Recently,significant research has been conducted on the conversion of carbon dioxide(CO_(2))into value-added chemicals.With the decreasing cost of clean electricity,electrochemical methods have emerged as potential ap...Recently,significant research has been conducted on the conversion of carbon dioxide(CO_(2))into value-added chemicals.With the decreasing cost of clean electricity,electrochemical methods have emerged as potential approaches for converting and fixing CO_(2).Organic electrochemical synthesis is a promising method for utilizing CO_(2)because it transforms CO_(2)into higher-value chemicals.This review introduces the research aspects of CO_(2)conversion and the mechanisms of CO_(2)organic electrocarboxylation reactions.Recent progress in electrocarboxylation with CO_(2)is discussed,considering organic substrates and cathode types under different reaction mechanisms.Finally,the challenges and prospects in this field are highlighted with the aim of further promoting the fundamental understanding of CO_(2)organic electrocarboxylation.展开更多
Electrochemical dicarboxylation of styrene in the presence of atmospheric pressure of CO2 with a Ti cathode and a Mg rod anode readily took place efficiently in an acetonitrile solution containing 0.1 mol·L^-1 te...Electrochemical dicarboxylation of styrene in the presence of atmospheric pressure of CO2 with a Ti cathode and a Mg rod anode readily took place efficiently in an acetonitrile solution containing 0.1 mol·L^-1 tetraethylammonium bromide to give 2-phenylsuccinic acid. Influences of the nature of the electrodes, the current density, the passed charge and the temperature on electrolysis were studied to optimize the electrolytic conditions, with the maximal isolated yield to be 86.07%. The mechanism of the elelctrocarboxylation process has been studied by cyclic voltammetry.展开更多
Electrolytic fixation of CO2 was investigated by electrocarboxylation of organic halides (RX), and four esters (I, II, III, IV) were obtained in moderate yields. Electrochemical reduction esterifications of RX in the ...Electrolytic fixation of CO2 was investigated by electrocarboxylation of organic halides (RX), and four esters (I, II, III, IV) were obtained in moderate yields. Electrochemical reduction esterifications of RX in the presence of CO2 were carried out on nanocrystalline TiO2-Pt electrode. The electrochemical behavior of RX in the presence of CO2 was investigated by the technique of cyclic voltammetry, and the probable reaction mechanism was proposed.展开更多
Benzil,1,2-diphenylethane-1,2-dione, was used as an excellent electrocatalyst for reduction of carbon dioxide, CO. The reduction overpotential of COwas reduced about 900 m V in the presence of a benzil mediator. The c...Benzil,1,2-diphenylethane-1,2-dione, was used as an excellent electrocatalyst for reduction of carbon dioxide, CO. The reduction overpotential of COwas reduced about 900 m V in the presence of a benzil mediator. The chemical reaction of the product of the electrocatalytic reduction of CO,(activated CO,CO) with pyridine at a glassy carbon electrode, GCE, surface and in an acetonitrile-ButNClOsolution was investigated by cyclic voltammetry, chronoamperometry and controlled potential coulometry.By chronoamperometry, the catalytic rate constant, k, for the electron transfer between benzil and COwas obtained as 8.1 ± 0.4 Ms. The results indicate that pyridine has a strong interaction with the activated CO. The coulometry method was used to obtain the product of the pyridine chemical reaction with CO. The spectral characterizations of FTIR,H andC NMR of the coulometry experiment product proved that the pyridine anion radical, Py, was carboxylated by CO, and isonicotinic acid is the final major product.展开更多
以烯丙基氯和CO_(2)为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸。其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征。为提高目标产物3-丁烯酸的产率,本文分析了阴...以烯丙基氯和CO_(2)为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸。其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征。为提高目标产物3-丁烯酸的产率,本文分析了阴极材料电镀时间、溶剂、支持电解质、电流密度、通电量和温度等因素对烯丙基氯电羧化反应的影响。在25℃反应温度、90 min Cu-In复合材料电镀时间、MeCN溶剂、四乙基碘化铵(TEAI)支持盐、3.0 F/mol电解电量、8 mA·cm^(2)电流密度的优化条件下,3-丁烯酸的产率可达56%。此外,在优化条件下还考察了烯丙基溴、肉桂基氯、肉桂基溴、3-氯-2-甲基丙烯等烯丙基卤代物的电羧化反应,结果表明均可得到相应的羧酸,意味着Cu-In双金属电极对催化烯丙基卤代物电羧化反应具一定的普适性。展开更多
Electrocarboxylation of anthrone in the presence of CO2 to anthrance-9-carboxylic acid directly was carried out. The electroreduction behavior of anthrone was examined by cyclic voltammetry in the absence and presence...Electrocarboxylation of anthrone in the presence of CO2 to anthrance-9-carboxylic acid directly was carried out. The electroreduction behavior of anthrone was examined by cyclic voltammetry in the absence and presence of CO2. Then the influences of the supporting electrolytes, temperature, electrode material and anthrone concentration on the carboxylation yield were investigated. Under the optimized conditions, anthrancene-9-carboxylic acid was obtained in a good yield（96.1%）.展开更多
The catalyzation of CoTPP for electrocarboxylation of alkyl halides, alkenes and ketones with CO_2 are studied. The electrocarboxylation of these organic compounds with CO_2 in the presenec of catalyst can occur at mo...The catalyzation of CoTPP for electrocarboxylation of alkyl halides, alkenes and ketones with CO_2 are studied. The electrocarboxylation of these organic compounds with CO_2 in the presenec of catalyst can occur at more positive potential than that of no catalyst. The products of electrocarboxylation were identified by UV, IR and GC-MS. The electrocarboxylation mechanisms of different organic compounds are discussed.展开更多
The effects of various factors on the electrocarboxylation of organic compounds with carbon dioxide catalyzed by metalloporphyrin are studied.The optimal potential of electrocar- boxylation is -1.6 V(vs.SCE).A weak pr...The effects of various factors on the electrocarboxylation of organic compounds with carbon dioxide catalyzed by metalloporphyrin are studied.The optimal potential of electrocar- boxylation is -1.6 V(vs.SCE).A weak protic solvent methanol can enhance catalytic activity. Tetrabutylammonium iodide is the best one of five electrolytes.The yields and current efficiencies of electrocarboxylation are increased slowly as the concentration of catalyst increases.展开更多
Electrosynthesis and carbon dioxide(CO_(2))utilization both have gained interest in recent years due to the efforts to alleviate the climate crisis.Significant progress in the field of electrochemical carboxylation us...Electrosynthesis and carbon dioxide(CO_(2))utilization both have gained interest in recent years due to the efforts to alleviate the climate crisis.Significant progress in the field of electrochemical carboxylation using CO_(2) or electrocarboxylation of organic substrates,particularly organohalides and alkenes,has been made in the past decade.Different components of electrocarboxylation experimental setup as well as the understandings of the mechanism play an important role in the success of the carboxylate syntheses.In this review,overview of the proposed mechanisms and the electrochemical setup are described.The significance of electrochemical components,such as the effect of different cathodes,sacrificial anode materials,and other additives,are explained.The examples of electrocarboxylation for both organohalides and olefins are provided.Lastly,the current trends in the field and future directions are discussed.展开更多
The electrocarboxylation reaction is an attractive means to convert CO_(2) into valuable chemicals under ambient conditions,while it still suffers from low efficiency due to the high stability of CO_(2).In this work,w...The electrocarboxylation reaction is an attractive means to convert CO_(2) into valuable chemicals under ambient conditions,while it still suffers from low efficiency due to the high stability of CO_(2).In this work,we report a double activation strategy for simultaneously activating CO_(2) and acetophenone by silver-doped CeO_(2)(Ag-CeO_(2)) nanowires,featuring as an effective electrocatalyst for electrocarboxylation of acetophenone with CO_(2).Compared to the Ag foil,Ag nanoparticles and CeO_(2) nanowires,the Ag-CeO_(2)nanowire catalyst allowed to reduce the onset potential difference between CO_(2) and acetophenone activation,thus enabling efficient electrocarboxylation to form 2-phenyllactic acid.The Faradaic efficiency for producing 2-phenyllactic acid reached 91%at−1.8 V versus Ag/AgI.This double activation strategy of activating both CO_(2)and organic substrate molecules can benefit the catalyst design to improve activities and selectivities in upgrading CO_(2)fixation for higher-value electrocarboxylation.展开更多
A novel electrochromic display composed of polymeric solid electrolyte and ferroin electroactive species has been assembled, which presents a reversible variation of the color between light blue and red when a potenti...A novel electrochromic display composed of polymeric solid electrolyte and ferroin electroactive species has been assembled, which presents a reversible variation of the color between light blue and red when a potential of 0.98 and 0.75 V is applied respectively. The results indicate that the response speed is increased by lowering the concentration of ferroin without decreasing color contrast.展开更多
The effects of peptides, amino acids and organic bases as axial ligands on reaction activities in the electrocarboxylation of benzyl chloride with CO2 catalyzed by CoTPP are reported. Imidazole, peptide containing -SH...The effects of peptides, amino acids and organic bases as axial ligands on reaction activities in the electrocarboxylation of benzyl chloride with CO2 catalyzed by CoTPP are reported. Imidazole, peptide containing -SH and amino acid containing imi dazyl can enhance the catalytic activity. As an axial ligand, imidazole is the best one, it can make the current efficency of electrocarboxylation catalyzed by CoTPP rising about 23%. The effects of different amount of imidazole on CoTPP’s catalytic activities have been studied, and the cause of these effects have been explaind predrinarily.展开更多
The effects of peptides,amino acids and organic bases as an axial ligand on reaction ac- tivities in the electrocarboxylation of benzyl chloride with CO_2 catalyzed by CoTPP are reported. The imidazole organic base,pe...The effects of peptides,amino acids and organic bases as an axial ligand on reaction ac- tivities in the electrocarboxylation of benzyl chloride with CO_2 catalyzed by CoTPP are reported. The imidazole organic base,peptide containing —SH and amino acid containing imidazolyl en- hance the catalytic activity.The effect of imidazole amounts on the catalytic activity of CoTPP is studied.展开更多
基金supported by the National Natural Science Foundation of China(22379054)and start-up funding from Jiangnan University.
文摘Recently,significant research has been conducted on the conversion of carbon dioxide(CO_(2))into value-added chemicals.With the decreasing cost of clean electricity,electrochemical methods have emerged as potential approaches for converting and fixing CO_(2).Organic electrochemical synthesis is a promising method for utilizing CO_(2)because it transforms CO_(2)into higher-value chemicals.This review introduces the research aspects of CO_(2)conversion and the mechanisms of CO_(2)organic electrocarboxylation reactions.Recent progress in electrocarboxylation with CO_(2)is discussed,considering organic substrates and cathode types under different reaction mechanisms.Finally,the challenges and prospects in this field are highlighted with the aim of further promoting the fundamental understanding of CO_(2)organic electrocarboxylation.
基金Project supported by the National Natural Science Foundation of China （No. 20573037） and the Natural Science Foundation of Shanghai （No 05JC 1470）.
文摘Electrochemical dicarboxylation of styrene in the presence of atmospheric pressure of CO2 with a Ti cathode and a Mg rod anode readily took place efficiently in an acetonitrile solution containing 0.1 mol·L^-1 tetraethylammonium bromide to give 2-phenylsuccinic acid. Influences of the nature of the electrodes, the current density, the passed charge and the temperature on electrolysis were studied to optimize the electrolytic conditions, with the maximal isolated yield to be 86.07%. The mechanism of the elelctrocarboxylation process has been studied by cyclic voltammetry.
基金Project supported by the Natural Science Foundation of the Anhui province in China (No. 00045317).
文摘Electrolytic fixation of CO2 was investigated by electrocarboxylation of organic halides (RX), and four esters (I, II, III, IV) were obtained in moderate yields. Electrochemical reduction esterifications of RX in the presence of CO2 were carried out on nanocrystalline TiO2-Pt electrode. The electrochemical behavior of RX in the presence of CO2 was investigated by the technique of cyclic voltammetry, and the probable reaction mechanism was proposed.
文摘Benzil,1,2-diphenylethane-1,2-dione, was used as an excellent electrocatalyst for reduction of carbon dioxide, CO. The reduction overpotential of COwas reduced about 900 m V in the presence of a benzil mediator. The chemical reaction of the product of the electrocatalytic reduction of CO,(activated CO,CO) with pyridine at a glassy carbon electrode, GCE, surface and in an acetonitrile-ButNClOsolution was investigated by cyclic voltammetry, chronoamperometry and controlled potential coulometry.By chronoamperometry, the catalytic rate constant, k, for the electron transfer between benzil and COwas obtained as 8.1 ± 0.4 Ms. The results indicate that pyridine has a strong interaction with the activated CO. The coulometry method was used to obtain the product of the pyridine chemical reaction with CO. The spectral characterizations of FTIR,H andC NMR of the coulometry experiment product proved that the pyridine anion radical, Py, was carboxylated by CO, and isonicotinic acid is the final major product.
文摘以烯丙基氯和CO_(2)为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸。其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征。为提高目标产物3-丁烯酸的产率,本文分析了阴极材料电镀时间、溶剂、支持电解质、电流密度、通电量和温度等因素对烯丙基氯电羧化反应的影响。在25℃反应温度、90 min Cu-In复合材料电镀时间、MeCN溶剂、四乙基碘化铵(TEAI)支持盐、3.0 F/mol电解电量、8 mA·cm^(2)电流密度的优化条件下,3-丁烯酸的产率可达56%。此外,在优化条件下还考察了烯丙基溴、肉桂基氯、肉桂基溴、3-氯-2-甲基丙烯等烯丙基卤代物的电羧化反应,结果表明均可得到相应的羧酸,意味着Cu-In双金属电极对催化烯丙基卤代物电羧化反应具一定的普适性。
基金Supported by the National Natural Science Foundation of China(No.20973065)the"Chen Guang"Project Supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation,China(No.10CG26)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20100076120020)the Foundation of Outstanding Yong Talent in University of Anhui Province,China(No.2010SQRL042)
文摘Electrocarboxylation of anthrone in the presence of CO2 to anthrance-9-carboxylic acid directly was carried out. The electroreduction behavior of anthrone was examined by cyclic voltammetry in the absence and presence of CO2. Then the influences of the supporting electrolytes, temperature, electrode material and anthrone concentration on the carboxylation yield were investigated. Under the optimized conditions, anthrancene-9-carboxylic acid was obtained in a good yield（96.1%）.
基金This work is supported by the National Natural Science Foundation of China
文摘The catalyzation of CoTPP for electrocarboxylation of alkyl halides, alkenes and ketones with CO_2 are studied. The electrocarboxylation of these organic compounds with CO_2 in the presenec of catalyst can occur at more positive potential than that of no catalyst. The products of electrocarboxylation were identified by UV, IR and GC-MS. The electrocarboxylation mechanisms of different organic compounds are discussed.
文摘The effects of various factors on the electrocarboxylation of organic compounds with carbon dioxide catalyzed by metalloporphyrin are studied.The optimal potential of electrocar- boxylation is -1.6 V(vs.SCE).A weak protic solvent methanol can enhance catalytic activity. Tetrabutylammonium iodide is the best one of five electrolytes.The yields and current efficiencies of electrocarboxylation are increased slowly as the concentration of catalyst increases.
基金project is supported by Mahidol University (Basic Research Fund: fiscal year 2021)the Young Scientist Scholarship from Faculty of Science, Mahidol University and Research Fellowship from Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University
文摘Electrosynthesis and carbon dioxide(CO_(2))utilization both have gained interest in recent years due to the efforts to alleviate the climate crisis.Significant progress in the field of electrochemical carboxylation using CO_(2) or electrocarboxylation of organic substrates,particularly organohalides and alkenes,has been made in the past decade.Different components of electrocarboxylation experimental setup as well as the understandings of the mechanism play an important role in the success of the carboxylate syntheses.In this review,overview of the proposed mechanisms and the electrochemical setup are described.The significance of electrochemical components,such as the effect of different cathodes,sacrificial anode materials,and other additives,are explained.The examples of electrocarboxylation for both organohalides and olefins are provided.Lastly,the current trends in the field and future directions are discussed.
文摘The electrocarboxylation reaction is an attractive means to convert CO_(2) into valuable chemicals under ambient conditions,while it still suffers from low efficiency due to the high stability of CO_(2).In this work,we report a double activation strategy for simultaneously activating CO_(2) and acetophenone by silver-doped CeO_(2)(Ag-CeO_(2)) nanowires,featuring as an effective electrocatalyst for electrocarboxylation of acetophenone with CO_(2).Compared to the Ag foil,Ag nanoparticles and CeO_(2) nanowires,the Ag-CeO_(2)nanowire catalyst allowed to reduce the onset potential difference between CO_(2) and acetophenone activation,thus enabling efficient electrocarboxylation to form 2-phenyllactic acid.The Faradaic efficiency for producing 2-phenyllactic acid reached 91%at−1.8 V versus Ag/AgI.This double activation strategy of activating both CO_(2)and organic substrate molecules can benefit the catalyst design to improve activities and selectivities in upgrading CO_(2)fixation for higher-value electrocarboxylation.
文摘A novel electrochromic display composed of polymeric solid electrolyte and ferroin electroactive species has been assembled, which presents a reversible variation of the color between light blue and red when a potential of 0.98 and 0.75 V is applied respectively. The results indicate that the response speed is increased by lowering the concentration of ferroin without decreasing color contrast.
文摘The effects of peptides, amino acids and organic bases as axial ligands on reaction activities in the electrocarboxylation of benzyl chloride with CO2 catalyzed by CoTPP are reported. Imidazole, peptide containing -SH and amino acid containing imi dazyl can enhance the catalytic activity. As an axial ligand, imidazole is the best one, it can make the current efficency of electrocarboxylation catalyzed by CoTPP rising about 23%. The effects of different amount of imidazole on CoTPP’s catalytic activities have been studied, and the cause of these effects have been explaind predrinarily.
文摘The effects of peptides,amino acids and organic bases as an axial ligand on reaction ac- tivities in the electrocarboxylation of benzyl chloride with CO_2 catalyzed by CoTPP are reported. The imidazole organic base,peptide containing —SH and amino acid containing imidazolyl en- hance the catalytic activity.The effect of imidazole amounts on the catalytic activity of CoTPP is studied.
