Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants f...Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.展开更多
Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high...Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.展开更多
A 3D/0D cobalt-embedded nitrogen-doped porous carbon nanocubes(Co-N-C)/supramolecular tetra(4-carboxylphenyl)porphyrin nanocrystals(SA-TCPP)photocatalyst was successfully self-assembled viaπ–πinteraction,hydrogen b...A 3D/0D cobalt-embedded nitrogen-doped porous carbon nanocubes(Co-N-C)/supramolecular tetra(4-carboxylphenyl)porphyrin nanocrystals(SA-TCPP)photocatalyst was successfully self-assembled viaπ–πinteraction,hydrogen bonding,and chemical bonding.Co-N-C/SA-TCPP heterostructure exhibited satisfactory visible photocatalytic oxidation performance on pollutant degradation and water evolution.The degradation rates of Co-N-C/ST(30%)composite towards 2,4-dichlorophenol,ofloxacin,and ethylene were10.9,7.2,and 2.1 times faster than SA-TCPP,respectively.The oxygen evolution efficiency was 1.9 times higher than SA-TCPP.The remarkably improved oxidation activities of Co-N-C/SA-TCPP were mainly ascribed to the following reasons:(1)Co-N-C could enhance the light absorption ability of SA-TCPP to produce more photoinduced carriers.(2)The well-developed porosity of Co-N-C could optimize the dispersibility of SA-TCPP to provide more reactive sites and charge separation channels.(3)Theπ–πinteraction between SA-TCPP and Co-N-C was beneficial to interlayer charge mobility,while the embedded cobalt nanoparticles(Co NPs)and N-doped carbon matrix could serve as electron traps to accelerate interfacial electron transfer.Additionally,the ferromagnetic Co NPs endowed Co-N-C/SA-TCPP with magnetic-separation function to promote recyclability in practical application.展开更多
The active sites of monodisperse transition metal Ni-clusters were anchored on carbon nitride(CN)by an in situ photoreduction deposition method to promote the efficient separation of photogenerated charges and achieve...The active sites of monodisperse transition metal Ni-clusters were anchored on carbon nitride(CN)by an in situ photoreduction deposition method to promote the efficient separation of photogenerated charges and achieve high-efficiency photocatalytic activity for hydrogen evolution.The Ni-cluster/CN exhibited a photocatalytic hydrogen production rate of 16.5 mmol·h^(-1)·g^(-1) and a total turnover frequency(TOF(H_(2)))value of 461.14 h^(-1).X-ray absorption spectroscopy based on synchrotron radiation indicated that CN had two reaction centers to form stable interface interactions with monodispersed Ni-clusters,in which carbon can act as an electron acceptor,while nitrogen can act as an electron donor.Meanwhile,the hybrid electronic structure of the Ni-cluster/CN system was constructed,which was favorable for photocatalytic activity for hydrogen production.An in-depth understanding of the interfacial interaction between CN and Ni-clusters will have important reference significance on the mechanistic study of development based on the cocatalyst.展开更多
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
CONSPECTUS:The photocatalytic generation of hydrogen peroxide(H_(2)O_(2))through the utilization of only H_(2)O,O_(2),and sunlight represents an energy-efficient and ecofriendly innovation in pursuit of a sustainable ...CONSPECTUS:The photocatalytic generation of hydrogen peroxide(H_(2)O_(2))through the utilization of only H_(2)O,O_(2),and sunlight represents an energy-efficient and ecofriendly innovation in pursuit of a sustainable society.Despite significant efforts that have been directed toward the development of H2O2 generation via photocatalysis,the solar-to-chemical conversion(SCC)efficiency has not yet reached the levels required for large-scale practical applications.Consequently,there is an urgent demand to develop and design novel photocatalysts characterized by several key attributes:high catalytic activity,cost-effectiveness,and good stability.However,traditional inorganic photocatalysts,such as TiO_(2),have exhibited limited activity,partly attributable to the potential decomposition of H_(2)O_(2)caused by metal cations.Recent research has found organic photocatalysts as highly promising candidates to address these limitations.Organic materials offer several remarkable advantages for photocatalysis,including narrow bandgap,adjustable band edge potentials,the ability to control surface configurations for use as active sites,and the potential for rational design of structural units that promote efficient charge separation and transfer.In the field of photocatalytic H_(2)O_(2)generation without sacrificial reagents,efficient organic photocatalysts have been widely studied,and various strategies to improve the activity and stability of organic photocatalysts have been explored.These strategies include the construction of donor−acceptor structures,the design of conjugated structures,the incorporation of heteroatoms,the enhancement of the internal electric field,and the substitution of functional groups.Currently,organic materials have exhibited exceptional activity,far exceeding that of well-established TiO_(2).In this Account,we introduce state-of-the-art organic materials for H_(2)O_(2)generation based on our recent works and typical results from other groups.This classification system encompasses the anthraquinone-mediated oxygen reduction reaction(ORR),the radical-related ORR,the water oxidation reaction(WOR),and the dual ORR and WOR pathways.Through this classification,we delve into essential kinetic parameters,such as production rate,apparent quantum efficiency(AQE),and SCC efficiency that have been achieved.Additionally,we highlight the early exploration of in situ utilization of generated H_(2)O_(2)for environmental remediation.Furthermore,we outline forthcoming challenges in the field,including suboptimal solar energy utilization,the need for a clearer understanding of the structure−activity relationship,and insufficient research on in situ H_(2)O_(2)utilization.In conclusion,this Account makes a substantial contribution to the field by providing a comprehensive overview of recent advancements based on typical works from us and other groups,addressing current challenges,and suggesting areas for future research in the development of organic photocatalysts for H_(2)O_(2) generation.The ultimate goal is to drive forward the practical applications of organic semiconductor materials in the environmental and energy fields,thereby advancing the cause of sustainable energy production and environmental remediation.展开更多
基金supported by the Natural Science Foundation of Jiangsu Province(BK20221541)National Natural Science Foundation of China(21707052)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108).
文摘Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.
基金This project was supported financially by the National Natural Science Foundation of China(21908079,21902009,21707052)Natural Science Foundation of Jiangsu Province(BK20201345)+3 种基金the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF2005)Startup Funding at Jiangnan University(1045210322190170,1045281602190010,1042050205204100)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108)Fundamental Research Funds for the Central Universities(JUSRP11905,JUSRP52004B).
文摘Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.
基金the Jiangsu Agriculture Science and Technology Innovation Fund(No.CX(20)3108)the National Natural Science Foundation of China(Nos.21707052,31871881,21908079,and 22172065)+3 种基金the Fundamental Research Funds for the Central Universities(No.JUSRP11905)the Key Research and Development Program of Jiangsu Province(No.BE2017623)the Natural Science Foundation of Jiangsu Province(Nos.BK20211239 and BK20201345)the National First-class Discipline Program of Food Science and Technology(No.JUFSTR20180303)。
文摘A 3D/0D cobalt-embedded nitrogen-doped porous carbon nanocubes(Co-N-C)/supramolecular tetra(4-carboxylphenyl)porphyrin nanocrystals(SA-TCPP)photocatalyst was successfully self-assembled viaπ–πinteraction,hydrogen bonding,and chemical bonding.Co-N-C/SA-TCPP heterostructure exhibited satisfactory visible photocatalytic oxidation performance on pollutant degradation and water evolution.The degradation rates of Co-N-C/ST(30%)composite towards 2,4-dichlorophenol,ofloxacin,and ethylene were10.9,7.2,and 2.1 times faster than SA-TCPP,respectively.The oxygen evolution efficiency was 1.9 times higher than SA-TCPP.The remarkably improved oxidation activities of Co-N-C/SA-TCPP were mainly ascribed to the following reasons:(1)Co-N-C could enhance the light absorption ability of SA-TCPP to produce more photoinduced carriers.(2)The well-developed porosity of Co-N-C could optimize the dispersibility of SA-TCPP to provide more reactive sites and charge separation channels.(3)Theπ–πinteraction between SA-TCPP and Co-N-C was beneficial to interlayer charge mobility,while the embedded cobalt nanoparticles(Co NPs)and N-doped carbon matrix could serve as electron traps to accelerate interfacial electron transfer.Additionally,the ferromagnetic Co NPs endowed Co-N-C/SA-TCPP with magnetic-separation function to promote recyclability in practical application.
文摘The active sites of monodisperse transition metal Ni-clusters were anchored on carbon nitride(CN)by an in situ photoreduction deposition method to promote the efficient separation of photogenerated charges and achieve high-efficiency photocatalytic activity for hydrogen evolution.The Ni-cluster/CN exhibited a photocatalytic hydrogen production rate of 16.5 mmol·h^(-1)·g^(-1) and a total turnover frequency(TOF(H_(2)))value of 461.14 h^(-1).X-ray absorption spectroscopy based on synchrotron radiation indicated that CN had two reaction centers to form stable interface interactions with monodispersed Ni-clusters,in which carbon can act as an electron acceptor,while nitrogen can act as an electron donor.Meanwhile,the hybrid electronic structure of the Ni-cluster/CN system was constructed,which was favorable for photocatalytic activity for hydrogen production.An in-depth understanding of the interfacial interaction between CN and Ni-clusters will have important reference significance on the mechanistic study of development based on the cocatalyst.
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the financial grants from National Natural Science Foundation of China(22136002,22172065)National Key Research and Development Project of China(2020YFA0710304)+2 种基金Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality(BK20220023)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_2455,the Fundamental Research Funds for the Central Universities)Natural Science Foundation of Jiangsu Province(BK20201345)。
文摘CONSPECTUS:The photocatalytic generation of hydrogen peroxide(H_(2)O_(2))through the utilization of only H_(2)O,O_(2),and sunlight represents an energy-efficient and ecofriendly innovation in pursuit of a sustainable society.Despite significant efforts that have been directed toward the development of H2O2 generation via photocatalysis,the solar-to-chemical conversion(SCC)efficiency has not yet reached the levels required for large-scale practical applications.Consequently,there is an urgent demand to develop and design novel photocatalysts characterized by several key attributes:high catalytic activity,cost-effectiveness,and good stability.However,traditional inorganic photocatalysts,such as TiO_(2),have exhibited limited activity,partly attributable to the potential decomposition of H_(2)O_(2)caused by metal cations.Recent research has found organic photocatalysts as highly promising candidates to address these limitations.Organic materials offer several remarkable advantages for photocatalysis,including narrow bandgap,adjustable band edge potentials,the ability to control surface configurations for use as active sites,and the potential for rational design of structural units that promote efficient charge separation and transfer.In the field of photocatalytic H_(2)O_(2)generation without sacrificial reagents,efficient organic photocatalysts have been widely studied,and various strategies to improve the activity and stability of organic photocatalysts have been explored.These strategies include the construction of donor−acceptor structures,the design of conjugated structures,the incorporation of heteroatoms,the enhancement of the internal electric field,and the substitution of functional groups.Currently,organic materials have exhibited exceptional activity,far exceeding that of well-established TiO_(2).In this Account,we introduce state-of-the-art organic materials for H_(2)O_(2)generation based on our recent works and typical results from other groups.This classification system encompasses the anthraquinone-mediated oxygen reduction reaction(ORR),the radical-related ORR,the water oxidation reaction(WOR),and the dual ORR and WOR pathways.Through this classification,we delve into essential kinetic parameters,such as production rate,apparent quantum efficiency(AQE),and SCC efficiency that have been achieved.Additionally,we highlight the early exploration of in situ utilization of generated H_(2)O_(2)for environmental remediation.Furthermore,we outline forthcoming challenges in the field,including suboptimal solar energy utilization,the need for a clearer understanding of the structure−activity relationship,and insufficient research on in situ H_(2)O_(2)utilization.In conclusion,this Account makes a substantial contribution to the field by providing a comprehensive overview of recent advancements based on typical works from us and other groups,addressing current challenges,and suggesting areas for future research in the development of organic photocatalysts for H_(2)O_(2) generation.The ultimate goal is to drive forward the practical applications of organic semiconductor materials in the environmental and energy fields,thereby advancing the cause of sustainable energy production and environmental remediation.
