The synergistic integration of metal catalysis with electrochemistry has emerged as a powerful tool for organic synthesis.However,in nickel-catalyzed electrochemical crosscoupling reactions,mismatches between external...The synergistic integration of metal catalysis with electrochemistry has emerged as a powerful tool for organic synthesis.However,in nickel-catalyzed electrochemical crosscoupling reactions,mismatches between external conditions and reaction rates often lead to side reactions such as catalyst deactivation,homocoupling,and protonation.Addressing this issue through the development of strategies is highly desirable.Herein,we report the successful merging of photochemistry with electrochemistry to facilitate nickel-catalyzed C−O cross-coupling reactions,providing a practical method for the synthesis of alkyl aryl ethers.Preliminary mechanistic studies suggest that this photoelectrochemical strategy effectively enhances the efficiency of nickelcatalyzed C−O cross-coupling reactions compared to traditional electrochemical methods by regenerating the active Ni^(Ⅰ) catalyst from the Ni^(Ⅱ) species through photochemistry.展开更多
Electrodeposition of CulnSe, was investigated in acidic solutions containing Cu^(2+), In^(3+) and HSeO_2^+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium s...Electrodeposition of CulnSe, was investigated in acidic solutions containing Cu^(2+), In^(3+) and HSeO_2^+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium substrate. The mechanism of the electrodeposition process is discussed. Structure analysis of the deposited film shows a typical polycrystalline chalcopyrite structure, good crystallinity and homogeneous dispersion. The photoelectrochemical cells made of these kinds of deposited films in polysulfide redox solution give distinct photoresponse.展开更多
Precise and sensitive bioanalysis has been the major and urgent pursuit in pathologic diagnosis,food safety,environment monitoring,and drug evaluation.Photoelectrochemical(PEC)bioanalysis,as one of the most promising ...Precise and sensitive bioanalysis has been the major and urgent pursuit in pathologic diagnosis,food safety,environment monitoring,and drug evaluation.Photoelectrochemical(PEC)bioanalysis,as one of the most promising detection technologies,has rapidly expanded within the field of analysis.However,most of reported PEC analysis approaches still suffer from weak external anti-interference ability,high background,and the risk of false positive or negative errors due to their inherent single-signal readout.To overcome these shortcomings,new PEC-coupled dual-modal analysis approaches have been developed,where a dual-response signal can be derived through two completely different mechanisms and independent signal transduction pathways.This review introduces the basic principles of PEC biosensing and enumerates and classifies the substrate or probe selections,constructions,and applications of PEC-coupled dual-modal biosensors.Furthermore,the challenges and developmental prospects of PEC-coupled dual-mode sensing technologies are evaluated and discussed.We hope that this review will provide valuable insights into the latest advancements and practical applications of dual-mode PEC bioanalysis,which will be of great interest to those seeking to stay informed in this field.展开更多
Organometallic halide perovskites have garnered significant attention in various fields of material science,particularly solar energy conversion,due to their desirable optoelectronic properties and compatibility with ...Organometallic halide perovskites have garnered significant attention in various fields of material science,particularly solar energy conversion,due to their desirable optoelectronic properties and compatibility with scalable fabrication techniques.It is often unclear,however,how carrier generation and transport within complex polycrystalline films are influenced by variations in local structure.Elucidating how distinct structural motifs within these heterogeneous systems affect behavior could help guide the continued improvement of perovskite-based solar cells.Here,we present studies applying scanning electron microscopy(SECCM)to map solar energy harvesting within well-defined model systems of organometallic halide perovskites.Methylammonium lead bromide(MAPbBr3)single crystals were prepared via a low-temperature solution-based route,and their photoelectrochemical properties were mapped via SECCM using p-benzoquinone(BQ)in dichloromethane as a redox mediator.Correlated SECCM mapping and electron microscopy studies enabled facet-to-facet variations in photoelectrochemical performance to be revealed and carrier transport lengths to be evaluated.The photoelectrochemical behavior observed within individual single crystals was quite heterogeneous,attributable to local variations in crystal structure/orientations,intrafacet junctions,and the presence of other structural defects.These observations underscore the significance of controlling the microstructure of single perovskite crystals,presenting a promising avenue for further enhancement of perovskitebased solar cells.展开更多
The potentiostatic deposition of cadmium-rich CMT films onto Ti, Mo, Ni substrates from an aqueous bath was carried out. The photoelectrochemical properties of film electrodes were investigated when used in a solid-li...The potentiostatic deposition of cadmium-rich CMT films onto Ti, Mo, Ni substrates from an aqueous bath was carried out. The photoelectrochemical properties of film electrodes were investigated when used in a solid-liquid junction photoelectrochemical cell (PEC). A.C. capacitance was determined.展开更多
Solar water splitting is an emerging technology for producing clean and renewable hydrogen fuel from sunlight and water.Among various photoelectrode materials,bismuth vanadate(BiVO_(4))has attracted considerable atten...Solar water splitting is an emerging technology for producing clean and renewable hydrogen fuel from sunlight and water.Among various photoelectrode materials,bismuth vanadate(BiVO_(4))has attracted considerable attention due to its visible light absorption,favorable band edge positions,good chemical stability,and low cost.However,the solar water splitting efficiency of BiVO_(4) photoanodes is still far from satisfactory,mainly because of the low charge carrier mobility,high recombination rate,and slow water oxidation kinetics.In this review,we summarize the recent progress in the synthesis,modification,and application of BiVO_(4)-based photoelectrodes for photoelectrochemical(PEC)water splitting.The working principle of PEC water splitting and the fundamental properties of BiVO_(4) are introduced.Then,the synthesis methods of BiVO_(4) films are reviewed,and the strategies to enhance the PEC properties of BiVO_(4) are critically discussed.Furthermore,the applications of BiVO_(4)-based photoelectrodes in different scenarios are highlighted.Finally,the summary and outlook for the future development of BiVO_(4)-based photoelectrodes for PEC water splitting are presented.展开更多
Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor...Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.展开更多
A series of Zr-doped CaTiO3 powders were prepared with the mild co-precipitation method and calcined at 850℃ for 3 h. The as-prepared Zr-doped CaTiO3 samples were characterized by scanning electron microscopy （SEM）...A series of Zr-doped CaTiO3 powders were prepared with the mild co-precipitation method and calcined at 850℃ for 3 h. The as-prepared Zr-doped CaTiO3 samples were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, UV-Vis diffuse reflectance spectra （DRS） and X-ray photoelectron spectra （XPS）. XRD result revealed the presence of single perovskite phase of CaTiO3. UV-Vis diffusive reflection spectra of Zr-doped CaTiO3 indicated that the absorbance obviously increased in the visible light irradiation. XPS analysis showed that two types of oxygen existed on the photocatalyst surface, including lattice oxygen and absorbed oxygen. Their photocatalytic activity in the case of the degradation of methyl orange in water and photoelectrochemical activity were also tested. The 5%Zr-doped （mole fraction） CaTiO3 sample showed the highest photocatalytic activity. The enhanced photocatalytic activity was ascribed to the change of the lattice structure, existence of oxygen vacancies and increase of the photogenerated charge separation efficiency.展开更多
Photocatalysis and electrocatalysis have been essential parts of electrochemical processes for over half a century.Recent progress in the controllable synthesis of 2D nanomaterials has exhibited enhanced catalytic per...Photocatalysis and electrocatalysis have been essential parts of electrochemical processes for over half a century.Recent progress in the controllable synthesis of 2D nanomaterials has exhibited enhanced catalytic performance compared to bulk materials.This has led to significant interest in the exploitation of 2D nanomaterials for catalysis.There have been a variety of excellent reviews on 2D nanomaterials for catalysis,but related issues of differences and similarities between photocatalysis and electrocatalysis in 2D nanomaterials are still vacant.Here,we provide a comprehensive overview on the differences and similarities of photocatalysis and electrocatalysis in the latest 2D nanomaterials.Strategies and traps for performance enhancement of 2D nanocatalysts are highlighted,which point out the differences and similarities of series issues for photocatalysis and electrocatalysis.In addition,2D nanocatalysts and their catalytic applications are discussed.Finally,opportunities,challenges and development directions for 2D nanocatalysts are described.The intention of this review is to inspire and direct interest in this research realm for the creation of future 2D nanomaterials for photocatalysis and electrocatalysis.展开更多
Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and tita...Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and titanium dioxide(TiO2) is the most widely used photoanode.This review summarizes the progress in TiO2 photo gene rated protection in recent years.Different types of semiconductors,including sulfides,metals,metal oxide s,polymers,and other materials,are used to design and modify TiO2.The strategy to dramatically improve the efficiency of photoactivity is proposed,and the mechanism is investigated in detail.Characterization methods are also introduced,including morphology testing,light absorption,photoelectrochemistry,and protected metal observation.This review aims to provide a comprehensive overview of Ti02 development and guide photocathodic protection.展开更多
Industrial NH3 production mainly employs the well‐known Haber‐Bosch(H‐B)process,which is associated with significant energy consumption and carbon emissions.Photoelectrochemical nitro‐gen reduction reaction(PEC‐N...Industrial NH3 production mainly employs the well‐known Haber‐Bosch(H‐B)process,which is associated with significant energy consumption and carbon emissions.Photoelectrochemical nitro‐gen reduction reaction(PEC‐NRR)under ambient conditions is considered a promising alternative to the H‐B process and has been attracting increasing attention owing to its associated energy effi‐ciency and environmentally friendly characteristics.The performance of a PEC‐NRR system,such as the NH_(3) yield,selectivity,and stability,is essentially determined by its key component,the photo‐cathode.In this review,the latest progress in the development of photocathode materials employed in PEC‐NRR is evaluated.The fundamental mechanisms and essential features required for the PEC‐NRR are introduced,followed by a discussion of various types of photocathode materials,such as oxides,sulfides,selenides,black silicon,and black phosphorus.In particular,the PEC‐NRR reac‐tion mechanisms associated with these photocathode materials are reviewed in detail.Finally,the present challenges and future opportunities related to the further development of PEC‐NRR are also discussed.This review aims to improve the understanding of PEC‐NRR photocathode materials while also shedding light on the new concepts and significant innovations in this field.展开更多
Ag-TiO2/ITO film electrode was used as photoanode to investigate the feasibility of a hybrid technology of Ag nanoparticles combined with the application of anodic bias. The results showed that the deposited Ag and a...Ag-TiO2/ITO film electrode was used as photoanode to investigate the feasibility of a hybrid technology of Ag nanoparticles combined with the application of anodic bias. The results showed that the deposited Ag and applied anodic bias have an apparent additive effect.展开更多
Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe3N nanoparticles encapsulated into N...Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe3N nanoparticles encapsulated into N-doped graphene nanoshells(Fe_(3)N@NG)as OER electrocatalysts in alkaline media were reported.Both the experimental and theoretical comparison between Fe_(3) N@NG and Fe_(3)N/NG,specifically including in situ Mossbauer analyses,demonstrated that the NG nanoshells improved interfacial electron transfer process from Fe_(3)N to NG to form high-valence Fe^(4+)ions(Fe^(4+)@NG),thus modifying electronic properties of the outer NG shells and subsequently electron transfer from oxygen intermediate to NG nanoshells for OER catalytic process.Meanwhile,the NG nanoshells also protected Fe-based cores from forming OER inactive and insulated Fe_(2)O_(3),leading to high OER stability.As a result,the as-formed Fe^(4+)@NG shows one of the highest electrocatalytic efficiency among reported Fe-based OER electrocatalysts,which can as well highly improve the photoelectrochemical water oxidation when used as the cocatalysts for the Fe_(2)O_(3) nanoarray photoanode.展开更多
Highly oriented ZnO nanotube array films on the conducting substrates have been synthesized by a simple hydrothermal method and characterized by scanning electron microscopy (SEM) and UV-Vis spectroscopy. The thin fi...Highly oriented ZnO nanotube array films on the conducting substrates have been synthesized by a simple hydrothermal method and characterized by scanning electron microscopy (SEM) and UV-Vis spectroscopy. The thin films consisting of laterally fragmentized ZnO nanotubes with controlled orientation have been tested as photoanode in Gr鋞zel-type solar cell. For a sandwich-type cell, with 0.5 mol/L LiI and 0.05 mol/L I2 in propylene carbonate electrolyte, the overall solar energy conversion efficiency reaches 2.3%.展开更多
Iron oxide nanostructures are promising materials to be used as photocatalysts in different photoelectrochemical applications. There are different techniques in order to synthesize these nanostructures, but one of the...Iron oxide nanostructures are promising materials to be used as photocatalysts in different photoelectrochemical applications. There are different techniques in order to synthesize these nanostructures, but one of the most inexpensive and simple method is electrochemical anodization. This method can lead to different nanostructures by controlling its parameters. Anodization time is one of the most critical parameters since it considerably affects the properties of the obtained nanostructures. In this work, different anodization times(5, 10, 15, 30 and 60 min) were studied. The resulting nanotubes were characterized by field emission scanning electron microscopy, Raman laser confocal microscopy, water splitting measurements, Mott-Schottky analysis and electrochemical impedance spectroscopy, in order to test their viability for being used as photocatalysts in photoelectrochemical applications. Results showed that the best photocurrent density values in water splitting tests(0.263 m A m-2) were achieved for the sample anodized for 10 min under hydrodynamic conditions.展开更多
A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was charac...A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was characterized by X‐ray powder diffraction,scanning electron microscopy,and energy dispersive X‐ray spectroscopy.Linear sweep voltammetry,chronoamperometry,and electrochemical impedance measurements were performed in aqueous Na2SO4solution(0.1molL?1).We found that a higher applied voltage led to better catalytic performance by AgPW11.The AgPW11‐TiO2/ITO electrode gave currents respectively10and2.5times as high as those of the TiO2/ITO and AgNO3‐TiO2/ITO electrodes at an applied voltage of1.5V vs Ag/AgCl.This result was attributed to the lower charge transfer resistance at the electrode‐electrolyte interface for the AgPW11‐TiO2/ITO electrode.Under illumination,the photocurrent was not obviously enhanced although the total anode current increased.The AgPW11‐TiO2/ITO electrode was relatively stable.Cyclic voltammetry of AgPW11was performed in phosphate buffer solution(0.1mol L?1).We found that oxidation of AgPW11was a quasi‐reversible process related to one‐electron and one‐proton transfer.We deduced that disproportionation of the oxidized[H2AgII(H2O)PW11O39]3?might have occurred and the resulting[H3AgIIIOPW11O39]3?oxidized water to O2.展开更多
Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water ...Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water to oxygen,particularly with readily available and inexpensive electrolyte solutions such as seawater.While metal oxide materials have demonstrated their advantages in promoting efficiency by reducing overpotential and improving light utilization,stability remains limited by corrosion in multicomponent seawater.In this paper,we reviewed the relationship between four basic concepts including photoelectrochemistry,metal oxide,water oxidation and seawater to better understand the challenges and opportunities in photoelectrochemical(PEC)seawater oxidation.To overcome these challenges,the advances in material design,interfacial modification,local environment control and reactor design have been further reviewed to benefit the industrial PEC seawater oxidation.Noticeably,we demonstrate engineered layered metal oxide electrodes and cell structures that enable powerful and stable seawater oxidation.We also outline and advise on the future direction in this area.展开更多
Core–shell nanoparticles containing plasmonic metals（Ag or Au） have been frequently reported to enhance performance of photo-electrochemical（PEC） devices. However, the stability of these particles in water-splitt...Core–shell nanoparticles containing plasmonic metals（Ag or Au） have been frequently reported to enhance performance of photo-electrochemical（PEC） devices. However, the stability of these particles in water-splitting conditions is usually not addressed. In this study we demonstrate that Ag@SiOcore–shell particles are instable in the acidic conditions in which WO-based PEC cells typically operate, Ag in the core being prone to oxidation, even if the SiOshell has a thickness in the order of 10 nm. This is evident from in situ voltammetry studies of several anode composites. Similar to the results of the PEC experiments, the Ag@SiOcore–shell particles are instable in slurry-based, Pt/ZnO induced photocatalytic water-splitting. This was evidenced by in situ photodeposition of Ag nanoparticles on the Pt-loaded ZnO catalyst, observed in TEM micrographs obtained after reaction. We explain the instability of Ag@SiOby OH-radical induced oxidation of Ag, yielding dissolved Ag+. Our results imply that a decrease in shell permeability for OH-radicals is necessary to obtain stable, Ag-based plasmonic entities in photo-electrochemical and photocatalytic water splitting.展开更多
Accurate detection of important biomarkers with ultra-low levels in complex biological matrix is one of the frontier scientific issues because of possible signal interference of potential reductive agents and protein ...Accurate detection of important biomarkers with ultra-low levels in complex biological matrix is one of the frontier scientific issues because of possible signal interference of potential reductive agents and protein molecules.Herein,a self-powered anti-interference photoelectrochemical(PEC)immunosensor was explored for sensitive and specific detection of model target of cardiac troponinⅠ(cTnI).Specifically,a novel ternary heterojunction served as the photocathode to offer a remarkable current output and a zwitterionic peptide was introduced to build a robust antifouling biointerface.CuInS(CIS)film with porous network nanostructure was first prepared and then modified in order with ZnInS(ZIS)nanocrystals and Au nanoparticles to fabricate the Au/ZIS/CIS heterojunction photocathode.After capture cTnI antibody(Ab)was immobilized,the zwitterionic peptide KAEAKAEAPPPPC was then anchored to compete the immunosensor.The elaborated PEC immunosensor exhibited high sensitivity for target cTnI antigen(Ag)detection,with good anti-interference against reductive agents and nonspecific proteins.This integration strategy of heterojunction photocathode with zwitterionic peptide provides a new sight to develop advanced PEC immunosensors applying in practical biosamples.展开更多
The MWCNT-Ti02 hybrid materials were prepared by a simply mixing method and used as a counter electrode （CE） for dye-sensitized solar cells. Compared with the platinum CE, MWCNT-TiO2 CE has the similar redox voltage...The MWCNT-Ti02 hybrid materials were prepared by a simply mixing method and used as a counter electrode （CE） for dye-sensitized solar cells. Compared with the platinum CE, MWCNT-TiO2 CE has the similar redox voltage and current response in the cyclic voltammetry. The electrochemical catalytic activity was characterized by the electrochemical impedance spectroscopy and Tafel curve, including the equivalent circuit, the exchange current density, the limiting diffusion current density, and the diffusion coefficient of triiodide/iodide redox species. The results indicate that the reduction process from triiodide to iodide is determined by the kinetic-controlled and diffusion-limited processes. The device performance is optimal based on the MWCNT-TiO2 （mass ratio of 2：1） CE, such as the open-circuit voltage of 0.72 V, the short-circuit photocurrent density of 15.71 mA/cm2, the fill factor of 0.68, and the photon-to-electron conversion efficiency of 7.69%.展开更多
基金supported by National Key R&D Program of China(2021YFA1500100)NSF of China(21821002,22101294,22425111,22361142834)+2 种基金S&TCSM of Shanghai(21ZR1476500)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000)Natural Science Foundation of Ningbo Municipality(2023J035).
文摘The synergistic integration of metal catalysis with electrochemistry has emerged as a powerful tool for organic synthesis.However,in nickel-catalyzed electrochemical crosscoupling reactions,mismatches between external conditions and reaction rates often lead to side reactions such as catalyst deactivation,homocoupling,and protonation.Addressing this issue through the development of strategies is highly desirable.Herein,we report the successful merging of photochemistry with electrochemistry to facilitate nickel-catalyzed C−O cross-coupling reactions,providing a practical method for the synthesis of alkyl aryl ethers.Preliminary mechanistic studies suggest that this photoelectrochemical strategy effectively enhances the efficiency of nickelcatalyzed C−O cross-coupling reactions compared to traditional electrochemical methods by regenerating the active Ni^(Ⅰ) catalyst from the Ni^(Ⅱ) species through photochemistry.
基金Project supported by the National Natural Science Foundation of China
文摘Electrodeposition of CulnSe, was investigated in acidic solutions containing Cu^(2+), In^(3+) and HSeO_2^+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium substrate. The mechanism of the electrodeposition process is discussed. Structure analysis of the deposited film shows a typical polycrystalline chalcopyrite structure, good crystallinity and homogeneous dispersion. The photoelectrochemical cells made of these kinds of deposited films in polysulfide redox solution give distinct photoresponse.
基金the National Natural Science Foundation of China(Nos.52303153 and 51873145)the Basic science(Natural science)research project in universities of Jiangsu Province(No.23KJB150035)+2 种基金the Excellent Youth Foundation of Jiangsu Scientific Committee(No.BK20170065)the Qing Lan Project,the 5th 333 High-level Talents Training Project of Jiangsu Province(No.BRA2018340)the Six Talent Peaks Project in Jiangsu Province(No.XCL-79).
文摘Precise and sensitive bioanalysis has been the major and urgent pursuit in pathologic diagnosis,food safety,environment monitoring,and drug evaluation.Photoelectrochemical(PEC)bioanalysis,as one of the most promising detection technologies,has rapidly expanded within the field of analysis.However,most of reported PEC analysis approaches still suffer from weak external anti-interference ability,high background,and the risk of false positive or negative errors due to their inherent single-signal readout.To overcome these shortcomings,new PEC-coupled dual-modal analysis approaches have been developed,where a dual-response signal can be derived through two completely different mechanisms and independent signal transduction pathways.This review introduces the basic principles of PEC biosensing and enumerates and classifies the substrate or probe selections,constructions,and applications of PEC-coupled dual-modal biosensors.Furthermore,the challenges and developmental prospects of PEC-coupled dual-mode sensing technologies are evaluated and discussed.We hope that this review will provide valuable insights into the latest advancements and practical applications of dual-mode PEC bioanalysis,which will be of great interest to those seeking to stay informed in this field.
基金support for this work from the National Science Foundation(CHE-2045593)the University of Wyoming School of Energy Resources.
文摘Organometallic halide perovskites have garnered significant attention in various fields of material science,particularly solar energy conversion,due to their desirable optoelectronic properties and compatibility with scalable fabrication techniques.It is often unclear,however,how carrier generation and transport within complex polycrystalline films are influenced by variations in local structure.Elucidating how distinct structural motifs within these heterogeneous systems affect behavior could help guide the continued improvement of perovskite-based solar cells.Here,we present studies applying scanning electron microscopy(SECCM)to map solar energy harvesting within well-defined model systems of organometallic halide perovskites.Methylammonium lead bromide(MAPbBr3)single crystals were prepared via a low-temperature solution-based route,and their photoelectrochemical properties were mapped via SECCM using p-benzoquinone(BQ)in dichloromethane as a redox mediator.Correlated SECCM mapping and electron microscopy studies enabled facet-to-facet variations in photoelectrochemical performance to be revealed and carrier transport lengths to be evaluated.The photoelectrochemical behavior observed within individual single crystals was quite heterogeneous,attributable to local variations in crystal structure/orientations,intrafacet junctions,and the presence of other structural defects.These observations underscore the significance of controlling the microstructure of single perovskite crystals,presenting a promising avenue for further enhancement of perovskitebased solar cells.
文摘The potentiostatic deposition of cadmium-rich CMT films onto Ti, Mo, Ni substrates from an aqueous bath was carried out. The photoelectrochemical properties of film electrodes were investigated when used in a solid-liquid junction photoelectrochemical cell (PEC). A.C. capacitance was determined.
基金financially supported by the National Natural Science Foundation of China(No.52372292)Shenzhen Science and Technology Program(No.JCYJ20220530161615035)+1 种基金the Fundamental Research Funds for the Central Universitiesthe International Science and Technology Cooperation Program of Henan Province(No.232102520018).
文摘Solar water splitting is an emerging technology for producing clean and renewable hydrogen fuel from sunlight and water.Among various photoelectrode materials,bismuth vanadate(BiVO_(4))has attracted considerable attention due to its visible light absorption,favorable band edge positions,good chemical stability,and low cost.However,the solar water splitting efficiency of BiVO_(4) photoanodes is still far from satisfactory,mainly because of the low charge carrier mobility,high recombination rate,and slow water oxidation kinetics.In this review,we summarize the recent progress in the synthesis,modification,and application of BiVO_(4)-based photoelectrodes for photoelectrochemical(PEC)water splitting.The working principle of PEC water splitting and the fundamental properties of BiVO_(4) are introduced.Then,the synthesis methods of BiVO_(4) films are reviewed,and the strategies to enhance the PEC properties of BiVO_(4) are critically discussed.Furthermore,the applications of BiVO_(4)-based photoelectrodes in different scenarios are highlighted.Finally,the summary and outlook for the future development of BiVO_(4)-based photoelectrodes for PEC water splitting are presented.
基金supported by the Natural Science Foundation of Guangxi Province(2021GXNSFBA220077,GUIKE AD23026050)National Natural Science Foundation of China(22102035 and 22162006)Innovation Project of Guangxi Graduate Education(XYCBZ2024021).
文摘Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.
基金Projects(5070202051402100+5 种基金81171461)supported by the National Natural Science Foundation of ChinaProject(11JJ4013)supported by the Natural Science Foundation of Hunan Province,ChinaProject(2013GK3155)supported by Science&Technology Project of Hunan Province,ChinaProject supported by the Youth 1000 Talent Program of ChinaProject supported by the Interdisciplinary Research Program of Hunan University,ChinaProject supported by the Young Teacher Promotion Fund by Hunan University,China
文摘A series of Zr-doped CaTiO3 powders were prepared with the mild co-precipitation method and calcined at 850℃ for 3 h. The as-prepared Zr-doped CaTiO3 samples were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, UV-Vis diffuse reflectance spectra （DRS） and X-ray photoelectron spectra （XPS）. XRD result revealed the presence of single perovskite phase of CaTiO3. UV-Vis diffusive reflection spectra of Zr-doped CaTiO3 indicated that the absorbance obviously increased in the visible light irradiation. XPS analysis showed that two types of oxygen existed on the photocatalyst surface, including lattice oxygen and absorbed oxygen. Their photocatalytic activity in the case of the degradation of methyl orange in water and photoelectrochemical activity were also tested. The 5%Zr-doped （mole fraction） CaTiO3 sample showed the highest photocatalytic activity. The enhanced photocatalytic activity was ascribed to the change of the lattice structure, existence of oxygen vacancies and increase of the photogenerated charge separation efficiency.
基金supported by the National Key R&D Project from Minister of Science and Technology in China(No.2016YFA0202701,No.2018YFB2200500)the National Natural Science Foundation of China(No.52072041,No.61604012,No.61974170)the University of Chinese Academy of Sciences(Grant No.Y8540XX2D2)。
文摘Photocatalysis and electrocatalysis have been essential parts of electrochemical processes for over half a century.Recent progress in the controllable synthesis of 2D nanomaterials has exhibited enhanced catalytic performance compared to bulk materials.This has led to significant interest in the exploitation of 2D nanomaterials for catalysis.There have been a variety of excellent reviews on 2D nanomaterials for catalysis,but related issues of differences and similarities between photocatalysis and electrocatalysis in 2D nanomaterials are still vacant.Here,we provide a comprehensive overview on the differences and similarities of photocatalysis and electrocatalysis in the latest 2D nanomaterials.Strategies and traps for performance enhancement of 2D nanocatalysts are highlighted,which point out the differences and similarities of series issues for photocatalysis and electrocatalysis.In addition,2D nanocatalysts and their catalytic applications are discussed.Finally,opportunities,challenges and development directions for 2D nanocatalysts are described.The intention of this review is to inspire and direct interest in this research realm for the creation of future 2D nanomaterials for photocatalysis and electrocatalysis.
基金the CAS Strategic Priority Project(No.XDA13040404)the National Natural Science Foundation of China for Exploring Key Scientific Instrument(No.41827805)the Shandong Key Laboratory of Corrosion Science。
文摘Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and titanium dioxide(TiO2) is the most widely used photoanode.This review summarizes the progress in TiO2 photo gene rated protection in recent years.Different types of semiconductors,including sulfides,metals,metal oxide s,polymers,and other materials,are used to design and modify TiO2.The strategy to dramatically improve the efficiency of photoactivity is proposed,and the mechanism is investigated in detail.Characterization methods are also introduced,including morphology testing,light absorption,photoelectrochemistry,and protected metal observation.This review aims to provide a comprehensive overview of Ti02 development and guide photocathodic protection.
文摘Industrial NH3 production mainly employs the well‐known Haber‐Bosch(H‐B)process,which is associated with significant energy consumption and carbon emissions.Photoelectrochemical nitro‐gen reduction reaction(PEC‐NRR)under ambient conditions is considered a promising alternative to the H‐B process and has been attracting increasing attention owing to its associated energy effi‐ciency and environmentally friendly characteristics.The performance of a PEC‐NRR system,such as the NH_(3) yield,selectivity,and stability,is essentially determined by its key component,the photo‐cathode.In this review,the latest progress in the development of photocathode materials employed in PEC‐NRR is evaluated.The fundamental mechanisms and essential features required for the PEC‐NRR are introduced,followed by a discussion of various types of photocathode materials,such as oxides,sulfides,selenides,black silicon,and black phosphorus.In particular,the PEC‐NRR reac‐tion mechanisms associated with these photocathode materials are reviewed in detail.Finally,the present challenges and future opportunities related to the further development of PEC‐NRR are also discussed.This review aims to improve the understanding of PEC‐NRR photocathode materials while also shedding light on the new concepts and significant innovations in this field.
基金Financial support by NNSF(20277046)NSF(990274)+1 种基金EPA(1999-14)Sci.and Technol.Proj.(A3030502)of Guangdong and The Key Lab.of Environ.Sci.Technol.of Hennan.
文摘Ag-TiO2/ITO film electrode was used as photoanode to investigate the feasibility of a hybrid technology of Ag nanoparticles combined with the application of anodic bias. The results showed that the deposited Ag and applied anodic bias have an apparent additive effect.
基金supported primarily by the National Key Research and Development Program of China(2018YFE0208500)the Major Research Plan of the National Natural Science Foundation of China(91963206)+4 种基金the National Natural Science Foundation of China(U1508202,51627810,51972164)the Natural Science Foundation of Jiangsu Province(SBK2018022120)the open fund of Wuhan National Laboratory for Optoelectronics(2018WNLOKF020)the open fund of Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies(EEST2018-1)the civil aerospace technology preliminary research project of the State Administration of Science,Technology and Industry for National Defense。
文摘Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe3N nanoparticles encapsulated into N-doped graphene nanoshells(Fe_(3)N@NG)as OER electrocatalysts in alkaline media were reported.Both the experimental and theoretical comparison between Fe_(3) N@NG and Fe_(3)N/NG,specifically including in situ Mossbauer analyses,demonstrated that the NG nanoshells improved interfacial electron transfer process from Fe_(3)N to NG to form high-valence Fe^(4+)ions(Fe^(4+)@NG),thus modifying electronic properties of the outer NG shells and subsequently electron transfer from oxygen intermediate to NG nanoshells for OER catalytic process.Meanwhile,the NG nanoshells also protected Fe-based cores from forming OER inactive and insulated Fe_(2)O_(3),leading to high OER stability.As a result,the as-formed Fe^(4+)@NG shows one of the highest electrocatalytic efficiency among reported Fe-based OER electrocatalysts,which can as well highly improve the photoelectrochemical water oxidation when used as the cocatalysts for the Fe_(2)O_(3) nanoarray photoanode.
文摘Highly oriented ZnO nanotube array films on the conducting substrates have been synthesized by a simple hydrothermal method and characterized by scanning electron microscopy (SEM) and UV-Vis spectroscopy. The thin films consisting of laterally fragmentized ZnO nanotubes with controlled orientation have been tested as photoanode in Gr鋞zel-type solar cell. For a sandwich-type cell, with 0.5 mol/L LiI and 0.05 mol/L I2 in propylene carbonate electrolyte, the overall solar energy conversion efficiency reaches 2.3%.
基金financial support granted to Bianca Lucas Granados by the Ministerio de Economía y Competitividad(Reference,BES-2014-068713 and Project CTQ2016-79203-R)for its help in the Laser Raman Microscope acquisition(UPOV08-3E-012)+1 种基金the co-finance by the European Social Fundthe UPV for the concession of a postdoctoral grant(PAID-10-17)to Ramón M.Fernández Domene.
文摘Iron oxide nanostructures are promising materials to be used as photocatalysts in different photoelectrochemical applications. There are different techniques in order to synthesize these nanostructures, but one of the most inexpensive and simple method is electrochemical anodization. This method can lead to different nanostructures by controlling its parameters. Anodization time is one of the most critical parameters since it considerably affects the properties of the obtained nanostructures. In this work, different anodization times(5, 10, 15, 30 and 60 min) were studied. The resulting nanotubes were characterized by field emission scanning electron microscopy, Raman laser confocal microscopy, water splitting measurements, Mott-Schottky analysis and electrochemical impedance spectroscopy, in order to test their viability for being used as photocatalysts in photoelectrochemical applications. Results showed that the best photocurrent density values in water splitting tests(0.263 m A m-2) were achieved for the sample anodized for 10 min under hydrodynamic conditions.
基金supported by the National Natural Science Foundation of China (21573099, 21601077, 21573100)~~
文摘A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was characterized by X‐ray powder diffraction,scanning electron microscopy,and energy dispersive X‐ray spectroscopy.Linear sweep voltammetry,chronoamperometry,and electrochemical impedance measurements were performed in aqueous Na2SO4solution(0.1molL?1).We found that a higher applied voltage led to better catalytic performance by AgPW11.The AgPW11‐TiO2/ITO electrode gave currents respectively10and2.5times as high as those of the TiO2/ITO and AgNO3‐TiO2/ITO electrodes at an applied voltage of1.5V vs Ag/AgCl.This result was attributed to the lower charge transfer resistance at the electrode‐electrolyte interface for the AgPW11‐TiO2/ITO electrode.Under illumination,the photocurrent was not obviously enhanced although the total anode current increased.The AgPW11‐TiO2/ITO electrode was relatively stable.Cyclic voltammetry of AgPW11was performed in phosphate buffer solution(0.1mol L?1).We found that oxidation of AgPW11was a quasi‐reversible process related to one‐electron and one‐proton transfer.We deduced that disproportionation of the oxidized[H2AgII(H2O)PW11O39]3?might have occurred and the resulting[H3AgIIIOPW11O39]3?oxidized water to O2.
基金supported by the National Key Research and Development Program of China (2022YFB3803600)the National Natural Science Foundation of China (22302067)+2 种基金the Innovation Program of Shanghai Municipal Education Commission (2021-0107-00-02-E00106)the Science and Technology Commission of Shanghai Municipality (22230780200,20DZ2250400)Fundamental Research Funds for the Central Universities (222201717003)。
文摘Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water to oxygen,particularly with readily available and inexpensive electrolyte solutions such as seawater.While metal oxide materials have demonstrated their advantages in promoting efficiency by reducing overpotential and improving light utilization,stability remains limited by corrosion in multicomponent seawater.In this paper,we reviewed the relationship between four basic concepts including photoelectrochemistry,metal oxide,water oxidation and seawater to better understand the challenges and opportunities in photoelectrochemical(PEC)seawater oxidation.To overcome these challenges,the advances in material design,interfacial modification,local environment control and reactor design have been further reviewed to benefit the industrial PEC seawater oxidation.Noticeably,we demonstrate engineered layered metal oxide electrodes and cell structures that enable powerful and stable seawater oxidation.We also outline and advise on the future direction in this area.
基金part of the research programme of the Foundation for Fundamental Research on Matter(FOM,project 10TBSC07-1),which is part of the Netherlands Organisation for Scientific Research(NWO)
文摘Core–shell nanoparticles containing plasmonic metals（Ag or Au） have been frequently reported to enhance performance of photo-electrochemical（PEC） devices. However, the stability of these particles in water-splitting conditions is usually not addressed. In this study we demonstrate that Ag@SiOcore–shell particles are instable in the acidic conditions in which WO-based PEC cells typically operate, Ag in the core being prone to oxidation, even if the SiOshell has a thickness in the order of 10 nm. This is evident from in situ voltammetry studies of several anode composites. Similar to the results of the PEC experiments, the Ag@SiOcore–shell particles are instable in slurry-based, Pt/ZnO induced photocatalytic water-splitting. This was evidenced by in situ photodeposition of Ag nanoparticles on the Pt-loaded ZnO catalyst, observed in TEM micrographs obtained after reaction. We explain the instability of Ag@SiOby OH-radical induced oxidation of Ag, yielding dissolved Ag+. Our results imply that a decrease in shell permeability for OH-radicals is necessary to obtain stable, Ag-based plasmonic entities in photo-electrochemical and photocatalytic water splitting.
基金supported by the National Natural Science Foundation of China(Nos.22074073,21275087)the Natural Science Foundation of Shandong Province of China(No.ZR2021YQ11)the Taishan Scholar Program of Shandong Province of China(No.ts20110829)。
文摘Accurate detection of important biomarkers with ultra-low levels in complex biological matrix is one of the frontier scientific issues because of possible signal interference of potential reductive agents and protein molecules.Herein,a self-powered anti-interference photoelectrochemical(PEC)immunosensor was explored for sensitive and specific detection of model target of cardiac troponinⅠ(cTnI).Specifically,a novel ternary heterojunction served as the photocathode to offer a remarkable current output and a zwitterionic peptide was introduced to build a robust antifouling biointerface.CuInS(CIS)film with porous network nanostructure was first prepared and then modified in order with ZnInS(ZIS)nanocrystals and Au nanoparticles to fabricate the Au/ZIS/CIS heterojunction photocathode.After capture cTnI antibody(Ab)was immobilized,the zwitterionic peptide KAEAKAEAPPPPC was then anchored to compete the immunosensor.The elaborated PEC immunosensor exhibited high sensitivity for target cTnI antigen(Ag)detection,with good anti-interference against reductive agents and nonspecific proteins.This integration strategy of heterojunction photocathode with zwitterionic peptide provides a new sight to develop advanced PEC immunosensors applying in practical biosamples.
基金the National Natural Science Foundation of China(No.21173042)National Basic Research Program of China(No.2013CB932902)+2 种基金Fundamental Research Funds for the Central Universities(No.3207043401)Science&Technology Support Project of Jiangsu(No.BE2013118)Jiangsu Key Laboratory of Environmental Material&Environmental Engineering(No.JHCG201012)
文摘The MWCNT-Ti02 hybrid materials were prepared by a simply mixing method and used as a counter electrode （CE） for dye-sensitized solar cells. Compared with the platinum CE, MWCNT-TiO2 CE has the similar redox voltage and current response in the cyclic voltammetry. The electrochemical catalytic activity was characterized by the electrochemical impedance spectroscopy and Tafel curve, including the equivalent circuit, the exchange current density, the limiting diffusion current density, and the diffusion coefficient of triiodide/iodide redox species. The results indicate that the reduction process from triiodide to iodide is determined by the kinetic-controlled and diffusion-limited processes. The device performance is optimal based on the MWCNT-TiO2 （mass ratio of 2：1） CE, such as the open-circuit voltage of 0.72 V, the short-circuit photocurrent density of 15.71 mA/cm2, the fill factor of 0.68, and the photon-to-electron conversion efficiency of 7.69%.
