Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and tita...Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and titanium dioxide(TiO2) is the most widely used photoanode.This review summarizes the progress in TiO2 photo gene rated protection in recent years.Different types of semiconductors,including sulfides,metals,metal oxide s,polymers,and other materials,are used to design and modify TiO2.The strategy to dramatically improve the efficiency of photoactivity is proposed,and the mechanism is investigated in detail.Characterization methods are also introduced,including morphology testing,light absorption,photoelectrochemistry,and protected metal observation.This review aims to provide a comprehensive overview of Ti02 development and guide photocathodic protection.展开更多
Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire composite films were successfully prepared using a hydrothermal method.The results show that the light absorption for Bi_(2)WO_(6)/T...Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire composite films were successfully prepared using a hydrothermal method.The results show that the light absorption for Bi_(2)WO_(6)/TiO_(2) composite films is extended to the visible region after Bi_(2)WO_(6) nanoplates and nanoflowers are assembled onto TiO_(2) nanowires.Furthermore,Bi_(2)WO_(6) nanoflower/TiO_(2) nano wire composite film exhibits a better absorption property compared to Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire film,which is mainly ascribed to the narrower bandgap of Bi_(2)WO_(6) nanoflower compared to that of Bi_(2)WO_(6) nanoplate.The photocurrent density for Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire and Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire composite films can reach 95 and 62.5 μA cm-2,respectively,which are much higher than that obtained for a pure TiO_(2) nanowire film(25 μA cm-2).Meanwhile,under illumination,the pure TiO_(2) nanowire,Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire films can reduce the potential of the coupled 304 stainless steel in 3.5 wt.%NaCl solution by 299,719 and 739 mV,respectively.Thus,Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire film is found to provide the best effective photocathodic protection for 304 stainless steel.This work not only provides an example of shape-dependent photocathodic protection based on Bi_(2)WO_(6) but also opens up new possibilities to design an ideal microstructure on the basis of semiconductor materials for future applications of photocathodic protection.展开更多
Highly ordered Ag2 S/ZnS/ZnO nanorod array film photoanodes were prepared on a Ti substrate for photocathodic cathodic protection.The results indicated that the photoresponse range of the Ag2S/ZnS/ZnO composite film w...Highly ordered Ag2 S/ZnS/ZnO nanorod array film photoanodes were prepared on a Ti substrate for photocathodic cathodic protection.The results indicated that the photoresponse range of the Ag2S/ZnS/ZnO composite film was extended compared to those of the ZnO and ZnS/ZnO films,indicating its higher light absorption capacity.When the Ag2S/ZnS/ZnO composite film served as a photoanode,the film can provide the best effective photocathodic protection for 304 stainless steel in a 3.5 wt%NaCl solution under white light illumination compared to the ZnO and ZnS/ZnO films.Additionally,in comparison to pure ZnO film,the photocurrent for the ZnS/ZnO film remained the same without noticeable fluctuation after illumination for 1 h,indicating that the ZnS functionalization improved the stability by overcoming the photocorrosion effect of the ZnO photoanode under light irradiation.展开更多
Photocathodic protection(PCP)is arguably an ideal alternative technology to the conventional electrochemical cathodic protection methods for corrosion mitigation of metallic infrastructure due to its eco-friendliness ...Photocathodic protection(PCP)is arguably an ideal alternative technology to the conventional electrochemical cathodic protection methods for corrosion mitigation of metallic infrastructure due to its eco-friendliness and low-energy-consumption,but the construction of highlyefficient PCP systems still remains challenging,caused primarily by the lack of driving force to guide the charge flow through the whole PCP photoanodes.Here,we tackle this key issue by equipping the PCP photoanode with ferroelectric single-domain PbTiO_(3)nanoplates,which can form a directional“macroscopic electric field”throughout the entire photoanode controllable by external polarization.The properly poled PCP photoanode allows the photogenerated electrons and holes to migrate in opposite directions,that is,electrons to the protected metal and holes to the photoanode/electrolyte interface,leading to largely suppressed charge annihilation and consequently a considerable boost in the overall solar energy conversion efficiency of the PCP system.The as-fabricated photoanode can not only supply sufficient photocurrent to 304 stainless steel to initiate cathodic protection,but also shift the metal potential to the corrosion-free range.Our findings provide a viable design strategy for future high-performance PCP systems based on ferroelectric nanomaterials with enhanced charge flow manipulation.展开更多
Low dark current photocathode guns are highly desired for high-brightness continuous-wave operations.Direct-current superconducting radio-frequency(DC-SRF)gun,a hybrid photocathode gun combining a DC gap and an SRF ca...Low dark current photocathode guns are highly desired for high-brightness continuous-wave operations.Direct-current superconducting radio-frequency(DC-SRF)gun,a hybrid photocathode gun combining a DC gap and an SRF cavity,effectively isolates the photocathode from the SRF cavity and offers significant advantages in terms of minimizing dark current levels.This paper presents an in-depth analysis of the dark current of a newly developed high-brightness DC-SRF photocathode gun(DC-SRF-Ⅱ gun).Particularly,a systematic experimental investigation of the dark current was conducted,and a comprehensive understanding of its formation was achieved through compliant simulations and measurements.Additionally,measures for attaining sub-nanoampere dark currents in the DC-SRF-Ⅱ gun are presented,including design considerations,cavity processing,assembly,and conditioning.The findings of this study establish a strong foundation for achieving high-performance operation of the DC-SRF-Ⅱ gun and provide a valuable reference for other photocathode guns.展开更多
The photoelectrocatalytic(PEC)CO_(2)reduction process includes photogenerated charge transport,multiphase interface,intermediate adsorption,and chemical bonding transformation,all of which are closely associated with ...The photoelectrocatalytic(PEC)CO_(2)reduction process includes photogenerated charge transport,multiphase interface,intermediate adsorption,and chemical bonding transformation,all of which are closely associated with the interface and surface layer on the photocathode.However,it is difficult to design the photocathode with an effective interface and surface active site for realizing the highly selective PEC CO_(2)reduction at ultralow potential.Here,we design a novel semiconductor p-n junction comprising Si nanowires and an indium-edited porphyrin-based metal-organic framework{Al/In-PMOF(Co)}for efficient CO_(2)reduction.The Al/In-PMOF(Co)catalyst containing In and Co metal atoms demonstrates quasidiatomic site behavior,where the introduced In causes redistribution of the electronic structure of the Co 3d states.Besides,the Al/In-PMOF(Co)layer promotes bulk charge transport and interfacial charge transfer of Si photocathode during PEC CO_(2)reduction.The Faradaic efficiency of the Si-Al/In-PMOF(Co)photocathode toward CO could increase to>90%at 0.2 V vs.RHE.Si-Al/In-PMOF(Co)photocathode also achieves a high applied bias solar-to-CO(STC)efficiency of 2.8%,which is at the state-of-the-art level.The enhanced PEC CO_(2)reduction performance is ascribed to the variation of the Fermi level of AlPMOF(Co)after the introduction of In atoms,expediting the charge transport and promoting the shift of potential of Si photocathode.Density functional theory(DFT)calculation also demonstrates that the molecular catalyst layer with quasi-diatomic sites facilitates the^(*)COOH absorption and^(*)CO desorption,thereby accelerating CO production.展开更多
CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport e...CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).展开更多
CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hi...CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hindered by poor charge separation efficiency.Herein,we introduce a characteristic in-situ solution Fe-doping strategy that markedly improves photoelectrochemical performance of CBO,doubling the photocurrent density and achieving an unprecedented 190 mV anodic shift in the onset potential.By integrating with an electrochemical oxidation post-treatment,a record incident photon-to-current efficiency(IPCE)exceeding 40% at 0.6 V vs.RHE under visible light illumination is achieved.The versatility of the doping strategy is demonstrated across CBO photocathodes synthesized by different methods with various morphologies,grain sizes,and crystallinities.Mechanistic studies reveal that the gradient distribution of Fe^(3+)ions generates an internal electric field that facilitates efficient charge separation and increases acceptor density.The strong Fe-O bonding also enhances structural stability against photoinduced corrosion.Notably,our investigation uncovers the non-temperature-dependent nature of CBO photocurrent,indicating that PEC performance enhancement primarily depends on reducing carrier recombination rather than improving bulk conductivity.This work lays the groundwork for future advancements in water splitting performance of CBO photocathodes,offering a complementary strategy to conventional methods for enhancing charge separation efficiency.展开更多
Developing photoelectrochemical(PEC)bioassays based on the principle of a photocathodic measurement of enzymatic product H_(2)O_(2) is highly attractive because it can naturally avoid interfering signals arising from ...Developing photoelectrochemical(PEC)bioassays based on the principle of a photocathodic measurement of enzymatic product H_(2)O_(2) is highly attractive because it can naturally avoid interfering signals arising from reductive species inherent to biofluids.However,fluctuant oxygen levels in the analyte solution can compromise the accuracy of photocathodic bioanalysis and restrict its application because oxygen reduction potential is similar to H_(2)O_(2).Herein,we addressed this restriction by constructing a triphase biophotocathode with air–liquid–solid joint interfaces by immobilizing an oxidase enzyme film on the tip part of superhydrophobic p-type semiconductor nanowire arrays.Such a triphase biophotocathode has a reaction zone with steady and air phasedependent oxygen concentration which stabilizes and increases the oxidase kinetics,and enables the photocathodic measurement principle in reliable PEC bioassay development with high selectivity,good accuracy,and a wide linear detection range.Moreover,the biophotocathode shows good stability during repeated testing under light illumination.This reliable PEC bioassay system has broad potential in the fields of disease diagnosis,medical research,and environmental monitoring.展开更多
Owing to the growing consumption of non-renewable resources and increased environmental pollution,significant attention has been directed toward developing renewable and environmentally friendly energy sources.Hydroge...Owing to the growing consumption of non-renewable resources and increased environmental pollution,significant attention has been directed toward developing renewable and environmentally friendly energy sources.Hydrogen has emerged as a clean energy carrier and is considered an ideal chemical for power generation via fuel cells.Using renewable energy to power hydrogen production is an attractive prospect,and hydrogen production through photoelectrochemical water splitting is considered a promising area of interest;consequently,significant research is being conducted on rationally designed photoelectrodes.Generally,a photocathode for hydrogen evolution must have a conduction band that is more negative than the reduction potential of hydrogen.Numerous photocathode materials have been developed based on this premise;these include p-Si,InP,and GaN.Compared with other photocathode materials,Cu-based compounds are advantageous owing to their low preparation costs and diverse chemical states.For example,Cu_(2)O is a non-toxic p-type metal oxide semiconductor material with an appropriate band structure for water splitting and a direct band gap of 1.9-2.2 eV.Furthermore,the production of Cu_(2)O is facile,and the required materials are abundant;thus,it has attracted significant interest as a material for photocathodes.However,Cu_(2)O suffers from rapid recombination of photogenerated carriers and severe photo-corrosion,leading to unsatisfactory efficiency and poor stability.Intrinsically,the poor photo-stability of Cu_(2)O can be attributed to the location of the redox potential of Cu_(2)O within its bandgap,owing to which photoelectrons tend to preferentially reduce Cu_(2)O to Cu rather than reduce water to reduction.Therefore,Cu_(2)O itself is not an ideal hydrogen evolution catalyst.Thus,co-catalysts are necessary to improve its hydrogen evolution activity and photostability.In addition to co-catalysts,combining Cu_(2)O with tailored n-type semiconductors to generate built-in electric fields of p-n junctions has attracted extensive attention owing to its ability of increasing the separation of photogenerated carriers.Similarly,applying a hole transfer layer on the substrate can promote photocarrier separation.Furthermore,considering that water is indispensable for Cu_(2)O reduction,one effective approach to improve the stability of Cu_(2)O is the addition of a protective/passivation layer to isolate Cu_(2)O from water in aqueous electrolytes.In this review,we provide a brief overview of the mechanism of photoelectrochemical water splitting and the band structure of Cu_(2)O ;preparation methods of Cu_(2)O photocathodes;strategies to improve the efficiency and stability of Cu_(2)O photocathodes,including the construction of p-n junctions,integration with co-catalysts,and modifications using hole transport layers;advanced photoelectrochemical characterization techniques;and a discussion regarding the direction of future photocathode research.展开更多
The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy.Si nanowires photocathodes own the advantages of effective photon absorp...The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy.Si nanowires photocathodes own the advantages of effective photon absorption,non toxicity and industrial applicability.Nevertheless,the photoelectrocatalytic(PEC)performance of Si nanowires photocathodes is still limited by ineffective or deficient active sites on their surfaces.Here,we develop an efficient Si based photocathode modified with Al-porphyrin-based MOF(Al-PMOF),consisted of an earth-abundant metal containing Al(OH)O_(4) cluster bridged by 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin.The assembled Al-PMOF significantly enhances the photocurrent density of bare Si nanowires photocathodes,resulting in a twofold increase under equivalent conditions,alongside a positive shift of 200 mV in the onset potential of the Si/Al-PMOF photocathode.The improved PEC hydrogen evolution performance is ascribed to accelerate surface charge transfer of Si photocathode and provision of favorable active site for the hydrogen evolution reaction.This work provides insights into the fabrication of semiconductor/molecule catalyst hybrid photocathodes,thus facilitating the realization of high-efficiency PEC water splitting.展开更多
Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, p...Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.展开更多
A Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite film with high performance of photogenerated cathodic protection was prepared by hydrothermal and photoreduction methods.The results showed that when the CuFe_(2)O_(4) hydrothe...A Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite film with high performance of photogenerated cathodic protection was prepared by hydrothermal and photoreduction methods.The results showed that when the CuFe_(2)O_(4) hydrothermal reaction time was 6 h and the AgNO_(3) concentration was 0.1 M,the Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite material performed the best cathodic protection capability for 304 stainless steel(304SS).In this case,the protective potential achieved-930 mV(versus SCE)associated with the photocurrent density of 475μA/cm^(2),which was 14.8 times that of pure TiO_(2) nanowires.In the dark,the nanocomposite provided cathodic protection of up to 485 mV for 304SS.Due to the heterogeneous junctions at the two interfaces among the three kinds of nanocomposite materials,the build-in electric field was fabricated,which promoted the separation efficiency of photogenerated electrons and holes and effectively improved the photochemical cathodic protection of 304SS.展开更多
By calculating the energy distribution of electrons reaching the photocathode surface and solving the Schrodinger equation that describes the behavior of an electron tunneling through the surface potential barrier,we ...By calculating the energy distribution of electrons reaching the photocathode surface and solving the Schrodinger equation that describes the behavior of an electron tunneling through the surface potential barrier,we obtain an equation to calculate the emitted electron energy distribution of transmission-mode NEA GaAs photocathodes. Accord- ing to the equation,we study the effect of cathode surface potential barrier on the electron energy distribution and find a significant effect of the barrier-Ⅰ thickness or end height,especially the thickness,on the quantum efficiency of the cath- ode. Barrier Ⅱ has an effect on the electron energy spread, and an increase in the vacuum level will lead to a narrower electron energy spread while sacrificing a certain amount of cathode quantum efficiency. The equation is also used to fit the measured electron energy distribution curve of the transmission-mode cathode and the parameters of the surface barri- er are obtained from the fitting. The theoretical curve is in good agreement with the experimental curve.展开更多
The effect of changing Be doping concentration in GaAs layer on the integrated photosensitivity for nega- tive-electron-affinity GaAs photocathodes is investigated. Two GaAs samples with the monolayer structure and th...The effect of changing Be doping concentration in GaAs layer on the integrated photosensitivity for nega- tive-electron-affinity GaAs photocathodes is investigated. Two GaAs samples with the monolayer structure and the muhilayer structure are grown by molecular beam epitaxy. The former has a constant Be concentration of 1 × 10^19 cm^-3, while the latter includes four layers with Be doping concentrations of 1 × 10^19, 7 × 10^18, 4 × 10^18, and 1 × 10^18 cm^-3 from the bottom to the surface. Negative-electron-affinity GaAs photocathodes are fabricated by exciting the sample surfaces with alternating input of Cs and O in the high vacuum system. The spectral response results measured by the on-line spectral response measurement system show that the integrated photosensitivity of the photocathode with the muhilayer structure enhanced by at least 50% as compared to that of the monolayer structure. This attributes to the improvement in the crystal quality and the increase in the surface escape probability. Different stress situations are observed on GaAs samples with monolayer structure and muhilayer structure, respectively.展开更多
The gradient-doping structure is first applied to prepare the transmission-mode GaAs photocathode and the integral sensitivity of the sealed image tube achieves 1420μA/lm. This paper studies the inner carrier concent...The gradient-doping structure is first applied to prepare the transmission-mode GaAs photocathode and the integral sensitivity of the sealed image tube achieves 1420μA/lm. This paper studies the inner carrier concentration distribution of the gradient-doping transmission-mode GaAs photocathode after molecular beam epitaxy （MBE） growth using the electrochemical capacitance-voltage profiling. The results show that an ideal gradient-doping structure can be obtained by using MBE growth. The total band-bending energy in the gradient-doping GaAs active-layer with doping concentration ranging from 1×10^19 cm-3 to 1×1018 cm-3 is calculated to be 46.3 meV, which helps to improve the photoexcited electrons movement toward surface for the thin epilayer. In addition,by analysis of the band offsets, it is found that the worse carrier concentration discrepancy between GaAs and GaA1As causes a lower back interface electron potential barrier which decreases the amount of high-energy photoelectrons and affects the short-wave response.展开更多
The photocurrent and spectral response characteristics of gallium arsenide （GaAs） are obtained by a multiinformation measurement system, and the evolution of the photocurrent versus the Cs：O flux ratio is investiga...The photocurrent and spectral response characteristics of gallium arsenide （GaAs） are obtained by a multiinformation measurement system, and the evolution of the photocurrent versus the Cs：O flux ratio is investigated. The experimental results show that the photocurrent increases approximately exponentially after the first exposure to Cs until a maximum sensitivity is reached, the detailed evolution process and the ultimate photocurrent are different for different samples. These differences are analysed, and according to the process of coadsorption of Cs and oxygen on GaAs, an equation is presented to explain the increase of photocurrent.展开更多
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 cle...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.展开更多
Photoelectrochemical(PEC)water splitting can convert renewable solar energy into clean hydrogen fuel.Photoelectrodes are the core components of water-splitting cells.In the past 40 years,a series of binary and ternary...Photoelectrochemical(PEC)water splitting can convert renewable solar energy into clean hydrogen fuel.Photoelectrodes are the core components of water-splitting cells.In the past 40 years,a series of binary and ternary transition metal oxides have been investigated as photo-electrode materials for solar water splitting,and numerous studies have been carried out to modify their water-split-ting performances.Although satisfactory transition metal oxide photoelectrode materials have not been found,it is necessary to summarize the recent advancements in tran-sition metal oxide photoelectrode materials to guide future research.In this review,the background and principle of PEC water splitting are introduced.The semiconductor properties and modification progress of typical binary and ternary metal oxide photoanodes and photocathodes for solar water splitting are summarized.Based on the newly developed strategies in recent years,a brief outlook is presented for efficient PEC water splitting using transition metal oxide photoelectrodes.展开更多
Industrial NH3 production mainly employs the well‐known Haber‐Bosch(H‐B)process,which is associated with significant energy consumption and carbon emissions.Photoelectrochemical nitro‐gen reduction reaction(PEC‐N...Industrial NH3 production mainly employs the well‐known Haber‐Bosch(H‐B)process,which is associated with significant energy consumption and carbon emissions.Photoelectrochemical nitro‐gen reduction reaction(PEC‐NRR)under ambient conditions is considered a promising alternative to the H‐B process and has been attracting increasing attention owing to its associated energy effi‐ciency and environmentally friendly characteristics.The performance of a PEC‐NRR system,such as the NH_(3) yield,selectivity,and stability,is essentially determined by its key component,the photo‐cathode.In this review,the latest progress in the development of photocathode materials employed in PEC‐NRR is evaluated.The fundamental mechanisms and essential features required for the PEC‐NRR are introduced,followed by a discussion of various types of photocathode materials,such as oxides,sulfides,selenides,black silicon,and black phosphorus.In particular,the PEC‐NRR reac‐tion mechanisms associated with these photocathode materials are reviewed in detail.Finally,the present challenges and future opportunities related to the further development of PEC‐NRR are also discussed.This review aims to improve the understanding of PEC‐NRR photocathode materials while also shedding light on the new concepts and significant innovations in this field.展开更多
基金the CAS Strategic Priority Project(No.XDA13040404)the National Natural Science Foundation of China for Exploring Key Scientific Instrument(No.41827805)the Shandong Key Laboratory of Corrosion Science。
文摘Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and titanium dioxide(TiO2) is the most widely used photoanode.This review summarizes the progress in TiO2 photo gene rated protection in recent years.Different types of semiconductors,including sulfides,metals,metal oxide s,polymers,and other materials,are used to design and modify TiO2.The strategy to dramatically improve the efficiency of photoactivity is proposed,and the mechanism is investigated in detail.Characterization methods are also introduced,including morphology testing,light absorption,photoelectrochemistry,and protected metal observation.This review aims to provide a comprehensive overview of Ti02 development and guide photocathodic protection.
基金supported by the National Natural Science Foundation of China(Nos.51822402,51671044 and 52001051)the National Key Research and Development Program of China(Nos.2019YFA0209901 and 2018YFA0702901)+4 种基金the fund of the State Key Laboratory of Solidification Processing in NWPU(Grant No.SKLSP201902)the Liao Ning Revitalization Talents Program(XLYC1807047)the National MCF Energy R&D Program(No.2018YFE0312400)the Fund of Science and Technology on Reactor Fuel and Materials Laboratory(STRFML-2020-04)the China Postdoctoral Science Foundation(No.2020M670747).
文摘Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire composite films were successfully prepared using a hydrothermal method.The results show that the light absorption for Bi_(2)WO_(6)/TiO_(2) composite films is extended to the visible region after Bi_(2)WO_(6) nanoplates and nanoflowers are assembled onto TiO_(2) nanowires.Furthermore,Bi_(2)WO_(6) nanoflower/TiO_(2) nano wire composite film exhibits a better absorption property compared to Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire film,which is mainly ascribed to the narrower bandgap of Bi_(2)WO_(6) nanoflower compared to that of Bi_(2)WO_(6) nanoplate.The photocurrent density for Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire and Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire composite films can reach 95 and 62.5 μA cm-2,respectively,which are much higher than that obtained for a pure TiO_(2) nanowire film(25 μA cm-2).Meanwhile,under illumination,the pure TiO_(2) nanowire,Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire films can reduce the potential of the coupled 304 stainless steel in 3.5 wt.%NaCl solution by 299,719 and 739 mV,respectively.Thus,Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire film is found to provide the best effective photocathodic protection for 304 stainless steel.This work not only provides an example of shape-dependent photocathodic protection based on Bi_(2)WO_(6) but also opens up new possibilities to design an ideal microstructure on the basis of semiconductor materials for future applications of photocathodic protection.
基金This work was supported financially by the Funding from the Taishan Scholarship of Climbing Plan(No.tspd20161006)the National Natural Science Foundation of China(No.51772176)the Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents(No.2017RCJJ018).
文摘Highly ordered Ag2 S/ZnS/ZnO nanorod array film photoanodes were prepared on a Ti substrate for photocathodic cathodic protection.The results indicated that the photoresponse range of the Ag2S/ZnS/ZnO composite film was extended compared to those of the ZnO and ZnS/ZnO films,indicating its higher light absorption capacity.When the Ag2S/ZnS/ZnO composite film served as a photoanode,the film can provide the best effective photocathodic protection for 304 stainless steel in a 3.5 wt%NaCl solution under white light illumination compared to the ZnO and ZnS/ZnO films.Additionally,in comparison to pure ZnO film,the photocurrent for the ZnS/ZnO film remained the same without noticeable fluctuation after illumination for 1 h,indicating that the ZnS functionalization improved the stability by overcoming the photocorrosion effect of the ZnO photoanode under light irradiation.
基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Numbers:2021A1515111234,2023A1515011552Natural Science Foundation of China,Grant/Award Number:22202237。
文摘Photocathodic protection(PCP)is arguably an ideal alternative technology to the conventional electrochemical cathodic protection methods for corrosion mitigation of metallic infrastructure due to its eco-friendliness and low-energy-consumption,but the construction of highlyefficient PCP systems still remains challenging,caused primarily by the lack of driving force to guide the charge flow through the whole PCP photoanodes.Here,we tackle this key issue by equipping the PCP photoanode with ferroelectric single-domain PbTiO_(3)nanoplates,which can form a directional“macroscopic electric field”throughout the entire photoanode controllable by external polarization.The properly poled PCP photoanode allows the photogenerated electrons and holes to migrate in opposite directions,that is,electrons to the protected metal and holes to the photoanode/electrolyte interface,leading to largely suppressed charge annihilation and consequently a considerable boost in the overall solar energy conversion efficiency of the PCP system.The as-fabricated photoanode can not only supply sufficient photocurrent to 304 stainless steel to initiate cathodic protection,but also shift the metal potential to the corrosion-free range.Our findings provide a viable design strategy for future high-performance PCP systems based on ferroelectric nanomaterials with enhanced charge flow manipulation.
基金partially supported by the National Key Research and Development Program of China(Nos.2016YFA0401904 and 2017YFA0701001)the State Key Laboratory of Nuclear Physics and Technology,Peking University(Nos.NPT2022ZZ01).
文摘Low dark current photocathode guns are highly desired for high-brightness continuous-wave operations.Direct-current superconducting radio-frequency(DC-SRF)gun,a hybrid photocathode gun combining a DC gap and an SRF cavity,effectively isolates the photocathode from the SRF cavity and offers significant advantages in terms of minimizing dark current levels.This paper presents an in-depth analysis of the dark current of a newly developed high-brightness DC-SRF photocathode gun(DC-SRF-Ⅱ gun).Particularly,a systematic experimental investigation of the dark current was conducted,and a comprehensive understanding of its formation was achieved through compliant simulations and measurements.Additionally,measures for attaining sub-nanoampere dark currents in the DC-SRF-Ⅱ gun are presented,including design considerations,cavity processing,assembly,and conditioning.The findings of this study establish a strong foundation for achieving high-performance operation of the DC-SRF-Ⅱ gun and provide a valuable reference for other photocathode guns.
基金supported by the National Natural Science Foundation of Hunan Province(2025JJ60094)the Hunan Provincial Natural Science Foundation for Distinguished Young Scholars(2025JJ20019)the National Natural Science Foundation of China(22078368)。
文摘The photoelectrocatalytic(PEC)CO_(2)reduction process includes photogenerated charge transport,multiphase interface,intermediate adsorption,and chemical bonding transformation,all of which are closely associated with the interface and surface layer on the photocathode.However,it is difficult to design the photocathode with an effective interface and surface active site for realizing the highly selective PEC CO_(2)reduction at ultralow potential.Here,we design a novel semiconductor p-n junction comprising Si nanowires and an indium-edited porphyrin-based metal-organic framework{Al/In-PMOF(Co)}for efficient CO_(2)reduction.The Al/In-PMOF(Co)catalyst containing In and Co metal atoms demonstrates quasidiatomic site behavior,where the introduced In causes redistribution of the electronic structure of the Co 3d states.Besides,the Al/In-PMOF(Co)layer promotes bulk charge transport and interfacial charge transfer of Si photocathode during PEC CO_(2)reduction.The Faradaic efficiency of the Si-Al/In-PMOF(Co)photocathode toward CO could increase to>90%at 0.2 V vs.RHE.Si-Al/In-PMOF(Co)photocathode also achieves a high applied bias solar-to-CO(STC)efficiency of 2.8%,which is at the state-of-the-art level.The enhanced PEC CO_(2)reduction performance is ascribed to the variation of the Fermi level of AlPMOF(Co)after the introduction of In atoms,expediting the charge transport and promoting the shift of potential of Si photocathode.Density functional theory(DFT)calculation also demonstrates that the molecular catalyst layer with quasi-diatomic sites facilitates the^(*)COOH absorption and^(*)CO desorption,thereby accelerating CO production.
基金supported by the National Natural Science Foundation of China(No.61804039)the University Natural Sciences Research Project of Anhui Province(No.2022AH010096)+1 种基金the Talent Research Fund of Hefei University(No.20RC35)the Natural Science Foundation of Anhui Higher Education Institution of China(No.2023AH040160).
文摘CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).
基金financial support by the National Natural Science Foundation of China(NSFC,Grant No.22379153 and 22109128)the Ningbo Key Research and Development Project(2023Z147)the Ningbo 3315 Program。
文摘CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hindered by poor charge separation efficiency.Herein,we introduce a characteristic in-situ solution Fe-doping strategy that markedly improves photoelectrochemical performance of CBO,doubling the photocurrent density and achieving an unprecedented 190 mV anodic shift in the onset potential.By integrating with an electrochemical oxidation post-treatment,a record incident photon-to-current efficiency(IPCE)exceeding 40% at 0.6 V vs.RHE under visible light illumination is achieved.The versatility of the doping strategy is demonstrated across CBO photocathodes synthesized by different methods with various morphologies,grain sizes,and crystallinities.Mechanistic studies reveal that the gradient distribution of Fe^(3+)ions generates an internal electric field that facilitates efficient charge separation and increases acceptor density.The strong Fe-O bonding also enhances structural stability against photoinduced corrosion.Notably,our investigation uncovers the non-temperature-dependent nature of CBO photocurrent,indicating that PEC performance enhancement primarily depends on reducing carrier recombination rather than improving bulk conductivity.This work lays the groundwork for future advancements in water splitting performance of CBO photocathodes,offering a complementary strategy to conventional methods for enhancing charge separation efficiency.
基金supported by the National Key R&D Program of China(no.2019YFA0709200)National Natural Science Foundation of China(nos.21988102,51772198,and 22002101).
文摘Developing photoelectrochemical(PEC)bioassays based on the principle of a photocathodic measurement of enzymatic product H_(2)O_(2) is highly attractive because it can naturally avoid interfering signals arising from reductive species inherent to biofluids.However,fluctuant oxygen levels in the analyte solution can compromise the accuracy of photocathodic bioanalysis and restrict its application because oxygen reduction potential is similar to H_(2)O_(2).Herein,we addressed this restriction by constructing a triphase biophotocathode with air–liquid–solid joint interfaces by immobilizing an oxidase enzyme film on the tip part of superhydrophobic p-type semiconductor nanowire arrays.Such a triphase biophotocathode has a reaction zone with steady and air phasedependent oxygen concentration which stabilizes and increases the oxidase kinetics,and enables the photocathodic measurement principle in reliable PEC bioassay development with high selectivity,good accuracy,and a wide linear detection range.Moreover,the biophotocathode shows good stability during repeated testing under light illumination.This reliable PEC bioassay system has broad potential in the fields of disease diagnosis,medical research,and environmental monitoring.
文摘Owing to the growing consumption of non-renewable resources and increased environmental pollution,significant attention has been directed toward developing renewable and environmentally friendly energy sources.Hydrogen has emerged as a clean energy carrier and is considered an ideal chemical for power generation via fuel cells.Using renewable energy to power hydrogen production is an attractive prospect,and hydrogen production through photoelectrochemical water splitting is considered a promising area of interest;consequently,significant research is being conducted on rationally designed photoelectrodes.Generally,a photocathode for hydrogen evolution must have a conduction band that is more negative than the reduction potential of hydrogen.Numerous photocathode materials have been developed based on this premise;these include p-Si,InP,and GaN.Compared with other photocathode materials,Cu-based compounds are advantageous owing to their low preparation costs and diverse chemical states.For example,Cu_(2)O is a non-toxic p-type metal oxide semiconductor material with an appropriate band structure for water splitting and a direct band gap of 1.9-2.2 eV.Furthermore,the production of Cu_(2)O is facile,and the required materials are abundant;thus,it has attracted significant interest as a material for photocathodes.However,Cu_(2)O suffers from rapid recombination of photogenerated carriers and severe photo-corrosion,leading to unsatisfactory efficiency and poor stability.Intrinsically,the poor photo-stability of Cu_(2)O can be attributed to the location of the redox potential of Cu_(2)O within its bandgap,owing to which photoelectrons tend to preferentially reduce Cu_(2)O to Cu rather than reduce water to reduction.Therefore,Cu_(2)O itself is not an ideal hydrogen evolution catalyst.Thus,co-catalysts are necessary to improve its hydrogen evolution activity and photostability.In addition to co-catalysts,combining Cu_(2)O with tailored n-type semiconductors to generate built-in electric fields of p-n junctions has attracted extensive attention owing to its ability of increasing the separation of photogenerated carriers.Similarly,applying a hole transfer layer on the substrate can promote photocarrier separation.Furthermore,considering that water is indispensable for Cu_(2)O reduction,one effective approach to improve the stability of Cu_(2)O is the addition of a protective/passivation layer to isolate Cu_(2)O from water in aqueous electrolytes.In this review,we provide a brief overview of the mechanism of photoelectrochemical water splitting and the band structure of Cu_(2)O ;preparation methods of Cu_(2)O photocathodes;strategies to improve the efficiency and stability of Cu_(2)O photocathodes,including the construction of p-n junctions,integration with co-catalysts,and modifications using hole transport layers;advanced photoelectrochemical characterization techniques;and a discussion regarding the direction of future photocathode research.
基金Project(22078368)supported by the National Natural Science Foundation of China。
文摘The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy.Si nanowires photocathodes own the advantages of effective photon absorption,non toxicity and industrial applicability.Nevertheless,the photoelectrocatalytic(PEC)performance of Si nanowires photocathodes is still limited by ineffective or deficient active sites on their surfaces.Here,we develop an efficient Si based photocathode modified with Al-porphyrin-based MOF(Al-PMOF),consisted of an earth-abundant metal containing Al(OH)O_(4) cluster bridged by 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin.The assembled Al-PMOF significantly enhances the photocurrent density of bare Si nanowires photocathodes,resulting in a twofold increase under equivalent conditions,alongside a positive shift of 200 mV in the onset potential of the Si/Al-PMOF photocathode.The improved PEC hydrogen evolution performance is ascribed to accelerate surface charge transfer of Si photocathode and provision of favorable active site for the hydrogen evolution reaction.This work provides insights into the fabrication of semiconductor/molecule catalyst hybrid photocathodes,thus facilitating the realization of high-efficiency PEC water splitting.
基金Project(cstc2011jj A50008)supported by the Natural Science Foundation of Chongqing,ChinaProject(14ZB0025)supported by Education Department of Sichuan Province,China
文摘Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.
基金financially supported by the National Natural Science Foundation of China(Nos.U1706225,42006046,2019GGX102014,2019YFC0312103)the Research Fund of Open Studio for Marine Corrosion and Protection,Pilot National Laboratory for Marine Science and Technology(Qingdao,No.HYFSKF201804)。
文摘A Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite film with high performance of photogenerated cathodic protection was prepared by hydrothermal and photoreduction methods.The results showed that when the CuFe_(2)O_(4) hydrothermal reaction time was 6 h and the AgNO_(3) concentration was 0.1 M,the Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite material performed the best cathodic protection capability for 304 stainless steel(304SS).In this case,the protective potential achieved-930 mV(versus SCE)associated with the photocurrent density of 475μA/cm^(2),which was 14.8 times that of pure TiO_(2) nanowires.In the dark,the nanocomposite provided cathodic protection of up to 485 mV for 304SS.Due to the heterogeneous junctions at the two interfaces among the three kinds of nanocomposite materials,the build-in electric field was fabricated,which promoted the separation efficiency of photogenerated electrons and holes and effectively improved the photochemical cathodic protection of 304SS.
文摘By calculating the energy distribution of electrons reaching the photocathode surface and solving the Schrodinger equation that describes the behavior of an electron tunneling through the surface potential barrier,we obtain an equation to calculate the emitted electron energy distribution of transmission-mode NEA GaAs photocathodes. Accord- ing to the equation,we study the effect of cathode surface potential barrier on the electron energy distribution and find a significant effect of the barrier-Ⅰ thickness or end height,especially the thickness,on the quantum efficiency of the cath- ode. Barrier Ⅱ has an effect on the electron energy spread, and an increase in the vacuum level will lead to a narrower electron energy spread while sacrificing a certain amount of cathode quantum efficiency. The equation is also used to fit the measured electron energy distribution curve of the transmission-mode cathode and the parameters of the surface barri- er are obtained from the fitting. The theoretical curve is in good agreement with the experimental curve.
文摘The effect of changing Be doping concentration in GaAs layer on the integrated photosensitivity for nega- tive-electron-affinity GaAs photocathodes is investigated. Two GaAs samples with the monolayer structure and the muhilayer structure are grown by molecular beam epitaxy. The former has a constant Be concentration of 1 × 10^19 cm^-3, while the latter includes four layers with Be doping concentrations of 1 × 10^19, 7 × 10^18, 4 × 10^18, and 1 × 10^18 cm^-3 from the bottom to the surface. Negative-electron-affinity GaAs photocathodes are fabricated by exciting the sample surfaces with alternating input of Cs and O in the high vacuum system. The spectral response results measured by the on-line spectral response measurement system show that the integrated photosensitivity of the photocathode with the muhilayer structure enhanced by at least 50% as compared to that of the monolayer structure. This attributes to the improvement in the crystal quality and the increase in the surface escape probability. Different stress situations are observed on GaAs samples with monolayer structure and muhilayer structure, respectively.
基金Project supported by the National Natural Science Foundation of China (Grant Nos 60678043 and 60801036)
文摘The gradient-doping structure is first applied to prepare the transmission-mode GaAs photocathode and the integral sensitivity of the sealed image tube achieves 1420μA/lm. This paper studies the inner carrier concentration distribution of the gradient-doping transmission-mode GaAs photocathode after molecular beam epitaxy （MBE） growth using the electrochemical capacitance-voltage profiling. The results show that an ideal gradient-doping structure can be obtained by using MBE growth. The total band-bending energy in the gradient-doping GaAs active-layer with doping concentration ranging from 1×10^19 cm-3 to 1×1018 cm-3 is calculated to be 46.3 meV, which helps to improve the photoexcited electrons movement toward surface for the thin epilayer. In addition,by analysis of the band offsets, it is found that the worse carrier concentration discrepancy between GaAs and GaA1As causes a lower back interface electron potential barrier which decreases the amount of high-energy photoelectrons and affects the short-wave response.
基金Supported by the National Natural Science Foundation of China under Grant No 60678043, and the Specialized Research Fund for the Doctoral Programme of Higher Education of China under Grant No 20050288010.
文摘The photocurrent and spectral response characteristics of gallium arsenide （GaAs） are obtained by a multiinformation measurement system, and the evolution of the photocurrent versus the Cs：O flux ratio is investigated. The experimental results show that the photocurrent increases approximately exponentially after the first exposure to Cs until a maximum sensitivity is reached, the detailed evolution process and the ultimate photocurrent are different for different samples. These differences are analysed, and according to the process of coadsorption of Cs and oxygen on GaAs, an equation is presented to explain the increase of photocurrent.
基金supported by the National Natural Science Foundation of China(No.62074102)Natural Science Foundation of Guangdong Province(2020A1515010805)China+1 种基金the Key Project of Department of Education of Guangdong Province(No.2018KZDXM059)Chinathe Science and Technology plan project of Shenzhen(20200812000347001,JCYJ20190808153409238)China。
文摘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.
基金financially supported by the National Key R&D Program of China (No. 2018YFE0208500)the National Natural Science Foundation of China (No. 41702037)
文摘Photoelectrochemical(PEC)water splitting can convert renewable solar energy into clean hydrogen fuel.Photoelectrodes are the core components of water-splitting cells.In the past 40 years,a series of binary and ternary transition metal oxides have been investigated as photo-electrode materials for solar water splitting,and numerous studies have been carried out to modify their water-split-ting performances.Although satisfactory transition metal oxide photoelectrode materials have not been found,it is necessary to summarize the recent advancements in tran-sition metal oxide photoelectrode materials to guide future research.In this review,the background and principle of PEC water splitting are introduced.The semiconductor properties and modification progress of typical binary and ternary metal oxide photoanodes and photocathodes for solar water splitting are summarized.Based on the newly developed strategies in recent years,a brief outlook is presented for efficient PEC water splitting using transition metal oxide photoelectrodes.
文摘Industrial NH3 production mainly employs the well‐known Haber‐Bosch(H‐B)process,which is associated with significant energy consumption and carbon emissions.Photoelectrochemical nitro‐gen reduction reaction(PEC‐NRR)under ambient conditions is considered a promising alternative to the H‐B process and has been attracting increasing attention owing to its associated energy effi‐ciency and environmentally friendly characteristics.The performance of a PEC‐NRR system,such as the NH_(3) yield,selectivity,and stability,is essentially determined by its key component,the photo‐cathode.In this review,the latest progress in the development of photocathode materials employed in PEC‐NRR is evaluated.The fundamental mechanisms and essential features required for the PEC‐NRR are introduced,followed by a discussion of various types of photocathode materials,such as oxides,sulfides,selenides,black silicon,and black phosphorus.In particular,the PEC‐NRR reac‐tion mechanisms associated with these photocathode materials are reviewed in detail.Finally,the present challenges and future opportunities related to the further development of PEC‐NRR are also discussed.This review aims to improve the understanding of PEC‐NRR photocathode materials while also shedding light on the new concepts and significant innovations in this field.
