Photocatalysis(PC)and photoelectrocatalysis(PEC)represent promising and efficient avenues for harnessing solar energy to produce sustainable clean energy products and environmental remediation.Yet the current reaction...Photocatalysis(PC)and photoelectrocatalysis(PEC)represent promising and efficient avenues for harnessing solar energy to produce sustainable clean energy products and environmental remediation.Yet the current reaction efficiencies remain inadequate,limiting their efficiencies for practice.Despite the growing interest in photo thermal-driven PC/PEC systems,there is no comprehensive review that systematically summarises the role of the photothermal effect in bridging the gap between PC and PEC efficiencies.This review initially introduces the fundamental principles of PC and PEC,alongside the primary photothermal materials and relevant conversion mechanisms.Subsequently,the key influences of photothermal effects on PC and PEC performance(e.g.,light absorption,charge separation and transport,and surface reactions)and optimization strategies are discussed.In addition,the latest advancements in solar photothermal conversion are discussed,mainly focused on the widely application of different types of photothermal drive PC and PEC applications,such as PC and PEC oxygen evolution reaction(OER),hydrogen evolution reaction(HER),CO_(2)reduction reaction(CO_(2)RR),pollutant degradation,and sterilization,serving to illustrate the widespread applicability of the photothermal conversion.Finally,the development prospects and challenges of photothermal-assisted PC and PEC are discussed from the perspective of basic research and practical application.This work provides a timely and systematic framework to guide the rational design of photothermal-enhanced PC/PEC systems for sustainable energy and environmental applications.展开更多
In this study, a 2D BiOI nanosheet/1D BiPO4 nanorod/fluorine-doped tin oxide (FTO) composite electrode with a p-n heterojunction structure was prepared by a two-step electrodeposition method. Field-emission scanning e...In this study, a 2D BiOI nanosheet/1D BiPO4 nanorod/fluorine-doped tin oxide (FTO) composite electrode with a p-n heterojunction structure was prepared by a two-step electrodeposition method. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy, and electrochemical testing were used to characterize its composition, crystal morphology, and optical properties. The Bi- OI/BiPO4/FTO composite electrode has higher photoelectrocatalytic (PEC) activity for the degradation of tetracycline than pure BiPO4 and BiOI. The PEC activity of the composite was 1.98 times and 2.46 times higher than those of the BiOI/FTO and BiPO4/FTO electrodes, respectively. The effects of the working voltage and BiOI deposition time on the degradation of tetracycline were investigated. The optimum BiOI deposition time was found to be 150 s and the optimum working voltage is 1.2 V. Trapping experiments showed that hydroxyl radicals (·OH) and superoxide radicals (·O2-) are the major reactive species in the PEC degradation process. The BiOI/BiPO4/FTO composite electrode has good stability, and the tetracycline removal efficiency remains substantially unchanged after four cycles in a static system. The reason for the PEC efficiency enhancement in the BiOI/BiPO4/FTO composite electrode is the increased visible light absorption range and the p-n heterojunction structure, which promotes the separation and migration of the photogenerated electrons and holes.展开更多
The recycling technology of photocatalyst powdery has hardly been mature in the photocatalytic oxidation so far.In this work,the hollow TiO_(2)microspheres with an appropriate thickness are confined in carbon microsph...The recycling technology of photocatalyst powdery has hardly been mature in the photocatalytic oxidation so far.In this work,the hollow TiO_(2)microspheres with an appropriate thickness are confined in carbon microspheres(CMSs)to form hollow TiO_(2)@CMSs,which are physically integrated with carbon-fiber textile by van der Waals(vdW)interactions to generate separable and recyclable hollow TiO_(2)@CMSs/carbon-fiber vdW heterostructures.Such separable and recyclable heterostructures show remarkable oxidation of 2,4-dinitrophenol.From our detailed characterization and density functional theory(DFT)calculations,we found that carbon fiber can trap electrons exerted from the excitation of hollow TiO_(2)@CMSs and creates holes in hollow TiO_(2)microspheres,which endow the carbon fiber with photocatalytic activity through coherent charge injection.This study indicates that our general strategy for the fabrication of hollow TiO_(2)@CMSs/carbon-fiber vdW heterostructures can be used as separable and recyclable photocatalyst and photoelectrocatalyst with potential industrial applications in environmentrelated fields.展开更多
Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In p...Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.展开更多
CONSPECTUS:Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies.Renewable energy conversion req...CONSPECTUS:Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies.Renewable energy conversion requires catalysts for multielectron redox reactions such as water oxidation and reduction(toward water splitting systems).Developing efficient catalysts for multielectron redox reactions is a great challenge in current science and technology.Metal oxides have been extensively researched to be applied to a large variety of photonic and electronic devices due to the wide range of electronic properties of conducting,semiconducting,and insulating and diverse catalytic properties at their surface depending on the exposing facet,as well as physical and chemical robustness under ambient conditions.We aspire to the development of an easy technique available for large-scale production of metal oxide films based on simple casting and calcination to adopt a strategy for controlling the formation and growth of metal oxide films by ligands to metal centers in precursors.We have developed an easy preparation technique of mono-and multimetallic oxide films,termed the“mixed metal-imidazole casting(MiMIC)method”,by which metal oxide films are generated tightly on various electrode substrates by casting precursor solutions or suspensions containing component metal salts in a mixed solvent of methanol/imidazole derivative as a ligand,followed by calcination.The general versatility of the MiMIC method encourages us to hunt new metal oxide films as efficient catalysts for the multielectron redox reactions,because the rigid adherability of films formed on a current collector electrode is necessary for essential evaluation of the catalytic performance of the metal oxide films.In this Account,we expound synthesis and characterization of a variety of mono-and multimetallic oxide films using the MiMIC method and its application to electro-and photoelectrocatalysis for water splitting and oxygen reduction,which are important key reactions in future sustainable technology.The adherability of these films onto the electrode surface is prominent although their morphology,crystallinity,and nanostructures depend on the metal oxide materials,which is one of the important factors to induce high performance of the metal oxide films for electro-and photoelectrocatalysis.Imidazole derivatives were found to act as a source of nitrogen for the N-doping to a metal oxide lattice,and a structure-directing agent for the anisotropic crystallization,as well as a binder among constituting nanoparticles to lead to the rigid adherability of films on the substrate.These findings surely expand material development to a great extent,by not only changing the metal compositions but also being based on band engineering due to doping of representative elements and crystal facet control of metal oxide films.展开更多
Green hydrogen is the most promising option and a two in one remedy that resolve the problem of both energy crisis and environmental pollution.Wide band gap semiconductors(WBG)(E_(g)>2 eV)are the most prominent and...Green hydrogen is the most promising option and a two in one remedy that resolve the problem of both energy crisis and environmental pollution.Wide band gap semiconductors(WBG)(E_(g)>2 eV)are the most prominent and leading catalytic materials in both electro and photocatalytic water splitting(WSR);two sustainable methods of green hydrogen production.WBGs guarantee long life time of photo charge carriers and thereby surface availability of electrons and holes.Therefore,WBG(with appropriate VB-CB potential)along with small band gap materials or sensitizers can yield extraordinary photocatalytic system for hydrogen production under solar light.The factors such as,free energy of hydrogen adsorption(ΔGH^(*))close to zero,high electron mobility,great thermal as well as electro chemical stability and high tunability make WBG an interesting and excellent catalyst in electrolysis too.Taking into account the current relevance and future scope,the present review article comprehends different dimensions of WBG materials as an electro/photo catalyst for hydrogen evolution reaction.Herein WBG semiconductors are presented under various classes;viz.II-VI,III-V,III-VI,lanthanide oxides,transition metal based systems,carbonaceous materials and other systems such as SiC and MXenes.Catalytic properties of WBGs favorable for hydrogen production are then reviewed.A detailed analysis on relationship between band structure and activity(electro,photo and photo-electrochemical WSR)is performed.The challenges involved in these reactions as well as the direction of advancement in WBG based catalysis are also debated.By virtue of this article authors aims to guideline and promote the development of new WBG based electro/photocatalyst for HER and other applications.展开更多
Electrochemical synthesis is a safe,mild and environmentally friendly alternative to chemical oxidants and reductants.It uses electricity to catalyze redox reactions.However,understanding the tools and techniques invo...Electrochemical synthesis is a safe,mild and environmentally friendly alternative to chemical oxidants and reductants.It uses electricity to catalyze redox reactions.However,understanding the tools and techniques involved is crucial for maximizing its benefits in academic and industrial applications.Still,for a novice,electrosynthesis can be a somewhat intimidating.Therefore,we provide guidance to synthetic chemists by highlighting key concepts and offering practical tips.In this review article,we focus on the utilization of electro-auxiliaries,indirect electrosynthesis,alternating electrode electrolysis(AEE),microreactors for electrochemical processes,and paired electrochemical reactions.These strategies are illustrated with selected examples.The use of electrodes and electroanalytical methods such as cyclic voltammetry are discussed.It highlights the advantages of merging electrochemistry and photochemistry,and the challenges of specific organic solvents and electrolytes.The incorporation of electrochemistry into a continuous chemical flow system further advances green activation technologies in terms of efficiency,applicability,sustainability,and selectivity to deliver more efficient and cleaner synthetic processes.Furthermore,this manuscript also emphasizes improvements in current approaches and future directions for large-scale electrosynthesis.展开更多
The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis.Especially,the sustainable photocatalytic,electroc...The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis.Especially,the sustainable photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane at ambient conditions is regarded as an alternative technology to replace with thermocatalysis.In this review,we summarize recent advances in photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane into alcohols.We firstly introduce the general principles of photocatalysis,electrocatalysis and photoelectrocatalysis.Then,we discuss the mechanism for selective activation of C-H bond and following oxygenation over metal,inorganic semiconductor,organic semiconductor,and heterojunction composite systems in the photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation in detail.Later,we present insights into the construction of effective photocatalyst,electrocatalyst and photoelectrocatalyst for methane conversion into alcohols from the perspective of band structures and active sites.Finally,the challenges and outlook for future designs of photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation systems are also proposed.展开更多
Photoelectrochemistry is a promising method for the direct conversion of sunlight into valuable chemicals by combining the functions of solar panels and electrolyzers in one technology.In most studies,semiconductor/ca...Photoelectrochemistry is a promising method for the direct conversion of sunlight into valuable chemicals by combining the functions of solar panels and electrolyzers in one technology.In most studies,semiconductor/catalyst photoelectrode assemblies are used to achieve reasonable efficiencies.At the same time,unlike in dark electrochemical processes,the role of the catalyst is not straightforward in photoelectrochemistry,where the onset potential of the redox process should be mostly determined by the flatband potential of the semiconductor.In addition,the energy of holes(i.e.,the surface potential)is independent of the applied bias;it is defined by the valence band(VB)position.In this study,we compared PdAu,Au,and Ni on Si photoanodes in the photoelectrochemical(PEC)oxidation of glycerol at record high current densities(>180 mA cm^(‒2)),coupled to H_(2) evolution at the cathode.We successfully decreased the energy requirement(i.e.,the cell voltage)of the paired conversion of glycerol and water by 0.7 V by exchanging the widely studied Ni catalyst with PdAu.The catalyst choice also dictates the product distribution,resulting mainly in C3 products on PdAu,glycolate(C2 product)on Au,and formate(C1 product)on Ni,without complete mineralization of glycerol(CO_(2) formation)that is difficult to rule out in dark electrochemical processes(as demonstrated by comparative measurements).Finally,we achieved a bias‐free(standalone)operation with PdAu/Si and Au/Si photoanodes by combining the PEC oxidation of glycerol with oxygen reduction reaction(ORR).展开更多
In this study,we present a self-driven photoelectrocatalytic(SD-PEC)system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power....In this study,we present a self-driven photoelectrocatalytic(SD-PEC)system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power.The system utilizes a titanium dioxide nanorod array(TNR)photoelectrode coupled with a silicon solar cell to optimize electron transport,while the cathode is composed of a carbon fiber coated with carboxylated carbon nanotubes(CCNT/CF),which efficiently reduce UO_(2)^(2+).The results demonstrate significant removal efficiency of uranium(complete removal in 25 min at a rate constant of~0.248 min^(-1)),as well as substantial degradation of organic impurities.Furthermore,the system generates sufficient power output to light an LED lamp and exhibits superior performance under various complex wastewater conditions,including simulated seawater and real uranium tailings wastewater.These findings underscore the potential of the SD-PEC system as a versatile approach for sustainable treatment and energy recovery of radioactive wastewater.The significance of this research extends to global environmental challenges,offering an innovative solution for managing radioactive wastewater while simultaneously contributing to renewable energy generation.展开更多
Converting CO_(2)and water into valuable chemicals like plant do is considered a promising approach to address both environmental and energy issues.Taking inspiration from the structures of natural leaves,we designed ...Converting CO_(2)and water into valuable chemicals like plant do is considered a promising approach to address both environmental and energy issues.Taking inspiration from the structures of natural leaves,we designed and synthesized a novel copper-coordinated covalent triazine framework(CuCTF)supported by silicon nanowire arrays on wafer chip.This marks the first-ever application of such a hybrid material in the photoelectrocatalytic reduction of CO_(2)under mild conditions.The Si@CuCTF6 heterojunction has exhibited exceptional selectivity of 95.6%towards multicarbon products(C_(2+))and apparent quantum efficiency(AQE)of 0.89%for carbon-based products.The active sites of the catalysts are derived from the nitrogen atoms of unique triazine ring structure in the ordered porous framework and the abundant Cu-N coordination sites with bipyridine units.Furthermore,through DFT calculations and operando FTIR spectra analysis,we proposed a comprehensive mechanism for the photoelectrocatalytic CO_(2)reduction,confirming the existence of key intermediate species such as*CO_(2)-,*=C=O,*CHO and*CO-CHO etc.This work not only provides a new way to mimic photosynthesis of plant leaves but also gives a new opportunity to enter this research field in the future.展开更多
Photoelectrocatalytic(PEC)seawater splitting as a green and sustainable route to harvest hydrogen is attractive yet hampered by low activity of photoanodes and unexpected high selectivity to the corrosive and toxic ch...Photoelectrocatalytic(PEC)seawater splitting as a green and sustainable route to harvest hydrogen is attractive yet hampered by low activity of photoanodes and unexpected high selectivity to the corrosive and toxic chlorine.Especially,it is full of challenges to unveil the key factors influencing the selectivity of such complex PEC processes.Herein,by regulating the energy band and surface structure of the anatase TiO_(2) nanotube array photoanode via nitrogen-doping,the seawater PEC oxidation shifts from Cl^(-)oxidation reaction(ClOR)dominant on the TiO_(2) photoanode(61.6%)to oxygen evolution reaction(OER)dominant on the N-TiO_(2) photoanode(62.9%).Comprehensive investigations including operando photoelectrochemical FTIR and DFT calculations unveil that the asymmetric hydrogen-bonding water at the N-TiO_(2) electrode/electrolyte interface enriches under illumination,facilitating proton transfer and moderate adsorption strength of oxygen-intermediates,which lowers the energy barrier for the OER yet elevates the energy barrier for the ClOR,resulting to a promoted selectivity towards the OER.The work sheds light on the underlying mechanism of the PEC water oxidation processes,and highlights the crucial role of interfacial water on the PEC selectivity,which could be regulated by controlling the energy band and the surface structure of semiconductors.展开更多
Accelerating the separation of carriers in the heterojunction plays vital role in the photoelectrocatalytic(PEC)process,yet it remains a challenging undertaking.Herein,a MOF-on-MOF based dual S-scheme heterojunction(B...Accelerating the separation of carriers in the heterojunction plays vital role in the photoelectrocatalytic(PEC)process,yet it remains a challenging undertaking.Herein,a MOF-on-MOF based dual S-scheme heterojunction(BiVO_(4)/NH_(2)-MIL-125(Ti)/NH_(2)-MIL-53(Fe),denoted as BVO/NM125/NM53)was rationally designed and prepared for PEC removing and detoxification of organic contaminants(phenol,tetracycline hydrochloride,ciprofloxacin and norfloxacin).The S-scheme heterojunction was double confirmed by DFT calculation and XPS analysis.The charge transfer resistance of BVO/NM125/NM53 photoanode decreases to 1/11 of bare BiVO_(4) photoanode.Meanwhile,the photocurrent densitywas 3 times higher,demonstrating a marked improvement in carrier separation efficiency due to dual S-scheme heterojunction.The photoanode achieved 94.3%removal of phenol within 60 min and maintained stable performance over 10 consecutive cycles,demonstrating good PEC efficiency and structural stability.The BVO/NM125/NM53 photoanode also showed effectiveness in removing antibiotics,with chlorophyll fluorescence imaging confirming a significant reduction in the ecotoxicity of intermediates.For example,wheat seed germination,growth,chlorophyll and Carotenoid production were not affected,which was similar to that of deionized water.Radical trapping experiments and electron paramagnetic resonance(EPR)analysis identified·O_(2)^(-)and·OH as the primary active species.This work demonstrates the effectiveness of developing MOF-on-MOF heterojunctions for visible-light response and enhancing charge separation in PEC.展开更多
Hydrogen is a highly promising energy carrier because of its renewable and clean qualities.Among the different methods for H_(2) production,photoelectrocatalysis(PEC)water splitting has garnered significant interest,t...Hydrogen is a highly promising energy carrier because of its renewable and clean qualities.Among the different methods for H_(2) production,photoelectrocatalysis(PEC)water splitting has garnered significant interest,thanks to the abundant and perennial solar energy.Single-atom catalysts(SACs),which feature well-distributed atoms anchored on supports,have gained great attention in PEC water splitting for their unique advantages in overcoming the limitations of conventional PEC reactions.Herein,we comprehensively review SAC-incorporated photoelectrocatalysts for efficient PEC water splitting.We begin by highlighting the benefits of SACs in improving charge transfer,catalytic selectivity,and catalytic activity,which address the limitations of conventional PEC reactions.Next,we provide a comprehensive overview of established synthetic techniques for optimizing the properties of SACs,along with modern characterization methods to confirm their unique structures.Finally,we discuss the challenges and future directions in basic research and advancements,providing insights and guidance for this developing field.展开更多
Photoelectrocatalysis(PEC)is extensively applied in diverse redox reactions.However,the traditional oxygen evolution reaction(OER)occurring at the(photo)anode is hindered by high thermodynamic demands and sluggish kin...Photoelectrocatalysis(PEC)is extensively applied in diverse redox reactions.However,the traditional oxygen evolution reaction(OER)occurring at the(photo)anode is hindered by high thermodynamic demands and sluggish kinetics,resulting in excessive energy consumption and limited economic value of the O2 produced,thereby impeding the practical application of PEC reactions.To overcome these limitations,advanced anodic-cathodic coupling systems,as an emerging energy conversion technology,have garnered significant research interest.These systems substitute OER with lower potential,valuable oxidation reactions,significantly enhancing energy conversion efficiency,yielding high-value chemicals,while reducing energy consumption and environmental pollution.More importantly,by designing and optimizing photoelectrodes to generate sufficient photovoltage under illumination,meeting the thermodynamic and kinetic potential requirements of the reactions,and by tuning the voltage to match the current densities of the cathode and anode,coupling reactions can be achieved under bias-free conditions.In this review,we provide an overview of the mechanisms of PEC coupling reactions and summarize photoelectrode catalysts along with their synthesis methods.We further explore advanced catalyst modification strategies and highlight the latest development in advanced PEC coupling systems,including photocathodic CO_(2)reduction,nitrate reduction,oxygen reduction,enzyme activation,coupled with photoanodic organic oxidation,biomass oxidation,and pollutant degradation.Additionally,advanced in situ characterization techniques for elucidating reaction mechanisms are discussed.Finally,we propose the challenges in catalyst design,reaction systems,and large-scale applications,while offering future perspectives for PEC coupling system.This work underscores the tremendous potential of PEC coupling systems in energy conversion and environmental remediation,and provides valuable insights for the future design of such coupling systems.展开更多
Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat micr...Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat microplastic waste and CO_(2)by using environmentally friendly and efficient technologies.In this work,we developed an efficient photoelectrocatalytic system composed of Ni single atoms(Ni SAs)supported by P,N-doped amorphous NiFe_(2)O_(4)(Ni SAs/A-P-N-NFO)as anode and Ag nanoparticles(Ag NPs)supported by CuO/Cu_(2)O nanocubes(Ag NPs@CuO/Cu_(2)O NCs)as cathode for microplastic oxidation and CO_(2)reduction.The Ni SAs/A-P-N-NFO was synthesized by calcination-H_(2)reduction method,and it achieved a Faraday efficiency of 93%for the oxidation reaction of poly(ethylene terephthalate)(PET)solution under AM 1.5 G light.As a photocathode,the synthesized Ag NPs@CuO/Cu_(2)O NCs was utilized to reduce CO_(2)to ethylene and CO at 1.5 V vs.RHE with selectivity of 42%and 55%,respectively.This work shows that the photoelectrocatalysis,as an environmentally friendly technology,is a feasible strategy for reducing the environmental and biological hazards of light plastics,as well as for efficient CO_(2)reduction.展开更多
A thin layer of TiO2 film was deposited on ITO surface via the liquid phase deposition （LPD） process. The photocurrent and electrochemical impedance spectroscopy （EIS） measurements indicated that the as-prepared L...A thin layer of TiO2 film was deposited on ITO surface via the liquid phase deposition （LPD） process. The photocurrent and electrochemical impedance spectroscopy （EIS） measurements indicated that the as-prepared LPD TiO2/ITO film had an excellent photoelectrochemical performance, which showed a sensitive and rapid response to the UV irradiation. The photogenerated electron-hole pairs could be effectively separated by applying an external bias to the TiO2 film electrode. The LPD TiO2/ITO film was employed to study the photoelectrocatalytic （PEC） degradation of 4-aminoantipyrine. Compared with other techniques, the PEC technique based on such a LPD film electrode had a synergetic effect for 4-aminoantipyrine degradation. When the applied bias potential was＋0.8 V and the supporting electrolyte concentration of Na2SO4 was 0.1 mol/L, the highest degradation efficiency within 120 min could reach 95%for 0.1 mmol/L 4-aminoantipyrine solution at pH 2.0.展开更多
Photocatalysis is critically important for environmental remediation and renewable energy technologies.The ability to objectively characterize photocatalyst properties and photocatalysis processes is paramount for mea...Photocatalysis is critically important for environmental remediation and renewable energy technologies.The ability to objectively characterize photocatalyst properties and photocatalysis processes is paramount for meaningful performance evaluation and fundamental studies to guide the design and development of high-performance photocatalysts and photocatalysis systems.Photocatalysis is essentially an electron transfer process,and photoelectrocatalysis(PEC)principles can be used to directly quantify transferred electrons to determine the intrinsic properties of photocatalysts and photocatalysis processes in isolation,without interference from counter reactions due to physically separated oxidation and reduction half-reactions.In this review,we discuss emphatically the PEC-based principles for characterizing intrinsic properties of photocatalysts and important processes of photocatalysis,with a particular focus on their environmental applications in the degradation of pollutants,disinfection,and detection of chemical oxygen demand(COD).An outlook towards the potential applications of PEC technique is given.展开更多
Rapid technological development and population growth are responsible for a series of imminent environmental problems and an ineluctable energy crisis.The application of semiconductor nanomaterials in photocatalysis o...Rapid technological development and population growth are responsible for a series of imminent environmental problems and an ineluctable energy crisis.The application of semiconductor nanomaterials in photocatalysis or photoelectrocatalysis(PEC)for either the degradation of contaminants in the environment or the generation of hydrogen as clean fuel is an effective approach to alleviate these problems.However,the efficiency of such processes remains suboptimal for real applications.Reasonable construction of a built-in electric field is considered to efficiently enhance carrier separation and reduce carrier recombination to improve catalytic performance.In the past decade,as a new method to enhance the built-in electric field,the piezoelectric effect from piezoelectric materials has been extensively studied.In this review,we provide an overview of the properties of piezoelectric materials and the mechanisms of piezoelectricity and ferroelectricity for a built-in electric field.Then,piezoelectric and ferroelectric polarization regulated built-in electric fields that mediate catalysis are discussed.Furthermore,the applications of piezoelectric semiconductor materials are also highlighted,including degradation of pollutants,bacteria disinfection,water splitting for H2 generation,and organic synthesis.We conclude by discussing the challenges in the field and the exciting opportunities to further improve piezo-catalytic efficiency.展开更多
Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a nov...Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.展开更多
基金partly supported by the National Natural Science Foundation of China(21978276)。
文摘Photocatalysis(PC)and photoelectrocatalysis(PEC)represent promising and efficient avenues for harnessing solar energy to produce sustainable clean energy products and environmental remediation.Yet the current reaction efficiencies remain inadequate,limiting their efficiencies for practice.Despite the growing interest in photo thermal-driven PC/PEC systems,there is no comprehensive review that systematically summarises the role of the photothermal effect in bridging the gap between PC and PEC efficiencies.This review initially introduces the fundamental principles of PC and PEC,alongside the primary photothermal materials and relevant conversion mechanisms.Subsequently,the key influences of photothermal effects on PC and PEC performance(e.g.,light absorption,charge separation and transport,and surface reactions)and optimization strategies are discussed.In addition,the latest advancements in solar photothermal conversion are discussed,mainly focused on the widely application of different types of photothermal drive PC and PEC applications,such as PC and PEC oxygen evolution reaction(OER),hydrogen evolution reaction(HER),CO_(2)reduction reaction(CO_(2)RR),pollutant degradation,and sterilization,serving to illustrate the widespread applicability of the photothermal conversion.Finally,the development prospects and challenges of photothermal-assisted PC and PEC are discussed from the perspective of basic research and practical application.This work provides a timely and systematic framework to guide the rational design of photothermal-enhanced PC/PEC systems for sustainable energy and environmental applications.
基金partly supported by the National Natural Science Foundations of China(21577132)the Fundamental Research Funds for the Central Universities(2652017377,2652017378)~~
文摘In this study, a 2D BiOI nanosheet/1D BiPO4 nanorod/fluorine-doped tin oxide (FTO) composite electrode with a p-n heterojunction structure was prepared by a two-step electrodeposition method. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy, and electrochemical testing were used to characterize its composition, crystal morphology, and optical properties. The Bi- OI/BiPO4/FTO composite electrode has higher photoelectrocatalytic (PEC) activity for the degradation of tetracycline than pure BiPO4 and BiOI. The PEC activity of the composite was 1.98 times and 2.46 times higher than those of the BiOI/FTO and BiPO4/FTO electrodes, respectively. The effects of the working voltage and BiOI deposition time on the degradation of tetracycline were investigated. The optimum BiOI deposition time was found to be 150 s and the optimum working voltage is 1.2 V. Trapping experiments showed that hydroxyl radicals (·OH) and superoxide radicals (·O2-) are the major reactive species in the PEC degradation process. The BiOI/BiPO4/FTO composite electrode has good stability, and the tetracycline removal efficiency remains substantially unchanged after four cycles in a static system. The reason for the PEC efficiency enhancement in the BiOI/BiPO4/FTO composite electrode is the increased visible light absorption range and the p-n heterojunction structure, which promotes the separation and migration of the photogenerated electrons and holes.
基金financial support from the National Natural Science Foundation of China(Grant No.:51464020)
文摘The recycling technology of photocatalyst powdery has hardly been mature in the photocatalytic oxidation so far.In this work,the hollow TiO_(2)microspheres with an appropriate thickness are confined in carbon microspheres(CMSs)to form hollow TiO_(2)@CMSs,which are physically integrated with carbon-fiber textile by van der Waals(vdW)interactions to generate separable and recyclable hollow TiO_(2)@CMSs/carbon-fiber vdW heterostructures.Such separable and recyclable heterostructures show remarkable oxidation of 2,4-dinitrophenol.From our detailed characterization and density functional theory(DFT)calculations,we found that carbon fiber can trap electrons exerted from the excitation of hollow TiO_(2)@CMSs and creates holes in hollow TiO_(2)microspheres,which endow the carbon fiber with photocatalytic activity through coherent charge injection.This study indicates that our general strategy for the fabrication of hollow TiO_(2)@CMSs/carbon-fiber vdW heterostructures can be used as separable and recyclable photocatalyst and photoelectrocatalyst with potential industrial applications in environmentrelated fields.
文摘Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.
基金supported by JSPS KAKENHI Grant Numbers JP21H02042,JP22K18309,and JP22K14762.
文摘CONSPECTUS:Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies.Renewable energy conversion requires catalysts for multielectron redox reactions such as water oxidation and reduction(toward water splitting systems).Developing efficient catalysts for multielectron redox reactions is a great challenge in current science and technology.Metal oxides have been extensively researched to be applied to a large variety of photonic and electronic devices due to the wide range of electronic properties of conducting,semiconducting,and insulating and diverse catalytic properties at their surface depending on the exposing facet,as well as physical and chemical robustness under ambient conditions.We aspire to the development of an easy technique available for large-scale production of metal oxide films based on simple casting and calcination to adopt a strategy for controlling the formation and growth of metal oxide films by ligands to metal centers in precursors.We have developed an easy preparation technique of mono-and multimetallic oxide films,termed the“mixed metal-imidazole casting(MiMIC)method”,by which metal oxide films are generated tightly on various electrode substrates by casting precursor solutions or suspensions containing component metal salts in a mixed solvent of methanol/imidazole derivative as a ligand,followed by calcination.The general versatility of the MiMIC method encourages us to hunt new metal oxide films as efficient catalysts for the multielectron redox reactions,because the rigid adherability of films formed on a current collector electrode is necessary for essential evaluation of the catalytic performance of the metal oxide films.In this Account,we expound synthesis and characterization of a variety of mono-and multimetallic oxide films using the MiMIC method and its application to electro-and photoelectrocatalysis for water splitting and oxygen reduction,which are important key reactions in future sustainable technology.The adherability of these films onto the electrode surface is prominent although their morphology,crystallinity,and nanostructures depend on the metal oxide materials,which is one of the important factors to induce high performance of the metal oxide films for electro-and photoelectrocatalysis.Imidazole derivatives were found to act as a source of nitrogen for the N-doping to a metal oxide lattice,and a structure-directing agent for the anisotropic crystallization,as well as a binder among constituting nanoparticles to lead to the rigid adherability of films on the substrate.These findings surely expand material development to a great extent,by not only changing the metal compositions but also being based on band engineering due to doping of representative elements and crystal facet control of metal oxide films.
文摘Green hydrogen is the most promising option and a two in one remedy that resolve the problem of both energy crisis and environmental pollution.Wide band gap semiconductors(WBG)(E_(g)>2 eV)are the most prominent and leading catalytic materials in both electro and photocatalytic water splitting(WSR);two sustainable methods of green hydrogen production.WBGs guarantee long life time of photo charge carriers and thereby surface availability of electrons and holes.Therefore,WBG(with appropriate VB-CB potential)along with small band gap materials or sensitizers can yield extraordinary photocatalytic system for hydrogen production under solar light.The factors such as,free energy of hydrogen adsorption(ΔGH^(*))close to zero,high electron mobility,great thermal as well as electro chemical stability and high tunability make WBG an interesting and excellent catalyst in electrolysis too.Taking into account the current relevance and future scope,the present review article comprehends different dimensions of WBG materials as an electro/photo catalyst for hydrogen evolution reaction.Herein WBG semiconductors are presented under various classes;viz.II-VI,III-V,III-VI,lanthanide oxides,transition metal based systems,carbonaceous materials and other systems such as SiC and MXenes.Catalytic properties of WBGs favorable for hydrogen production are then reviewed.A detailed analysis on relationship between band structure and activity(electro,photo and photo-electrochemical WSR)is performed.The challenges involved in these reactions as well as the direction of advancement in WBG based catalysis are also debated.By virtue of this article authors aims to guideline and promote the development of new WBG based electro/photocatalyst for HER and other applications.
文摘Electrochemical synthesis is a safe,mild and environmentally friendly alternative to chemical oxidants and reductants.It uses electricity to catalyze redox reactions.However,understanding the tools and techniques involved is crucial for maximizing its benefits in academic and industrial applications.Still,for a novice,electrosynthesis can be a somewhat intimidating.Therefore,we provide guidance to synthetic chemists by highlighting key concepts and offering practical tips.In this review article,we focus on the utilization of electro-auxiliaries,indirect electrosynthesis,alternating electrode electrolysis(AEE),microreactors for electrochemical processes,and paired electrochemical reactions.These strategies are illustrated with selected examples.The use of electrodes and electroanalytical methods such as cyclic voltammetry are discussed.It highlights the advantages of merging electrochemistry and photochemistry,and the challenges of specific organic solvents and electrolytes.The incorporation of electrochemistry into a continuous chemical flow system further advances green activation technologies in terms of efficiency,applicability,sustainability,and selectivity to deliver more efficient and cleaner synthetic processes.Furthermore,this manuscript also emphasizes improvements in current approaches and future directions for large-scale electrosynthesis.
文摘The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis.Especially,the sustainable photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane at ambient conditions is regarded as an alternative technology to replace with thermocatalysis.In this review,we summarize recent advances in photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane into alcohols.We firstly introduce the general principles of photocatalysis,electrocatalysis and photoelectrocatalysis.Then,we discuss the mechanism for selective activation of C-H bond and following oxygenation over metal,inorganic semiconductor,organic semiconductor,and heterojunction composite systems in the photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation in detail.Later,we present insights into the construction of effective photocatalyst,electrocatalyst and photoelectrocatalyst for methane conversion into alcohols from the perspective of band structures and active sites.Finally,the challenges and outlook for future designs of photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation systems are also proposed.
基金funding under the European Union's Horizon Europe research and innovation program from the European Research Council(ERC,Grant Agreement No.101043617)(C.J.).Project No.RRF‐2.3.1‐21‐2022‐00009titled National Laboratory for Renewable Energy,was implemented with the support provided by the Recovery and Resilience Facility of the European Union within the framework of the Program Széchenyi Plan Plus(C.J.)support from MICIU/AEI/10.13039/501100011033/(PID2020-116093RB−C41 and PID2023‐152771OB‐I00).European Innovation Council(EIC)(101071010).
文摘Photoelectrochemistry is a promising method for the direct conversion of sunlight into valuable chemicals by combining the functions of solar panels and electrolyzers in one technology.In most studies,semiconductor/catalyst photoelectrode assemblies are used to achieve reasonable efficiencies.At the same time,unlike in dark electrochemical processes,the role of the catalyst is not straightforward in photoelectrochemistry,where the onset potential of the redox process should be mostly determined by the flatband potential of the semiconductor.In addition,the energy of holes(i.e.,the surface potential)is independent of the applied bias;it is defined by the valence band(VB)position.In this study,we compared PdAu,Au,and Ni on Si photoanodes in the photoelectrochemical(PEC)oxidation of glycerol at record high current densities(>180 mA cm^(‒2)),coupled to H_(2) evolution at the cathode.We successfully decreased the energy requirement(i.e.,the cell voltage)of the paired conversion of glycerol and water by 0.7 V by exchanging the widely studied Ni catalyst with PdAu.The catalyst choice also dictates the product distribution,resulting mainly in C3 products on PdAu,glycolate(C2 product)on Au,and formate(C1 product)on Ni,without complete mineralization of glycerol(CO_(2) formation)that is difficult to rule out in dark electrochemical processes(as demonstrated by comparative measurements).Finally,we achieved a bias‐free(standalone)operation with PdAu/Si and Au/Si photoanodes by combining the PEC oxidation of glycerol with oxygen reduction reaction(ORR).
基金supported by the National Natural Science Foundation of China(Nos.52170083,51808143)the Science and Technology Innovation Program of Hunan Province(No.2022RC1125)the Hunan Provincial Natural Science Foundation of China(No.2021JJ20007)。
文摘In this study,we present a self-driven photoelectrocatalytic(SD-PEC)system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power.The system utilizes a titanium dioxide nanorod array(TNR)photoelectrode coupled with a silicon solar cell to optimize electron transport,while the cathode is composed of a carbon fiber coated with carboxylated carbon nanotubes(CCNT/CF),which efficiently reduce UO_(2)^(2+).The results demonstrate significant removal efficiency of uranium(complete removal in 25 min at a rate constant of~0.248 min^(-1)),as well as substantial degradation of organic impurities.Furthermore,the system generates sufficient power output to light an LED lamp and exhibits superior performance under various complex wastewater conditions,including simulated seawater and real uranium tailings wastewater.These findings underscore the potential of the SD-PEC system as a versatile approach for sustainable treatment and energy recovery of radioactive wastewater.The significance of this research extends to global environmental challenges,offering an innovative solution for managing radioactive wastewater while simultaneously contributing to renewable energy generation.
基金supported by Natural Science Foundation of Gansu Province(23JRRA745)the Fundamental Research Funds for the Central Universities(lzujbky2021-sp55).
文摘Converting CO_(2)and water into valuable chemicals like plant do is considered a promising approach to address both environmental and energy issues.Taking inspiration from the structures of natural leaves,we designed and synthesized a novel copper-coordinated covalent triazine framework(CuCTF)supported by silicon nanowire arrays on wafer chip.This marks the first-ever application of such a hybrid material in the photoelectrocatalytic reduction of CO_(2)under mild conditions.The Si@CuCTF6 heterojunction has exhibited exceptional selectivity of 95.6%towards multicarbon products(C_(2+))and apparent quantum efficiency(AQE)of 0.89%for carbon-based products.The active sites of the catalysts are derived from the nitrogen atoms of unique triazine ring structure in the ordered porous framework and the abundant Cu-N coordination sites with bipyridine units.Furthermore,through DFT calculations and operando FTIR spectra analysis,we proposed a comprehensive mechanism for the photoelectrocatalytic CO_(2)reduction,confirming the existence of key intermediate species such as*CO_(2)-,*=C=O,*CHO and*CO-CHO etc.This work not only provides a new way to mimic photosynthesis of plant leaves but also gives a new opportunity to enter this research field in the future.
文摘Photoelectrocatalytic(PEC)seawater splitting as a green and sustainable route to harvest hydrogen is attractive yet hampered by low activity of photoanodes and unexpected high selectivity to the corrosive and toxic chlorine.Especially,it is full of challenges to unveil the key factors influencing the selectivity of such complex PEC processes.Herein,by regulating the energy band and surface structure of the anatase TiO_(2) nanotube array photoanode via nitrogen-doping,the seawater PEC oxidation shifts from Cl^(-)oxidation reaction(ClOR)dominant on the TiO_(2) photoanode(61.6%)to oxygen evolution reaction(OER)dominant on the N-TiO_(2) photoanode(62.9%).Comprehensive investigations including operando photoelectrochemical FTIR and DFT calculations unveil that the asymmetric hydrogen-bonding water at the N-TiO_(2) electrode/electrolyte interface enriches under illumination,facilitating proton transfer and moderate adsorption strength of oxygen-intermediates,which lowers the energy barrier for the OER yet elevates the energy barrier for the ClOR,resulting to a promoted selectivity towards the OER.The work sheds light on the underlying mechanism of the PEC water oxidation processes,and highlights the crucial role of interfacial water on the PEC selectivity,which could be regulated by controlling the energy band and the surface structure of semiconductors.
基金supported by the National Natural Science Foundation of China(Nos.22276168 and 21876154)A Project Supported by Scientific Research Fund of Zhejiang Provincial Education Department(No.Y202456226)。
文摘Accelerating the separation of carriers in the heterojunction plays vital role in the photoelectrocatalytic(PEC)process,yet it remains a challenging undertaking.Herein,a MOF-on-MOF based dual S-scheme heterojunction(BiVO_(4)/NH_(2)-MIL-125(Ti)/NH_(2)-MIL-53(Fe),denoted as BVO/NM125/NM53)was rationally designed and prepared for PEC removing and detoxification of organic contaminants(phenol,tetracycline hydrochloride,ciprofloxacin and norfloxacin).The S-scheme heterojunction was double confirmed by DFT calculation and XPS analysis.The charge transfer resistance of BVO/NM125/NM53 photoanode decreases to 1/11 of bare BiVO_(4) photoanode.Meanwhile,the photocurrent densitywas 3 times higher,demonstrating a marked improvement in carrier separation efficiency due to dual S-scheme heterojunction.The photoanode achieved 94.3%removal of phenol within 60 min and maintained stable performance over 10 consecutive cycles,demonstrating good PEC efficiency and structural stability.The BVO/NM125/NM53 photoanode also showed effectiveness in removing antibiotics,with chlorophyll fluorescence imaging confirming a significant reduction in the ecotoxicity of intermediates.For example,wheat seed germination,growth,chlorophyll and Carotenoid production were not affected,which was similar to that of deionized water.Radical trapping experiments and electron paramagnetic resonance(EPR)analysis identified·O_(2)^(-)and·OH as the primary active species.This work demonstrates the effectiveness of developing MOF-on-MOF heterojunctions for visible-light response and enhancing charge separation in PEC.
基金supported by the National Natural Science Foundation of China(Nos.22209186,22479149)Self-deployed Projects of Ganjiang Innovation Academy,CAS(No.E355F006)+2 种基金Natural Science Foundation of Jiangxi Province(No.20242BAB23016)Key Research and Development Program of Jiangxi Province(Nos.20223BBG74004,20232BBG70003)Youth Innovation Promotion Association,Chinese Academy of Sciences(No.2023343).
文摘Hydrogen is a highly promising energy carrier because of its renewable and clean qualities.Among the different methods for H_(2) production,photoelectrocatalysis(PEC)water splitting has garnered significant interest,thanks to the abundant and perennial solar energy.Single-atom catalysts(SACs),which feature well-distributed atoms anchored on supports,have gained great attention in PEC water splitting for their unique advantages in overcoming the limitations of conventional PEC reactions.Herein,we comprehensively review SAC-incorporated photoelectrocatalysts for efficient PEC water splitting.We begin by highlighting the benefits of SACs in improving charge transfer,catalytic selectivity,and catalytic activity,which address the limitations of conventional PEC reactions.Next,we provide a comprehensive overview of established synthetic techniques for optimizing the properties of SACs,along with modern characterization methods to confirm their unique structures.Finally,we discuss the challenges and future directions in basic research and advancements,providing insights and guidance for this developing field.
文摘Photoelectrocatalysis(PEC)is extensively applied in diverse redox reactions.However,the traditional oxygen evolution reaction(OER)occurring at the(photo)anode is hindered by high thermodynamic demands and sluggish kinetics,resulting in excessive energy consumption and limited economic value of the O2 produced,thereby impeding the practical application of PEC reactions.To overcome these limitations,advanced anodic-cathodic coupling systems,as an emerging energy conversion technology,have garnered significant research interest.These systems substitute OER with lower potential,valuable oxidation reactions,significantly enhancing energy conversion efficiency,yielding high-value chemicals,while reducing energy consumption and environmental pollution.More importantly,by designing and optimizing photoelectrodes to generate sufficient photovoltage under illumination,meeting the thermodynamic and kinetic potential requirements of the reactions,and by tuning the voltage to match the current densities of the cathode and anode,coupling reactions can be achieved under bias-free conditions.In this review,we provide an overview of the mechanisms of PEC coupling reactions and summarize photoelectrode catalysts along with their synthesis methods.We further explore advanced catalyst modification strategies and highlight the latest development in advanced PEC coupling systems,including photocathodic CO_(2)reduction,nitrate reduction,oxygen reduction,enzyme activation,coupled with photoanodic organic oxidation,biomass oxidation,and pollutant degradation.Additionally,advanced in situ characterization techniques for elucidating reaction mechanisms are discussed.Finally,we propose the challenges in catalyst design,reaction systems,and large-scale applications,while offering future perspectives for PEC coupling system.This work underscores the tremendous potential of PEC coupling systems in energy conversion and environmental remediation,and provides valuable insights for the future design of such coupling systems.
文摘Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat microplastic waste and CO_(2)by using environmentally friendly and efficient technologies.In this work,we developed an efficient photoelectrocatalytic system composed of Ni single atoms(Ni SAs)supported by P,N-doped amorphous NiFe_(2)O_(4)(Ni SAs/A-P-N-NFO)as anode and Ag nanoparticles(Ag NPs)supported by CuO/Cu_(2)O nanocubes(Ag NPs@CuO/Cu_(2)O NCs)as cathode for microplastic oxidation and CO_(2)reduction.The Ni SAs/A-P-N-NFO was synthesized by calcination-H_(2)reduction method,and it achieved a Faraday efficiency of 93%for the oxidation reaction of poly(ethylene terephthalate)(PET)solution under AM 1.5 G light.As a photocathode,the synthesized Ag NPs@CuO/Cu_(2)O NCs was utilized to reduce CO_(2)to ethylene and CO at 1.5 V vs.RHE with selectivity of 42%and 55%,respectively.This work shows that the photoelectrocatalysis,as an environmentally friendly technology,is a feasible strategy for reducing the environmental and biological hazards of light plastics,as well as for efficient CO_(2)reduction.
基金Projects(12JJ3013,11JJ5010,10JJ5002)supported by the Natural Science Foundation of Hunan Province,ChinaProject(2013CL04)supported by the Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation,Changsha University of Science and Technology,ChinaProject(2011RS4069)supported by the Planned Science and Technology Program of Hunan Province,China
文摘A thin layer of TiO2 film was deposited on ITO surface via the liquid phase deposition （LPD） process. The photocurrent and electrochemical impedance spectroscopy （EIS） measurements indicated that the as-prepared LPD TiO2/ITO film had an excellent photoelectrochemical performance, which showed a sensitive and rapid response to the UV irradiation. The photogenerated electron-hole pairs could be effectively separated by applying an external bias to the TiO2 film electrode. The LPD TiO2/ITO film was employed to study the photoelectrocatalytic （PEC） degradation of 4-aminoantipyrine. Compared with other techniques, the PEC technique based on such a LPD film electrode had a synergetic effect for 4-aminoantipyrine degradation. When the applied bias potential was＋0.8 V and the supporting electrolyte concentration of Na2SO4 was 0.1 mol/L, the highest degradation efficiency within 120 min could reach 95%for 0.1 mmol/L 4-aminoantipyrine solution at pH 2.0.
基金financially supported by the Natural Science Foundation of China(52172106)the Anhui Provincial Natural Science Foundation(2108085QB60 and 2108085QB61)+2 种基金the China Postdoctoral Science Foundation(2020M682057)the Special Research Assistant Program,Chinese Academy of SciencesJiangsu Provincial Double-Innovation Doctor Program(JSSCBS20210996)。
文摘Photocatalysis is critically important for environmental remediation and renewable energy technologies.The ability to objectively characterize photocatalyst properties and photocatalysis processes is paramount for meaningful performance evaluation and fundamental studies to guide the design and development of high-performance photocatalysts and photocatalysis systems.Photocatalysis is essentially an electron transfer process,and photoelectrocatalysis(PEC)principles can be used to directly quantify transferred electrons to determine the intrinsic properties of photocatalysts and photocatalysis processes in isolation,without interference from counter reactions due to physically separated oxidation and reduction half-reactions.In this review,we discuss emphatically the PEC-based principles for characterizing intrinsic properties of photocatalysts and important processes of photocatalysis,with a particular focus on their environmental applications in the degradation of pollutants,disinfection,and detection of chemical oxygen demand(COD).An outlook towards the potential applications of PEC technique is given.
基金supported by the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2015023)National Natural Science Foundation of China(81471784,51802115)+3 种基金Natural Science Foundation of Beijing(2172058)Natural Science Foundation of Shandong Province(ZR2018BEM010,ZR2019YQ21)Major Program of Shandong Province Natural Science Foundation(ZR2018ZC0843)Scientific and Technology Project of University of Jinan(XKY1923)~~
文摘Rapid technological development and population growth are responsible for a series of imminent environmental problems and an ineluctable energy crisis.The application of semiconductor nanomaterials in photocatalysis or photoelectrocatalysis(PEC)for either the degradation of contaminants in the environment or the generation of hydrogen as clean fuel is an effective approach to alleviate these problems.However,the efficiency of such processes remains suboptimal for real applications.Reasonable construction of a built-in electric field is considered to efficiently enhance carrier separation and reduce carrier recombination to improve catalytic performance.In the past decade,as a new method to enhance the built-in electric field,the piezoelectric effect from piezoelectric materials has been extensively studied.In this review,we provide an overview of the properties of piezoelectric materials and the mechanisms of piezoelectricity and ferroelectricity for a built-in electric field.Then,piezoelectric and ferroelectric polarization regulated built-in electric fields that mediate catalysis are discussed.Furthermore,the applications of piezoelectric semiconductor materials are also highlighted,including degradation of pollutants,bacteria disinfection,water splitting for H2 generation,and organic synthesis.We conclude by discussing the challenges in the field and the exciting opportunities to further improve piezo-catalytic efficiency.
基金financially supported by the National Natural Science Foundation of China(21802089)Natural Science Foundation of Shandong Province(ZR2019BB015)+5 种基金The Science and Technology Plan of Shandong Province Colleges and Universities under Grant(No.J14LC16)the Natural Science Foundation of Shandong Province under Grant(No.ZR2017MB018)funding support from the Shandong Province Double Hundred Talents Program for Foreign Expertsthe Energy Education Trust of New Zealandthe Dodd Walls Centre for Photonic and Quantum Technologiesthe Mac Diarmid Institute for Advanced Materials and Nanotechnology
文摘Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.
