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 amphipat...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.展开更多
The oxygen evolution reaction(OER)activity of single-atom catalysts(SACs)is closely related to the coordination environment of the active site.Oxygencoordinated atomic metal species bring about unique features beyond ...The oxygen evolution reaction(OER)activity of single-atom catalysts(SACs)is closely related to the coordination environment of the active site.Oxygencoordinated atomic metal species bring about unique features beyond nitrogen-coordinated atomic metal species due to the fact that the M-O bond is weaker than the M-N bond.Herein,a series of metal-oxygen-carbon structured low-nucleus clusters(LNCs)are successfully anchored on the surface of multiwalled carbon nanotubes(M-MWCNTs,M=Ni,Co,or Fe)through a foolproof low-temperature gas transfer(300℃)method without any further treatment.The morphology and coordination configuration of the LNCs at the atomic level were confirmed by comprehensive characterizations.The synthetic Ni-MWCNTs electrocatalyst features excellent OER activity and stability under alkaline conditions,transcending the performances of Co-MWCNTs,Fe-MWCNTs and RuO_(2).Density functional theory calculations reveal that the moderate oxidation of low-nucleus Ni clusters changes the unoccupied orbital of Ni atoms,thereby lowering the energy barrier of the OER rate-limiting step and making the OER process more energy-efficient.This study demonstrates a novel versatile platform for large-scale manufacturing of oxygen-coordinated LNC catalysts.展开更多
Lead(Pb)-free halide perovskites have recently attracted increasing attention as potential catalysts for CO_(2) photoreduction to CO due to their potential to capture solar energy and drive catalytic reaction.However,...Lead(Pb)-free halide perovskites have recently attracted increasing attention as potential catalysts for CO_(2) photoreduction to CO due to their potential to capture solar energy and drive catalytic reaction.However,issues of the poor charge transfer still remain one of the main obstacles limiting their performance due to the overwhelming radiative and nonradiative charge-carrier recombination losses.Herein,Pb-free Sb-alloyed all-inorganic quadruple perovskite Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12)(0≤x≤1)is synthesized as efficient photocatalyst.By Sb alloying,the undesired relaxation of photogenerated electrons from conduction band to emission centers of[MnCl6]^(4-)is greatly suppressed,resulting in a weakened PL emission and enhanced charge transfer for photocatalyst.The ensuing Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12) photocatalyst accomplishes efficient conversion of CO_(2)into CO,accompanied by a surprising production of H_(2)O_(2),a high valueadded product associated with water oxidation.By optimizing Sb^(3+) concentration,a high CO evolution rate of 35.1μmol g^(-1)h^(-1)is achieved,superior to most other Pb and Pb-free halide perovskites.Our findings provide new insights into the mixed-cation alloying strategies for improved photocatalytic performance of Pb-free perovskites and shed light on the rational design of robust band structure toward efficient energy transfer.展开更多
The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an overwhelming problem if left to conventional treatment processes. Two options, incinerati...The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an overwhelming problem if left to conventional treatment processes. Two options, incineration and supercritical water oxidation (SCWO), exist for the complete destruction of toxic organic wastewaters. Incinerator has associated problems such as very high cost and public resentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaters with extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, the concepts of SCWO, result and present perspectives of application, and industrial status of SCWO are critically examined and discussed.展开更多
The 2,4,6-trinitrotoluene (TNT) is a potential carcinogens and TNT contaminated wastewater, which could not be effectively disposed with conventional treatments. The supercritical water oxidation (SCWO) to treat T...The 2,4,6-trinitrotoluene (TNT) is a potential carcinogens and TNT contaminated wastewater, which could not be effectively disposed with conventional treatments. The supercritical water oxidation (SCWO) to treat TNT contaminated wastewater was studied in this article, The TNT concentration in wastewater was measured by high-performance liquid chromatograph (HPLC) and the degraded intermediates were analyzed using GC-MS. The results showed that SCWO could degrade TNT efficiently in the presence of oxygen. The reaction temperature, pressure, residence time and oxygen excess were the main contributing factors in the process. The decomposition of TNT was accelerated as the temperature or residence time increased. At 550℃, 24 MPa, 120 s and oxygen excess 300%, TNT removal rate could exceed 99.9%. Partial oxidation occured in SCWO without oxygen. It was concluded that supercritical water was a good solvent and had excellent oxidation capability in the existence of oxygen. The main intermediates of TNT during SCWO included toluene, 1,3,5-trinitrobenzene, nitrophenol, naphthalene, fluorenone, dibutyl phthalate, alkanes and several dimers based on the intermediate analysis. Some side reactions, such as coupled reaction, hydrolysis reaction and isomerization reaction may take place simultaneously when TNT was oxidized by SCWO.展开更多
The realization of efficient oxygen evolution reaction(OER) is critical to the development of multiple sustainable energy conversion and storage technologies, especially hydrogen production via water electrolysis. To ...The realization of efficient oxygen evolution reaction(OER) is critical to the development of multiple sustainable energy conversion and storage technologies, especially hydrogen production via water electrolysis. To achieve the massive application of hydrogen energy and mass-scale hydrogen production from water splitting drives the pursuit of competent precious-metal-free electrocatalysts in acidic media, where the hydrogen evolution reaction(HER) is more facilitated. However, the development of high-efficient and acid-stable OER electrocatalysts, which are robust to function stably at high oxidation potentials in the acidic electrolyte, remains a great challenge. This article contributes a focused, perceptive review of the up-to-date approaches toward this emerging research field. The OER reaction mechanism and fundamental requirements for oxygen evolution electrocatalysts in acid are introduced. Then the progress and new discoveries of precious-metal-free active materials and design concepts with regard to the improvement of the intrinsic OER activity are discussed. Finally, the existing scientific challenges and the outlooks for future research directions to the fabrication of emerging, earth-abundant OER electrocatalysts in acid are pointed out.展开更多
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 photo...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.展开更多
Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe3N nanoparticles encapsulated into N...Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe3N nanoparticles encapsulated into N-doped graphene nanoshells(Fe_(3)N@NG)as OER electrocatalysts in alkaline media were reported.Both the experimental and theoretical comparison between Fe_(3) N@NG and Fe_(3)N/NG,specifically including in situ Mossbauer analyses,demonstrated that the NG nanoshells improved interfacial electron transfer process from Fe_(3)N to NG to form high-valence Fe^(4+)ions(Fe^(4+)@NG),thus modifying electronic properties of the outer NG shells and subsequently electron transfer from oxygen intermediate to NG nanoshells for OER catalytic process.Meanwhile,the NG nanoshells also protected Fe-based cores from forming OER inactive and insulated Fe_(2)O_(3),leading to high OER stability.As a result,the as-formed Fe^(4+)@NG shows one of the highest electrocatalytic efficiency among reported Fe-based OER electrocatalysts,which can as well highly improve the photoelectrochemical water oxidation when used as the cocatalysts for the Fe_(2)O_(3) nanoarray photoanode.展开更多
Providing efficient charge transfer through the interface between the semiconductor and co-catalyst is greatly desired in photoelectrocatalytic (PEC) energy conversion.Herein,we excogitate a novel and facile means,via...Providing efficient charge transfer through the interface between the semiconductor and co-catalyst is greatly desired in photoelectrocatalytic (PEC) energy conversion.Herein,we excogitate a novel and facile means,via electrochemical activation,to successfully load the amorphous CoOOH layer architecture onto the surface of TiO_(2).Intriguingly,the as-obtained 6%CoOOH-TiO_(2)photoelectrode manifests optimal PEC performance with a high photocurrent density of 1.3 mA/cm~2,3.5 times higher than that of pristine TiO_(2).Electrochemical impedance spectroscopy (EIS),Tafel analysis and cyclic voltammetry (CV) methods show that the carrier transfer barrier within the electrode and the transition of Co^(3+)OOH to Co^(4+)OOH have the dominating effects on the PEC performance.Theoretical calculation reveals that the interface between the CoOOH and TiO_(2)improves the homogeneity of effective d-orbital electronic-transfer ability among Co sites.This research sheds light on the water oxidation reaction and the design of more favorable PEC cocatalysts.展开更多
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 ...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.展开更多
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 ...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.展开更多
Surface engineering of active materials to generate desired energy state is critical to fabricate high-performance heterogeneous catalysts.However, its realization in a controllable level remains challenging. Using ox...Surface engineering of active materials to generate desired energy state is critical to fabricate high-performance heterogeneous catalysts.However, its realization in a controllable level remains challenging. Using oxygen evolution reaction(OER) as a model reaction, we report a surface-mediated Fe deposition strategy to electronically tailor surface energy states of porous Co_(3)O_(4)(Fe-pCo_(3)O_(4)) for enhanced activity towards OER. The Fe-pCo_(3)O_(4) exhibits a low overpotential of 280 mV to reach an OER current density of 100 mA cm^(-2), and a fast-kinetic behavior with a low Tafel slop of 58.2 mV dec^(-1), outperforming Co_(3)O_(4)-based OER catalysts recently reported and also the noble IrO_(2). The engineered material retains 100% of its original activity after operating at an overpotential of 350 m V for 100 h. A combination of theoretical calculations and experimental results finds out that the surface doped Fe promotes a high energy state and desired coordination environment in the near surface region, which enables optimized OER intermediates binding and favorably changes the rate-determining step.展开更多
In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]...In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.展开更多
Iron oxide nanoparticles(FeOx NPs, 5–30 nm size) prepared via laser ablation in liquid were supported onto Indium Tin Oxide conductive glass slides by magnetophoretic deposition(MD) technique. The resulting Fe O ...Iron oxide nanoparticles(FeOx NPs, 5–30 nm size) prepared via laser ablation in liquid were supported onto Indium Tin Oxide conductive glass slides by magnetophoretic deposition(MD) technique. The resulting Fe O x@ITO electrodes are characterized by a low amount of iron coverage of 16–50 nmol/cm^2,and show electrocatalytic activity towards water oxidation in neutral phosphate buffer pH 7 with 0.58 V overpotential and quantitative Faradaic efficiency towards oxygen production. XPS analysis on the oxygen region of the FeOx films reveals a substantial hydration of the surface after catalysis, recognized as a crucial step to access reactivity.展开更多
Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to ac...Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to achieve high efficiency. Molecular light absorbers offer flexibility in fine tuning of orbital energetics,and metal oxide nanoparticles have emerged as robust oxygen evolving catalysts. Hence, these material choices offer a promising approach for the development of photocatalytic systems for water oxidation.However, efficient charge transfer coupling of molecular light absorbers and metal oxide nanoparticle catalysts has proven a challenge. Recent new approaches toward the efficient coupling of these components based on synthetic design improvements combined with direct spectroscopic observation and kinetic evaluation of charge transfer processes are discussed.展开更多
Water oxidation is the key half reaction to achieve full splitting of water to hydrogen and oxygen.Herein,a binuclear complex,[(L^(4-))Co_(2)~Ⅲ(OH)]ClO_(4),was reported as a stable and efficient homogenous catalyst f...Water oxidation is the key half reaction to achieve full splitting of water to hydrogen and oxygen.Herein,a binuclear complex,[(L^(4-))Co_(2)~Ⅲ(OH)]ClO_(4),was reported as a stable and efficient homogenous catalyst for electrocatalytic water oxidation in 0.1 M phosphate buffer(pH 7.0).Cyclic voltammetry experiments indicated that the catalytic process proceed via "one-site catalysis with two-sites oxidation" mechanism in which both two metal sites store the required oxidation equivalents for water oxidation and O-O bond formation occurs by single-site water nucleophilic attack(WNA).展开更多
Herein,a cross-linked porous Ta3N5 film was prepared via a simple solution combustion route followed by a high-temperature nitridation process for photoelectrochemical(PEC) water oxidation.Meanwhile,the metal cations(...Herein,a cross-linked porous Ta3N5 film was prepared via a simple solution combustion route followed by a high-temperature nitridation process for photoelectrochemical(PEC) water oxidation.Meanwhile,the metal cations(Mg2+ and Zr4+) were incorporated into the porous Ta3N5 to enhance the PEC performance.The porous Mg/Zr co-doped Ta3N5 photoanode yielded a photocurrent density of 1.40 mA cm^(-2) at 1.23 V vs RHE,which is 5.6 times higher than that of the dense Ta3N5 photoanode.The enhanced performance should be ascribed to the synergistic effect of porous structure and cation doping,which can enlarge the electrochemical active surface area and accelerate the charge transfer by introducing ON substitution defects.Subsequently,Co(OH)2 cocatalyst was loaded on the Mg/Zr-Ta3N5 photoanode to negatively shift the onset potential to 0.45 V vs RHE and further improve the photocurrent density to 3.5 mA cm^(-2)at 1.23 V vs.RHE,with a maximum half-cell solar to hydrogen efficiency of 0.45%.The present study provides a new strategy to design efficient Ta3N5 photoelectrodes via the simultaneous control of the morphology and composition.展开更多
Tantalum nitride(Ta_(3)N_(5))is a very promising photoanode material due to its narrow band gap(2.1 eV)and suitable band alignment for solar water splitting.However,it suffers from severe photocorrosion during water o...Tantalum nitride(Ta_(3)N_(5))is a very promising photoanode material due to its narrow band gap(2.1 eV)and suitable band alignment for solar water splitting.However,it suffers from severe photocorrosion during water oxidation.In this work,it was found that surface passivation by AlO_(x) and TiO_(x) layers results in dramatically different PEC performance of Ta_(3)N_(5) photoanode for water oxidation.The mechanism study indicates that the negative charges on AlO_(x) can generate additional field to promote separation of photogenerated charges,while the positive charges on TiO_(x) layer show the opposite effect.As a result,the Ta_(3)N_(5) based photoanode modified with AlO_(x) layer gives a high photocurrent of 12.5 mA cm^(-2) for 24 h at 1.23 V versus the reversible hydrogen electrode(RHE).Dynamic analysis implies that the hole extraction and transfer are significantly improved by the modification with the AlO_(x) layer.This work reveals the importance of the charges on surface passivation layer in interface engineering of photoelectrodes.展开更多
The sluggish kinetics for water oxidation is recognized as one of the major problems for the unsatisfied photoelectrochemical(PEC) performance. Herein, we developed a feasible strategy based on in-situ selective surfa...The sluggish kinetics for water oxidation is recognized as one of the major problems for the unsatisfied photoelectrochemical(PEC) performance. Herein, we developed a feasible strategy based on in-situ selective surface cation exchange, for activating surface water oxidation reactivity toward boosted PEC water oxidation of BiVO_(4) photoanodes with fundamentally improved surface charge transfer. The asconstructed Co/BiVO_(4) photoanodes exhibit 2.6 times increase in photocurrent density with superior stability, in comparison to those of pristine counterpart. Moreover, the faradaic efficiency of as-fabricated photoanode can be up to ~ 95% at 1.23 V(vs. RHE). The unique selective replacement of Bi by Co on the surface could modify the electronic structure of BiVO_(4) with reduced energy barrier of the deprotonation of OH^(+) to O, thus favoring the overall excellent PEC performance of Co/BiVO_(4) photoanode.展开更多
The manipulation of the surface property of WO_(3) photoanode is the main breakthrough direction to improve its solar water oxidation performance both in thermodynamics and kinetics.Here,we report a WO_(3)(002)/m-WO_(...The manipulation of the surface property of WO_(3) photoanode is the main breakthrough direction to improve its solar water oxidation performance both in thermodynamics and kinetics.Here,we report a WO_(3)(002)/m-WO_(3) homojunction film that is composed of an upper WO_(3) layer with predominant(002)facet(WO_(3)(002))and a lower WO_(3) layer with multi-crystal facets(m-WO_(3))as a photoanode for solar water oxidation.Due to the synergistic effect of WO_(3)(002)layer and m-WO_(3) layer,better water oxidation activity and stability are achieved on the WO_(3)(002)/m-WO_(3) homojunction film relative to the m-WO_(3) and WO_(3)(002)film.Specifically,the improved water oxidation performance on the WO_(3)(002)/m-WO_(3) homojunction film is attributed to the followings.In thermodynamics,the band position differences between WO_(3)(002)layer and m-WO_(3) layer lead to the formation of WO_(3)(002)/m-WO_(3) homojunction,which has positive function of improving their charge separation and transfer.In kinetics,the upper WO_(3)(002)layer of the WO_(3)(002)/m-WO_(3) film has superior activity in the adsorption and activation of water molecules,water oxidation on this homojunction film photoanode is inclined to follow the four-holes pathway,and the corrosion of photoanode from the H_(2)O_(2) intermediate is restrained.The present work provides a new strategy to modify the WO_(3) photoanodes for thermodynamically and kinetically efficient water oxidation.展开更多
基金conducted by the Fundamental Research Center of Artificial Photosynthesis(FReCAP)financially supported by the National Natural Science Foundation of China(22172011 and 22088102)+1 种基金the National Key R&D Program of China(2022YFA0911904)the Fundamental Research Funds for the Central Universities(DUT22LK06,DUT22QN213 and DUT23LAB611)。
文摘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.
基金Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang,Grant/Award Number:2019R01006National Key R&D Program of China,Grant/Award Number:2018YFB0104300。
文摘The oxygen evolution reaction(OER)activity of single-atom catalysts(SACs)is closely related to the coordination environment of the active site.Oxygencoordinated atomic metal species bring about unique features beyond nitrogen-coordinated atomic metal species due to the fact that the M-O bond is weaker than the M-N bond.Herein,a series of metal-oxygen-carbon structured low-nucleus clusters(LNCs)are successfully anchored on the surface of multiwalled carbon nanotubes(M-MWCNTs,M=Ni,Co,or Fe)through a foolproof low-temperature gas transfer(300℃)method without any further treatment.The morphology and coordination configuration of the LNCs at the atomic level were confirmed by comprehensive characterizations.The synthetic Ni-MWCNTs electrocatalyst features excellent OER activity and stability under alkaline conditions,transcending the performances of Co-MWCNTs,Fe-MWCNTs and RuO_(2).Density functional theory calculations reveal that the moderate oxidation of low-nucleus Ni clusters changes the unoccupied orbital of Ni atoms,thereby lowering the energy barrier of the OER rate-limiting step and making the OER process more energy-efficient.This study demonstrates a novel versatile platform for large-scale manufacturing of oxygen-coordinated LNC catalysts.
基金financially supported by the National Natural Science Foundation of China(22179072,22002070)the Natural Science Foundation of Shandong Province(ZR2021QF006)+3 种基金the Outstanding Youth Science Foundation of Shandong Province(Overseas)(2022HWYQ-006)the Natural Science Foundation of Shandong Province(ZR2020QB059)the Fundamental Research Center of Artificial Photosynthesis(FReCAP)financially supported by the National Natural Science Foundation of China(22088102)the China Postdoctoral Science Foundation(No.2022M711898)。
文摘Lead(Pb)-free halide perovskites have recently attracted increasing attention as potential catalysts for CO_(2) photoreduction to CO due to their potential to capture solar energy and drive catalytic reaction.However,issues of the poor charge transfer still remain one of the main obstacles limiting their performance due to the overwhelming radiative and nonradiative charge-carrier recombination losses.Herein,Pb-free Sb-alloyed all-inorganic quadruple perovskite Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12)(0≤x≤1)is synthesized as efficient photocatalyst.By Sb alloying,the undesired relaxation of photogenerated electrons from conduction band to emission centers of[MnCl6]^(4-)is greatly suppressed,resulting in a weakened PL emission and enhanced charge transfer for photocatalyst.The ensuing Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12) photocatalyst accomplishes efficient conversion of CO_(2)into CO,accompanied by a surprising production of H_(2)O_(2),a high valueadded product associated with water oxidation.By optimizing Sb^(3+) concentration,a high CO evolution rate of 35.1μmol g^(-1)h^(-1)is achieved,superior to most other Pb and Pb-free halide perovskites.Our findings provide new insights into the mixed-cation alloying strategies for improved photocatalytic performance of Pb-free perovskites and shed light on the rational design of robust band structure toward efficient energy transfer.
基金Project supported by the Korea Institute of Science and Technology (KIST).
文摘The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an overwhelming problem if left to conventional treatment processes. Two options, incineration and supercritical water oxidation (SCWO), exist for the complete destruction of toxic organic wastewaters. Incinerator has associated problems such as very high cost and public resentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaters with extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, the concepts of SCWO, result and present perspectives of application, and industrial status of SCWO are critically examined and discussed.
基金Project supported by the Science Technology Foundation of Educational Department(No.204020).
文摘The 2,4,6-trinitrotoluene (TNT) is a potential carcinogens and TNT contaminated wastewater, which could not be effectively disposed with conventional treatments. The supercritical water oxidation (SCWO) to treat TNT contaminated wastewater was studied in this article, The TNT concentration in wastewater was measured by high-performance liquid chromatograph (HPLC) and the degraded intermediates were analyzed using GC-MS. The results showed that SCWO could degrade TNT efficiently in the presence of oxygen. The reaction temperature, pressure, residence time and oxygen excess were the main contributing factors in the process. The decomposition of TNT was accelerated as the temperature or residence time increased. At 550℃, 24 MPa, 120 s and oxygen excess 300%, TNT removal rate could exceed 99.9%. Partial oxidation occured in SCWO without oxygen. It was concluded that supercritical water was a good solvent and had excellent oxidation capability in the existence of oxygen. The main intermediates of TNT during SCWO included toluene, 1,3,5-trinitrobenzene, nitrophenol, naphthalene, fluorenone, dibutyl phthalate, alkanes and several dimers based on the intermediate analysis. Some side reactions, such as coupled reaction, hydrolysis reaction and isomerization reaction may take place simultaneously when TNT was oxidized by SCWO.
基金financial support of the National Natural Science Foundation of China (21962008, 51464028)Candidate Talents Training Fund of Yunnan Province (2017PY269SQ, 2018HB007)Yunnan Ten Thousand Talents Plan Young & Elite Talents Project (YNWR-QNBJ-2018-346)。
文摘The realization of efficient oxygen evolution reaction(OER) is critical to the development of multiple sustainable energy conversion and storage technologies, especially hydrogen production via water electrolysis. To achieve the massive application of hydrogen energy and mass-scale hydrogen production from water splitting drives the pursuit of competent precious-metal-free electrocatalysts in acidic media, where the hydrogen evolution reaction(HER) is more facilitated. However, the development of high-efficient and acid-stable OER electrocatalysts, which are robust to function stably at high oxidation potentials in the acidic electrolyte, remains a great challenge. This article contributes a focused, perceptive review of the up-to-date approaches toward this emerging research field. The OER reaction mechanism and fundamental requirements for oxygen evolution electrocatalysts in acid are introduced. Then the progress and new discoveries of precious-metal-free active materials and design concepts with regard to the improvement of the intrinsic OER activity are discussed. Finally, the existing scientific challenges and the outlooks for future research directions to the fabrication of emerging, earth-abundant OER electrocatalysts in acid are pointed out.
基金financially supported by the National Key Research and Development Program of China (2017YFA0402800)the National Natural Science Foundation of China (U1932214, 51772285)the National Synchrotron Radiation Laboratory at USTC。
文摘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.
基金supported primarily by the National Key Research and Development Program of China(2018YFE0208500)the Major Research Plan of the National Natural Science Foundation of China(91963206)+4 种基金the National Natural Science Foundation of China(U1508202,51627810,51972164)the Natural Science Foundation of Jiangsu Province(SBK2018022120)the open fund of Wuhan National Laboratory for Optoelectronics(2018WNLOKF020)the open fund of Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies(EEST2018-1)the civil aerospace technology preliminary research project of the State Administration of Science,Technology and Industry for National Defense。
文摘Developing highly active,cost-effective,and environmental friendly oxygen evolution reaction(OER)electrocatalysts facilitates various(photo)electrochemical processes.In this work,Fe3N nanoparticles encapsulated into N-doped graphene nanoshells(Fe_(3)N@NG)as OER electrocatalysts in alkaline media were reported.Both the experimental and theoretical comparison between Fe_(3) N@NG and Fe_(3)N/NG,specifically including in situ Mossbauer analyses,demonstrated that the NG nanoshells improved interfacial electron transfer process from Fe_(3)N to NG to form high-valence Fe^(4+)ions(Fe^(4+)@NG),thus modifying electronic properties of the outer NG shells and subsequently electron transfer from oxygen intermediate to NG nanoshells for OER catalytic process.Meanwhile,the NG nanoshells also protected Fe-based cores from forming OER inactive and insulated Fe_(2)O_(3),leading to high OER stability.As a result,the as-formed Fe^(4+)@NG shows one of the highest electrocatalytic efficiency among reported Fe-based OER electrocatalysts,which can as well highly improve the photoelectrochemical water oxidation when used as the cocatalysts for the Fe_(2)O_(3) nanoarray photoanode.
基金support from the National Key Research Program of China (2017YFA0204800, 2016YFA0202403)the Natural Science Foundation of China (No. 21603136)+3 种基金the Changjiang Scholar and Innovative Research Team (IRT_14R33)the Fundamental Research Funds for the Central Universities (GK202003042)The 111 Project (B14041)the Chinese National 1000-Talent-Plan program are also acknowledged。
文摘Providing efficient charge transfer through the interface between the semiconductor and co-catalyst is greatly desired in photoelectrocatalytic (PEC) energy conversion.Herein,we excogitate a novel and facile means,via electrochemical activation,to successfully load the amorphous CoOOH layer architecture onto the surface of TiO_(2).Intriguingly,the as-obtained 6%CoOOH-TiO_(2)photoelectrode manifests optimal PEC performance with a high photocurrent density of 1.3 mA/cm~2,3.5 times higher than that of pristine TiO_(2).Electrochemical impedance spectroscopy (EIS),Tafel analysis and cyclic voltammetry (CV) methods show that the carrier transfer barrier within the electrode and the transition of Co^(3+)OOH to Co^(4+)OOH have the dominating effects on the PEC performance.Theoretical calculation reveals that the interface between the CoOOH and TiO_(2)improves the homogeneity of effective d-orbital electronic-transfer ability among Co sites.This research sheds light on the water oxidation reaction and the design of more favorable PEC cocatalysts.
基金supported by the National Natural Science Foundation of China(Grant No.51672183)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘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.
基金supported by the Program for Innovation Research of Science in Harbin Institute of Technology(PIRS of HIT nos.A201418 and Q201508)
文摘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.
基金financially supported by National Natural Science Foundation of China (21972102)Natural Science Foundation of Jiangsu province (BK20200991)+3 种基金Suzhou Science and Technology Planning Project (SS202016)Jiangsu Laboratory for Biochemical Sensing and BiochipJiangsu Key Laboratory for Micro and Nano Heat Fluid Flow Technology and Energy ApplicationCollaborative Innovation Center of Water Treatment Technology & Material。
文摘Surface engineering of active materials to generate desired energy state is critical to fabricate high-performance heterogeneous catalysts.However, its realization in a controllable level remains challenging. Using oxygen evolution reaction(OER) as a model reaction, we report a surface-mediated Fe deposition strategy to electronically tailor surface energy states of porous Co_(3)O_(4)(Fe-pCo_(3)O_(4)) for enhanced activity towards OER. The Fe-pCo_(3)O_(4) exhibits a low overpotential of 280 mV to reach an OER current density of 100 mA cm^(-2), and a fast-kinetic behavior with a low Tafel slop of 58.2 mV dec^(-1), outperforming Co_(3)O_(4)-based OER catalysts recently reported and also the noble IrO_(2). The engineered material retains 100% of its original activity after operating at an overpotential of 350 m V for 100 h. A combination of theoretical calculations and experimental results finds out that the surface doped Fe promotes a high energy state and desired coordination environment in the near surface region, which enables optimized OER intermediates binding and favorably changes the rate-determining step.
基金supported by the National Natural Science Foundation of China(51502078)the Major Project of Science and Technology,Education Department of Henan Province(19A150019 and 19A150018)+2 种基金the Science and Technology Research Project of Henan Province(192102310490 and 182102410090)the program for Science&Technology Innovation Team in Universities of Henan Province(19IRTSTHN029)supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,Chemical Sciences,Geosciences,and Biosciences Division,Catalysis Science program。
文摘In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.
基金supported by the Italian Ministero dell’Università e della Ricerca (MIUR), (FIRB RBAP11C58Y, "Nano Solar" and PRIN 2010 "Hi-Phuture")COST action CM1205 "CARISMA: CAtalytic Rout Ines for Small Molecule Activation"
文摘Iron oxide nanoparticles(FeOx NPs, 5–30 nm size) prepared via laser ablation in liquid were supported onto Indium Tin Oxide conductive glass slides by magnetophoretic deposition(MD) technique. The resulting Fe O x@ITO electrodes are characterized by a low amount of iron coverage of 16–50 nmol/cm^2,and show electrocatalytic activity towards water oxidation in neutral phosphate buffer pH 7 with 0.58 V overpotential and quantitative Faradaic efficiency towards oxygen production. XPS analysis on the oxygen region of the FeOx films reveals a substantial hydration of the surface after catalysis, recognized as a crucial step to access reactivity.
基金supported by the Director,Office of Science,Office of Basic Energy Sciences,Division of Chemical,Geological and Biosciences of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231
文摘Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to achieve high efficiency. Molecular light absorbers offer flexibility in fine tuning of orbital energetics,and metal oxide nanoparticles have emerged as robust oxygen evolving catalysts. Hence, these material choices offer a promising approach for the development of photocatalytic systems for water oxidation.However, efficient charge transfer coupling of molecular light absorbers and metal oxide nanoparticle catalysts has proven a challenge. Recent new approaches toward the efficient coupling of these components based on synthetic design improvements combined with direct spectroscopic observation and kinetic evaluation of charge transfer processes are discussed.
基金financially supported by the National Natural Science Foundation of China (21933007)。
文摘Water oxidation is the key half reaction to achieve full splitting of water to hydrogen and oxygen.Herein,a binuclear complex,[(L^(4-))Co_(2)~Ⅲ(OH)]ClO_(4),was reported as a stable and efficient homogenous catalyst for electrocatalytic water oxidation in 0.1 M phosphate buffer(pH 7.0).Cyclic voltammetry experiments indicated that the catalytic process proceed via "one-site catalysis with two-sites oxidation" mechanism in which both two metal sites store the required oxidation equivalents for water oxidation and O-O bond formation occurs by single-site water nucleophilic attack(WNA).
基金the financial support from the China National Key Research and Development Plan Project (No. 2018YFB1502003)the National Natural Science Foundation of China (No. 21606175)the Shaanxi Technical Innovation Guidance Project (Grant no. 2018HJCG-14)。
文摘Herein,a cross-linked porous Ta3N5 film was prepared via a simple solution combustion route followed by a high-temperature nitridation process for photoelectrochemical(PEC) water oxidation.Meanwhile,the metal cations(Mg2+ and Zr4+) were incorporated into the porous Ta3N5 to enhance the PEC performance.The porous Mg/Zr co-doped Ta3N5 photoanode yielded a photocurrent density of 1.40 mA cm^(-2) at 1.23 V vs RHE,which is 5.6 times higher than that of the dense Ta3N5 photoanode.The enhanced performance should be ascribed to the synergistic effect of porous structure and cation doping,which can enlarge the electrochemical active surface area and accelerate the charge transfer by introducing ON substitution defects.Subsequently,Co(OH)2 cocatalyst was loaded on the Mg/Zr-Ta3N5 photoanode to negatively shift the onset potential to 0.45 V vs RHE and further improve the photocurrent density to 3.5 mA cm^(-2)at 1.23 V vs.RHE,with a maximum half-cell solar to hydrogen efficiency of 0.45%.The present study provides a new strategy to design efficient Ta3N5 photoelectrodes via the simultaneous control of the morphology and composition.
基金supported by the National Natural Science Foundation of China(No.21573230,21761142018)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB 17000000).
文摘Tantalum nitride(Ta_(3)N_(5))is a very promising photoanode material due to its narrow band gap(2.1 eV)and suitable band alignment for solar water splitting.However,it suffers from severe photocorrosion during water oxidation.In this work,it was found that surface passivation by AlO_(x) and TiO_(x) layers results in dramatically different PEC performance of Ta_(3)N_(5) photoanode for water oxidation.The mechanism study indicates that the negative charges on AlO_(x) can generate additional field to promote separation of photogenerated charges,while the positive charges on TiO_(x) layer show the opposite effect.As a result,the Ta_(3)N_(5) based photoanode modified with AlO_(x) layer gives a high photocurrent of 12.5 mA cm^(-2) for 24 h at 1.23 V versus the reversible hydrogen electrode(RHE).Dynamic analysis implies that the hole extraction and transfer are significantly improved by the modification with the AlO_(x) layer.This work reveals the importance of the charges on surface passivation layer in interface engineering of photoelectrodes.
基金supported by the project funded by the National Natural Science Foundation of China (52172222, 5197226 and 51972178)the China Postdoctoral Science Foundation(2020 M681966)+1 种基金the exchange project of the sixth ChinaNorthern Macedonia Science and Technology Meeting (6-11)the Natural Science Foundation of Ningbo Municipal Government(202003 N4164 and 2021J145)。
文摘The sluggish kinetics for water oxidation is recognized as one of the major problems for the unsatisfied photoelectrochemical(PEC) performance. Herein, we developed a feasible strategy based on in-situ selective surface cation exchange, for activating surface water oxidation reactivity toward boosted PEC water oxidation of BiVO_(4) photoanodes with fundamentally improved surface charge transfer. The asconstructed Co/BiVO_(4) photoanodes exhibit 2.6 times increase in photocurrent density with superior stability, in comparison to those of pristine counterpart. Moreover, the faradaic efficiency of as-fabricated photoanode can be up to ~ 95% at 1.23 V(vs. RHE). The unique selective replacement of Bi by Co on the surface could modify the electronic structure of BiVO_(4) with reduced energy barrier of the deprotonation of OH^(+) to O, thus favoring the overall excellent PEC performance of Co/BiVO_(4) photoanode.
基金supported by the National Natural Science Foundation of China(41702037,41831285 and 41872039)Project of State Key Laboratory of Environment-friendly Energy Materials,Southwest University of Science and Technology(18fksy0216)。
文摘The manipulation of the surface property of WO_(3) photoanode is the main breakthrough direction to improve its solar water oxidation performance both in thermodynamics and kinetics.Here,we report a WO_(3)(002)/m-WO_(3) homojunction film that is composed of an upper WO_(3) layer with predominant(002)facet(WO_(3)(002))and a lower WO_(3) layer with multi-crystal facets(m-WO_(3))as a photoanode for solar water oxidation.Due to the synergistic effect of WO_(3)(002)layer and m-WO_(3) layer,better water oxidation activity and stability are achieved on the WO_(3)(002)/m-WO_(3) homojunction film relative to the m-WO_(3) and WO_(3)(002)film.Specifically,the improved water oxidation performance on the WO_(3)(002)/m-WO_(3) homojunction film is attributed to the followings.In thermodynamics,the band position differences between WO_(3)(002)layer and m-WO_(3) layer lead to the formation of WO_(3)(002)/m-WO_(3) homojunction,which has positive function of improving their charge separation and transfer.In kinetics,the upper WO_(3)(002)layer of the WO_(3)(002)/m-WO_(3) film has superior activity in the adsorption and activation of water molecules,water oxidation on this homojunction film photoanode is inclined to follow the four-holes pathway,and the corrosion of photoanode from the H_(2)O_(2) intermediate is restrained.The present work provides a new strategy to modify the WO_(3) photoanodes for thermodynamically and kinetically efficient water oxidation.