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
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion.However,their applications are challenged by the sluggish oxygen reducton reaction(ORR)kinetics at c...Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion.However,their applications are challenged by the sluggish oxygen reducton reaction(ORR)kinetics at cathodes owning to the low O_(2) solubility and diffusion rate.Herein,we proposed a photobiocatalytic fuel cell(PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase(ZIF-8/CDs/BOD@algae).Microalgae absorbed CO_(2) and provided O_(2) in situ for BOD catalysts.Due to effective absorption of O_(2) by imidazole and confinement of hydrophobic porous ZIF-8,oxygen diffusion has been accelerated in MOF/enzyme systems.Importantly,the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD.Thus,the biocathode exhibited a high current density of 1767 μA/cm^(2),a 2.26-fold increase compared with that of CDs/BOD/algae biocathode.Also,it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation.When coupled with Mo:BiVO_(4) photoanodes,the PBFC exhibited a remarkable power output of 131.8 μW/cm^(2) using tetracycline hydrochloride(TCH) as a fuel and an increased degradation rate of TCH.Therefore,this work not only establishs an effective confinement strategy for enzyme to enrich oxygen,but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.展开更多
Fractal assembly in discrete structures,especially for artificial supramolecular species,has attracted significantly increased interest over the past two decades.In this study,we present the precisely controlled fract...Fractal assembly in discrete structures,especially for artificial supramolecular species,has attracted significantly increased interest over the past two decades.In this study,we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face,which was achieved through a module-intervened self-expansion strategy.The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn^(2+)ions.Based on the triangular-faced prism S1,we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties.The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy,high-resolution electrospray ionization mass spectrometry,transmission electron microscopy,and atomic force microscopy.Furthermore,the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1.This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity,potentially opening new avenues for structural regulation of artificial fractal molecules.展开更多
The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environ...The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environmental purification.A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes,which can lead to over-oxidation and reduced selectivity and efficiency.To address these issues,we have developed a sodium-doped zinc oxide(Na-ZnO) modified with cobalt oxide(CoO) catalyst.This catalyst has demonstrated excellent performance in converting methane to low alcohols,achieving a yield of 130 μmol g^(-1)h^(-1) and a selectivity of up to 96 %.The doping of Na in ZnO significantly enhances methane adsorption,while the surface-modified CoO effectively captures photogenerated holes,activates water molecules,and uses hydroxyl radicals to activate methane,thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products.This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols,offering a new perspective for the application of photocatalytic technology in energy and environmental fields.展开更多
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia,helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network.Ohmic junct...Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia,helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network.Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination,but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes.In this study,density functional theory(DFT) calculations were used to confirm the work function matching between Bi and Bi_(2)Ti_(2)O_(7)(BTO),ensuring the formation of an Ohmic junction.A Bi-Bi_(2)Ti_(2)O_(7)(B-BTO) composite was successfully synthesized via a one-step hydrothermal method,using bismuth nitrate and titanium sulfate as precursors.Compared to pure BTO,the B-BTO heterojunction,driven by dual electron injection from both metal Bi and BTO,significantly increased the ammonia synthesis rate to 686.95 μmol g^(-1)h^(-1),making it the most active nitrogen fixation material among similar pyrochlorebased catalysts to date.The differential charge density calculations,photocurrent(i-t) measurements,and photoluminescence(PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes.This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.展开更多
Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchan...Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.展开更多
Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent...Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.展开更多
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.
基金support from National Natural Science Foundation of China (Nos.22176086,52100014)Natural Science Foundation of Jiangsu Province (No.BK20210189)+7 种基金State Key laboratory of Pollution Control and Resource Reuse,the Fundamental Research Funds for the Central Universities (Nos.021114380183,021114380189,021114380199)the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing UniversityResearch Funds for Jiangsu Distinguished ProfessorCarbon Peaking and Carbon Neutrality Technological Innovation Foundation of Jiangsu Province (No.BE2022861)the Central Universities - Cemac “Geo X” Interdisciplinary Program (No.021114380217)Frontiers Science Center for Critical Earth Material Cycling of Nanjing University (No.2024QNXZ07)Postdoctoral Fellowship Program of CPSF (No.GZC20231105)the Jiangsu Funding Program for Excellent Postdoctoral Talent (No.2023ZB226)。
文摘Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion.However,their applications are challenged by the sluggish oxygen reducton reaction(ORR)kinetics at cathodes owning to the low O_(2) solubility and diffusion rate.Herein,we proposed a photobiocatalytic fuel cell(PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase(ZIF-8/CDs/BOD@algae).Microalgae absorbed CO_(2) and provided O_(2) in situ for BOD catalysts.Due to effective absorption of O_(2) by imidazole and confinement of hydrophobic porous ZIF-8,oxygen diffusion has been accelerated in MOF/enzyme systems.Importantly,the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD.Thus,the biocathode exhibited a high current density of 1767 μA/cm^(2),a 2.26-fold increase compared with that of CDs/BOD/algae biocathode.Also,it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation.When coupled with Mo:BiVO_(4) photoanodes,the PBFC exhibited a remarkable power output of 131.8 μW/cm^(2) using tetracycline hydrochloride(TCH) as a fuel and an increased degradation rate of TCH.Therefore,this work not only establishs an effective confinement strategy for enzyme to enrich oxygen,but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
基金supported by the Major Science and Technology Projects of Yunnan Province(No.202302AB080016)the National Natural Science Foundation of China(Nos.22101060,22371056,and 52303269)the Science and Technology Research Project of Guangzhou(Nos.202201020201 and 2023A03J0624)。
文摘Fractal assembly in discrete structures,especially for artificial supramolecular species,has attracted significantly increased interest over the past two decades.In this study,we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face,which was achieved through a module-intervened self-expansion strategy.The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn^(2+)ions.Based on the triangular-faced prism S1,we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties.The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy,high-resolution electrospray ionization mass spectrometry,transmission electron microscopy,and atomic force microscopy.Furthermore,the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1.This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity,potentially opening new avenues for structural regulation of artificial fractal molecules.
基金support from the Zhejiang Provincial Natural Science Foundation of China (No.LQ24B030011)the Ningbo Natural Science Foundation (No.2023J181)+4 种基金the Open Research Fund of Key Laboratory of Functional Inorganic Materials Chemistry of the Ministry of Education (Heilongjiang University)the Start-up Funding offered by Ningbo University of Technology to J.D.LiNational Natural Science Foundation of China (No.U24A2071)Postdoctoral Research Start-up Fund (No.2111224002)Harbin Normal University Talent Plan (No.1305124213) to Y.D.Liu。
文摘The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environmental purification.A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes,which can lead to over-oxidation and reduced selectivity and efficiency.To address these issues,we have developed a sodium-doped zinc oxide(Na-ZnO) modified with cobalt oxide(CoO) catalyst.This catalyst has demonstrated excellent performance in converting methane to low alcohols,achieving a yield of 130 μmol g^(-1)h^(-1) and a selectivity of up to 96 %.The doping of Na in ZnO significantly enhances methane adsorption,while the surface-modified CoO effectively captures photogenerated holes,activates water molecules,and uses hydroxyl radicals to activate methane,thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products.This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols,offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
基金supported by the Natural Science Foundation of China (NSFC,No.52372212)。
文摘Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia,helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network.Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination,but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes.In this study,density functional theory(DFT) calculations were used to confirm the work function matching between Bi and Bi_(2)Ti_(2)O_(7)(BTO),ensuring the formation of an Ohmic junction.A Bi-Bi_(2)Ti_(2)O_(7)(B-BTO) composite was successfully synthesized via a one-step hydrothermal method,using bismuth nitrate and titanium sulfate as precursors.Compared to pure BTO,the B-BTO heterojunction,driven by dual electron injection from both metal Bi and BTO,significantly increased the ammonia synthesis rate to 686.95 μmol g^(-1)h^(-1),making it the most active nitrogen fixation material among similar pyrochlorebased catalysts to date.The differential charge density calculations,photocurrent(i-t) measurements,and photoluminescence(PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes.This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
基金financially supported the National Key R&D Program of China (No.2022YFA1502902)the National Natural Science Foundation of China (NSFC,Nos.22475152 and U21A20286)the 111 Project of China (No.D17003)。
文摘Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.
基金financially supported by the Innovation Capability Support Program of Shaanxi—Science and Technology Innovation Team Project(No.2025RS-CXTD-024)the Fundamental Research Foundation of SHCCIG New Materials Technology Research Institute Co.,Ltd(No.D5204230171)+3 种基金the Fundamental Research Funds for the Central Universities(G2025KY05240)the Natural Science Basic Research Program of Shaanxi(Program No.2024JC-YBQN-0073)the Fundamental Research Funds for the Central Universities(No.D5000250204)Young Talent Fund of Association for Science and Technology in Shaanxi(No.20230101)。
文摘Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.
