Insights on advanced substrates for controllable fabrication of photoanodes toward efficient and stable photoelectrochemical water splitting

Conversion of solar energy into H2 by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of photoanodes is crucial to guarantee the high efficiency and stability of PEC reactions,which fundamentally rely on rationally designed semiconductors(as the active materials)and substrates(as the current collectors).In this review work,we start with a brief introduction of the roles of substrates in the PEC process.Then,we provide a systematic overview of representative strategies for the controlled fabrication of photoanodes on rationally designed substrates,including conductive glass,metal,sapphire,silicon,silicon carbide,and flexible substrates.Finally,some prospects concerning the challenges and research directions in this area are proposed.

High efficiency and stable solid-state fiber dye-sensitized solar cells obtained using TiO_(2) photoanodes enhanced with metal organic frameworks

Solid-state fiber dye-sensitized solar cells(SS-FDSSCs) have been the subject of intensive attention and development in recent years. Although this field is only in its infancy, metal–organic frameworks(MOFs) are one such material that has been utilized to further improve the power conversion efficiency of solar cells. In this study, MOF-integrated DSSCs were shown to have potential in the development of solar cell devices with efficiency comparable to or better than that of conventional solar cells. The power conversion efficiency(PCE) of SS-FDSSCs was improved by embedding MOF-801 into a mesoporous-TiO_(2)(mp-TiO_(2)) layer, which was used as a photoanode in SS-FDSSCs, which are inherently flexible. The PCE of the MOF-integrated SS-FDSSCs was 6.50%, which is comparable to that of the reference devices(4.19%).The MOF-801 enhanced SS-FDSSCs decreased the series resistance(R_(s)) value, resulting in effective electron extraction with improved short-circuit current density(J_(SC)), while also increasing the shunt resistance(R_(sh)) value to prevent the recombination of photo-induced electrons. The result is an improved fill factor and, consequently, a higher value for the PCE.

Improved water oxidation via Fe doping of CuWO4 photoanodes:Influence of the Fe source and concentration

Iron(Fe)was successfully doped in CuWO4 photoanode films with a combined liquid-phase spin-coating method via the dopant sources of Fe(NO3)3,FeSO4 and FeCl3.The microstructure of the prepared films was characterized by x-ray diffraction,scanning electron microscopy,and atomic force microscopy.The light absorption and photoelectric conversion properties were evaluated by the UV-visible absorption spectra and monochromatic incident photon-to-electron conversion efficiency.The chemical composition and element combination of the samples were examined by x-ray photoelectron spectroscopy.A linear sweep voltammetric and stability test(I-t)were performed with an electrochemical workstation.The results show that the samples are uniform with a thickness of approximately 800 nm and that the photoelectrochemical performance of the doped films is heavily dependent on the Fe source and dopant concentration.Upon optimizing the doping conditions of Fe(NO3)3 and the optimal source,the photocurrent density in the Fe-doped CuWO4 photoanode film is improved by 78%from 0.267 mA/cm2 to 0.476 mA/cm2 at 1.23 V vs reversible hydrogen electrode.The underlying causes are discussed.

Organic ligand nanoarchitectonics for BiVO_(4) photoanodes surface passivation and cocatalyst grafting

Bismuth vanadate(BiVO_(4))is a promising photoanode material for efficient photoelectrochemical(PEC)water splitting,whereas its performance is inhibited by detrimental surface states.To solve the problem,herein,a low-cost organic molecule 1,3,5-benzenetricarboxylic acid(BTC)is selected for surface passivation of BiVO_(4) photoanodes(BVOs),which also provides bonding sites for Co^(2+)to anchor,resulting in a Co-BTC-BVO photoanode.Owing to its strong coordination with metal ions,BTC not only passivates surface states of BVO,but also provides bonding between BVO and catalytic active sites(Co^(2+))to form a molecular cocatalyst.Computational study and interfacial charge kinetic investigation reveal that chemical bonding formed at the interface greatly suppresses charge recombination and accelerates charge transfer.The obtained Co-BTC-BVO photoanode exhibits a photocurrent density of 4.82 mA/cm^(2) at 1.23 V vs.reversible hydrogen electrode(RHE)and a low onset potential of 0.22 VRHE under AM 1.5 G illumination,which ranks among the best photoanodes coupled with Co-based cocatalysts.This work presents a novel selection of passivation layers and emphasizes the significance of interfacial chemical bonding for the construction of efficient photoanodes.

Architecture modification and In^(3+)-doping of WO_(3) photoanodes to boost the photoelectrochemical water oxidation performance

WO_(3) photoanodes have been widely utilized for the oxygen evolution reaction(OER)in the photoelectrochemical water splitting system.Herein,the effects of hydrazine hydrate modification and In^(3+)-doping on the physicochemical properties and photocurrent density of the WO_(3) photoanode prepared by hydrothermally treating at 160℃followed by calcining at 500℃are investigated.Among them,the hydrazine hydrate in the hydrothermal solution can serve as a texture regulator,resulting in the formation of WO_(3) films with the layered architecture stacked by nanosheets dominantly exposed(020)facets,which allows the WO_(3) films to have faster charge separation and larger specific surface area for OER according to the characterization results of microstructures and photoelectrochemcial behaviors;while the In^(3+)-doping can optimize the energy band structure of WO_(3) and adjust the work function to increase the driving force of OER based on the ultraviolet photoelectron spectroscopy,Mott–Schottky and open-circuit photovoltage plots.Under the simulated sunlight(AM1.5G)illumination,the designed In^(3+)–WO_(3)(N_2H_4)photoanode in Na_2SO_4 solution delivers amaximum incident photon-to-current efficiency of 38.6%at 410 nm and a photocurrent density of 1.93 mA cm^(-2)at 1.23 V vs.RHE,which is 2.8 and 3.0 times higher than the pristine WO_(3) photoanode,respectively.This study provides a promising strategy to improve the water splitting performance of nanostructured WO_(3) photoanodes by altering the architecture and introducing heteroatoms.

Current progress in developing metal oxide nanoarrays-based photoanodes for photoelectrochemical water splitting

Solar energy driven photoelectrochemical(PEC) water splitting is a clean and powerful approach for renewable hydrogen production. The design and construction of metal oxide based nanoarray photoanodes is one of the promising strategies to make the continuous breakthroughs in solar to hydrogen conversion efficiency of PEC cells owing to their owned several advantages including enhanced reactive surface at the electrode/electrolyte interface, improved light absorption capability, increased charge separation efficiency and direct electron transport pathways. In this Review, we first introduce the structure,work principle and their relevant efficiency calculations of a PEC cell. We then give a summary of the state-of the-art research in the preparation strategies and growth mechanism for the metal oxide based nanoarrays, and some details about the performances of metal oxide based nanoarray photoanodes for PEC water splitting. Finally, we discuss key aspects which should be addressed in continued work on realizing high-efficiency metal oxide based nanoarray photoanodes for PEC solar water splitting systems.

Dye-sensitized solar cells based on Cr-doped TiO2 nanotube photoanodes

The effect of chromium doping on the photo- voltaic efficiency of dye-sensitized solar cells （DSSCs） with anodized TiO2 nanotubes followed by an annealing process was investigated. Cr-doped TiO2 nanotubes （CrTNs） with different amounts of chromium were obtained by anodizing of titanium foils in a single-step process using potassium chro- mate as the chromium source. Film features were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, energy-dispersive X-ray spectroscopy （EDX）, and ultraviolet-visible （UV-Vis） spectroscopy. It is clearly seen that highly ordered TiO2 nanotubes are formed in an anodizing solution free of potassium chromate, and with a gradual increase in the potassium chromate concentration, these nanotube structures change to nanoporous and compact films without porosity. The photovoltaic efficiencies of fabricated DSSCs were characterized by a solar cell measurement sys- tem via the photocurrent-voltage （l-V） curves. It is found that the photovoltaic efficiency of DSSCs with CrTNsl sample is improved by more than three times compared to that of DSSCs with undoped TNs. The energy conversion efficiency increases from 1.05 % to 3.89 % by doping of chromium.

Enhancing BiVO_(4)photoanode performance by insertion of an epitaxial BiFeO_(3)ferroelectric layer

BiVO_(4)(BVO)is a promising material as the photoanode for use in photoelectrochemical applications.However,the high charge recombination and slow charge transfer of the BVO have been obstacles to achieving satisfactory photoelectrochemical performance.To address this,various modifications have been attempted,including the use of ferroelectric materials.Ferroelectric materials can form a permanent polarization within the layer,enhancing the separation and transport of photo-excited electron-hole pairs.In this study,we propose a novel approach by depositing an epitaxial BiFeO_(3)(BFO)thin film underneath the BVO thin film(BVO/BFO)to harness the ferroelectric property of BFO.The self-polarization of the inserted BFO thin film simultaneously functions as a buffer layer to enhance charge transport and a hole-blocking layer to reduce charge recombination.As a result,the BVO/BFO photoanodes showed more than 3.5 times higher photocurrent density(0.65 mA cm^(-2))at 1.23 V_(RHE)under the illumination compared to the bare BVO photoanodes(0.18 m A cm^(-2)),which is consistent with the increase of the applied bias photon-to-current conversion efficiencies(ABPE)and the result of electrochemical impedance spectroscopy(EIS)analysis.These results can be attributed to the self-polarization exhibited by the inserted BFO thin film,which promoted the charge separation and transfer efficiency of the BVO photoanodes.

Efficient flexible dye-sensitized solar cells from rear illumination based on different morphologies of titanium dioxide photoanode

The TiO_(2) with nanoparticles(NPs),nanowires(NWs),nanorods(NRs)and nanotubes(NTs)structures were prepared by using a in-situ hydrothermal technique,and then proposed as a photoanode for flexible dye-sensitized solar cell(FDSSC).The influences of the morphology of TiO_(2) on the photovoltaic performances of FDSSCs were investigated.Under rear illumination of 100 mW·cm^(−2),the power conversion efficiencies of FDSSCs achieved 6.96%,7.36%,7.65%,and 7.83%with the TiO_(2) photoanodes of NPs,NWs,NRs,and NTs and PEDOT counter electrode.The FDSSCs based on TiO_(2) NRs and NTs photoanodes have higher short circuit current densities and power conversion efficiencies than that of the others.The enhanced power conversion efficiency is responsible for their nanotubes and rod-shaped ordered structures,which are more beneficial to transmission of electron and hole in semiconductor compared to the TiO_(2) nanoparticles and nanowires disordered structure.

Enabling silicon photoanodes for efficient solar water splitting by electroless-deposited nickel

Enabling Si photoanodes for efficient solar water oxidation would facilitate the development of solar fuel conversion, but it is challenging owing to Si surface passivation via photo-induced corrosion in aqueous electrolytes. To overcome this challenge, most approaches have focused on improving the stability of Si by coating dense and thin protective layers using high vacuum-based techniques such as atomic layer deposition. However, these procedures are costly, making scalability for practical applications difficult. Herein, we report a modified electroless deposition （ELD） method to uniformly deposit protective and catalytic Ni films on Si wafers, resulting in efficient and stable Si photoanodes for solar water oxidation. The optimized Ni/n-Si photoanode achieves an onset potential of -1.09 V vs. a reversible hydrogen electrode and a saturation current density of -27.5 mA/cm^2 under AM 1.5 G illumination at pH 14. The ELD method is additionally capable of Ni deposition on a 4-inch n-Si wafer, demonstrating the first 4-inch Si photoanode. The solar water oxidation of the ELD-Ni/n-Si photoanode can be further improved by surface texturing, built-in n-p junctions, or coupling with more efficient catalysts.

Recent research progress on operational stability of metal oxide/sulfide photoanodes in photoelectrochemical cells

Photoelectrochemical(PEC)water splitting can directly convert solar energy into hydrogen energy for storage,effectively ending the energy crisis and solving environmental problems.With their modification by many researchers,photoanodes have rapidly improved in PEC performance.Nevertheless,the poor stability of PEC water-splitting devices has not been effectively corrected,seriously hindering their practical application and large-scale commercialization.In this review,we provide a detailed introduction to the photocorrosion mechanism of photoanodes and characterizations of stability,summarizing the current research progress on the stability of metal oxide/sulfide photoanode materials.According to the specificity of each semiconductor,the corrosion mechanism and modification strategy of each photoanode are discussed in detail.Finally,we summarize the deficiencies in the current stability research and propose influencing factors and possible solutions that need to be considered in the photocorrosion research field of photoanodes.This review can provide a reference for the stability research of photoanodes based on metal oxides and sulfides,especially for the design of efficient and stable metal sulfide-based photoanodes.

Progress in nanostructured photoanodes for dye-sensitized solar cells

Solar cells represent a principal energy technology to convert light into electricity. Commercial solar cells are at present predominately produced by single- or multi-crystalline silicon wafers. The main drawback to silicon-based solar cells, however, is high material and manufacturing costs. Dye-sensitized solar cells （DSSCs） have attracted much attention during recent years because of the low production cost and other advantages. The photoanode （working electrode） plays a key role in determining the performance of DSSCs. In particular, nanostructured photoanodes with a large surface area, high electron transfer efficiency, and low electron recombination facilitate to prepare DSSCs with high energy conversion efficiency. In this review article, we summarize recent progress in the development of novel photoanodes for DSSCs. Effect of semiconductor material （e.g. TiO2, ZnO, SnO2, N2O5, and nano carbon）, preparation, morphology and structure （e.g. nanoparticles, nanorods, nanofibers, nanotubes, fiber/ particle composites, and hierarchical structure） on photovoltaic performance of DSSCs is described. The possibility of replacing silicon-based solar cells with DSSCs is discussed.

Selectively converting CO_(2) to HCOOH on Cu-alloys integrated in hematite-driven artificial photosynthetic cells

The integration of electrochemical CO_(2)reduction(CO_(2)RR) and photoelectrochemical water oxidation offers a sustainable access to valuable chemicals and fuels. Here, we develop a rapidly annealed hematite photoanode with a photocurrent density of 2.83 mA cm^(-2)at 1.7 VRHEto drive the full-reaction. We also present Cu-alloys electrocatalysis extended from CuInSnS4, which are superior in both activity and selectivity for CO_(2)RR. Specifically, the screened CuInSn achieves a CO_(2)to HCOOH Faradaic efficiency of 93% at a cell voltage of-2.0 V by assembling into artificial photosynthesis cell. The stability test of IT exhibits less than 3% degradation over 24 h. Furthermore, in-situ Raman spectroscopy reveals that both CO_(3)^(-2)and CO_(2)are involved in CO_(2)RR as reactants. The preferential affinity of C for H in the ^(*)HCO_(2)intermediate enables an improved HCOOH-selectivity, highlighting the role of multifunctional Cu in reducing the cell voltage and enhancing the photocurrent density.

Efficient quantum dot sensitized solar cells via improved loading amount management

High light-harvesting efficiency and low interfacial charge transfer loss are essential for the fabrication of high-efficiency quantum dot-based solar cells(QDSCs). Increasing the thickness of mesoporous TiO2films can improve the loading of pre-synthesized QDs on the film and enhance the absorbance of photoanode, but commonly accompanied by the increase in the unfavorable charge recombination due to prolonged electron transmission paths. Herein, we systematically studied the influence of the balance between QD loading and TiO2film thickness on the performance of QDSCs. It is found that the relative thin photoanode prepared by the cationic surfactant-assisted multiple deposition procedure has achieved a high QD loading which is comparable to that of the thick photoanode commonly used. Under AM 1.5G illumination, Zn–Cu–In–Se and Zn–Cu–In–S based QDSCs with optimized 11.8 μm photoanodes show the PCE of 10.03% and 8.53%, respectively, which are comparable to the corresponding highest PCE of Zn–Cu–In–Se and Zn–Cu–In–S QDSCs(9.74% and 8.75%) with over 25.0 μm photoanodes. Similarly, an impressive PCE of 6.14% was obtained for the CdSe based QDSCs with a 4.1 μm photoanode, which is slightly lower than the best PCE(7.05%)of reference CdSe QDSCs with 18.1 μm photoanode.

Recent advances in elaborate interface regulation of BiVO_(4)photoanode for photoelectrochemical water splitting

Bismuth vanadate(BiVO_(4))is an excellent photoanode material for photoelectrochemical(PEC)water splitting system,possessing high theoretical photoelectrocatalytic conversion efficiency.However,the actual PEC activity and stability of BiVO_(4)are faced with great challenges due to factors such as severe charge recombination and slow water oxidation kinetics at the interface.Therefore,various interface regulation strategies have been adopted to optimize the BiVO_(4)photoanode.This review provides an in-depth analysis for the mechanism of interface regulation strategies from the perspective of factors affecting the PEC performance of BiVO_(4)photoanodes.These interface regulation strategies improve the PEC performance of BiVO_(4)photoanode by promoting charge separation and transfer,accelerating interfacial reaction kinetics,and enhancing stability.The research on the interface regulation strategies of BiVO_(4)photoanode is of great significance for promoting the development of PEC water splitting technology.At the same time,it also has inspiration for providing new ideas and methods for designing and preparing efficient and stable catalytic materials.

A review on photoelectrochemical cathodic protection semiconductor thin films for metals

Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for metal to achieve cathodic protection. Comparing with traditional PEC photoanode for water splitting, it requires the photoanode providing a suitable cathodic potential for the metal, instead of pursuit ultimate photon to electric conversion efficiency, thus it is a more possible PEC technology for engineering application. To date, great efforts have been devoted to developing novel n-type semiconductors and advanced modification method to improve the performance on PEC cathodic protection metals. Herein, recent progresses in this field are summarized. We highlight the fabrication process of PEC cathodic protection thin film, various nanostructure controlling, doping, compositing methods and their operation mechanism. Finally, the current challenges and future potential works on improving the PEC cathodic protection performance are discussed.

Engineering the photoelectrochemical behaviors of ZnO for efficient solar water splitting

Solar water splitting is a promising strategy for the sustainable production of renewable hydrogen and solving the world’s crisis of energy and environment.The third-generation direct bandgap semiconductor of zinc oxide(ZnO)with properties of environmental friendliness and high efficiency for various photocatalytic reactions,is a suitable material for photoanodes because of its appropriate band structure,fine surface structure,and high electron mobility.However,practical applications of ZnO are usually limited by its high recombination rate of photogenerated electron–hole pairs,lack of surface reaction force,inadequate visible light response,and intrinsic photocorrosion.Given the lack of review on ZnO’s application in photoelectrochemical(PEC)water splitting,this paper reviews ZnO’s research progress in PEC water splitting.It commences with the basic principle of PEC water splitting and the structure and properties of ZnO.Then,we explicitly describe the related strategies to solve the above problems of ZnO as a photoanode,including morphology control,doping modification,construction of heterostructure,and the piezo-photoelectric enhancement of ZnO.This review aims to comprehensively describe recent findings and developments of ZnO in PEC water splitting and to provide a useful reference for the further application and development of ZnO nanomaterials in highly efficient PEC water splitting.

Bismuth based photoelectrodes for solar water splitting

Photoelectrochemical water splitting is a sustainable path to generate valuable hydrogen using sunlight and water as the only inputs.Despite significant efforts to date,it is still a challenge to achieve photoelectrode with superior performance and long-term stability.Many bismuth-based semiconductor materials have demonstrated excellent visible light harvesting capability and suitable band edge for water splitting.Herein,we summarized the latest studies conducted on bismuth-based photoelectrodes for photoelectrochemical water splitting.Specifically,photoelectrochemical properties of copper bismuth oxide(CuBi_(2)O_(4)),bismuth ferrites(BiFeO_(3),Bi_(2)Fe_(4)O_(9)),bismuth vanadate(BiVO_(4)),bismuth tungstate(Bi_(2)WO_(6)),bismuth molybdate(Bi_(2)MoO_(6))and bismuth oxyhalids(BiOX,X=I,Cl,Br)are presented.Strategies to achieve high stability and photolectrochemical performance were discussed in the aspects of nanostructure formation,heterostructure assembly,practical defect engineering,preferential facet growth and oxygen evolution catalyst incorporation.

Sulfide@hydroxide core–shell nanostructure via a facile heating-electrodeposition method for enhanced electrochemical and photoelectrochemical water oxidation

Designing low-cost,easy-fabricated,highly stable and active electrocatalysts for oxygen evolution reaction(OER) is crucial for electrochemical(EC) and solar-driven photoelectrochemical(PEC) water splitting.By using a facile heating-electrodeposition method,here we fabricated a porous but crystalline Fe-doped Ni3 S2.A thin porous surface NiFe hydroxide layer(~10 nm) is then formed through OER-running.By virtue of the core Fe-doped Ni3 S2 with good conductivity and the shell NiFe hydroxide surface with good electrocatalytic activity,the core-shell nanostructure on Ni foam exhibits excellent OER activity in 1 M NaOH,needing only 195 and 230 mV to deliver 10 and 100 mA/cm^(2),respectively,much more superior to those of 216 and 259 mV for the sample deposited under normal temperature.The enhanced photo-response of the sulfide@hydroxide core-shell structure was also demonstrated,due to the efficient transfer of photo-generated carriers on the core/shell interface.More interestingly,it shows a good compatibility with Si based photoanode,which exhibits an excellent PEC performance with an onset potential of 0.86 V vs.reversible hydrogen electrode,an applied bias photon-to-current efficiency of 5.5% and a durability for over 120 h under AM 1.5 G 1 sun illumination,outperforming the state-of-the-art Si based photoanodes.

A fast approach to optimize dye loading of photoanode via ultrasonic technique for highly efficient dye-sensitized solar cells

A distinctive method is proposed by simply utilizing ultrasonic technique in Ti02 electrode fabrication in order to improve the optoelectronic performance of dye-sensitized solar cells （DSSCs）. Dye molecules are at random and single molecular state in the ultrasonic field and the ultrasonic wave favors the diffusion and adsorption processes of dye molecules. As a result, the introduction of ultrasonic technique at room temperature leads to faster and more well-distributed dye adsorption on TiO2 as well as higher cell efficiency than regular deposition, thus the fabrication time is markedly reduced. It is found that the device based on 40 kHz ultrasonic （within 1 h） with N719 exhibits a Voc of 789 mV, Jsc of 14.94 mA]cm2 and fill factor （FF） of 69.3, yielding power conversion efficiency （PCE） of 8.16%, which is higher than device regularly dyed for 12 h （PCE = 8.06%）. In addition, the DSSC devices obtain the best efficiency （PCE = 8.68%） when the ultrasonic deposition time increases to 2.5 h. The DSSCs fabricated via ultrasonic technique presents more dye loading, larger photocurrent, less charge recombination and higher photovoltage. The charge extraction and electron impedance spectroscopy （EIS） were performed to understand the influence of ultrasonic technique on the electron recombination and performance of DSSCs.