Indirect electrocatalysis has emerged as a prevalent electrochemical technology in various small molecule conversions.This method offers solutions to challenges such as high overpotential,low selectivity,and electrode...Indirect electrocatalysis has emerged as a prevalent electrochemical technology in various small molecule conversions.This method offers solutions to challenges such as high overpotential,low selectivity,and electrode deactivation faced by conventional direct electrolysis.Redox mediators,acting as electron shuttles or catalytic species,play a key role in advancing indirect electrocatalytic systems.By establishing an efficient electron transfer pathway and substrate activation mechanism,these species significantly enhance reaction efficiency and product selectivity.Recently,novel indirect electrocatalysis systems mediated by reactive species have been established.This review comprehensively summarizes the latest advancements of reactive oxygen species,reactive halogen species,metal-based redox couples,and organic redox couples in indirect electrocatalytic transformations.Herein,particular emphasis is placed on discussing the selection criteria,reaction mechanisms,performance optimization strategies,and practical implementation of these mediators.Finally,a roadmap for future research is outlined,highlighting the integration of in situ characterization,computational screening,reactor engineering,and sustainability assessment to accelerate the development of efficient and sustainable indirect electrocatalytic systems.展开更多
The development of new strategy for environmentally friendly,cost-effective and large-scale electro-synthesis of anticancer drugs is highly desirable to replace high-cost traditional methods and realize high atomic ec...The development of new strategy for environmentally friendly,cost-effective and large-scale electro-synthesis of anticancer drugs is highly desirable to replace high-cost traditional methods and realize high atomic economy.GW 610,an antitumor agent with potent and selective anticancer activity against lung,colon,and breast cancer cell lines in real medical treatment processes,has a market price of~10……(7) USD/kg and calls for novel methods like electro-synthesis to reduce the cost.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of microwave-synthesized polyoxometalate-based metal-organic framework(MW-POMOF)that can converse S-S bond substrates into valuable C-S bond products like anticancer drug molecules(e.g.,GW 610).Specifically,the solid-phase MW-POMOF as heterogeneous redox mediator exhibits the excellent electrocatalytic efficiency for the formation of liquid-phase C-S bond products(yields up to 95%)coupling with the generation of gas-phase H_(2) product(~402μmol·g^(-1)·h^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the kilo-scale production(~1 kg in a batch experiment)of GW 610 at one thousandth of the market price(from~10^(7) to~3200 USD/kg).This work may inaugurate a new electrocatalytic avenue to explore porous crystalline materials in electrocatalysis field.展开更多
Inspired by high-entropy materials,it is a worthwhile direction to develop multi-metal integrated catalysts to study their synergistic catalytic effects in catalysis field.However,achieving this in porous crystalline ...Inspired by high-entropy materials,it is a worthwhile direction to develop multi-metal integrated catalysts to study their synergistic catalytic effects in catalysis field.However,achieving this in porous crystalline materials like covelent organic frameworks(COFs)for backend catalysis reactions remains scarce and challenging to date.Herein,a series of multimetal-variate COFs(i.e.,Quint-MMV-COF,Tetra-MMV-COF and Tri-n-MMV-COF(n=1,2 and 3))have been prepared that can be applied in indirect electrocatalysis.These MMV-COFs with advantages of multi-metal sites,porous structures and appropriate work function can serve as solid-phase redox mediators for the catalytic production of liquid-phase S-S bond products and gas-phase H_(2)product.Interestingly,the optimal Quint-MMV-COF presents excellent electrocatalytic efficiency for S-S bond products(yields up to 99%)and H_(2)(~1.62 mmol·g^(-1)·h^(-1))and can be readily recycled for 6 cycles.At the same time,1.52 g product with a yield of~92%can be obtained in the amplification reaction,showing much potential in industrial production.Validated by theoretical calculations,the synergistic effect of multi-metal sites can result in appropriate work function to boost the electron transfer and intermediate adsorption/conversion to achieve excellent overall S-S coupling efficiency.展开更多
基金the National Key R&D Program of China(grant no.2023YFA1507400)the National Natural Science Foundation of China(grant nos.22325805 and 22402107)+3 种基金the Haihe Laboratory of Sustainable Chemical Transformations(grant no.24HHWCSS00007)the Beijing Natural Science Foundation(grant no.JQ22003)the Tsinghua University Dushi Program,China Petroleum&Chemical Corporation(SINOPEC)Research Projects(grant no.223061)the Center of High Performance Computing,Tsinghua University.
文摘Indirect electrocatalysis has emerged as a prevalent electrochemical technology in various small molecule conversions.This method offers solutions to challenges such as high overpotential,low selectivity,and electrode deactivation faced by conventional direct electrolysis.Redox mediators,acting as electron shuttles or catalytic species,play a key role in advancing indirect electrocatalytic systems.By establishing an efficient electron transfer pathway and substrate activation mechanism,these species significantly enhance reaction efficiency and product selectivity.Recently,novel indirect electrocatalysis systems mediated by reactive species have been established.This review comprehensively summarizes the latest advancements of reactive oxygen species,reactive halogen species,metal-based redox couples,and organic redox couples in indirect electrocatalytic transformations.Herein,particular emphasis is placed on discussing the selection criteria,reaction mechanisms,performance optimization strategies,and practical implementation of these mediators.Finally,a roadmap for future research is outlined,highlighting the integration of in situ characterization,computational screening,reactor engineering,and sustainability assessment to accelerate the development of efficient and sustainable indirect electrocatalytic systems.
基金supported by the National Natural Science Foundation of China(Nos.21871125,22475057,22171139 and 22201116)Natural Science Foundation of Guangdong Province(No.2023B1515020076)+1 种基金Natural Science Foundation of Shandong Province(No.ZR2022QB066 and ZR2023MB018)Foundation of State Key Laboratory of Coal Conversion(No.J24-25-902).
文摘The development of new strategy for environmentally friendly,cost-effective and large-scale electro-synthesis of anticancer drugs is highly desirable to replace high-cost traditional methods and realize high atomic economy.GW 610,an antitumor agent with potent and selective anticancer activity against lung,colon,and breast cancer cell lines in real medical treatment processes,has a market price of~10……(7) USD/kg and calls for novel methods like electro-synthesis to reduce the cost.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of microwave-synthesized polyoxometalate-based metal-organic framework(MW-POMOF)that can converse S-S bond substrates into valuable C-S bond products like anticancer drug molecules(e.g.,GW 610).Specifically,the solid-phase MW-POMOF as heterogeneous redox mediator exhibits the excellent electrocatalytic efficiency for the formation of liquid-phase C-S bond products(yields up to 95%)coupling with the generation of gas-phase H_(2) product(~402μmol·g^(-1)·h^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the kilo-scale production(~1 kg in a batch experiment)of GW 610 at one thousandth of the market price(from~10^(7) to~3200 USD/kg).This work may inaugurate a new electrocatalytic avenue to explore porous crystalline materials in electrocatalysis field.
基金supported by the National Key Research and Development Program of China(2022YFA1505700)the National Natural Science Foundation of China(52102216)+3 种基金the Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power,the Key Laboratory of Applied Surface and Colloid Chemistry(Shaanxi Normal University),Ministry of Education(2025067)the Anhui Key Laboratory of Nanomaterials and Nanotechnology,the Major Science and Technology Projects in Anhui Province(202305a12020006)the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2025-22)the Hubei Key Laboratory of Photoelectronic Conversion Materials and Devices,Hubei Normal University,the Fujian Normal University and the Innovation Training Program for College Students(cxxl-2025137,cxxl-2025131,2025019300A,20250193008).
文摘Inspired by high-entropy materials,it is a worthwhile direction to develop multi-metal integrated catalysts to study their synergistic catalytic effects in catalysis field.However,achieving this in porous crystalline materials like covelent organic frameworks(COFs)for backend catalysis reactions remains scarce and challenging to date.Herein,a series of multimetal-variate COFs(i.e.,Quint-MMV-COF,Tetra-MMV-COF and Tri-n-MMV-COF(n=1,2 and 3))have been prepared that can be applied in indirect electrocatalysis.These MMV-COFs with advantages of multi-metal sites,porous structures and appropriate work function can serve as solid-phase redox mediators for the catalytic production of liquid-phase S-S bond products and gas-phase H_(2)product.Interestingly,the optimal Quint-MMV-COF presents excellent electrocatalytic efficiency for S-S bond products(yields up to 99%)and H_(2)(~1.62 mmol·g^(-1)·h^(-1))and can be readily recycled for 6 cycles.At the same time,1.52 g product with a yield of~92%can be obtained in the amplification reaction,showing much potential in industrial production.Validated by theoretical calculations,the synergistic effect of multi-metal sites can result in appropriate work function to boost the electron transfer and intermediate adsorption/conversion to achieve excellent overall S-S coupling efficiency.
