Realizing fast and continuous generation of reactive oxygen species(ROSs)via iron-based advanced oxidation processes(AOPs)is significant in the environmental and biological fields.However,current AOPs assisted by co-c...Realizing fast and continuous generation of reactive oxygen species(ROSs)via iron-based advanced oxidation processes(AOPs)is significant in the environmental and biological fields.However,current AOPs assisted by co-catalysts still suffer from the poor mass/electron transfer and non-durable promotion effect,giving rise to the sluggish Fe^(2+)/Fe^(3+)cycle and low dynamic concentration of Fe^(2+)for ROS production.Herein,we present a three-dimensional(3D)macroscale co-catalyst functionalized with molybdenum disulfide(MoS_(2))to achieve ultra-efficient Fe^(2+)regeneration(equilibrium Fe^(2+)ratio of 82.4%)and remarkable stability(more than 20 cycles)via a circulating flow-through process.Unlike the conventional batch-type reactor,experiments and computational fluid dynamics simulations demonstrate that the optimal utilization of the 3D active area under the flow-through mode,initiated by the convectionenhanced mass/charge transfer for Fe^(2+)reduction and then strengthened by MoS_(2)-induced flow rotation for sufficient reactant mixing,is crucial for oxidant activation and subsequent ROS generation.Strikingly,the flow-through co-catalytic system with superwetting capabilities can even tackle the intricate oily wastewater stabilized by different surfactants without the loss of pollutant degradation efficiency.Our findings highlight an innovative co-catalyst system design to expand the applicability of AOPs based technology,especially in large-scale complex wastewater treatment.展开更多
Since their seminal discovery in 2011,two-dimensional(2D)transition metal carbides/nitrides known as MXenes,that constitute a large family of 2D materials,have been targeted toward various applications due to their ou...Since their seminal discovery in 2011,two-dimensional(2D)transition metal carbides/nitrides known as MXenes,that constitute a large family of 2D materials,have been targeted toward various applications due to their outstanding electronic properties.MXenes functioning as co-catalyst in combination with certain photocatalysts have been applied in photocatalytic systems to enhance photogenerated charge separation,suppress rapid charge recombination,and convert solar energy into chemical energy or use it in the degradation of organic compounds.The photocatalytic performance greatly depends on the composition and morphology of the photocatalyst,which,in turn,are determined by the method of preparation used.Here,we review the four different synthesis methods(mechanical mixing,self-assembly,in situ decoration,and oxidation)reported for MXenes in view of their application as co-catalyst in photocatalysis.In addition,the working mechanism for MXenes application in photocatalysis is discussed and an outlook for future research is also provided.展开更多
The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metall...The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.展开更多
Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited...Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited choice of catalysts with wide light absorption range,long-term stability and excellent selectivity for CO_(2) reduction makes the process sluggish.Here,a core-shell-structured nonnoble-metal Ni@In co-catalyst loaded p-type silicon nanowire arrays(SiNWs)for efficient CO_(2) reduction to formate is demonstrated.The formation rate and Faradaic efficiency of formate over the Ni@In/SiNWs catalyst reach 58μmol h^(-1) cm^(-2) and 87% under the irradiation of one simulated sunlight(AM 1.5 G,100 mW cm^(-2)),respectively,which are about 24 and 12 times those over the pristine SiNWs.The enhanced photoelectrocatalytic performance for CO_(2) reduction is attributed to the rational combination of Ni capable of effectively extracting the photogenerated electrons and In responsible for the selective activation of CO_(2).展开更多
A green and efficient method for the selective aerobic oxidation of p-cresol to p-hydroxybenzaldehyde catalyzed by co-catalysts between metalloporphyrins and metal salts was investigated and developed. The relationshi...A green and efficient method for the selective aerobic oxidation of p-cresol to p-hydroxybenzaldehyde catalyzed by co-catalysts between metalloporphyrins and metal salts was investigated and developed. The relationship between the synergistic catalytic effects and the composition as well as amount of co-catalysts was investigated. Moreover, the influence of different reaction conditions was studied in details. A high p-cresol conversion(N 99%) and p-hydroxybenzaldehyde selectivity(83%) were obtained using only 1.125 × 10^(-5) mol T(p-CH_3 O)PPFe^(III)Cl-Co(OAc)_2 used under mild, optimized reaction conditions. A possible mechanism for the reaction was also proposed. This work would be meaningful and instructive for the further researches and applications of co-catalyst system on oxidation of cresols and could give some enlightenment on the selectively catalytic oxidation of the side-chain alkyls of aromatics.展开更多
Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant...Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant challenge.Here,we integrate bifunctional Cu2O and Cu-MOF(MOF=metal-organic framework)core–shell co-catalysts(Cu2O@Cu-MOF)with semiconductor TiO_(2).Experiments and theoretical calculations demonstrate that Cu2O(Cu+facilitates charge separation)and Cu-MOF(Cu2+improves the CO_(2) adsorption and activation)in the core–shell structure have a synergistic effect on photocatalytic CO_(2) reduction,reducing the formation barrier of the key intermediate*COOH and*CHO.The photocatalyst exhibits high CH_(4) yield(366.0μmol·g^(-1)·h^(-1)),efficient electron transfer(3283μmol·g^(-1)·h^(-1))and hydrocarbon selectivity(95.5%),which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO_(2) reduction reaction.This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components.展开更多
Carbon nitride(g-C_(3)N_(4))is a promising metal-free and visible-light-responsive photocatalyst.However,its photocatalytic efficiency still suffers from high recombination rates of photoinduced charge carriers,slow k...Carbon nitride(g-C_(3)N_(4))is a promising metal-free and visible-light-responsive photocatalyst.However,its photocatalytic efficiency still suffers from high recombination rates of photoinduced charge carriers,slow kinetics of surface redox reactions,and relatively poor light absorption.Herein,a non-noble metal photocatalyst of MoS_(2) nanodots anchored on P-doped g-C_(3)N_(4) via in situ photodeposition was constructed.With the synergetic effect of the P-doping and MoS_(2) co-catalyst,the as-prepared P-doped g-C_(3)N_(4)/MoS_(2) catalyst has achieved efficient photocatalytic overall water splitting with a hydrogen evolution rate of 121.7μmol h−1 g−1.Experimental results and Density functional theory(DFT)simulations indicate that the enhanced photo-absorption capacity originates from the reduced band gaps by P doping.Meanwhile,the MoS_(2) reduces the overpotential of the water oxidation process and improves hydrogen adsorption capability in the hydrogen evolution reaction.This work can pave a new avenue to design and develop noble-metal-free water-splitting photocatalysts for future large-scale applications.展开更多
In the presentwork,functional diamine groups into indium frameworks to synthesize cyclic carbonates from CO_(2)and epoxides with efficient catalytic activity in the absence of cocatalyst and solvent are reported for t...In the presentwork,functional diamine groups into indium frameworks to synthesize cyclic carbonates from CO_(2)and epoxides with efficient catalytic activity in the absence of cocatalyst and solvent are reported for the first time.Crystalline porous materials(CPM)-5 modified with 1,2-phenylene diamine and ethylene diamine(CPM-5-PhDA and CPM-5-EDA),were prepared using a post-synthetic modification(PSM)method.The properties of the modified CPM-5 were characterized by powder X-ray diffraction(PXRD),Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),N2-adsorption,scanning electron microscopy(SEM),CO_(2)adsorption,and temperature programmed desorption TPD methods.The presence of diamine groups as basic sites and indium Lewis acid sites in the framework structure were desirable for high catalytic activity.For a given catalyst weight,CPM-5-PhDA was the best candidate to appear with great catalytic activity and selectivity for the cycloaddition reaction at 100°C and1MPa CO_(2)under co-catalyst and solvent free conditions.CPM-5-PhDA alsowas found to afford large and bulky epoxides.The catalyst can be easily separated and reused five times without any decline in activity.展开更多
Photocatalytic N2 fixation involves a nitrogen reduction reaction on the surface of the photocatalyst to convert N2 into ammonia.Currently,the adsorption of N2 is the limiting step for the N2 reduction reaction on the...Photocatalytic N2 fixation involves a nitrogen reduction reaction on the surface of the photocatalyst to convert N2 into ammonia.Currently,the adsorption of N2 is the limiting step for the N2 reduction reaction on the surface of the catalyst.Based on the concept of photocatalytic water splitting,the photocatalytic efficiency can be greatly enhanced by introducing a co-catalyst.In this report,we proposed a new strategy,namely,the loading of a NiS co-catalyst on CdS nanorods for photocatalytic N2 fixation.Theoretical calculation results indicated that N2 was effectively adsorbed onto the NiS/CdS surface.Temperature programmed desorption studies confirmed that the N2 molecules preferred to adsorb onto the NiS/CdS surface.Linear sweep voltammetry results revealed that the overpotential of the N2 reduction reaction was reduced by loading NiS.Furthermore,transient photocurrent and electrochemical impedance spectroscopy indicated that the charge separation was enhanced by introducing NiS.Photocatalytic N2 fixation was carried out in the presence of the catalyst dispersed in water without any sacrificial agent.As a result,1.0 wt% NiS/CdS achieved an ammonia production rate of 2.8 and 1.7 mg L-1 for the first hour under full spectrum and visible light(λ>420 nm),respectively.The catalyst demonstrated apparent quantum efficiencies of 0.76%,0.39% and 0.09% at 420,475 and 520 nm,res pectively.This study provides a new method to promote the photocatalytic efficiency of N2 fixation.展开更多
基金supported by National Natural Science Foundation of China(52003240)Zhejiang Provincial Natural Science Foundation of China(LQ21B070007)China Postdoctoral Science Foundation(2022M722818).
文摘Realizing fast and continuous generation of reactive oxygen species(ROSs)via iron-based advanced oxidation processes(AOPs)is significant in the environmental and biological fields.However,current AOPs assisted by co-catalysts still suffer from the poor mass/electron transfer and non-durable promotion effect,giving rise to the sluggish Fe^(2+)/Fe^(3+)cycle and low dynamic concentration of Fe^(2+)for ROS production.Herein,we present a three-dimensional(3D)macroscale co-catalyst functionalized with molybdenum disulfide(MoS_(2))to achieve ultra-efficient Fe^(2+)regeneration(equilibrium Fe^(2+)ratio of 82.4%)and remarkable stability(more than 20 cycles)via a circulating flow-through process.Unlike the conventional batch-type reactor,experiments and computational fluid dynamics simulations demonstrate that the optimal utilization of the 3D active area under the flow-through mode,initiated by the convectionenhanced mass/charge transfer for Fe^(2+)reduction and then strengthened by MoS_(2)-induced flow rotation for sufficient reactant mixing,is crucial for oxidant activation and subsequent ROS generation.Strikingly,the flow-through co-catalytic system with superwetting capabilities can even tackle the intricate oily wastewater stabilized by different surfactants without the loss of pollutant degradation efficiency.Our findings highlight an innovative co-catalyst system design to expand the applicability of AOPs based technology,especially in large-scale complex wastewater treatment.
基金supported by the National Natural Science Foundation of China(No.11574111 and No.11974129 to X.-F.W.)“the Fundamental Research Funds for the Central Universities.”.
文摘Since their seminal discovery in 2011,two-dimensional(2D)transition metal carbides/nitrides known as MXenes,that constitute a large family of 2D materials,have been targeted toward various applications due to their outstanding electronic properties.MXenes functioning as co-catalyst in combination with certain photocatalysts have been applied in photocatalytic systems to enhance photogenerated charge separation,suppress rapid charge recombination,and convert solar energy into chemical energy or use it in the degradation of organic compounds.The photocatalytic performance greatly depends on the composition and morphology of the photocatalyst,which,in turn,are determined by the method of preparation used.Here,we review the four different synthesis methods(mechanical mixing,self-assembly,in situ decoration,and oxidation)reported for MXenes in view of their application as co-catalyst in photocatalysis.In addition,the working mechanism for MXenes application in photocatalysis is discussed and an outlook for future research is also provided.
基金fundings from the National Natural Science Foundation of China (Nos. 51872173 and 51772167)Taishan Scholarship of Young Scholars (No. tsqn201812068)+2 种基金Natural Science Foundation of Shandong Province (No. ZR2017JL020)Taishan Scholarship of Climbing Plan (No. tspd20161006)Key Research and Development Program of Shandong Province (No. 2018GGX102028)
文摘The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.
基金supported by the National Natural Science Foundation of China(Nos.21972115,91945301,21690082 and 21503176)the China Postdoctoral Science Foundation(Nos.2015M570555,2016T90597)。
文摘Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited choice of catalysts with wide light absorption range,long-term stability and excellent selectivity for CO_(2) reduction makes the process sluggish.Here,a core-shell-structured nonnoble-metal Ni@In co-catalyst loaded p-type silicon nanowire arrays(SiNWs)for efficient CO_(2) reduction to formate is demonstrated.The formation rate and Faradaic efficiency of formate over the Ni@In/SiNWs catalyst reach 58μmol h^(-1) cm^(-2) and 87% under the irradiation of one simulated sunlight(AM 1.5 G,100 mW cm^(-2)),respectively,which are about 24 and 12 times those over the pristine SiNWs.The enhanced photoelectrocatalytic performance for CO_(2) reduction is attributed to the rational combination of Ni capable of effectively extracting the photogenerated electrons and In responsible for the selective activation of CO_(2).
基金Supported by the National Natural Science Foundation of China(21776259,21776321,21706233,21576297,21476270)
文摘A green and efficient method for the selective aerobic oxidation of p-cresol to p-hydroxybenzaldehyde catalyzed by co-catalysts between metalloporphyrins and metal salts was investigated and developed. The relationship between the synergistic catalytic effects and the composition as well as amount of co-catalysts was investigated. Moreover, the influence of different reaction conditions was studied in details. A high p-cresol conversion(N 99%) and p-hydroxybenzaldehyde selectivity(83%) were obtained using only 1.125 × 10^(-5) mol T(p-CH_3 O)PPFe^(III)Cl-Co(OAc)_2 used under mild, optimized reaction conditions. A possible mechanism for the reaction was also proposed. This work would be meaningful and instructive for the further researches and applications of co-catalyst system on oxidation of cresols and could give some enlightenment on the selectively catalytic oxidation of the side-chain alkyls of aromatics.
基金We acknowledge the National Key Research and Development Program of China （2016YFB0600901）, the National Natural Science Foundation of China （21525626, U1463205, U1662111）, the Special- ized Research Fund for the Doctoral Program of Higher Education （20130032120018）, and the Program of Introducing Talents of Disci- pline to Universities （B06006） for financial support.
基金supported by the National Natural Science Foundation of China(Nos.51802171,52072197,and 52003136)the Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)+2 种基金the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)the Major Scientific and Technological Innovation Project(No.2019JZZY020405)Taishan Scholar Program,and the Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09).
文摘Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant challenge.Here,we integrate bifunctional Cu2O and Cu-MOF(MOF=metal-organic framework)core–shell co-catalysts(Cu2O@Cu-MOF)with semiconductor TiO_(2).Experiments and theoretical calculations demonstrate that Cu2O(Cu+facilitates charge separation)and Cu-MOF(Cu2+improves the CO_(2) adsorption and activation)in the core–shell structure have a synergistic effect on photocatalytic CO_(2) reduction,reducing the formation barrier of the key intermediate*COOH and*CHO.The photocatalyst exhibits high CH_(4) yield(366.0μmol·g^(-1)·h^(-1)),efficient electron transfer(3283μmol·g^(-1)·h^(-1))and hydrocarbon selectivity(95.5%),which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO_(2) reduction reaction.This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components.
基金supported by Guangdong Basic and Ap-plied Basic Research Foundation(Nos.2021A1515110003 and 2020A1515110332)financial support from the National Natural Science Foundation of China(Nos.51974158 and 21902070)+2 种基金Scientific Research Projects of Key Disciplines in Guangdong Province(No.2019-GDXK-0023)Projects of“Leiyang Scholar”post plan of Lingnan Normal University(2021)Open Project of Key Laboratory of Chean Energy Material Chemistry in Guangdong General University(No.CEMC2022011).
文摘Carbon nitride(g-C_(3)N_(4))is a promising metal-free and visible-light-responsive photocatalyst.However,its photocatalytic efficiency still suffers from high recombination rates of photoinduced charge carriers,slow kinetics of surface redox reactions,and relatively poor light absorption.Herein,a non-noble metal photocatalyst of MoS_(2) nanodots anchored on P-doped g-C_(3)N_(4) via in situ photodeposition was constructed.With the synergetic effect of the P-doping and MoS_(2) co-catalyst,the as-prepared P-doped g-C_(3)N_(4)/MoS_(2) catalyst has achieved efficient photocatalytic overall water splitting with a hydrogen evolution rate of 121.7μmol h−1 g−1.Experimental results and Density functional theory(DFT)simulations indicate that the enhanced photo-absorption capacity originates from the reduced band gaps by P doping.Meanwhile,the MoS_(2) reduces the overpotential of the water oxidation process and improves hydrogen adsorption capability in the hydrogen evolution reaction.This work can pave a new avenue to design and develop noble-metal-free water-splitting photocatalysts for future large-scale applications.
基金Alzahra University Research Council for the financial support
文摘In the presentwork,functional diamine groups into indium frameworks to synthesize cyclic carbonates from CO_(2)and epoxides with efficient catalytic activity in the absence of cocatalyst and solvent are reported for the first time.Crystalline porous materials(CPM)-5 modified with 1,2-phenylene diamine and ethylene diamine(CPM-5-PhDA and CPM-5-EDA),were prepared using a post-synthetic modification(PSM)method.The properties of the modified CPM-5 were characterized by powder X-ray diffraction(PXRD),Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),N2-adsorption,scanning electron microscopy(SEM),CO_(2)adsorption,and temperature programmed desorption TPD methods.The presence of diamine groups as basic sites and indium Lewis acid sites in the framework structure were desirable for high catalytic activity.For a given catalyst weight,CPM-5-PhDA was the best candidate to appear with great catalytic activity and selectivity for the cycloaddition reaction at 100°C and1MPa CO_(2)under co-catalyst and solvent free conditions.CPM-5-PhDA alsowas found to afford large and bulky epoxides.The catalyst can be easily separated and reused five times without any decline in activity.
基金financially supported by the Beijing Municipal High-Level Innovative Team Building Program (IDHT20180504)the National Natural Science Foundation of China (21805004, 21671011, 21872001 and 51801006)+3 种基金the Beijing Natural Science Foundation (KZ201710005002 and 2192005)the China Postdoctoral Science Foundation (2018M641133)the Beijing Postdoctoral Research Foundation (2018-ZZ-021)the Chaoyang District Postdoctoral Research Foundation, China (2018-ZZ-026)
文摘Photocatalytic N2 fixation involves a nitrogen reduction reaction on the surface of the photocatalyst to convert N2 into ammonia.Currently,the adsorption of N2 is the limiting step for the N2 reduction reaction on the surface of the catalyst.Based on the concept of photocatalytic water splitting,the photocatalytic efficiency can be greatly enhanced by introducing a co-catalyst.In this report,we proposed a new strategy,namely,the loading of a NiS co-catalyst on CdS nanorods for photocatalytic N2 fixation.Theoretical calculation results indicated that N2 was effectively adsorbed onto the NiS/CdS surface.Temperature programmed desorption studies confirmed that the N2 molecules preferred to adsorb onto the NiS/CdS surface.Linear sweep voltammetry results revealed that the overpotential of the N2 reduction reaction was reduced by loading NiS.Furthermore,transient photocurrent and electrochemical impedance spectroscopy indicated that the charge separation was enhanced by introducing NiS.Photocatalytic N2 fixation was carried out in the presence of the catalyst dispersed in water without any sacrificial agent.As a result,1.0 wt% NiS/CdS achieved an ammonia production rate of 2.8 and 1.7 mg L-1 for the first hour under full spectrum and visible light(λ>420 nm),respectively.The catalyst demonstrated apparent quantum efficiencies of 0.76%,0.39% and 0.09% at 420,475 and 520 nm,res pectively.This study provides a new method to promote the photocatalytic efficiency of N2 fixation.
