Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical...Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.展开更多
Organic electrosynthesis as an emerging green and advantageous alternative to traditional synthetic methods has achieved remarkable progress in recent years because sustainable electricity can be employed as traceless...Organic electrosynthesis as an emerging green and advantageous alternative to traditional synthetic methods has achieved remarkable progress in recent years because sustainable electricity can be employed as traceless redox agents. To surmount the over-oxidation/reduction issues of direct electrolysis,mediated or indirect electrochemical processes are attaining remarkable significance and promoting the selectivity of products. Molecular electrocatalysts, benefiting from the easily electronic and steric modulation, suffers from readily degradation issue in most cases. Remarkably, heterogeneous catalysts have drawn more attention due to their high activity, stability, and recyclability. Hence, in this review, the most recent growth of heterogeneous catalysts modified electrodes for organic electrosynthesis were summarized, highlighting structural optimization and electrochemical performance of these materials as well as reaction mechanism. Furthermore, key challenges and future directions in this area were also discussed.展开更多
Compared with general redox chemistry,electrochemistry using the electron as a potent,controllable,yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving select...Compared with general redox chemistry,electrochemistry using the electron as a potent,controllable,yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis.With its environmentally benign features gradually being uncovered and studied,organic electrosynthesis is currently undergoing a revival and becoming a rapidly growing area within the synthetic community.Among the electrochemical transformations,the anodically enabled ones have been far more extensively exploited than those driven by cathodic reduction,although both approaches are conceptually attractive.To stimulate the development of cathodically enabled organic reactions,this review summarizes the recently developed reductive electrosynthetic protocols,discussing and highlighting reaction features,substrate scopes,applications,and plausible mechanisms to reveal the recent trends in this area.Herein,cathodic reduction-enabled preparative organic transformations are categorized into four types:reduction of(1)unsaturated hydrocarbons,(2)heteroatom-containing carbon-based unsaturated systems,(3)saturated C-hetero or C–C polar/strained bonds,and(4)hetero-hetero linkages.Apart from net electroreductive reactions,a few examples of reductive photo-electrosynthesis as well as paired electrolysis are also introduced,which offer opportunities to overcome certain limitations and improve synthetic versatility.The electrochemically driven,transition metal-catalyzed reductive cross-couplings that have been comprehensively discussed in several other recent reviews are not included here.展开更多
Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineere...Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.展开更多
The direct electrochemical synthesis of metal alkoxides [Ti（OEt）4, Ti（OPr-i）4, Ti（OBu）4, Ti（OEt）2（acac）, Cu（OEt）2, Cu（OBu）2, Mg（OEt）2 and Ni（OEt）2] were studied by anode dissolution of metals in abso...The direct electrochemical synthesis of metal alkoxides [Ti（OEt）4, Ti（OPr-i）4, Ti（OBu）4, Ti（OEt）2（acac）, Cu（OEt）2, Cu（OBu）2, Mg（OEt）2 and Ni（OEt）2] were studied by anode dissolution of metals in absolute ethanol in the presence of a conductive additives. The anodic behaviour of Ti electrode in ethanol was investigated by using cyclic voltammetry（CV）. These metal alkoxides were characterized by FTIR spectra. The results show that direct electrochemical synthesis of metal alkoxides have a high current efficiency and electrolysis yield. These alkoxides have a high purity and can be directly used as the precursor of nanosize oxides prepared by sol-gel procedure. The anodic behaviour of Ti electrode in alcohol is markedly the feature of the pitting corrosion. The passivation of Ti anode would occur in the presence of trace water.展开更多
基金supported by the National Natural Science Foundation of China (21821002, 21772222, and 91956112)Chinese Academy of Sciences (XDB20000000)Science and Technology Commission of Shanghai Municipality (18JC1415600 and 20JC1417100)。
文摘Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.
基金the financial support from the National Natural Science Foundation of China (No. 22171154)the Youth Innovative Talents Recruitment and Cultivation Program of Shandong Higher Education+2 种基金the Natural Science Foundation of Shandong Province (Nos. ZR^(2)020QB114, ZR^(2)020QB008 and ZR^(2)019BB031)Jinan Science&Technology Bureau (No. 2021GXRC080)The project supported by the Foundation (No. ZZ20190312) of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology (Shandong Academy of Sciences)。
文摘Organic electrosynthesis as an emerging green and advantageous alternative to traditional synthetic methods has achieved remarkable progress in recent years because sustainable electricity can be employed as traceless redox agents. To surmount the over-oxidation/reduction issues of direct electrolysis,mediated or indirect electrochemical processes are attaining remarkable significance and promoting the selectivity of products. Molecular electrocatalysts, benefiting from the easily electronic and steric modulation, suffers from readily degradation issue in most cases. Remarkably, heterogeneous catalysts have drawn more attention due to their high activity, stability, and recyclability. Hence, in this review, the most recent growth of heterogeneous catalysts modified electrodes for organic electrosynthesis were summarized, highlighting structural optimization and electrochemical performance of these materials as well as reaction mechanism. Furthermore, key challenges and future directions in this area were also discussed.
基金Beijing Normal University is acknowledged for providing financial support.
文摘Compared with general redox chemistry,electrochemistry using the electron as a potent,controllable,yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis.With its environmentally benign features gradually being uncovered and studied,organic electrosynthesis is currently undergoing a revival and becoming a rapidly growing area within the synthetic community.Among the electrochemical transformations,the anodically enabled ones have been far more extensively exploited than those driven by cathodic reduction,although both approaches are conceptually attractive.To stimulate the development of cathodically enabled organic reactions,this review summarizes the recently developed reductive electrosynthetic protocols,discussing and highlighting reaction features,substrate scopes,applications,and plausible mechanisms to reveal the recent trends in this area.Herein,cathodic reduction-enabled preparative organic transformations are categorized into four types:reduction of(1)unsaturated hydrocarbons,(2)heteroatom-containing carbon-based unsaturated systems,(3)saturated C-hetero or C–C polar/strained bonds,and(4)hetero-hetero linkages.Apart from net electroreductive reactions,a few examples of reductive photo-electrosynthesis as well as paired electrolysis are also introduced,which offer opportunities to overcome certain limitations and improve synthetic versatility.The electrochemically driven,transition metal-catalyzed reductive cross-couplings that have been comprehensively discussed in several other recent reviews are not included here.
基金support from the Natural Science Foundation of Liaoning Province(general program)(2020-MS-137)T.J.White would like to thank the MOE2019-T2-2-032 grant and Monetary Academic Resources for Research Grant 001561-00001 in Nanyang Technological University,Singapore+9 种基金T.Ma would like to thank the National Natural Science Foundation of China(Nos.52071171,52202248)Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)F.Wei would like to thank the A^(*)STAR career development fund C210112054Singapore structural metal alloy program grant No.A18b1B0061.A.K.Cheetham would like to thank the Ras al Khaimah Centre for Advanced Materials.
文摘Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.
基金supported by the National Natural Science Foundation of China (No. 22225101)Fundamental Research Funds for the Central Universities (No. 20720210003)。
基金This work was financially supported by the National Key R&D Program of China(No.2021YFA1500100)the NSF of China(Grants 21821002,21772222,and 91956112)the S&TCSM of Shanghai(Grants 20XD1425100 and 20JC1417100).
文摘The direct electrochemical synthesis of metal alkoxides [Ti（OEt）4, Ti（OPr-i）4, Ti（OBu）4, Ti（OEt）2（acac）, Cu（OEt）2, Cu（OBu）2, Mg（OEt）2 and Ni（OEt）2] were studied by anode dissolution of metals in absolute ethanol in the presence of a conductive additives. The anodic behaviour of Ti electrode in ethanol was investigated by using cyclic voltammetry（CV）. These metal alkoxides were characterized by FTIR spectra. The results show that direct electrochemical synthesis of metal alkoxides have a high current efficiency and electrolysis yield. These alkoxides have a high purity and can be directly used as the precursor of nanosize oxides prepared by sol-gel procedure. The anodic behaviour of Ti electrode in alcohol is markedly the feature of the pitting corrosion. The passivation of Ti anode would occur in the presence of trace water.
