 nanoparticles encapsulated in carbon paper(RuCP)are rationally designed and employed as both Na anode host and CO_(2)cathode in Na-CO_(2)batteries.The outstanding sodiophilicity and high catalytic activity of RuCP electrodes can simultaneously contribute to homogenous Na+distribution and dendrite-free sodium structure at the anode,as well as strengthen discharge and charge kinetics at the cathode.The morphological evolution confirmed the uniform deposition of Na on RuCP anode with dense and flat interfaces,delivering enhanced Coulombic efficiency of 99.5%and cycling stability near 1500 cycles.Meanwhile,Na-CO_(2)batteries with RuCP cathode demonstrated excellent cycling stability(>350 cycles).Significantly,implementation of a dendrite-free RuCP@Na anode and catalytic-site-rich RuCP cathode allowed for the construction of a symmetric Na-CO_(2)battery with long-duration cyclability,offering inspiration for extensive practical uses of Na-CO_(2)batteries.展开更多
The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added valu...The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.展开更多
Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand ...Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand impedes the adsorption and activation of CO_(2)molecules in practical applications.Here,a ligand modulation technology is employed to enhance the photocatalytic CO_(2)reduction activity of lead-free Cs_(2)AgInCl_(6)microcrystals(MCs).The Cs_(2)AgInCl_(6)MCs passivated by Oleic acid(OLA)and Octanoic acid(OCA)are used for photocatalytic CO_(2)reduction.The results show that the surface defects and electronic properties of Cs_(2)AgInCl_(6)MCs can be adjusted through ligand modulation.Compared with the OLA-Cs_(2)AgInCl_(6),the OCA-Cs_(2)AgInCl_(6)catalyst demonstrated a significant improvement in the catalytic yield of CO and CH_(4).The CO and CH_(4)catalytic yields of OCA-Cs_(2)AgInCl_(6)reached 171.88 and34.15μmol g^(-1)h^(-1)which were 2.03 and 12.98 times higher than those of OLA-Cs_(2)AgInCl_(6),and the total electron consumption rate of OCA-Cs_(2)AgInCl_(6)was 615.2μmol g^(-1)h^(-1)which was 3.25 times higher than that of OLA-Cs_(2)AgInCl_(6).Furthermore,in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs_(2)AgInCl_(6)MCs induced by ligand modulation.This study illustrates the potential of lead-free Cs_(2)AgInCl_(6)MCs for efficient photocatalytic CO_(2)reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.展开更多
At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organ...At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.展开更多
基金support from the German Research Foundation(DFG:LE 2249/15-1)the Sino-German Center for Research Promotion(GZ1579)support from the China Scholarship Council(No.202106370041)
文摘Sodium-carbon dioxide(Na-CO_(2))batteries are regarded as promising energy storage technologies because of their impressive theoretical energy density and CO_(2)reutilization,but their practical applications are restricted by uncontrollable sodium dendrite growth and poor electrochemical kinetics of CO_(2)cathode.Constructing suitable multifunctional electrodes for dendritefree anodes and kinetics-enhanced CO_(2)cathodes is considered one of the most important ways to advance the practical application of Na-CO_(2)batteries.Herein,RuO2 nanoparticles encapsulated in carbon paper(RuCP)are rationally designed and employed as both Na anode host and CO_(2)cathode in Na-CO_(2)batteries.The outstanding sodiophilicity and high catalytic activity of RuCP electrodes can simultaneously contribute to homogenous Na+distribution and dendrite-free sodium structure at the anode,as well as strengthen discharge and charge kinetics at the cathode.The morphological evolution confirmed the uniform deposition of Na on RuCP anode with dense and flat interfaces,delivering enhanced Coulombic efficiency of 99.5%and cycling stability near 1500 cycles.Meanwhile,Na-CO_(2)batteries with RuCP cathode demonstrated excellent cycling stability(>350 cycles).Significantly,implementation of a dendrite-free RuCP@Na anode and catalytic-site-rich RuCP cathode allowed for the construction of a symmetric Na-CO_(2)battery with long-duration cyclability,offering inspiration for extensive practical uses of Na-CO_(2)batteries.
基金supported by the National Key R&D Program of China (2018YFA0901700)National Natural Science Foundation of China (22278241)+1 种基金a grant from the Institute Guo Qiang, Tsinghua University (2021GQG1016)Department of Chemical Engineering-iBHE Joint Cooperation Fund。
文摘The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.
基金the National Natural Science Foundation of China(Grant No.62375032)the Natural Science Foundation of Chongqing(Grant No.CSTB2023TIADKPX0017)+2 种基金the Open Fund of the State Key Laboratory of High Field Laser Physics(Shanghai Institute of Optics and Fine Mechanics)the China Postdoctoral Science Foundation(Grant No.BX20230355)the Department of Education of Guizhou Province(Guizhou Teaching and Technology[2023]015)。
文摘Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand impedes the adsorption and activation of CO_(2)molecules in practical applications.Here,a ligand modulation technology is employed to enhance the photocatalytic CO_(2)reduction activity of lead-free Cs_(2)AgInCl_(6)microcrystals(MCs).The Cs_(2)AgInCl_(6)MCs passivated by Oleic acid(OLA)and Octanoic acid(OCA)are used for photocatalytic CO_(2)reduction.The results show that the surface defects and electronic properties of Cs_(2)AgInCl_(6)MCs can be adjusted through ligand modulation.Compared with the OLA-Cs_(2)AgInCl_(6),the OCA-Cs_(2)AgInCl_(6)catalyst demonstrated a significant improvement in the catalytic yield of CO and CH_(4).The CO and CH_(4)catalytic yields of OCA-Cs_(2)AgInCl_(6)reached 171.88 and34.15μmol g^(-1)h^(-1)which were 2.03 and 12.98 times higher than those of OLA-Cs_(2)AgInCl_(6),and the total electron consumption rate of OCA-Cs_(2)AgInCl_(6)was 615.2μmol g^(-1)h^(-1)which was 3.25 times higher than that of OLA-Cs_(2)AgInCl_(6).Furthermore,in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs_(2)AgInCl_(6)MCs induced by ligand modulation.This study illustrates the potential of lead-free Cs_(2)AgInCl_(6)MCs for efficient photocatalytic CO_(2)reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.
基金supported by National Natural Science Foundation of China (Nos. 22274039 and 22178089)Hunan Provincial Innovation Foundation for Postgraduate (No.CX20220392)。
文摘At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.
