Artificial synthesis is an environment friendly photocatalytic strategy to converse carbon dioxide(CO_(2))into useful chemicals.However,water(H_(2)O)splitting,producing(hydrogen)H_(2) strongly,is always a competitive ...Artificial synthesis is an environment friendly photocatalytic strategy to converse carbon dioxide(CO_(2))into useful chemicals.However,water(H_(2)O)splitting,producing(hydrogen)H_(2) strongly,is always a competitive reaction to CO_(2) conversion.Therefore,proper cocatalysts are generally needed to enhance CO_(2) conversion but suppress H_(2) production.In this work,zinc/gallium(Zn/Ga)dual co-catalysts consisting of Zn0 and amorphous ZnGa_(2)O_(4) species were found to selectively produce carbon monoxide(CO)during the photocatalytic conversion of carbon dioxide(CO_(2))using water(H_(2)O)as an electron donor over photocatalysts such as NaTaO_(3),Ga_(2)O_(3),and ZnGa_(2)O_(4),and in the electrochemical reduction of CO_(2) over Zn0 electrodes.It is considered that there are two effects associated with the Zn/Ga dual co-catalysts:(1)a galvanic cell effect between Zn0 and amorphous ZnGa_(2)O_(4),and(2)a Z-scheme effect in NaTaO_(3)/Zn0/amorphous ZnGa_(2)O_(4).The coupling of these two effects favored the active and selective evolution of CO during the photocatalytic conversion of CO_(2) by H_(2)O.In the case of Ga_(2)O_(3) photocatalyst,480.8μmol/h of CO was produced with the presence of Zn/Ga dual cocatalysts.Moreover,the Zn/Ga dual cocatalysts universally worked in the electrochemical reduction of CO_(2).The partial current toward CO_(2) conversion was increased from 2.6 to 6.6 mA/cm,and the selectivity toward CO was promoted to from 46.4%to 74.2%.展开更多
Dual co-catalyst loading is a viable strategy to enhance charge carrier separation in photocatalysis.How-ever,conventional randomly-loaded dual co-catalysts often fail to effectively direct charge transfer.In this stu...Dual co-catalyst loading is a viable strategy to enhance charge carrier separation in photocatalysis.How-ever,conventional randomly-loaded dual co-catalysts often fail to effectively direct charge transfer.In this study,a strategically designed spatially separated dual co-catalyst system(MnO_(x)/CdS/Pt)optimizes redox site orientation to address the challenge of disordered carrier transfer.This configuration maxi-mizes the utilization of both electrons and holes while establishing ultrafast electron transfer channels between CdS and Pt.The ultrafast electron transfer channels between spatially separated redox sites are demonstrated by femtosecond transient absorption(fs-TA)spectroscopy and in situ characterization.The average lifetime of MnO_(x)/CdS/Pt(MCSP)in a real reaction environment reduced from∼1352.6 to∼996.6 ps,compared to CdS alone.The interfacial electron transfer rate is accelerated to∼2.6×108 s^(-1),a substantial improvement over the CdS/Pt(∼6.0×10^(7) s^(-1)).Consequently,this system achieves efficient hydrogen production coupled with fine chemical synthesis.This work underscores the potential of ra-tional dual co-catalyst design with spatially separated redox sites as a promising strategy for developing high-performance photocatalytic platforms for solar fuel production.展开更多
The facet effect of metal-organic frameworks(MOF)on regulating the property of loaded co-catalysts is an important but unexplored issue in the field of photocatalysis.In this work,a series of MIL-125-NH_(2)polyhedrons...The facet effect of metal-organic frameworks(MOF)on regulating the property of loaded co-catalysts is an important but unexplored issue in the field of photocatalysis.In this work,a series of MIL-125-NH_(2)polyhedrons(MIL=Materials Institute Lavoisier)with facet exposure of{001},{001}/{111}and{111}are synthesized and used to load Pd-based co-catalysts for photocatalytic oxygen reduction reaction(ORR)toward H_(2)O_(2)production.The different facets with distinct chemical environments(Ti-O clusters on{111}facets and carboxyl ligands on{001}facets)result in the selective loading of Pd0and PdO dominated cocatalysts on{001}and{111}facets,respectively.The{001}/{111}co-exposed MIL-125-NH_(2)thus enables the spatially separated loading of Pd0and Pd O dual cocatalysts respectively.Pd0efficiently traps the photoexcited electrons and PdO trends to capture the holes,collaboratively promoting the directional separation of photogenerated electron-hole pairs.As a result,the photocatalytic ORR activity is significantly enhanced with a H_(2)O_(2)production rate of 128.6 mmol L^(-1)g^(-1)h^(-1),superior than pristine and single cocatalyst modified MIL-125-NH_(2)samples.Our findings provide new insight into the design of high-performance photocatalysts.展开更多
Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to en...Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.展开更多
采用溶胶-凝胶法制备系列Mn-CoO_(x)复合氧化物催化剂。在质量空速为90000 m L/(g·h)的条件下,考察了Mn-CoO_(x)复合氧化物催化剂分别在电场辅助和常规条件下的CO催化氧化性能。结果表明:Mn-CoO_(x)催化剂在电场中展现了更优良的低...采用溶胶-凝胶法制备系列Mn-CoO_(x)复合氧化物催化剂。在质量空速为90000 m L/(g·h)的条件下,考察了Mn-CoO_(x)复合氧化物催化剂分别在电场辅助和常规条件下的CO催化氧化性能。结果表明:Mn-CoO_(x)催化剂在电场中展现了更优良的低温CO氧化活性,其中,Mn1Co5O_(x)在电场辅助下T _(50)(CO转化率为50%时对应的温度)较常规条件(不施加电场,仅通过管式炉升温)降低13℃(110℃完全转化)。催化剂的表征结果发现,引入电场可优化催化剂样品孔道结构,促进催化剂的电子转移,实现晶格氧活化而提升氧化还原能力。展开更多
基金supported by the National Key R&D Program of China(No.2023YFC3710800)the National Natural Science Foundation of China(No.22376207)+1 种基金the Research Fund of High-Level Training Talents of“333”Project in Jiangsu provinceFunding for school-level research projects of Yancheng Institute of Technology(Nos.xjr2024008 and xjr2023055).
文摘Artificial synthesis is an environment friendly photocatalytic strategy to converse carbon dioxide(CO_(2))into useful chemicals.However,water(H_(2)O)splitting,producing(hydrogen)H_(2) strongly,is always a competitive reaction to CO_(2) conversion.Therefore,proper cocatalysts are generally needed to enhance CO_(2) conversion but suppress H_(2) production.In this work,zinc/gallium(Zn/Ga)dual co-catalysts consisting of Zn0 and amorphous ZnGa_(2)O_(4) species were found to selectively produce carbon monoxide(CO)during the photocatalytic conversion of carbon dioxide(CO_(2))using water(H_(2)O)as an electron donor over photocatalysts such as NaTaO_(3),Ga_(2)O_(3),and ZnGa_(2)O_(4),and in the electrochemical reduction of CO_(2) over Zn0 electrodes.It is considered that there are two effects associated with the Zn/Ga dual co-catalysts:(1)a galvanic cell effect between Zn0 and amorphous ZnGa_(2)O_(4),and(2)a Z-scheme effect in NaTaO_(3)/Zn0/amorphous ZnGa_(2)O_(4).The coupling of these two effects favored the active and selective evolution of CO during the photocatalytic conversion of CO_(2) by H_(2)O.In the case of Ga_(2)O_(3) photocatalyst,480.8μmol/h of CO was produced with the presence of Zn/Ga dual cocatalysts.Moreover,the Zn/Ga dual cocatalysts universally worked in the electrochemical reduction of CO_(2).The partial current toward CO_(2) conversion was increased from 2.6 to 6.6 mA/cm,and the selectivity toward CO was promoted to from 46.4%to 74.2%.
基金financial support from the Na-tional Key Research and Development Program of China(No.2022YFB3803600)the National Natural Science Foundation of China(Nos.52322214,22361132529,22278383,22361142704,and 22238009)+1 种基金the National Science Foundation of Hubei Province of China(Nos.2022CFA001 and 2023AFA088)supported by the Fundamental Research Funds for the Central Uni-versities,China University of Geosciences(Wuhan)(Nos.CUG22061 and CUG240614).
文摘Dual co-catalyst loading is a viable strategy to enhance charge carrier separation in photocatalysis.How-ever,conventional randomly-loaded dual co-catalysts often fail to effectively direct charge transfer.In this study,a strategically designed spatially separated dual co-catalyst system(MnO_(x)/CdS/Pt)optimizes redox site orientation to address the challenge of disordered carrier transfer.This configuration maxi-mizes the utilization of both electrons and holes while establishing ultrafast electron transfer channels between CdS and Pt.The ultrafast electron transfer channels between spatially separated redox sites are demonstrated by femtosecond transient absorption(fs-TA)spectroscopy and in situ characterization.The average lifetime of MnO_(x)/CdS/Pt(MCSP)in a real reaction environment reduced from∼1352.6 to∼996.6 ps,compared to CdS alone.The interfacial electron transfer rate is accelerated to∼2.6×108 s^(-1),a substantial improvement over the CdS/Pt(∼6.0×10^(7) s^(-1)).Consequently,this system achieves efficient hydrogen production coupled with fine chemical synthesis.This work underscores the potential of ra-tional dual co-catalyst design with spatially separated redox sites as a promising strategy for developing high-performance photocatalytic platforms for solar fuel production.
基金the National Natural Science Foundation of China(NSFC,Nos.51908218 and 21905092)the Youth Elite Sailing Program of Shanghai Institute of Technology(No.1021GK240006002-A07)+2 种基金Scientific Research Foundation of Shanghai Institute of Technology(No.10120K226156-A06-YJ2022-62)Shanghai Higher Education Institution Young Teacher Training Funding Program(No.ZZ202312031)the Key Laboratory of Jiangsu Province for Chemical Pollution Control and Resources Reuse(Nanjing University of Science and Technology)。
文摘The facet effect of metal-organic frameworks(MOF)on regulating the property of loaded co-catalysts is an important but unexplored issue in the field of photocatalysis.In this work,a series of MIL-125-NH_(2)polyhedrons(MIL=Materials Institute Lavoisier)with facet exposure of{001},{001}/{111}and{111}are synthesized and used to load Pd-based co-catalysts for photocatalytic oxygen reduction reaction(ORR)toward H_(2)O_(2)production.The different facets with distinct chemical environments(Ti-O clusters on{111}facets and carboxyl ligands on{001}facets)result in the selective loading of Pd0and PdO dominated cocatalysts on{001}and{111}facets,respectively.The{001}/{111}co-exposed MIL-125-NH_(2)thus enables the spatially separated loading of Pd0and Pd O dual cocatalysts respectively.Pd0efficiently traps the photoexcited electrons and PdO trends to capture the holes,collaboratively promoting the directional separation of photogenerated electron-hole pairs.As a result,the photocatalytic ORR activity is significantly enhanced with a H_(2)O_(2)production rate of 128.6 mmol L^(-1)g^(-1)h^(-1),superior than pristine and single cocatalyst modified MIL-125-NH_(2)samples.Our findings provide new insight into the design of high-performance photocatalysts.
基金support from the National Key Technologies R&D Program of China(2022YFE0114800)National Natural Science Foundation of China(22075047),and the 111 Project(D16008)。
文摘Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.
文摘采用溶胶-凝胶法制备系列Mn-CoO_(x)复合氧化物催化剂。在质量空速为90000 m L/(g·h)的条件下,考察了Mn-CoO_(x)复合氧化物催化剂分别在电场辅助和常规条件下的CO催化氧化性能。结果表明:Mn-CoO_(x)催化剂在电场中展现了更优良的低温CO氧化活性,其中,Mn1Co5O_(x)在电场辅助下T _(50)(CO转化率为50%时对应的温度)较常规条件(不施加电场,仅通过管式炉升温)降低13℃(110℃完全转化)。催化剂的表征结果发现,引入电场可优化催化剂样品孔道结构,促进催化剂的电子转移,实现晶格氧活化而提升氧化还原能力。
