β-Ga_(2)O_(3)is a promising candidate for solarblind ultraviolet photodetection owing to its suitable bandgap of approximately 4.9 eV,excellent photoresponse characteristics,and high stability.However,the lack of a s...β-Ga_(2)O_(3)is a promising candidate for solarblind ultraviolet photodetection owing to its suitable bandgap of approximately 4.9 eV,excellent photoresponse characteristics,and high stability.However,the lack of a sufficient driving force within the material leads to extensive bulk charge recombination,limiting its photocurrent and thus posing significant challenges in designing high-performance Ga_(2)O_(3)-based photodetection.In this study,we propose a gradient doping strategy to achieve a Sn-doping concentration gradient along theβ-Ga_(2)O_(3)film thickness.By combining sol-gel synthesis with rapid thermal annealing,a spatially graded band structure with a full-space built-in electric field is constructed,which increases the width of band bending over a large region and is crucial for significantly enhancing carrier separation and transport in the bulk.The resulting gradient Sn-dopedβ-Ga_(2)O_(3)enables exceptional photoelectric performance without an external bias under 254 nm irradiation,including a superior responsivity of 66.88 mA W^(-1),a high detectivity of 8.12×10^(11)Jones,and a fast rise/decay time of 79/65 ms,outstanding most existing similar reported photoelectrochemical(PEC)type optoelectronic devices.Additionally,the device exhibits excellent long-term stability and enables high-resolution underwater ultraviolet imaging.This study demonstrates that the gradient doping strategy provides a feasible approach for enhancing the PEC performance ofβ-Ga_(2)O_(3)photoelectrodes.展开更多
To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.He...To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.Here,we report a low-potential photoelectrochemical(PEC)system that selectively and efficiently extracts Li metals from multi-cation electrolytes under 1 sun illumination.Based on the difference of redox potential,we can get rid of the disturbance of other cations(i.e.,Fe,Co and Ni ions)by a bias-free PEC device to realize the extraction of high-purity Li metals on a coplanar Si-based photocathode-TiO_(2) photoanode tandem device at 2 V of applied bias(far less than the redox potentials of Li^(+)/Li).In such system,the extraction rate of Li metals(purity>99.5%)exceeds 1.35 g h^(-1)m^(-2)with 90%of Faradaic efficiency.Long-term experiments,different electrode/electrolyte tests,and various price assessments further demonstrate the stability,compatibility and economy of PEC extraction system,enabling a solar-driven pathway for the recycling of critical metal resources.展开更多
Photoelectrochemical CO_(2)reduction to multi-carbon products fuels remains challenged by inefficient C–C coupling and competing proton reduction reaction.Herein,we designed a cationic covalent organic framework(COF+...Photoelectrochemical CO_(2)reduction to multi-carbon products fuels remains challenged by inefficient C–C coupling and competing proton reduction reaction.Herein,we designed a cationic covalent organic framework(COF+)to create an electrostatic microenvironment that synergizes with CuPt alloy nanoparticles for selective ethylene/ethane production.By spatially decoupling CO_(2)enrichment from proton exclusion,the COF^(+)/CuPt interface simultaneously facilitates CO_(2)accessibility while impeding H+migration,suppressing the hydrogen evolution reaction(HER).This unique microenvironment stabilizes key anionic intermediates(*COO^(−),*OCCO^(−))and promotes*CO dimerization,steering electron transfer toward C–C coupling.The optimized system achieves a record-high Faradaic efficiency of 51.5%±5.3%for ethane and 10.6%±2.5%for ethylene with a total C2+yield exceeding 62%at−0.25 V vs.RHE and high stability(>300 min),representing the highest performance for photoelectrochemical CO_(2)reduction to ethane.The combined analyses of in situ spectroscopy and theoretical calculations reveal that electrostatic field effects lower the energy barrier for*OCCO formation while accelerating hydrogenation kinetics.Therefore,this work demonstrates that microenvironment modification of the active site by cationic covalent organic framework is a versatile strategy for solar-driven CO_(2)conversion into value-added hydrocarbons.展开更多
Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water spli...Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water splitting stands out as a promising approach for direct solar-driven hydrogen production.Enhancing the efficiency and stability of photoelectrodes is a key focus in PEC water-splitting research.Tantalum nitride(Ta_(3)N_(5)),with its suitable band gap and band-edge positions for PEC water splitting,has emerged as a highly promising photoanode material.This review begins by introducing the history and fundamental characteristics of Ta_(3)N_(5),emphasizing both its advantages and challenges.It then explores methods to improve light absorption efficiency,charge separation and transfer efficiency,surface reaction rate,and the stability of Ta_(3)N_(5) photoanodes.Additionally,the review discusses the progress of research on tandem PEC cells incorporating Ta_(3)N_(5) photoanodes.Finally,it looks ahead to future research directions for Ta_(3)N_(5) photoanodes.The strategic approach outlined in this review can also be applied to other photoelectrode materials,providing guidance for their development.展开更多
Iron-porphyrin metal-organic frameworks(MOFs)have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities,yet their full potential remains largely...Iron-porphyrin metal-organic frameworks(MOFs)have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities,yet their full potential remains largely unexplored.The organic photoelectrochemical transistor(OPECT)has been proven to be a prominent platform for diverse applications.Herein,iron-porphyrin MOFs,as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme,is explored for novel OPECT bioanalysis.Exemplified by alpha-fetoprotein(AFP)-dependent sandwich immunorecognition and therein glucose oxidase(GOx)-generated H_(2)O_(2)to etch CdS quantum dots on the surface of iron-porphyrin MOFs,this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL.This work featured a bifunctional iron-porphyrin MOFs gated OPECT,which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.展开更多
Rational interface engineering via regulating the anchoring groups between molecular catalysts and light-absorbing semiconductors is essential and emergent to stabilize the semiconductor/molecular complex interaction ...Rational interface engineering via regulating the anchoring groups between molecular catalysts and light-absorbing semiconductors is essential and emergent to stabilize the semiconductor/molecular complex interaction and facilitate the photocarriers transport,thus realizing highly active and stable photoelectrochemical(PEC)water splitting.In this mini review,following a showcasing of the fundamental details of hybrid PEC systems containing semiconductor photoelectrodes and molecular catalysts for water splitting,the state-of-the-art progress of anchoring group regulation at semiconductor/molecular complex interface for efficient and stable PEC water splitting,as well as its effect on charge transfer kinetics,are comprehensively reviewed.Finally,potential research directions aimed at building high-efficiency hybrid PEC water splitting systems are summarized.展开更多
Development of accurate analytical protocols for cancer biomarkers is used for the initial prescreening of malignant tumors,disease surveillance,and efficacy assessment with significant clinical benefits.In this work,...Development of accurate analytical protocols for cancer biomarkers is used for the initial prescreening of malignant tumors,disease surveillance,and efficacy assessment with significant clinical benefits.In this work,we reported a liposome-mediated signal-off photoelectrochemical(PEC)immunoassay for the sensitive detection of carcinoembryonic antigen(CEA)using ternary transition metal sulfide CuS/ZnCdS as the photoactive material.Good photocurrents were acquired on the basis of specific oxidation reaction of dopamine on the CuS/ZnCdS.The energy band relationship of CuS/ZnCdS was determined,and the wellmatched oxidation potential of dopamine was verified.To achieve accurate recovery of low-abundance CEA,systematic PEC evaluation from human serum samples was performed by combining with classical immunoreaction and liposome-induced dopamine amplification strategy with high stability and selectivity.Under optimum conditions,PEC immunoassay displayed good photocurrent responses toward target CEA with a dynamic linear range of 0.1-50 ng/mL with a detection limit of 31.6 pg/mL.Importantly,this system by combining with a discussion of energy level matching between semiconductor energy bands and small-molecules opens a new horizon for development of high-efficient PEC immunoassays.展开更多
Bisphenol S(BPS)is an environmental endocrine disruptor that poses substantial risks to both ecosystems and human health.Its widespread occurrence necessitates the development of sensitive,rapid,cost-effective,and fie...Bisphenol S(BPS)is an environmental endocrine disruptor that poses substantial risks to both ecosystems and human health.Its widespread occurrence necessitates the development of sensitive,rapid,cost-effective,and field-deployable analytical tools for environmental monitoring.Herein,we developed a plasmon-enhanced CdIn_(2)S_(4)/Bi_(2)WO_(6)Z-scheme heterojunction to construct a photoelectrochemical(PEC)aptasensor for BPS detection.The Z-scheme configuration between CdIn_(2)S_(4)and Bi_(2)WO_(6)significantly enhances the PEC response by suppressing recombination of photogenerated electronhole pairs.Further integration with gold nanoparticles(AuNPs)amplifies the photocurrent through the surface plasmon resonance(SPR)effect,yielding a highly efficient PEC sensing platform.A BPS-specific aptamer was immobilized on the electrode to enable selective target capture.The resulting aptamer-target complex,upon exposure to BPS,impedes interfacial electron transfer,resulting in a concentration-dependent decrease in the photocurrent.The PEC aptasensor exhibited a wide linear detection range of 5 nM to 50μM and a detection limit of 0.64 nM.The sensor demonstrated high selectivity against structurally similar interfering substances.Application to real water samples yielded results consistent with that of HPLC-MS/MS,confirming the sensor's reliability and practical applicability.This work establishes a sensitive,rapid,and robust PEC strategy for monitoring BPS in complex environmental matrices with potential for routine environmental analysis.展开更多
In situ growth of co-catalysts on BiVO_(4)(BVO)to enhance photoelectrochemical(PEC)water splitting performance has been extensively reported.However,the understanding of the synergistic effects among various elements,...In situ growth of co-catalysts on BiVO_(4)(BVO)to enhance photoelectrochemical(PEC)water splitting performance has been extensively reported.However,the understanding of the synergistic effects among various elements,especially at the interface between the semiconductor and cocatalyst,has received insufficient attention.In this study,we report a Co,Ni and Mn trimetallic fluoride-modified BVO photoanode featuring a unique interfacial chemical bond(V-F).Under AM 1.5 G illumination,an exciting photocurrent density of 6.05 mA cm^(-2)was achieved at 1.23 V vs.RHE by the integrated BVO/CoNi_(0.18)Mn_(0.12)(OH)_(x)F photoanode and over 98%of the initial photocurrent was maintained after 10 h of photoelectrolysis.Control experiments and theoretical calculations demonstrate that the V-F interfacial bond stabilizes the Co^(2+)active sites.It serves as a transmission gear,interlinking the migration of interfacial charge and the regeneration of cocatalyst,endowing the photoanode with significant activity and stability.Furthermore,we have systematically elucidated the role of the individual Co,Ni,and Mn components in the synergistic cocatalyst layer.The interfacial modification provides novel insights into developing advanced photoanodes towards PEC water splitting.展开更多
The integration of artificial nanozymes with photoelectrochemical(PEC)biosensing remains underexplored,primarily due to challenges in balancing catalytic efficiency,material stability,and interfacial charge dynamics.H...The integration of artificial nanozymes with photoelectrochemical(PEC)biosensing remains underexplored,primarily due to challenges in balancing catalytic efficiency,material stability,and interfacial charge dynamics.Herein,we present a novel split-type PEC biosensor that leverages Au@CeO_(2)yolk-shell nanozymes with robust phosphatase-mimicking activity and staggered band structure of WO_(3)/BiVO_(4)heterojunction for ultrasensitive detection of the breast cancer biomarker HER-2.Unlike conventional nanoenzymes,the yolk-shell architecture encases AuNPs within a CeO_(2)shell,synergistically enhancing catalytic efficiency by maximizing the active surface area while simultaneously preventing nanoparticle aggregation and leaching through a protective barrier.Density functional theory(DFT)calculations reveal that the CeO_(2)(111)/Au(111)interface drastically reduces the energy barrier for phosphate ester bond cleavage(-16.94 eV vs.5.69 eV for free molecules),thereby enabling rapid hydrolysis of ascorbic acid 2-phosphate(AAP)into ascorbic acid.This catalytic amplification strategy,when integrated with a visible-light-responsive semiconductor substrate,enables zero-bias detection and while effectively eliminating interference from high-voltage operations.The biosensor achieves a detection limit of 41 fg/mL(S/N=3)for HER-2 across a linear range of 0.0001-100 ng/mL,surpassing existing methods.Remarkable selectivity,reproducibility(RSD=3.9%),and recovery rates(95.1%–102.4%)in serum further validate its clinical applicability.This work establishes a universal platform for nanozyme-driven PEC biosensing,presenting significant promise for future use in pathological diagnostics.展开更多
Rapid hole extraction from photoanodes to cocatalysts is a crucial prerequisite for the realization of highly efficient photoelectrochemical(PEC)water splitting.Herein,Mn-doped nickel-iron layered double hydroxides(Mn...Rapid hole extraction from photoanodes to cocatalysts is a crucial prerequisite for the realization of highly efficient photoelectrochemical(PEC)water splitting.Herein,Mn-doped nickel-iron layered double hydroxides(Mn:NiFe-LDHs),as a co-catalyst,were grafted on bismuth vanadate(BVO)for significantly improved charge transfer and stability simultaneously,in addition to the accelerated water oxidation kinetics.The detailed experimental and theoretical analysis collectively verify that Mn doping increases charge density around Ni and Fe sites.The electron-rich Ni sites boost the kinetics of oxygen evolution reaction and promote the hole extraction simultaneously.Moreover,the electrons are transferred from electron-rich Fe sites to V sites,which effectively restrains the dissolution of V^(5+)ions and enhances the stability of BVO photoanodes.Consequently,the resulting Mn:NiFe-LDH/BVO photoanode achieves a remarkable photocurrent density of 5.5 mA cm^(-2)at 1.23 V versus reversible hydrogen electrode(RHE)with excellent stability.The construction of electron-rich oxygen evolution cocatalysts provides a promising strategy to promote the hole extraction and increase the stability for improved PEC performance.展开更多
A novel and long-lasting N_(3)BD/TiO_(2) composite photoanode with stable and superior photoelectrochemical and photoelectrochemical cathodic protection(PECCP)performances was achieved by synthesizing and depositing c...A novel and long-lasting N_(3)BD/TiO_(2) composite photoanode with stable and superior photoelectrochemical and photoelectrochemical cathodic protection(PECCP)performances was achieved by synthesizing and depositing covalent organic framework(N_(3)BD)on titanium oxide(TiO_(2))nanotube arrays.The composite's increased visible light absorption capability enhanced the galvanic corrosion protection of nickel-phosphorus alloy-coated magnesium alloy(Mg/Ni)through PECCP technology.The open circuit potential(OCP)drops of the Mg/Ni electrode coupling with the N_(3)BD/TiO_(2) composite were 310 and 630 mV at dark state and under illumination,respectively.They remained relatively stable under intermittent visible light irradiation within 72 h,demonstrating excellent long-term stability.The superior photoelectrochemical and PECCP properties of the N_(3)BD/TiO_(2) are attributed to forming S-scheme heterojunctions,which effectively promote the separation and transfer of photogenerated electron-hole pairs and retain a strong redox capacity.This finding provides new insight into the design and synthesis of COF-modified photoanode with highly efficient and stable photoelectrochemical and PECCP performances.展开更多
Low power consumption,high responsivity,and self-powering are key objectives for photoelectrochemical ultravio-let detectors.In this research,In-dopedα-Ga_(2)O_(3) nanowire arrays were fabricated on fluorine-doped ti...Low power consumption,high responsivity,and self-powering are key objectives for photoelectrochemical ultravio-let detectors.In this research,In-dopedα-Ga_(2)O_(3) nanowire arrays were fabricated on fluorine-doped tin oxide(FTO)substrates through a hydrothermal approach,with subsequent thermal annealing.These arrays were then used as photoanodes to con-struct a ultraviolet(UV)photodetector.In doping reduced the bandgap ofα-Ga_(2)O_(3),enhancing its absorption of UV light.Conse-quently,the In-dopedα-Ga_(2)O_(3) nanowire arrays exhibited excellent light detection performance.When irradiated by 255 nm deep ultraviolet light,they obtained a responsivity of 38.85 mA/W.Moreover,the detector's response and recovery times are 13 and 8 ms,respectively.The In-dopedα-Ga_(2)O_(3) nanowire arrays exhibit a responsivity that is about three-fold higher than the undoped one.Due to its superior responsivity,the In-doped device was used to develop a photoelectric imaging system.This study demonstrates that dopingα-Ga_(2)O_(3) nanowire with indium is a potent approach for optimizing their photoelectrochemi-cal performance,which also has significant potential for optoelectronic applications.展开更多
Constructing a photoanode with both high dark-state protection performance and high stability remains a top priority for photoelectrochemical cathodic protection technology,especially in a marine environment(dark-stat...Constructing a photoanode with both high dark-state protection performance and high stability remains a top priority for photoelectrochemical cathodic protection technology,especially in a marine environment(dark-state or rainy conditions)without hole scavenging agents.In this work,we developed a class of energy-storage quasi-planar heterojunctions(WO_(3)-Nb_(2)O_(5)-ZnIn_(2)S_(4))with directional paths(low onset potential and well-matched energy band)and embedded morphology.The co-design of embedded and directional paths reduces the carrier transport energy barrier at the composite interface,and increases the interface contact area,thereby achieving highly stable and sensitive dark-state energy storage and photoelectrochemical cathodic protection performance in 3.5 wt.%NaCl solution without hole scavenging agent(Dark-state energy storage efficiency increased by 43%.For carbon steel,the performance retention rate is 99.6%after 500 cycles,the performance retention rate is 89%after 5000 s).展开更多
Rational design of porous metal oxide films that serve as not only the scaffolds for light absorbers but also the transfer layer of photo generated charges is essential for fabricating highly efficient photoanodes for...Rational design of porous metal oxide films that serve as not only the scaffolds for light absorbers but also the transfer layer of photo generated charges is essential for fabricating highly efficient photoanodes for photoelectrochemical(PEC)hydrogen generation.In this work,w report a facile one-step pyrolysis method which can convert Zn-based MOF to porous ZnO(m-ZnO)with rough surface and abundant oxygen vacancies(O_(v)).When incorporating core-shell quantum dots(QDs)as the light absorbers,the obtained photoanodes(m-ZnO@QDs)achieved outstanding PEC performance for hydrogen generation,exhibiting 1.6 times and 5.8 times higher saturated photocurrent density(J_(sc))than thos of conventional TiO_(2)@QDs and ZnO@QDs photoanodes,respectively.Comprehensive optical and electrochemical measurements reveal tha the rough surface of m-ZnO can significantly improve the light-harvesting capacity of corresponding photoanodes through surface-enhanced light scattering.Moreover,the O_(v)in m-ZnO facilitate the interfacial transfer of photogenerated electrons.Our findings indicate that the MOF are valuable precursors for the preparation of porous films,offering a promising route to develop high-performance QDs-based PEC devices.展开更多
Quantitative determination of tetracycline(TC)in environment and foods is of great importance,as excessive residues might have negative effects on human health and environmental risks.Herein,a selfpowered molecularly ...Quantitative determination of tetracycline(TC)in environment and foods is of great importance,as excessive residues might have negative effects on human health and environmental risks.Herein,a selfpowered molecularly imprinted photoelectrochemical(PEC)sensor based on the Zn O/C photoanode and the Fe-doped CuBi_(2)O_(4)(CBFO)photocathode is developed for the sensitive detection of TC.The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode.Furthermore,molecularly imprinted polymers(MIPs)at photocathode can selectivity identify the TC templates and thus improve the specificity.Under the optimal conditions,the sensor has a linear range of 10^(-2)-1.0×10^(5) nmol/L,and a limit of detection(LOD)of 0.007 nmol/L(S/N=3).More crucially,the milk sample detection is carried out using the as-prepared sensor,and the outcome is satisfactory.The research gives us a novel sensing platform for quick and accurate antibiotic(like TC)in environment and food monitoring.展开更多
In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC...In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.展开更多
Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more ...Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more difficult than to O_(2)via a 4e^(-)pathway.Herein,with a series of BiVO_(4)-based photoanodes,the decisive factors determining the PEC activity and selectivity are elucidated,combining a comprehensive experimental and theoretical investigations.It is discovered that the ZnO/BiVO_(4)photoanode(ZnO/BVO)forms a Type-Ⅱheterojunction in energy level alignment.The accelerated photogenerated charge separation/transfer dynamics generates denser surface holes and higher surface photovoltage.Therefore,the activity of water oxidation reaction is promoted.The selectivity of PEC-WO to H_(2)O_(2)is found to be potential-dependent,i.e.,at the lower potentials(PEC-dominated),surface hole density determines the selectivity;and at the higher potentials(electrochemical-dominated),surface reaction barriers govern the selectivity.For the ZnO/BVO heterojunction photoanode,the higher surface hole density facilitates the generation of OH·and the subsequent OH·/OH·coupling to form H_(2)O_(2),thus rising up with potentials;at the higher potentials,the 2-electron pathway barrier over ZnO/BVO surface is lower than over BVO surface,which benefits from the electronic structure regulation by the underlying ZnO alleviating the over-strong adsorption of^(*)OH on BVO,thus,the two-electron pathway to produce H_(2)O_(2)is more favored than on BVO surface.This work highlights the crucial role of band energy structure of semiconductors on both PEC reaction activity and selectivity,and the knowledge gained is expected to be extended to other photoeletrochemical reactions.展开更多
Elemental doping of BiVO_(4) crystal lattices effectively enhances carrier separation,thereby facilitating efficient photoelectrochemical water splitting.However,the positive effect of elementally induced lattice dist...Elemental doping of BiVO_(4) crystal lattices effectively enhances carrier separation,thereby facilitating efficient photoelectrochemical water splitting.However,the positive effect of elementally induced lattice distortions on hole extraction has been neglected.Herein,the crystal lattice of BiVO_(4) is distorted by doping with an inexpensive Cs metal;then,CoFe_(2)O_(4) is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode.Benefiting from the above design,the newly prepared CoFe_(2)O_(4)-Cs-BiVO_(4) photoanode achieved a photocurrent density of 5.66 mA cm^(–2) at 1.23 V vs.a reversible hydrogen electrode,indicating a 3.9-fold improvement in photocurrent density.Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO_(4) bulk-phase holes to the CoFe_(2)O_(4) layer.Additionally,the coupled CoFe_(2)O_(4) can be used as a hole extraction layer to further enhance the interfacial migration of carriers.The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO_(4) bulk phase to the active sites of the oxygen evolution reaction,thereby effectively inhibiting carrier recombination.This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion,thereby opening new avenues for the rational design of photoanodes.展开更多
Antimony sulfide(Sb_(2)S_(3))is a promising material for photoelectrochemical(PEC)devices that generate green hydrogen from sunlight and water.In this study,we present a synthesis of high-performance Sb_(2)S_(3)photoa...Antimony sulfide(Sb_(2)S_(3))is a promising material for photoelectrochemical(PEC)devices that generate green hydrogen from sunlight and water.In this study,we present a synthesis of high-performance Sb_(2)S_(3)photoanodes via an interface-engineered hydrothermal growth followed by rapid thermal annealing(RTA).A TiO_(2)interfacial layer plays a crucial role in ensuring homogeneous precursor deposition,enhancing light absorption,and forming efficient heterojunctions with Sb_(2)S_(3),thereby significantly improving charge separation and transport.RTA further improves crystallinity and interfacial contact,resulting in dense and uniform Sb_(2)S_(3)films with enlarged grains and fewer defects.The optimized Sb_(2)S_(3)photoanode achieves a photocurrent density of 2.51 mA/cm^(2)at 1.23 V vs.the reversible hydrogen electrode(RHE),one of the highest reported for Sb_(2)S_(3)without additional catalysts or passivation layers.To overcome the limitations of oxygen evolution reaction(OER),we employ the iodide oxidation reaction(IOR)as an alternative,significantly lowering the overpotential and improving charge transfer kinetics.Consequently,it produces a record photocurrent density of 8.9 mA/cm^(2)at 0.54 V vs.RHE.This work highlights the synergy between TiO_(2)interfacial engineering,RTA-induced crystallization,and IOR-driven oxidation,offering a promising pathway for efficient and scalable PEC hydrogen production.展开更多
基金supported by the National Natural Science Foundation of China(12304102,62574029)Natural Science Foundation of Chongqing(CSTB2023NSCQ-MSX0479)+1 种基金Science and Technology Research Project of Chongqing Education Committee(KJQN202400558)Doctoral Scientific Research Fund of Chongqing Normal University(23XLB029)。
文摘β-Ga_(2)O_(3)is a promising candidate for solarblind ultraviolet photodetection owing to its suitable bandgap of approximately 4.9 eV,excellent photoresponse characteristics,and high stability.However,the lack of a sufficient driving force within the material leads to extensive bulk charge recombination,limiting its photocurrent and thus posing significant challenges in designing high-performance Ga_(2)O_(3)-based photodetection.In this study,we propose a gradient doping strategy to achieve a Sn-doping concentration gradient along theβ-Ga_(2)O_(3)film thickness.By combining sol-gel synthesis with rapid thermal annealing,a spatially graded band structure with a full-space built-in electric field is constructed,which increases the width of band bending over a large region and is crucial for significantly enhancing carrier separation and transport in the bulk.The resulting gradient Sn-dopedβ-Ga_(2)O_(3)enables exceptional photoelectric performance without an external bias under 254 nm irradiation,including a superior responsivity of 66.88 mA W^(-1),a high detectivity of 8.12×10^(11)Jones,and a fast rise/decay time of 79/65 ms,outstanding most existing similar reported photoelectrochemical(PEC)type optoelectronic devices.Additionally,the device exhibits excellent long-term stability and enables high-resolution underwater ultraviolet imaging.This study demonstrates that the gradient doping strategy provides a feasible approach for enhancing the PEC performance ofβ-Ga_(2)O_(3)photoelectrodes.
基金the National Natural Science Foundation of China(22479047,22409058)the Outstanding Youth Scientist Foundation of Hunan Province(2022JJ10023)the Provincial Natural Science Foundation of Guangdong(2023A1515011745)for financial support of this research。
文摘To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.Here,we report a low-potential photoelectrochemical(PEC)system that selectively and efficiently extracts Li metals from multi-cation electrolytes under 1 sun illumination.Based on the difference of redox potential,we can get rid of the disturbance of other cations(i.e.,Fe,Co and Ni ions)by a bias-free PEC device to realize the extraction of high-purity Li metals on a coplanar Si-based photocathode-TiO_(2) photoanode tandem device at 2 V of applied bias(far less than the redox potentials of Li^(+)/Li).In such system,the extraction rate of Li metals(purity>99.5%)exceeds 1.35 g h^(-1)m^(-2)with 90%of Faradaic efficiency.Long-term experiments,different electrode/electrolyte tests,and various price assessments further demonstrate the stability,compatibility and economy of PEC extraction system,enabling a solar-driven pathway for the recycling of critical metal resources.
基金financial support from the National Natural Science Foundation of China(No.52273187)the Guangdong Basic and Applied Basic Research Foundation(2022A1515110372,2023A1515011306,2023A1515240077)+1 种基金the National Key Research and Development Program of China(2022YFA1502900)the Guangdong-Hong Kong Joint Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province(2023B1212120011).
文摘Photoelectrochemical CO_(2)reduction to multi-carbon products fuels remains challenged by inefficient C–C coupling and competing proton reduction reaction.Herein,we designed a cationic covalent organic framework(COF+)to create an electrostatic microenvironment that synergizes with CuPt alloy nanoparticles for selective ethylene/ethane production.By spatially decoupling CO_(2)enrichment from proton exclusion,the COF^(+)/CuPt interface simultaneously facilitates CO_(2)accessibility while impeding H+migration,suppressing the hydrogen evolution reaction(HER).This unique microenvironment stabilizes key anionic intermediates(*COO^(−),*OCCO^(−))and promotes*CO dimerization,steering electron transfer toward C–C coupling.The optimized system achieves a record-high Faradaic efficiency of 51.5%±5.3%for ethane and 10.6%±2.5%for ethylene with a total C2+yield exceeding 62%at−0.25 V vs.RHE and high stability(>300 min),representing the highest performance for photoelectrochemical CO_(2)reduction to ethane.The combined analyses of in situ spectroscopy and theoretical calculations reveal that electrostatic field effects lower the energy barrier for*OCCO formation while accelerating hydrogenation kinetics.Therefore,this work demonstrates that microenvironment modification of the active site by cationic covalent organic framework is a versatile strategy for solar-driven CO_(2)conversion into value-added hydrocarbons.
文摘Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water splitting stands out as a promising approach for direct solar-driven hydrogen production.Enhancing the efficiency and stability of photoelectrodes is a key focus in PEC water-splitting research.Tantalum nitride(Ta_(3)N_(5)),with its suitable band gap and band-edge positions for PEC water splitting,has emerged as a highly promising photoanode material.This review begins by introducing the history and fundamental characteristics of Ta_(3)N_(5),emphasizing both its advantages and challenges.It then explores methods to improve light absorption efficiency,charge separation and transfer efficiency,surface reaction rate,and the stability of Ta_(3)N_(5) photoanodes.Additionally,the review discusses the progress of research on tandem PEC cells incorporating Ta_(3)N_(5) photoanodes.Finally,it looks ahead to future research directions for Ta_(3)N_(5) photoanodes.The strategic approach outlined in this review can also be applied to other photoelectrode materials,providing guidance for their development.
基金financially supported by the National Natural Science Foundation of China(Nos.22034003,22374066)the Fundamental Research Funds for the Central Universities(No.2022300285)+1 种基金the Excellent Research Program of Nanjing University(No.ZYJH004)State Key Laboratory of Analytical Chemistry for Life Science(No.5431ZZXM2203).
文摘Iron-porphyrin metal-organic frameworks(MOFs)have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities,yet their full potential remains largely unexplored.The organic photoelectrochemical transistor(OPECT)has been proven to be a prominent platform for diverse applications.Herein,iron-porphyrin MOFs,as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme,is explored for novel OPECT bioanalysis.Exemplified by alpha-fetoprotein(AFP)-dependent sandwich immunorecognition and therein glucose oxidase(GOx)-generated H_(2)O_(2)to etch CdS quantum dots on the surface of iron-porphyrin MOFs,this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL.This work featured a bifunctional iron-porphyrin MOFs gated OPECT,which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.
基金support of the Natural Science Foundation of Shaanxi Province(2023-JC-QN-0415)the Special Project on Functional Materials from Shaanxi Provincial Department of Finance(0801YC2305)+1 种基金the Talent Project from Northwest Institute for Non-ferrous Metal Research(YK2310)the National Natural Science Foundation of China(52225606 and 52304334).
文摘Rational interface engineering via regulating the anchoring groups between molecular catalysts and light-absorbing semiconductors is essential and emergent to stabilize the semiconductor/molecular complex interaction and facilitate the photocarriers transport,thus realizing highly active and stable photoelectrochemical(PEC)water splitting.In this mini review,following a showcasing of the fundamental details of hybrid PEC systems containing semiconductor photoelectrodes and molecular catalysts for water splitting,the state-of-the-art progress of anchoring group regulation at semiconductor/molecular complex interface for efficient and stable PEC water splitting,as well as its effect on charge transfer kinetics,are comprehensively reviewed.Finally,potential research directions aimed at building high-efficiency hybrid PEC water splitting systems are summarized.
基金financial support from the National Natural Science Foundation of China(Nos.22274022 and 21874022).
文摘Development of accurate analytical protocols for cancer biomarkers is used for the initial prescreening of malignant tumors,disease surveillance,and efficacy assessment with significant clinical benefits.In this work,we reported a liposome-mediated signal-off photoelectrochemical(PEC)immunoassay for the sensitive detection of carcinoembryonic antigen(CEA)using ternary transition metal sulfide CuS/ZnCdS as the photoactive material.Good photocurrents were acquired on the basis of specific oxidation reaction of dopamine on the CuS/ZnCdS.The energy band relationship of CuS/ZnCdS was determined,and the wellmatched oxidation potential of dopamine was verified.To achieve accurate recovery of low-abundance CEA,systematic PEC evaluation from human serum samples was performed by combining with classical immunoreaction and liposome-induced dopamine amplification strategy with high stability and selectivity.Under optimum conditions,PEC immunoassay displayed good photocurrent responses toward target CEA with a dynamic linear range of 0.1-50 ng/mL with a detection limit of 31.6 pg/mL.Importantly,this system by combining with a discussion of energy level matching between semiconductor energy bands and small-molecules opens a new horizon for development of high-efficient PEC immunoassays.
基金supported by the National Natural Science Foundation of China(Grant No.22276088,22576093)the Shenzhen Science and Technology Program(KCXFZ20230731093601003,KQTD20240729102048052,20231116144111001)the High Level of Special Funds(G03034K006)。
文摘Bisphenol S(BPS)is an environmental endocrine disruptor that poses substantial risks to both ecosystems and human health.Its widespread occurrence necessitates the development of sensitive,rapid,cost-effective,and field-deployable analytical tools for environmental monitoring.Herein,we developed a plasmon-enhanced CdIn_(2)S_(4)/Bi_(2)WO_(6)Z-scheme heterojunction to construct a photoelectrochemical(PEC)aptasensor for BPS detection.The Z-scheme configuration between CdIn_(2)S_(4)and Bi_(2)WO_(6)significantly enhances the PEC response by suppressing recombination of photogenerated electronhole pairs.Further integration with gold nanoparticles(AuNPs)amplifies the photocurrent through the surface plasmon resonance(SPR)effect,yielding a highly efficient PEC sensing platform.A BPS-specific aptamer was immobilized on the electrode to enable selective target capture.The resulting aptamer-target complex,upon exposure to BPS,impedes interfacial electron transfer,resulting in a concentration-dependent decrease in the photocurrent.The PEC aptasensor exhibited a wide linear detection range of 5 nM to 50μM and a detection limit of 0.64 nM.The sensor demonstrated high selectivity against structurally similar interfering substances.Application to real water samples yielded results consistent with that of HPLC-MS/MS,confirming the sensor's reliability and practical applicability.This work establishes a sensitive,rapid,and robust PEC strategy for monitoring BPS in complex environmental matrices with potential for routine environmental analysis.
文摘In situ growth of co-catalysts on BiVO_(4)(BVO)to enhance photoelectrochemical(PEC)water splitting performance has been extensively reported.However,the understanding of the synergistic effects among various elements,especially at the interface between the semiconductor and cocatalyst,has received insufficient attention.In this study,we report a Co,Ni and Mn trimetallic fluoride-modified BVO photoanode featuring a unique interfacial chemical bond(V-F).Under AM 1.5 G illumination,an exciting photocurrent density of 6.05 mA cm^(-2)was achieved at 1.23 V vs.RHE by the integrated BVO/CoNi_(0.18)Mn_(0.12)(OH)_(x)F photoanode and over 98%of the initial photocurrent was maintained after 10 h of photoelectrolysis.Control experiments and theoretical calculations demonstrate that the V-F interfacial bond stabilizes the Co^(2+)active sites.It serves as a transmission gear,interlinking the migration of interfacial charge and the regeneration of cocatalyst,endowing the photoanode with significant activity and stability.Furthermore,we have systematically elucidated the role of the individual Co,Ni,and Mn components in the synergistic cocatalyst layer.The interfacial modification provides novel insights into developing advanced photoanodes towards PEC water splitting.
基金supported by the National Natural Science Foundation of China(No.22206056,22274062,22574062,22574063)the Shandong Provincial Natural Science Foundation(No.ZR2022QB117)Special Foundation for Taishan Scholar Professorship of Shandong Province。
文摘The integration of artificial nanozymes with photoelectrochemical(PEC)biosensing remains underexplored,primarily due to challenges in balancing catalytic efficiency,material stability,and interfacial charge dynamics.Herein,we present a novel split-type PEC biosensor that leverages Au@CeO_(2)yolk-shell nanozymes with robust phosphatase-mimicking activity and staggered band structure of WO_(3)/BiVO_(4)heterojunction for ultrasensitive detection of the breast cancer biomarker HER-2.Unlike conventional nanoenzymes,the yolk-shell architecture encases AuNPs within a CeO_(2)shell,synergistically enhancing catalytic efficiency by maximizing the active surface area while simultaneously preventing nanoparticle aggregation and leaching through a protective barrier.Density functional theory(DFT)calculations reveal that the CeO_(2)(111)/Au(111)interface drastically reduces the energy barrier for phosphate ester bond cleavage(-16.94 eV vs.5.69 eV for free molecules),thereby enabling rapid hydrolysis of ascorbic acid 2-phosphate(AAP)into ascorbic acid.This catalytic amplification strategy,when integrated with a visible-light-responsive semiconductor substrate,enables zero-bias detection and while effectively eliminating interference from high-voltage operations.The biosensor achieves a detection limit of 41 fg/mL(S/N=3)for HER-2 across a linear range of 0.0001-100 ng/mL,surpassing existing methods.Remarkable selectivity,reproducibility(RSD=3.9%),and recovery rates(95.1%–102.4%)in serum further validate its clinical applicability.This work establishes a universal platform for nanozyme-driven PEC biosensing,presenting significant promise for future use in pathological diagnostics.
基金financially supported by the National Natural Science Foundation of China(Nos.52472241,52403108 and 52301285)the Department of Science and Technology of Hubei Province(Nos.2025AFA114 and 2024CSA076)+1 种基金Wuhan Science and Technology Bureau(Nos.2023020201010116 and 2024040801020319)Hubei Provincial Department of Education(No.Q20231703)
文摘Rapid hole extraction from photoanodes to cocatalysts is a crucial prerequisite for the realization of highly efficient photoelectrochemical(PEC)water splitting.Herein,Mn-doped nickel-iron layered double hydroxides(Mn:NiFe-LDHs),as a co-catalyst,were grafted on bismuth vanadate(BVO)for significantly improved charge transfer and stability simultaneously,in addition to the accelerated water oxidation kinetics.The detailed experimental and theoretical analysis collectively verify that Mn doping increases charge density around Ni and Fe sites.The electron-rich Ni sites boost the kinetics of oxygen evolution reaction and promote the hole extraction simultaneously.Moreover,the electrons are transferred from electron-rich Fe sites to V sites,which effectively restrains the dissolution of V^(5+)ions and enhances the stability of BVO photoanodes.Consequently,the resulting Mn:NiFe-LDH/BVO photoanode achieves a remarkable photocurrent density of 5.5 mA cm^(-2)at 1.23 V versus reversible hydrogen electrode(RHE)with excellent stability.The construction of electron-rich oxygen evolution cocatalysts provides a promising strategy to promote the hole extraction and increase the stability for improved PEC performance.
基金supported by the Sichuan Science and Technology Program(No.2024NSFJQ0034)the National Natural Science Foundation of China(No.52271073)+1 种基金the Education and Teaching Reform Program for Graduate Students of Sichuan Province(No.YJGXM24-C047)the Innovation Team Funds of China West Normal University(No.KCXTD2024-1).
文摘A novel and long-lasting N_(3)BD/TiO_(2) composite photoanode with stable and superior photoelectrochemical and photoelectrochemical cathodic protection(PECCP)performances was achieved by synthesizing and depositing covalent organic framework(N_(3)BD)on titanium oxide(TiO_(2))nanotube arrays.The composite's increased visible light absorption capability enhanced the galvanic corrosion protection of nickel-phosphorus alloy-coated magnesium alloy(Mg/Ni)through PECCP technology.The open circuit potential(OCP)drops of the Mg/Ni electrode coupling with the N_(3)BD/TiO_(2) composite were 310 and 630 mV at dark state and under illumination,respectively.They remained relatively stable under intermittent visible light irradiation within 72 h,demonstrating excellent long-term stability.The superior photoelectrochemical and PECCP properties of the N_(3)BD/TiO_(2) are attributed to forming S-scheme heterojunctions,which effectively promote the separation and transfer of photogenerated electron-hole pairs and retain a strong redox capacity.This finding provides new insight into the design and synthesis of COF-modified photoanode with highly efficient and stable photoelectrochemical and PECCP performances.
基金supported by the National Key Research and Development Program of China(2023YFB3610500)National Natural Science Foundation of China(62104110,62374094)+1 种基金the Project funded by China Postdoctoral Science Foundation(2023T160332)Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY224084,NY224131).
文摘Low power consumption,high responsivity,and self-powering are key objectives for photoelectrochemical ultravio-let detectors.In this research,In-dopedα-Ga_(2)O_(3) nanowire arrays were fabricated on fluorine-doped tin oxide(FTO)substrates through a hydrothermal approach,with subsequent thermal annealing.These arrays were then used as photoanodes to con-struct a ultraviolet(UV)photodetector.In doping reduced the bandgap ofα-Ga_(2)O_(3),enhancing its absorption of UV light.Conse-quently,the In-dopedα-Ga_(2)O_(3) nanowire arrays exhibited excellent light detection performance.When irradiated by 255 nm deep ultraviolet light,they obtained a responsivity of 38.85 mA/W.Moreover,the detector's response and recovery times are 13 and 8 ms,respectively.The In-dopedα-Ga_(2)O_(3) nanowire arrays exhibit a responsivity that is about three-fold higher than the undoped one.Due to its superior responsivity,the In-doped device was used to develop a photoelectric imaging system.This study demonstrates that dopingα-Ga_(2)O_(3) nanowire with indium is a potent approach for optimizing their photoelectrochemi-cal performance,which also has significant potential for optoelectronic applications.
基金financially supported by the Henan Province Key R&D and Promotion Project(Technology Research)(NO.232102230011)the Fundamental Research Fund of Henan Academy of Sciences(NO.230618026)+1 种基金Joint Fund of Henan Province Science and Technology R&D Program(NO.225200810120)High-level Talent Research Start-up Project Funding of Henan Academy of Sciences(NOs.231818022 and 232018001).
文摘Constructing a photoanode with both high dark-state protection performance and high stability remains a top priority for photoelectrochemical cathodic protection technology,especially in a marine environment(dark-state or rainy conditions)without hole scavenging agents.In this work,we developed a class of energy-storage quasi-planar heterojunctions(WO_(3)-Nb_(2)O_(5)-ZnIn_(2)S_(4))with directional paths(low onset potential and well-matched energy band)and embedded morphology.The co-design of embedded and directional paths reduces the carrier transport energy barrier at the composite interface,and increases the interface contact area,thereby achieving highly stable and sensitive dark-state energy storage and photoelectrochemical cathodic protection performance in 3.5 wt.%NaCl solution without hole scavenging agent(Dark-state energy storage efficiency increased by 43%.For carbon steel,the performance retention rate is 99.6%after 500 cycles,the performance retention rate is 89%after 5000 s).
基金supported by the National Natural Science Foundation of China(Grant No.12275190,12105201)Jiangsu Funding Program for Excellent Postdoctoral Talent(Grant No.2024ZB723)。
文摘Rational design of porous metal oxide films that serve as not only the scaffolds for light absorbers but also the transfer layer of photo generated charges is essential for fabricating highly efficient photoanodes for photoelectrochemical(PEC)hydrogen generation.In this work,w report a facile one-step pyrolysis method which can convert Zn-based MOF to porous ZnO(m-ZnO)with rough surface and abundant oxygen vacancies(O_(v)).When incorporating core-shell quantum dots(QDs)as the light absorbers,the obtained photoanodes(m-ZnO@QDs)achieved outstanding PEC performance for hydrogen generation,exhibiting 1.6 times and 5.8 times higher saturated photocurrent density(J_(sc))than thos of conventional TiO_(2)@QDs and ZnO@QDs photoanodes,respectively.Comprehensive optical and electrochemical measurements reveal tha the rough surface of m-ZnO can significantly improve the light-harvesting capacity of corresponding photoanodes through surface-enhanced light scattering.Moreover,the O_(v)in m-ZnO facilitate the interfacial transfer of photogenerated electrons.Our findings indicate that the MOF are valuable precursors for the preparation of porous films,offering a promising route to develop high-performance QDs-based PEC devices.
基金supported by the Fuxiaquan Collaborative Innovation Platform(No.K30001)Major Scientific Research Program for Young and Middle-aged Health Professionals of Fujian Province,China(No.2022ZQNZD007)Youth Innovation Technology Project of Higher School in Shandong Province(Food Nanotechnology Innovation Team)。
文摘Quantitative determination of tetracycline(TC)in environment and foods is of great importance,as excessive residues might have negative effects on human health and environmental risks.Herein,a selfpowered molecularly imprinted photoelectrochemical(PEC)sensor based on the Zn O/C photoanode and the Fe-doped CuBi_(2)O_(4)(CBFO)photocathode is developed for the sensitive detection of TC.The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode.Furthermore,molecularly imprinted polymers(MIPs)at photocathode can selectivity identify the TC templates and thus improve the specificity.Under the optimal conditions,the sensor has a linear range of 10^(-2)-1.0×10^(5) nmol/L,and a limit of detection(LOD)of 0.007 nmol/L(S/N=3).More crucially,the milk sample detection is carried out using the as-prepared sensor,and the outcome is satisfactory.The research gives us a novel sensing platform for quick and accurate antibiotic(like TC)in environment and food monitoring.
基金supported by the Fundamental Research Funds for the Central Universities(No.2019ZDPY04).
文摘In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.
基金financially supported by the National Natural Science Foundation of China(22478211,22179067,22372017)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10)。
文摘Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more difficult than to O_(2)via a 4e^(-)pathway.Herein,with a series of BiVO_(4)-based photoanodes,the decisive factors determining the PEC activity and selectivity are elucidated,combining a comprehensive experimental and theoretical investigations.It is discovered that the ZnO/BiVO_(4)photoanode(ZnO/BVO)forms a Type-Ⅱheterojunction in energy level alignment.The accelerated photogenerated charge separation/transfer dynamics generates denser surface holes and higher surface photovoltage.Therefore,the activity of water oxidation reaction is promoted.The selectivity of PEC-WO to H_(2)O_(2)is found to be potential-dependent,i.e.,at the lower potentials(PEC-dominated),surface hole density determines the selectivity;and at the higher potentials(electrochemical-dominated),surface reaction barriers govern the selectivity.For the ZnO/BVO heterojunction photoanode,the higher surface hole density facilitates the generation of OH·and the subsequent OH·/OH·coupling to form H_(2)O_(2),thus rising up with potentials;at the higher potentials,the 2-electron pathway barrier over ZnO/BVO surface is lower than over BVO surface,which benefits from the electronic structure regulation by the underlying ZnO alleviating the over-strong adsorption of^(*)OH on BVO,thus,the two-electron pathway to produce H_(2)O_(2)is more favored than on BVO surface.This work highlights the crucial role of band energy structure of semiconductors on both PEC reaction activity and selectivity,and the knowledge gained is expected to be extended to other photoeletrochemical reactions.
文摘Elemental doping of BiVO_(4) crystal lattices effectively enhances carrier separation,thereby facilitating efficient photoelectrochemical water splitting.However,the positive effect of elementally induced lattice distortions on hole extraction has been neglected.Herein,the crystal lattice of BiVO_(4) is distorted by doping with an inexpensive Cs metal;then,CoFe_(2)O_(4) is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode.Benefiting from the above design,the newly prepared CoFe_(2)O_(4)-Cs-BiVO_(4) photoanode achieved a photocurrent density of 5.66 mA cm^(–2) at 1.23 V vs.a reversible hydrogen electrode,indicating a 3.9-fold improvement in photocurrent density.Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO_(4) bulk-phase holes to the CoFe_(2)O_(4) layer.Additionally,the coupled CoFe_(2)O_(4) can be used as a hole extraction layer to further enhance the interfacial migration of carriers.The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO_(4) bulk phase to the active sites of the oxygen evolution reaction,thereby effectively inhibiting carrier recombination.This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion,thereby opening new avenues for the rational design of photoanodes.
基金supported by the National Research Foundation of Korea(NRF)grant fu nded by the Korean government(MSIT)(No.RS-2024-00335976)。
文摘Antimony sulfide(Sb_(2)S_(3))is a promising material for photoelectrochemical(PEC)devices that generate green hydrogen from sunlight and water.In this study,we present a synthesis of high-performance Sb_(2)S_(3)photoanodes via an interface-engineered hydrothermal growth followed by rapid thermal annealing(RTA).A TiO_(2)interfacial layer plays a crucial role in ensuring homogeneous precursor deposition,enhancing light absorption,and forming efficient heterojunctions with Sb_(2)S_(3),thereby significantly improving charge separation and transport.RTA further improves crystallinity and interfacial contact,resulting in dense and uniform Sb_(2)S_(3)films with enlarged grains and fewer defects.The optimized Sb_(2)S_(3)photoanode achieves a photocurrent density of 2.51 mA/cm^(2)at 1.23 V vs.the reversible hydrogen electrode(RHE),one of the highest reported for Sb_(2)S_(3)without additional catalysts or passivation layers.To overcome the limitations of oxygen evolution reaction(OER),we employ the iodide oxidation reaction(IOR)as an alternative,significantly lowering the overpotential and improving charge transfer kinetics.Consequently,it produces a record photocurrent density of 8.9 mA/cm^(2)at 0.54 V vs.RHE.This work highlights the synergy between TiO_(2)interfacial engineering,RTA-induced crystallization,and IOR-driven oxidation,offering a promising pathway for efficient and scalable PEC hydrogen production.
