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
TiO2 nanosheets mainly exposed （001） facet were prepared through a hydrothermal process with HF as the morphology-directing agent. Ru and RuO2 species were loaded by photo-deposition methods to prepare the photocata...TiO2 nanosheets mainly exposed （001） facet were prepared through a hydrothermal process with HF as the morphology-directing agent. Ru and RuO2 species were loaded by photo-deposition methods to prepare the photocatalysts. The structural features of the catalysts were characterized by X-ray di raction, transmission electron microscopy, inductively cou-pled plasma atomic emission spectrum, and H2 Temperature-programmed reduction. The photocatalytic property was studied by the O2 evolution from water oxidation, which was examined with respect to the in uences of Ru contents as well as the oxidation and reduction treatments, suggesting the charge separation effect of the Ru species co-catalysts on di erent facets of TiO2 nanosheets. In contrast to Ru/TiO2 and RuO2/TiO2 with the single deposited co-catalyst, the optimized catalyst 0.5%Ru-1.0%RuO2/TiO2 with dual co-catalysts achieved a much improved catalytic performance, in terms of the synergetic effect of dual co-catalysts and the enhanced charge separation effect.展开更多
Graphitic carbon nitride(g-C3N4)was synthesized by heating melamine and was then treated with sodium hydroxide solution under a hydrothermal condition to obtain g-C3N4 with a large specific surface area(HSSA).HSSA sho...Graphitic carbon nitride(g-C3N4)was synthesized by heating melamine and was then treated with sodium hydroxide solution under a hydrothermal condition to obtain g-C3N4 with a large specific surface area(HSSA).HSSA shows higher photocatalytic activity for decomposition of acetaldehyde than that of original g-C3N4.HSSA was modified with RuO2 as a co-catalyst by the impregnation method.HSSA loaded with 0.05 wt%RuO2 shows the highest photocatalytic activity for acetaldehyde decomposition under visible light(k=455 nm).展开更多
精确构建了试剂体系,采用分阶段调控pH值策略制备镍基催化剂前驱体。在污水处理优化阶段,使用四维参数响应曲面优化方法,通过湿式浸渍法分散催化剂,利用响应曲面法设计实验,实施动态调控策略。结果表明:在温度为25℃、pH值为10和次氯酸...精确构建了试剂体系,采用分阶段调控pH值策略制备镍基催化剂前驱体。在污水处理优化阶段,使用四维参数响应曲面优化方法,通过湿式浸渍法分散催化剂,利用响应曲面法设计实验,实施动态调控策略。结果表明:在温度为25℃、pH值为10和次氯酸钠用量为15 m L时,去除率最高,达99.5%。镍基催化剂累计补加量在30~40 g范围内的去除率最高,达98.5%。研究提出的尿素共沉淀法合成的镍基催化剂能优化次氯酸钠分解速率和氧化性能,提高污水处理效果。展开更多
Accelerating the separation efficiency of photoexcited electron-hole pairs with the help of highly active co-catalysts has proven to be a promising approach for improving photocatalytic activity. Thus far, the most de...Accelerating the separation efficiency of photoexcited electron-hole pairs with the help of highly active co-catalysts has proven to be a promising approach for improving photocatalytic activity. Thus far, the most developed co-catalysts for semiconductor-based photocatalysis are inorganic materials;the employment of a specific organic molecule as a co-catalyst for photocatalytic hydrogen evolution and pollutant photodegradation is rare and still remains a challenging task. Herein, we report on the use of an organic molecule, oxamide (OA), as a novel co-catalyst to enhance electron- hole separation, photocatalytic H2 evolution, and dye degradation over TiO2 nanosheets. OA-modified TiO2 samples were prepared by a wet chemical route and demonstrated improved light absorption in the visible-light region and more efficient charge transport. The photocatalytic performance of H2 evolution from water splitting and rhodamine B (RhB) degradation for an optimal OA-modified TiO2 photocatalyst reached 2.37 mmol g^–1 h^–1 and 1.43 × 10^-2 min^-1, respectively, which were 2.4 and 3.8 times higher than those of pristine TiO2, respectively. A possible mechanism is proposed, in which the specific π-conjugated structure of OA is suggested to play a key role in the enhancement of the charge transfer and catalytic capability of TiO2. This work may provide advanced insight into the development of a variety of metal-free organic molecules as functional co-catalysts for improved solar-to-fuel conversion and environmental remediation.展开更多
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。
文摘TiO2 nanosheets mainly exposed （001） facet were prepared through a hydrothermal process with HF as the morphology-directing agent. Ru and RuO2 species were loaded by photo-deposition methods to prepare the photocatalysts. The structural features of the catalysts were characterized by X-ray di raction, transmission electron microscopy, inductively cou-pled plasma atomic emission spectrum, and H2 Temperature-programmed reduction. The photocatalytic property was studied by the O2 evolution from water oxidation, which was examined with respect to the in uences of Ru contents as well as the oxidation and reduction treatments, suggesting the charge separation effect of the Ru species co-catalysts on di erent facets of TiO2 nanosheets. In contrast to Ru/TiO2 and RuO2/TiO2 with the single deposited co-catalyst, the optimized catalyst 0.5%Ru-1.0%RuO2/TiO2 with dual co-catalysts achieved a much improved catalytic performance, in terms of the synergetic effect of dual co-catalysts and the enhanced charge separation effect.
基金financially supported by the Programs of Japan Science and Technology Agency:Promoting Individual Research to Nature the Seeds of Future Innovation and Organizing the Unique and Innovative Network,and Advanced Catalytic Transformation Program for Carbon Utilization
文摘Graphitic carbon nitride(g-C3N4)was synthesized by heating melamine and was then treated with sodium hydroxide solution under a hydrothermal condition to obtain g-C3N4 with a large specific surface area(HSSA).HSSA shows higher photocatalytic activity for decomposition of acetaldehyde than that of original g-C3N4.HSSA was modified with RuO2 as a co-catalyst by the impregnation method.HSSA loaded with 0.05 wt%RuO2 shows the highest photocatalytic activity for acetaldehyde decomposition under visible light(k=455 nm).
文摘精确构建了试剂体系,采用分阶段调控pH值策略制备镍基催化剂前驱体。在污水处理优化阶段,使用四维参数响应曲面优化方法,通过湿式浸渍法分散催化剂,利用响应曲面法设计实验,实施动态调控策略。结果表明:在温度为25℃、pH值为10和次氯酸钠用量为15 m L时,去除率最高,达99.5%。镍基催化剂累计补加量在30~40 g范围内的去除率最高,达98.5%。研究提出的尿素共沉淀法合成的镍基催化剂能优化次氯酸钠分解速率和氧化性能,提高污水处理效果。
基金supported by the National Natural Science Foundation of China(51672113,51602132)the Six Talent Peaks Project in Jiangsu Province(2015-XCL-026)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20171299)the Training Project of Jiangsu University for Young Cadre Teachers(5521220009)the Youth Research Project of Jiangsu Health and Family Planning Commission in 2016(Q201609)~~
文摘Accelerating the separation efficiency of photoexcited electron-hole pairs with the help of highly active co-catalysts has proven to be a promising approach for improving photocatalytic activity. Thus far, the most developed co-catalysts for semiconductor-based photocatalysis are inorganic materials;the employment of a specific organic molecule as a co-catalyst for photocatalytic hydrogen evolution and pollutant photodegradation is rare and still remains a challenging task. Herein, we report on the use of an organic molecule, oxamide (OA), as a novel co-catalyst to enhance electron- hole separation, photocatalytic H2 evolution, and dye degradation over TiO2 nanosheets. OA-modified TiO2 samples were prepared by a wet chemical route and demonstrated improved light absorption in the visible-light region and more efficient charge transport. The photocatalytic performance of H2 evolution from water splitting and rhodamine B (RhB) degradation for an optimal OA-modified TiO2 photocatalyst reached 2.37 mmol g^–1 h^–1 and 1.43 × 10^-2 min^-1, respectively, which were 2.4 and 3.8 times higher than those of pristine TiO2, respectively. A possible mechanism is proposed, in which the specific π-conjugated structure of OA is suggested to play a key role in the enhancement of the charge transfer and catalytic capability of TiO2. This work may provide advanced insight into the development of a variety of metal-free organic molecules as functional co-catalysts for improved solar-to-fuel conversion and environmental remediation.
