Unassisted overall water splitting with a solar-to-hydrogen efficiency of over 10% by coupled lead halide perovskite photoelectrodes

Hydrogen is a promising future sustainable fuel candidate with boundless opportunities.Research into photoelectrochemical(PEC)water splitting based on a lead halide perovskite(LHP)has progressed significantly with the aim of more efficient solar hydrogen production.Herein,we unite a well-known photo-absorbing LHP with cost-effective water-splitting catalysts,and we introduce two types of monolithic LHP-based PEC devices that act as a photocathode and a photoanode for the hydrogen evolution reaction and oxygen evolution reaction,leading to efficient unbiased overall water splitting.Through the integration of these two monolithic LHP-based photoelectrodes,an unbiased solar-to-hydrogen conversion efficiency of 10.64%and a photocurrent density of 8.65 mA cm^(−2) are achieved.

Preparation of TiO_2/Ti mesh photoelectrode and properties

An innovative photoelectrode, TiO_2/Ti mesh electrode, was prepared by anodisation. In anodisation, 0.5 mol/L H_2SO_4 was used as electrolytic solution, the current had been constantly 1A from the beginning of the oxidation until reaching a designed voltage. Results showed that the photocatalytic activity of electrode was better when the designed voltage was 160 V. The morphology and the crystalline texture of the TiO_2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rhodamine B in photocatalytic (PC) and photoelectrocatalytic (PEC) reaction was investigated.

Enhanced photocatalytic degradation of methyl orange by CdS quantum dots sensitized platelike WO_3 photoelectrodes

CdS quantum dots sensitized platelike WO_3 photoelectrodes were successfully synthesized by a facile hydrothermal method and a modified chemical bath deposition(CBD) technique.To further improve the stability of the photoelectrodes in alkaline environment,the platelike WO_3 films were treated with TiCl_4 to form a nano-TiO_2 buffer layer on the WO_3 plate surface before loading CdSQDs.The resulting electrodes were characterized by using XRD,SEM,HR-TEM and UV-vis spectrum.The photocatalytic activity of the resulting electrodes was investigated by degradation of methyl orange(MO) in aqueous solution.The photoelectrochemical(PEC) property of the resulting electrodes was also characterized by the linear sweep voltammetry.The results of both the degradation of MO and photocurrent tests indicated that the as-prepared CdSQDs sensitized WO_3 platelike photoelectrodes exhibit a significant improvement in photocatalytic degradation and PEC activity under visible light irradiation,compared with unsupported CdSQDs electrodes.Significantly,coating the WO_3 plates with nano-TiO_2 obviously facilitate the charge separation and retards the charge-pair recombination,and results in a highest activity for QDsCdS/TiO_2/WO_3 photoelectrodes.

Nanocarbon-Enhanced 2D Photoelectrodes:A New Paradigm in Photoelectrochemical Water Splitting

Solar-driven photoelectrochemical(PEC)water splitting systems are highly promising for converting solar energy into clean and sustainable chemical energy.In such PEC systems,an integrated photoelectrode incorporates a light harvester for absorbing solar energy,an interlayer for transporting photogenerated charge carriers,and a co-catalyst for triggering redox reactions.Thus,understanding the correlations between the intrinsic structural properties and functions of the photoelectrodes is crucial.Here we critically examine various 2D layered photoanodes/photocathodes,including graphitic carbon nitrides,transition metal dichalcogenides,layered double hydroxides,layered bismuth oxyhalide nanosheets,and MXenes,combined with advanced nanocarbons(carbon dots,carbon nanotubes,graphene,and graphdiyne)as co-catalysts to assemble integrated photoelectrodes for oxygen evolution/hydrogen evolution reactions.The fundamental principles of PEC water splitting and physicochemical properties of photoelectrodes and the associated catalytic reactions are analyzed.Elaborate strategies for the assembly of 2D photoelectrodes with nanocarbons to enhance the PEC performances are introduced.The mechanisms of interplay of 2D photoelectrodes and nanocarbon co-catalysts are further discussed.The challenges and opportunities in the field are identified to guide future research for maximizing the conversion efficiency of PEC water splitting.

Enhancement in solar hydrogen generation efficiency using InGaN photoelectrode after surface roughening treatment with nano-sized Ni mask

A significant enhancement in solar hydrogen generation efficiency has been achieved by inductive coupled etching （ICP） surface roughening treatment using nano-sized nickel mask. As much as 7 times improvement of photocurrent is demonstrated in comparison with a planar one fabricated from the same parent wafer. Under identical illumination conditions in HBr solution, the incident photon conversion efficiency （IPCE） shows an enhancement with a factor of 3, which even exceed 54% at 400 nm wavelength. We believe the enhancement is attributed to several facts including improvement in absorption, reacting area, carder localization and carrier lifetime.

Metal chalcogenide-based photoelectrodes for photoelectrochemical water splitting

Photoelectrochemical water splitting(PEC-WS)is a promising technique for transforming solar energy into storable and environmentally friendly chemical energy.Designing semiconductor photoelectrodes with high light absorption capability,rapid e-/h+separation and transfer,and sufficient chemical stability is vital for developing an efficient PEC-WS system.Metal chalcogenides(MCs)have emerged as promising candidates for light absorbers because of their unique electrical and optical characteristics.In this review,we present recent developments in hydrogen generation via PEC-WS using MC-based photoelectrodes.First,we present a simple illustration of PEC-WS fundamentals.Second,the current performance of various metal(mono-,di-,and tri-)chalcogenide/semiconductor photoelectrodes in PEC-WS is summarized.Then,the charge transfer mechanism at the MC/semiconductor interface and the PEC-WS mechanism is thoroughly explained.Finally,we discuss future research perspectives toward developing efficient and stable MC/semiconductor photoelectrodes.

Kinetics of photoelectrocatalytic degradation of endocrine disrupting chemicals using sulfur-doped TiO_2 /Ti photoelectrodes

In this study,sulfur-doped TiO2 /Ti photoelectrodes were prepared by anodization. The morphology, crystalline structure,composition of sulfur-doped TiO2 /Ti film and light absorption property were examined by SEM,XRD,XRF,XPS and UV/VIS respectively. Dimethyl phthalate( DMP) ,one kind of environmental disrupting chemicals( EDCs) ,was degraded by the optimized photoelectrodes. Power of xenon light,initial concentration of DMP,photoelectrocatalytic( PEC) area of photoelectrode and bias were investigated in the study on kinetics of PEC degradation of DMP. Hence,this study concluded that the optimum conditions were power of xenon light 150 W,initial concentration of DMP 1 mg/L,PEC area of sulfur-doped TiO2 /Ti photoelectrode 10 cm2,bias 1. 3 V in the PEC reaction system.

Physicochemical Characterization of Photoelectrodes of Ti/TiO₂Prepared by Thermal Oxidation of Titanium

The preparation and study of supported TiO2 for photocatalytic application in solar cell devices is a relevant research field. Thin films of TiO2 prepared on Ti by thermal oxidation in a wide range of temperatures (450°C - 900°C) were characterized by electrochemical impedance spectroscopy, potentiometry and amperometry. This material presents photoelectrochemical activity, which depends dramatically of the oxidation temperature and the exposition time at the studied temperatures. The flatband potential as well as the donor density and the resistance to the charge transfer were measured. All these parameters are temperature dependent, and the optimal values are observed on the photoelectrodes prepared at 750°C. This result is consistent with the photochemical response reported in the literature for thin films of Ti/TiO2 prepared under similar conditions.

Photoelectrochemical Detection of Glucose by Using an Enzyme-Modified Photoelectrode

A new photoelectrochemical method for the determination of glucose based on the photoelectrochemical effect of poly（thionine） photoelectrode to hydrogen peroxide （H202） was reported. The H2Oz-sensitive photoelectrode was fabricated by electropolymerizing thionine on the surface of ITO electrode. And then glucose oxidase was immobilized on the photoelectrode via the aid of chitosan enwrapping, forming an enzyme-modified photoelectrode. The photoelectrode was employed as an electron acceptor; H2O2 from the catalytic reaction of enzyme was employed as an electron donor, developing an analytical method of glucose without hydrogen peroxidase. In the paper, the pho- toelectrochemical effects of photoelectrode to H202 and glucose were studied. The effects of the bias voltage and the electrolyte pH on the photocurrent were investigated. The linear response of glucose concentrations ranged from 0.05 to 2.00 mmol/L was obtained with a detection limit of 22.0 μmol/L and sensitivity of 73.2 nA/（mmol·L-1）. The applied feasibility of method was acknowledged through monitoring the glucose in practical samples.

Efficient photoelectrodes based on two-dimensional transition metal dichalcogenides heterostructures:from design to construction

Hydrogen production by photoelectrochemical(PEC) water splitting converts the inexhaustible supply of solar radiation to storable H2 as clean energy and thus has received widespread attention.The efficiency of PEC water splitting is largely determined by the properties of the photoelectrodes.Two-dimensional(2 D) layered transition metal dichalcogenides(TMDs) are promising candidates for photoelectrodes due to their atomic layer thickness,tunable bandgap,large specific surface area,and high carrier mobility.Moreover,the construction of 2 D TMDs heterostructures provides freedom in material design,which facilitates the further improvement of PEC water splitting.This review begins by describing the mechanism of PEC water splitting and the advantages of 2 D TMDbased heterostructures for photo electrodes.Then,the design considerations of the heterostructures for enhanced PEC efficiency are comprehensively reviewed with a focus on material selection,band engineering,surface modification,and long-term durability.Finally,current challenges and future perspectives for the development of photoelectrodes based on 2 D TMDs heterostructures are addressed.

Graded bandgap semiconductor thin film photoelectrodes

<Abstract>A graded bandgap oxide semiconductor thin film electrode was designed in order to obtain a photoelec-trochemically stable photoelectrode, with wide absorption range. The graded bandgap Ti1-xVxO2 film electrode was prepared by heating the stacked layers of V/Ti in varying ratios, which were coated on the substrate by the sol-gel method using the starting solution with various V/Ti ratios. XPS result showed that the composition gradient was achieved for the film. The Ti1-xVxO2 film electrode was found to be photoelectrochemically stable. Its photovoltage was about 360 mV. Obvious visible light photoresponse was observed for the Ti1-xVxO2 film electrode. Compared with the pure TiO2 electrode, the photocurrent onset potential of the Ti1-xVxO2 film electrode was shifted positively, probably because the accumulation of vanadium at the electrode surface causes the recombination of the electrons and holes, and the lowest level of the conduction band of Ti1-xVxO2 is lower than that of TiO2. Impedance

Rational design on photoelectrodes and devices to boost photoelectrochemical performance of solar-driven water splitting: a mini review

As an eco-friendly,efficient,and low-cost technique,photoelectrochemical water splitting has attracted growing interest in the production of clean and sustainable hydrogen by the conversion of abundant solar energy.In the photoelectrochemical system,the photoelectrode plays a vital role in absorbing the energy of sunlight to trigger the water splitting process and the overall efficiency depends largely on the integration and design of photoelectrochemical devices.In recent years,the optimization of photoelectrodes and photoelectrochemical devices to achieve highly efficient hydrogen production has been extensively investigated.In this paper,a concise review of recent advances in the modification of nanostructured photoelectrodes and the design of photoelectrochemical devices is presented.Meanwhile,the general principles of structural and morphological factors in altering the photoelectrochemical performance of photoelectrodes are discussed.Furthermore,the performance indicators and first principles to describe the behaviors of charge carriers are analyzed,which will be of profound guiding significance to increasing the overall efficiency of the photoelectrochemical water splitting system.Finally,current challenges and prospects for an in-depth understanding of reaction mechanisms using advanced characterization technologies and potential strategies for developing novel photoelectrodes and advanced photoelectrochemical water splitting devices are demonstrated.

Anodized metal oxide nanostructures for photoelectrochemical water splitting

Photoelectrochemical(PEC) water splitting offers the capability of harvesting, storing, and converting solar energy into clean and sustainable hydrogen energy. Metal oxides are appealing photoelectrode materials because of their easy manufacturing and relatively high stability. In particular, metal oxides prepared by electrochemical anodization are typical of ordered nanostructures, which are beneficial for light harvesting, charge transfer and transport, and the adsorption and desorption of reactive species due to their high specific surface area and rich channels. However, bare anodic oxides still suffer from low charge separation and sunlight absorption efficiencies. Accordingly, many strategies of modifying anodic oxides have been explored and investigated. In this review, we attempt to summarize the recent advances in the rational design and modifications of these oxides from processes before, during, and after anodization. Rational design strategies are thoroughly addressed for each part with an aim to boost overall PEC performance. The ongoing efforts and challenges for future development of practical PEC electrodes are also presented.

Current trending and beyond for solar-driven water splitting reaction on WO_(3)photoanodes

This review shows the importance of WO_(3)photoanode as a potentially low-cost,efficient,stable,and photoactive material for light-driven water splitting.For such,this manuscript aims to review the most recent publications regarding the strategies to improve the phoelectroactivity of WO_(3)films for water oxidation.In addition,this review aims to graphically highlight and discuss the general trendings of the photocurrent density response and stability test of the recent outstanding studies in the literature for photoelectrochemical water splitting application.The strategies covered in this review will not only concern the WO_(3)morphology and crystal plane growth,but also the many arrangements possibilities to improve the WO_(3)efficiency for water photoelectrooxidation,such as defect engineering based on oxygen vacancies,doping,decorations,and homo and heterojunctions.All these strategies are compared by the photocurrent density results and by the stability of these photocatalysts.The best results in this sense were observed in cases where the use of heterojunction was applied together with a desired morphology and crystal plane of the WO_(3)photoanode.However,the modifications that caused a decrease in the photocurrent density reaching values that are even lower than the pure WO_(3)were also discussed.In this way,this review intends to improve the knowledge about the synthesis and design of WO_(3)photoanodes to further obtain an efficient photocatalyst to minimize the recombination losses or losses across the interfaces and improve the photoelectroactivity for water splitting in the large-scale application.

Visible Light Photoelectrocatalytic Degradation of Rhodamine B Using Ti/TiO2-NiO Photoanode

The method of Ti/TiO2-NiO photoelectrode prepared by using sol-gel method continued by calcination process was introduced. The prepared TiO2-NiO film was observed with XRD and TEM. The anatase-rutile TiO2 was mainly on the prepared TiO2-NiO composite surface electrode. In addition to NiO, the composite also formed NiTiO3 that increased with increasing calcination temperature. Photoelectrocatalytic degradation of Rhodamine B (RB) using this electrode was investigated, and anodic potential and pH were optimized. RB degradation was investigated under different conditions, and it showed that photoelectrocatalytic degradation could achieve efficient and complete mineralization of organic pollutant. Through comparison of the photoelectrocatalytic oxidation using the Ti/TiO2-NiO electrode operated by single photoanode with the Ti/TiO2-NiO electrode operated by several photoanode, it was found that the photoelectrocatalytic efficiency of that by series photoanodes was higher. Additionally, photoelectrocatalytic system was performed at the several different photoelectrodes, which verified the higher photocatalytic activity compared with the single photoelectrode.

Effect of Tantalum Doping on TiO₂Nanotube Arrays for Water-Splitting

This work is intended to define a new possible methodology for TiO2 doping through the use of electrochemical deposition of tantalum directly on the titanium nanotubes obtained by a previous galvanostatic anodization treatment in an ethylene glycol solution. This method does not seem to cause any influence on the nanotube structure, showing final products with news and interesting features with respect to the unmodified sample. Together with a decrease in the band gap and flat band potential of the TiO2 nanotubes, the tantalum doped specimen reports an increase of the photo conversion efficiency under UV light.

液态金属镶嵌半导体颗粒光电极中金属/半导体3D界面电子结构调控促进光电化学分解水

光电极通常由半导体吸光层和导电集流体两部分组成,两者间的界面电子结构直接影响导电集流体从半导体光吸收层中收集光生电荷的效率,尤其对于具有3D界面结构的液态金属镶嵌半导体颗粒的光电极.为此,本工作通过改变金属组分改变液态金属的功函数,从而调节导电集流体与半导体吸光材料间3D界面的电子能带排列和接触类型,促进光生电荷的跨界面转移与收集,提升光电极的光电化学分解水活性.系统研究半导体与液态金属的功函数匹配关系发现,将ZnO颗粒嵌入铟锡(IT)低温液态金属中,会形成欧姆接触;而将其嵌入铋铟锡(BIT)低温液态金属中,则会形成肖特基接触.由于欧姆接触不存在肖特基接触的界面能垒而有利于光生电荷的跨界面转移与收集,因此,与铟锡低温液态金属镶嵌ZnO颗粒的光电极(IT/ZnO)相比铋铟锡低温液态金属镶嵌ZnO颗粒的光电极(BIT/ZnO)具有更为优异的电荷收集和分离能力,其光电化学分解水光电流密度可达0.62 mA cm^(-2),相比BIT/ZnO光电极的光电流密度(0.52 mA cm^(-2))提升了约19%,且在已报道的代表性ZnO光电极中处于前列.而与之相比,WO3、TiO_(2)或Cu2O因分别与IT和BIT形成相同的欧姆或肖特基型接触,两种低温液态金属镶嵌的WO3、TiO_(2)或Cu2O光电极具有几乎相同的光电催化活性.本工作展示了通过选择具有不同功函数的液态金属来改变金属/半导体接触类型以增强低温液态金属镶嵌半导体光电极性能的潜力,为规模化构建高效光电极提供了新的策略.

Recent Advancements in Photoelectrochemical Water Splitting for Hydrogen Production

Sunlight is the most abundant and inexhaustible energy source on earth.However,its low energy density,dispersibility and intermittent nature make its direct utilization with industrial relevance challenging,suggesting that converting sunlight into chemical energy and storing it is a valuable measure to achieve global sustainable development.Carbon–neutral,clean and secondary pollution-free solar-driven water splitting to produce hydrogen is one of the most attractive avenues among all the current options and is expected to realize the transformation from dependence on fossil fuels to zero-pollution hydrogen.Artificial photosynthetic systems(APSs)based on photoelectrochemical(PEC)devices appear to be an ideal avenue to efficiently achieve solar-to-hydrogen conversion.In this review,we comprehensively highlight the recent developments in photocathodes,including architectures,semiconductor photoabsorbers and performance optimization strategies.In particular,frontier research cases of organic semiconductors,dye sensitization and surface grafted molecular catalysts applied to APSs based on frontier(molecular)orbital theory and semiconductor energy band theory are discussed.Moreover,research advances in typical photoelectrodes with the metal–insulator–semiconductor(MIS)architecture based on quantum tunnelling are also introduced.Finally,we discuss the benchmarks and protocols for designing integrated tandem photoelectrodes and PEC systems that conform to the solar spectrum to achieve high-efficiency and cost-effective solar-to-hydrogen conversion at an industrial scale in the near future.

Fabrication of three-dimensional WO_(3)/ZnWO_(4)/ZnO multiphase heterojunction system with electron storage capability for significantly enhanced photoinduced cathodic protection performance

A novel three-dimensional hierarchical WO_(3)photoelectrode was prepared by solvothermal method,and ZnO was deposited on its surface by electrochemical method.The WO_(3)/ZnWO_(4)/ZnO multiphaseheterojunction photoelectrode was prepared by further annealing treatment to explore the photoinduced cathodic protection(CP)performance.Compared with WO_(3)and ZnO,the photoinduced CP and electron storage capacity performance of WO_(3)/ZnWO_(4)/ZnO is significantly improved in 3.5%NaCl solution without adding any hole scavenger.The electron storage capacity of the WO_(3)/ZnWO_(4)/ZnO heterojunction makes it possible to continuously protect metallic materials in the dark after switching off the light,which can realize long-term and effective photoinduced CP.