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

Conversion of solar energy into H_(2) 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.

Recent progress and perspectives on Sb_(2)Se_(3)-based photocathodes for solar hydrogen production via photoelectrochemical water splitting

Photoelectrochemical(PEC) cells involved with semiconductor electrodes can simultaneously absorb solar energy and perform chemical reactions, which are considered as an attractive strategy to produce renewable and clean hydrogen energy. Sb_(2)Se_(3) has been widely investigated in constructing PEC photocathodes benefitting of its low toxicity, suitable band gap, superior optoelectronic properties, and outstanding photocorrosion stability. We first present a brief overview of basic concepts and principles of PEC water splitting as well as a comparison between Sb_(2)Se_(3) and other numerous candidates. Then the material characteristics and preparation methods of Sb_(2)Se_(3) are introduced. The development of Sb_(2)Se_(3)-based photocathodes in PEC water splitting with various architectures and engineering efforts(i.e., absorber engineering, interfaces engineering, co-catalyst engineering and tandem engineering) to improve solar-to-hydrogen(STH) efficiency are highlighted. Finally, we debate the possible future directions to further explore the researching fields of Sb_(2)Se_(3)-based photocathodes with a strongly positive outlook in PEC processed solar hydrogen production.

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.

MXene-based hybrid materials for electrochemical and photoelectrochemical H_(2) generation

The conversion of solar energy to produce clean hydrogen fuel through water splitting is an emerging strategy for efficiently storing solar energy in the form of solar fuel.This aligns with the increasing global demand for the development of an ideal energy alternative to fossil fuels that does not emit greenhouse gases.Electrochemical(EC) and photoelectrochemical(PEC) water splitting technologies have garnered significant attention worldwide for advanced hydrogen solar fuel production in recent decades.To achieve sustainable green H_(2) production,it is essential to create efficient catalyst materials that are low-cost and can replace expensive noble metal-based catalysts.These characteristics make them an ideal catalyst material for the process.Two-dimensional MXenes with M_(n+1)X_(n) structure have been identified as a promising option for EC and PEC water splitting due to their superior hydrophilicity,metal-like conductivity,large surface area,and adjustable surface chemistry.Here,we present a summary of recent advancements in the synthesis and performance enhancement methods for MXene hybrid materials in hydrogen production through EC and PEC water splitting.Furthermore,we examine the challenges and insights associated with the rational design of MXene-based hybrid materials to facilitate efficient water splitting for sustainable solar fuel production.

Influence of O-O formation pathways and charge transfer mediator on lipid bilayer membrane-like photoanodes for water oxidation

Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipathic Ru(bda)-based catalysts(bda=2,2'-bipyrdine-6,6'-dicarbonoxyl acid)and aliphatic chain decorated electrode surfaces,forming lipid bilayer membrane(LBM)-like structures.The Ru(bda)catalysts on electrode-supported LBM films demonstrated remarkable water oxidation performance with different O-O formation mechanisms.However,compared to the slow charge transfer process,the O-O formation pathways did not determine the PEC water oxidation efficiency of the dyesensitized photoanodes,and the different reaction rates for similar catalysts with different catalytic paths did not determine the PEC performance of the DSPECs.Instead,charge transfer plays a decisive role in the PEC water oxidation rate.When an indolo[3,2-b]carbazole derivative was introduced between the Ru(bda)catalysts and aliphatic chain-modified photosensitizer in LBM films,serving as a charge transfer mediator for the tyrosine-histidine pair in PSⅡ,the PEC water oxidation performance of the corresponding photoanodes was dramatically enhanced.

基于PEC技术的水电站照明电源设计研究

本研究针对水电站的照明用电需求,设计了一套基于光电化学电池(Photoelectrochemical Cell,PEC)技术的自主照明电源系统。该系统采用高效率的单晶硅光伏组件作为光电转换设备,结合镍氢电池构建储能单元,并通过最大功率点跟踪(Maximum Power Point Tracking,MPPT)技术和智能化控制策略,实现了对水电站照明负荷的稳定供电。实验结果表明,系统在连续运行15 d的测试中,光伏发电量、储能容量以及负荷供电均达到预期目标,证明了系统的高效性、稳定性以及可靠性。此外,系统的模块化设计和智能控制策略提高了系统的灵活性与可维护性,为水电站提供了一种环保、高效且经济的照明解决方案。

Recent Advances in Visible-Light-Driven Photoelectrochemical Water Splitting: Catalyst Nanostructures and Reaction Systems

Photoelectrochemical(PEC) water splitting using solar energy has attracted great attention for generation of renewable hydrogen with less carbon footprint, while there are enormous challenges that still remain for improving solar energy water splitting efficiency, due to limited light harvesting, energy loss associated to fast recombination of photogenerated charge carriers, as well as electrode degradation. This overview focuses on the recent development about catalyst nanomaterials and nanostructures in different PEC water splitting systems. As photoanode, Au nanoparticle-decorated TiO_2 nanowire electrodes exhibited enhanced photoactivity in both the UV and the visible regions due to surface plasmon resonance of Au and showed the largest photocurrent generation of up to 710 nm. Pt/Cd S/CGSe electrodes were developed as photocathode. With the role of p–n heterojunction, the photoelectrode showed high stability and evolved hydrogen continuously for more than 10 days. Further, in the Z-scheme system(Bi_2S_3/TNA as photoanode and Pt/Si PVC as photocathode at the same time), a self-bias(open-circuit voltage Voc= 0.766 V) was formed between two photoelectrodes, which could facilitate photogenerated charge transfers and enhance the photoelectrochemical performance, and which might provide new hints for PEC water splitting. Meanwhile, the existing problems and prospective solutions have also been reviewed.

Efficient Photoelectrochemical Water Splitting by g-C_3N_4/TiO_2 Nanotube Array Heterostructures

Well-ordered TiO_2 nanotube arrays(TNTAs)decorated with graphitic carbon nitride(g-C_3N_4) were fabricated by anodic oxidization and calcination process.First, TNTAs were prepared via the anodic oxidation of Ti foil in glycerol solution containing fluorinion and 20%deionized water. Subsequently, g-C_3N_4 film was hydrothermally grown on TNTAs via the hydrogen-bonded cyanuric acid melamine supramolecular complex. The results showed that g-C_3N_4 was successfully decorated on the TNTAs and the g-C_3N_4/TNTAs served as an efficient and stable photoanode for photoelectrochemical water splitting. The facile deposition method enables the fabrication of efficient and low-cost photoanodes for renewable energy applications.

Recent advances in non-metal doped titania for solar-driven photocatalytic/photoelectrochemical water-splitting

Photocatalytic (PC) / Photoelectrochemical (PEC) water splitting under solar light irradiation is considered as a prospective technique to support the sustainable and renewable H_(2) economy and to reach the ultime goal of carbon neutral. TiO_(2) based photocatalysts with high chemical stability and excellent photocatalytic properties have great potential for solar-to-H_(2) conversion. To conquer the challenges of the large band-gap and rapid recombination of photo generated electron-holepairs in TiO_(2), non-metal doping turns out to be economic, facile, and effective on boosting the visible light activity. The localized defect states such as oxygen vacancy and Ti^(3+) generated by non-metal doping are located in the band-gap of TiO_(2), which result in the reduction of band-gap, thus a red-shift of the absorption edge. The hetero doping atoms such as B^(3+), I^(7+), S^(4+)/S^(6+), P^(5+) can also act as electron donors or trap sites which facilitate the charge carrier separation and suppress the recombination of electron-hole pairs. In this comprehensive review, we present the most recent advances on non-metal doped TiO_(2) photocatalysts in terms of fundamental aspects, origin of visible light activity and the PC / PEC behaviours for water splitting. In particular, the characteristics of different non-metal elements (N, C, B, S, P, Halogens) as dopants are discussed in details focusing on the synthesis approaches, characterization as well as the efficiency of PC and PEC water splitting. The present review aims at guiding the readers who want quick access to helpful information about how to efficiently improve the performance of photocatalysts by simple doping strategies and could stimulate new intuitive into the new doping strategies.

A molecular cobaloxime cocatalyst and ultrathin FeOOH nanolayers co-modifiedBiVO_(4) photoanode for efficient photoelectrochemical water oxidation

BiVO_(4) has been attracting a lot of interest in photoelectrochemical (PEC) water oxidation due to its efficient solar absorption and appropriate band positions.So far,sluggish water oxidation kinetics and fast photogenerated charge recombination still hinder the PEC performance ofBiVO_(4) .In this study,a novel PEC photoanode was designed by depositing ultrathin FeOOH nanolayers on the surface of nanoporousBiVO_(4) electrode,followed by modification with a cobaloxime (Co(dmgH)_(2)(4-COOH-py)Cl) molecular cocatalyst.Under irradiation of a 100 mW cm^(-2)(AM 1.5G) Xe lamp,the photocurrent density of the cobaloxime/FeOOH/BiVO_(4) composite photoanode reached 5.1 mA cm^(-2)at 1.23 V vs.RHE in 1.0 M potassium borate buffer solution (pH=9.0).The onset potential of the optimal cobaloxime/FeOOH/BiVO_(4) photoanode exhibited a 460 m V cathodic shift relative to bareBiVO_(4) .In addition,the surface charge injection efficiency of the composite photoanode reached~80%at 1.23 V vs.RHE and the incident photon-to-current efficiency (IPCE) reached~88%at 420 nm.

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.

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.

Graphitic carbon nitride (g-C3N4)-based nanosized heteroarrays: Promising materials for photoelectrochemical water splitting

Photoelectrochemical(PEC)water splitting is recognized as a sustainable strategy for hydrogen generation due to its abundant hydrogen source,utilization of inexhaustible solar energy,high-purity product,and environment-friendly process.To actualize a practical PEC water splitting,it is paramount to develop efficient,stable,safe,and low-cost photoelectrode materials.Recently,graphitic carbon nitride(g-C3N4)has aroused a great interest in the new generation photoelectrode materials because of its unique features,such as suitable band structure for water splitting,a certain range of visible light absorption,nontoxicity,and good stability.Some inherent defects of g-C3N4,however,seriously impair further improvement on PEC performance,including low electronic conductivity,high recombination rate of photogenerated charges,and limited visible light absorption at long wavelength range.Construction of g-C3N4-based nanosized heteroarrays as photoelectrodes has been regarded as a promising strategy to circumvent these inherent limitations and achieve the high-performance PEC water splitting due to the accelerated exciton separation and the reduced combination of photogenerated electrons/holes.Herein,we summarize in detail the latest progress of g-C3N4-based nanosized heteroarrays in PEC water-splitting photoelectrodes.Firstly,the unique advantages of this type of photoelectrodes,including the highly ordered nanoarray architectures and the heterojunctions,are highlighted.Then,different g-C3N4-based nanosized heteroarrays are comprehensively discussed,in terms of their fabrication methods,PEC capacities,and mechanisms,etc.To conclude,the key challenges and possible solutions for future development on g-C3N4-based nanosized heteroarray photoelectrodes are discussed.

Ti, Zn co-doped hematite photoanode for solar driven photoelectrochemical water oxidation

Although there have been many reports of metal doping to ameliorate the drawbacks of hematite as the photoanode for water oxidation, most of them focused on monometallic doping, and only a few of them payed attention to bimetallic doping. What is worse, the synergetic mechanism between two metal dopants was not sufficiently studied, especially the density functional theory(DFT) calculation. In this work, the n-type hematite was synthesized by introducing Ti dopant into hematite through the hydrothermal method, and dipping-sintering treatment was employed to further introduce homogeneously dispersed Zn dopant into that, forming the Ti, Zn co-doped hematite. Under the optimal condition, Tidoped hematite photoanode reached approximately 2-times enhancement of the photocurrent density compared with the pristine one at 1.23 V vs. RHE, while Ti, Zn co-doped hematite anode obtained another25% elevation. UV–Vis spectroscopy, Mott–Schottky plots, EIS analysis, photo-oxidation of hole scavenger(H2O2), and DFT calculation were employed to understand the role of Ti, Zn dopant. Based on the obtained results, the synergetic mechanism of two dopants was discussed, i.e., the improvement of PEC performance of Ti, Zn co-doped hematite photoanode was possibly attributed to greater carrier density and improved charge separation efficiency at the surface of hematite. This work provides new strategy and understanding of the improvement of PEC performance of hematite by doping engineering.

Work function tuned, surface Cs intercalated BiVO_(4) for enhanced photoelectrochemical water splitting reactions

Monoclinic BiVO_(4) is a widely researched semiconductor in solar water splitting owing to its suitable characteristics. However, BiVO_(4) faces limitations, such as the inefficient separation and transportation of photogenerated charges in the bulk and poor catalytic water oxidation reactions at the surface that affect the water-splitting efficiency. In this work, the Cs intercalation strategy at the surface of BiVO_(4) is proposed for the enhanced water splitting to H_(2) and O_(2) productions via the effective separation and transportation photogenerated charges and improved surface catalytic water oxidation reactions. The Cs ions are found to intercalate at the surface of BiVO_(4) and regulate the oxygen vacancies to provide active O_(2) production sites and stability. The surface intercalation of Cs boosts the photocurrent to 1.89 mA cm^(-2)at 1.23 V vs.reference hydrogen electrode(RHE). A stoichiometric evolution of H_(2) and O_(2) is recorded with a faradaic efficiency of 92%. The open-circuit voltage measurements confirmed the increase in the carrier lifetime with the work function tuning upon Cs intercalation. The proposed Cs intercalation strategy suggests an effective route to suppress the charge recombination with an increase in carrier lifetime and charge separation in BiVO_(4) for the enhanced PEC application.

Toward practical photoelectrochemical water splitting and CO_(2) reduction using earth-abundant materials

Photoelectrochemical(PEC)fuel generation from water splitting and CO_(2)reduction(CO_(2)R)utilizing solar energy holds immense potential to solve the current energy and environmental issues.In the past decades,numerous studies have been devoted to this fast-growing research field,and it is essential to develop efficient photoelectrodes with earth-abundant materials for the practical application of PEC systems.A thorough review of earth-abundant materials and associated devices for PEC fuel generation is beneficial to uncover the inherent obstacles and pave the way for future research.Herein,we summarize the recent progress of earth-abundant light-absorbers and cocatalysts in the PEC systems.The unbiased configurations and scaling-up strategies of PEC devices using earth-abundant materials are examined.A comparison between PEC water splitting and CO_(2)R is carried out to promote better understanding of the design principles for practical materials and devices.Last,the prospects on advanced materials,underlying mechanisms,and reaction systems of PEC water splitting and CO_(2)R are proposed.

New strategy to incorporate nano-particle sized water oxidation catalyst into dye-sensitized photoelectrochemical cell for water splitting

In order to develop a new strategy to deposit nano-particle sized water oxidation catalyst based on earth abundant element to the photoanode in a photoelectrochemical cell for water splitting, Co;O;as water oxidation catalyst was prepared and subsequently modified by 3-aminopropyltriethoxysilane. The amino functionalized Co;O;catalyst was carefully characterized and then integrated to the ruthenium dye sensitized photoelectrode through fast Schiff base reaction. Cyclic voltammetry experiments in the dark confirmed that the modified Co;O;catalyst was still active toward water oxidation, which could be initiated by oxidation of the ruthenium photosensitizer. Under visible light irradiation, incorporation of the modified Co;O;catalyst resulted in dramatic enhancement of the transient photocurrent density for the photoanode, which was 8 times higher than that of without Co;O;catalyst.

Black phosphorus-based heterostructures for photocatalysis and photoelectrochemical water splitting

Semiconductor-based photocatalytic and photoelectrochemical(PEC) processes can convert solar energy into high-density chemical energy or for the treatment of environmental pollutants, which are ideal ways to deal with environmental and energy crises. The development of high-efficiency photocatalysts and photoelectrodes is the key to the in-depth development and practical application of the two technologies.Black phosphorus(BP) has excellent physicalcochemical properties such as adjustable band gap, high carrier mobility, large specific surface area and anisotropy, making it one of the most promising catalysts.BP-based heterostructure can not only realize the effective separation of photogenerated carriers but also improve the stability of BP, and is widely used in photocatalytic and PEC reactions. In this review, we first introduce the crystal structure, band structure, anisotropy, and preparation of BP with different dimensions(bulk, zero-dimension and two-dimension). Then, according to the transfer path of the photogenerated carriers and the components, the BP-based heterostructures are divided into type I heterojunction, type II heterojunction, Z-scheme heterojunction, S-scheme heterojunction, BP/carbonbased material heterostructure, BP/metal heterostructure and multi-component heterostructure.Highlighted are the diverse photocatalytic applications of BP-based heterostructure, such as water splitting and CO_(2)reduction, N_(2)fixation, pollutant degradation, photothermal and photodynamic therapy.Finally, some concluding views and opinions are stated on the challenges and opportunities faced by the further development of BP-based heterostructures in photocatalysis and PEC water splitting.

Direct Synthesis of Molybdenum Phosphide Nanorods on Silicon Using Graphene at the Heterointerface for Efficient Photoelectrochemical Water Reduction

Transition metal phosphides(TMPs)and transition metal dichalcogenides(TMDs)have been widely investigated as photoelectrochemical(PEC)catalysts for hydrogen evolution reaction(HER).Using high-temperature processes to get crystallized compounds with large-area uniformity,it is still challenging to directly synthesize these catalysts on silicon photocathodes due to chemical incompatibility at the heterointerface.Here,a graphene interlayer is applied between p-Si and MoP nanorods to enable fully engineered interfaces without forming a metallic secondary compound that absorbs a parasitic light and provides an inefficient electron path for hydrogen evolution.Furthermore,the graphene facilitates the photogenerated electrons to rapidly transfer by creating Mo-O-C covalent bondings and energetically favorable band bending.With a bridging role of graphene,numerous active sites and anti-reflectance of MoP nanorods lead to significantly improved PEC-HER performance with a high photocurrent density of 21.8 mA cm−2 at 0 V versus RHE and high stability.Besides,low dependence on pH and temperature is observed with MoP nanorods incorporated photocathodes,which is desirable for practical use as a part of PEC cells.These results indicate that the direct synthesis of TMPs and TMDs enabled by graphene interlayer is a new promising way to fabricate Si-based photocathodes with high-quality interfaces and superior HER performance.

Unraveling the role of Ti3C2 MXene underlayer for enhanced photoelectrochemical water oxidation of hematite photoanodes

Hematite is regarded as a promising photoanode for photoelectrochemical(PEC) water splitting.However,the charge recombination occurred at the interface of FTO/hematite strictly limits the PEC performance of hematite.Herein,we reported a Ti3C2 MXene underlayer modified hematite(Ti-Fe2O3) photoanode via a simple drop-casting followed by hydrothermal and annealing processes.Owing to the bifunctional role of Ti3C2 MXene underlayer in improving the interfacial properties of FTO/hematite and providing Ti source for the construction of Fe2 TiO5/Fe2O3 heterostructure in hematite nanostructure,the bulk and interfacial charge transfer dynamics of hematite are significantly enhanced,and consequently enhancing the PEC performance.Compared with the pristine hematite,the as-prepared Ti-Fe2O3 photoanode shows an increased photocurrent density from 0.80 mA/cm^(2) to 1.30 mA/cm^(2) at 1.23 V vs.RHE.Moreover,a further promoted PEC performance including a dramatically increased photocurrent density of 2.49 mA/cm^(2) at1.23 V vs.RHE and an obviously lowered onset potential is achieved for the Ti-Fe2O3 sample after the subsequent surface F-treatment and the loading of FeNiOOH cocatalyst.Such results suggest that the introduction of Ti3C2 MXene underlayer is a facile but effective approach to improve the PEC water splitting activity of hematite.