The photoanodic characteristics of layer-structured n-InSe were investigated in polysulfide solution as a solid-liquid junction photoelectro- chemical cell(PEC).A quantum yield approaching about 90% and a photocurrent...The photoanodic characteristics of layer-structured n-InSe were investigated in polysulfide solution as a solid-liquid junction photoelectro- chemical cell(PEC).A quantum yield approaching about 90% and a photocurrent density as high as 30 mA/cm^2 were obtained.But the stabilization experiment demonstrates that about 8% of the photocurrent is attributed to a photoanodic corrosion ceaction.展开更多
This study first demonstrates the potential of organic photoabsorbing blends in overcoming a critical limitation of metal oxide photoanodes in tandem modules:insufficient photogenerated current.Various organic blends,...This study first demonstrates the potential of organic photoabsorbing blends in overcoming a critical limitation of metal oxide photoanodes in tandem modules:insufficient photogenerated current.Various organic blends,including PTB7-Th:FOIC,PTB7-Th:O6T-4F,PM6:Y6,and PM6:FM,were systematically tested.When coupled with electron transport layer(ETL)contacts,these blends exhibit exceptional charge separation and extraction,with PM6:Y6 achieving saturation photocurrents up to 16.8 mA cm^(-2) at 1.23 VRHE(oxygen evolution thermodynamic potential).For the first time,a tandem structure utilizing organic photoanodes has been computationally designed and fabricated and the implementation of a double PM6:Y6 photoanode/photovoltaic structure resulted in photogenerated currents exceeding 7mA cm^(-2) at 0 VRHE(hydrogen evolution thermodynamic potential)and anodic current onset potentials as low as-0.5 VRHE.The herein-presented organic-based approach paves the way for further exploration of different blend combinations to target specific oxidative reactions by selecting precise donor/acceptor candidates among the multiple existing ones.展开更多
Developing BiVO_(4)photoanode with efficient carrier transfer and fast water oxidation kinetics is the permanent pursuit to achieve the state-of-art solar-driven photoelectrochemical(PEC)water splitting.The capacity t...Developing BiVO_(4)photoanode with efficient carrier transfer and fast water oxidation kinetics is the permanent pursuit to achieve the state-of-art solar-driven photoelectrochemical(PEC)water splitting.The capacity to increase the PEC activity of BiVO_(4)by loading oxygen evolution co-catalysts(OECs)has been proven,however it suffers from sluggish charge carriers dynamics brought on by the complicated interface between BiVO_(4)and OECs as well as poor long-term durability.Herein,we connected OECs(NiFeOx)and photoanode with a Al-O bridge for bettering the PEC performance of BiVO_(4).The Al-O bridge served as a channel to extract hole from BiVO_(4)to Ni Fe Ox,thus boosting charge carriers separation and preventing BiVO_(4) from photo-corrosion.The Al-O bridging photoanode(NiFeO_(x)/Al_(2)O_(3)/BiVO_(4))demonstrated a high photocurrent density of 5.87 m A/cm^(2)at 1.23 V vs.RHE and long-term photostability in comparison to Ni Fe Ox/BiVO_(4)photoanode.This study proposes a unique technique to boost charge carriers separation between BiVO_(4) and OECs for high-efficiency solar-driven PEC water splitting.展开更多
The photochemical conversion of plastic waste into valuable resources under ambient conditions is challenging.Achieving efficient photocatalytic conversion necessitates intimate contact between the photocatalyst and p...The photochemical conversion of plastic waste into valuable resources under ambient conditions is challenging.Achieving efficient photocatalytic conversion necessitates intimate contact between the photocatalyst and plastic substrate,as water molecules are readily oxidized by photogenerated holes,potentially bypassing the plastic as the electron donor.This study demonstrated a novel strategy for depositing polystyrene(PS)waste onto a photoanode by leveraging its solubility in specific organic solvents,including acetone and chloroform,thus enhancing the interface contact.We used an anodization technique to fabricate a skeleton-like porous tungsten oxide(WO_(3))structure,which exhibited higher durability against detachment from a conductive substrate than the WO_(3) photoanode fabricated using the doctor blade method.Upon illumination,the photogenerated holes were transferred from WO_(3) to PS,promoting the oxidative degradation of plastic waste under ambient conditions.Consequently,the oxidative degradation of PS on the anode side generated carbon dioxide,while the cathodic process produced hydrogen gas through water reduction.Our findings pave the way for sunlight-driven plastic waste treatment technologies that concurrently generate valuable fuels or chemicals and offer the dual benefits of cost savings and environmental protection.展开更多
Atomically precise metal nanoclusters(NCs)have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner,quantum confinement effects,ligh...Atomically precise metal nanoclusters(NCs)have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner,quantum confinement effects,light-harvesting capability and multitude of active sites.Nonetheless,wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan,uncontrollable charge transport pathway,and light-induced poor stability,impeding the construction of robust and stable metal NC-based photosystems.Herein,we report the fabrication of stable alloy(Au_(1-x)Pt_(x))NCs photosystem,for which tailor-made negatively charged l-glutathione(GSH)-capped Au_(1-x)Pt_(x)NCs as the building blocks are controllably deposited on the Bi VO_(4)(BVO)by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes(Au_(1-x)Pt_(x)/BVO).The self-assembled Au_(1-x)Pt_(x)/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Au_(x)/BVO photoanodes,which is caused by the Pt atom doping into the Au_(x)NCs for elevating photosensitivity and boosting the stability.The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation,improving the photostability and accelerating the surface charge transfer kinetics.Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.展开更多
Solar water splitting is an emerging technology for producing clean and renewable hydrogen fuel from sunlight and water.Among various photoelectrode materials,bismuth vanadate(BiVO_(4))has attracted considerable atten...Solar water splitting is an emerging technology for producing clean and renewable hydrogen fuel from sunlight and water.Among various photoelectrode materials,bismuth vanadate(BiVO_(4))has attracted considerable attention due to its visible light absorption,favorable band edge positions,good chemical stability,and low cost.However,the solar water splitting efficiency of BiVO_(4) photoanodes is still far from satisfactory,mainly because of the low charge carrier mobility,high recombination rate,and slow water oxidation kinetics.In this review,we summarize the recent progress in the synthesis,modification,and application of BiVO_(4)-based photoelectrodes for photoelectrochemical(PEC)water splitting.The working principle of PEC water splitting and the fundamental properties of BiVO_(4) are introduced.Then,the synthesis methods of BiVO_(4) films are reviewed,and the strategies to enhance the PEC properties of BiVO_(4) are critically discussed.Furthermore,the applications of BiVO_(4)-based photoelectrodes in different scenarios are highlighted.Finally,the summary and outlook for the future development of BiVO_(4)-based photoelectrodes for PEC water splitting are presented.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 slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction.A method is proposed to accelerate proton transfer by building up local electric fields.Modifying acetic,etha...The slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction.A method is proposed to accelerate proton transfer by building up local electric fields.Modifying acetic,ethanedioic and propanetricarboxylic(C_(6)H_(8)O_(6))ligands on BiVO_(4)surface results in a potential difference between BiVO_(4)and ligands that generates a local electric field which serves as a driving force for proton transfer.Among the ligands,carrying the strongest electron-withdrawing ability,the modification of C_(6)H_(8)O_(6) forms the strongest local electric field and leads to the fastest proton transfer and the smallest thermodynamic overpotential.C_(6)H_(8)O_(6)-BiVO_(4)exhibits 3.5 times photocurrent density as high as that of pure BiVO_(4),which is 3.50 mA cm^(-2)at 1.23 VRHE.The onset potential of C_(6)H_(8)O_(6)-BiVO_(4)shifts negatively from 0.70 to 0.38 VRHE.The mechanism for OER transitions from thermodynamically high energy proton-coupled electron transfer to thermodynamically low energy electron transfer as proton transfer is accelerated.展开更多
Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seri...Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seriously limited the overall conversion efficiencies of solar energy to chemical fuels.Herein,we demonstrated a facile and feasible strategy to rationally regulate the coordination environment and electronic structure of surface-active sites on both photoanode and cathode.More specifically,the defect engineering has been employed to reduce the coordination number of ultrathin FeNi catalysts decorated on BiVO4 photoanodes,resulting in one of the highest OER activities of 6.51 mA cm^(−2)(1.23 VRHE,AM 1.5G).Additionally,single-atom cobalt(II)phthalocyanine anchoring on the N-rich carbon substrates to increase Co–N coordination number remarkably promotes CO_(2) adsorption and activation for high selective CO production.Their integration achieved a record activity of 109.4μmol cm^(−2) h−1 for CO production with a faradaic efficiency of>90%,and an outstanding solar conversion efficiency of 5.41%has been achieved by further integrating a photovoltaic utilizing the sunlight(>500 nm).展开更多
Solar-driven carbon dioxide reduction reaction(CO_(2)RR)provides an oppor tunity to produce value-added chemical feedstocks and fuels.However,achieving efficient and stable photoelectrochemical(PEC)CO_(2)RR into selec...Solar-driven carbon dioxide reduction reaction(CO_(2)RR)provides an oppor tunity to produce value-added chemical feedstocks and fuels.However,achieving efficient and stable photoelectrochemical(PEC)CO_(2)RR into selec tive products is challenging owing to the difficulties associated with the optical and the electrical configuration of PEC devices and electrocatalyst properties.Herein,we construct an efficient,concentrated sunlight-driven CO_(2)RR setup consisting of InGaP/GaAs/Ge triple-junction cell as a photoanode and oxide-derived Au(Ox-Au)as a cathode to perform the unassisted PEC CO_(2)RR.Under one-sun illumination,a maximum operating current density of 11.5 mA cm^(-2) with an impressive Faradaic efficiency(FE)of~98%is achieved for carbon monoxide(CO)production,leading to a solar-to-fuel conversion efficiency of~15%.Under concentrated intensity of 10 sun,the photoanode records a maximum current density of~124 mAcm^(-2) and maintains~60%of FE for CO production.The results demonstrate crucial advancements in usingⅢ-Ⅴbased photoanodes for concentrated PEC CO_(2)RR.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
A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer...A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.展开更多
A film of mesoporous single-crystal rutile TiO2 rod arrays supported on a transparent conductive glass substrate was synthesized with the assistance of a template layer of closely packed silica nanospheres. This film ...A film of mesoporous single-crystal rutile TiO2 rod arrays supported on a transparent conductive glass substrate was synthesized with the assistance of a template layer of closely packed silica nanospheres. This film was used as a photoanode and showed significant improvement for photoelectrochemical water oxidation compared with a reference film of nonporous single-crystal rutile TiO2rod arrays.展开更多
Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for m...Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for metal to achieve cathodic protection. Comparing with traditional PEC photoanode for water splitting, it requires the photoanode providing a suitable cathodic potential for the metal, instead of pursuit ultimate photon to electric conversion efficiency, thus it is a more possible PEC technology for engineering application. To date, great efforts have been devoted to developing novel n-type semiconductors and advanced modification method to improve the performance on PEC cathodic protection metals. Herein, recent progresses in this field are summarized. We highlight the fabrication process of PEC cathodic protection thin film, various nanostructure controlling, doping, compositing methods and their operation mechanism. Finally, the current challenges and future potential works on improving the PEC cathodic protection performance are discussed.展开更多
Photoelectrochemical(PEC)water splitting capable of reducing and oxidizing water into hydrogen and oxygen in a generation mode of spatial separation has gained extensive popularity.In order to effectively produce hydr...Photoelectrochemical(PEC)water splitting capable of reducing and oxidizing water into hydrogen and oxygen in a generation mode of spatial separation has gained extensive popularity.In order to effectively produce hydrogen at the photocathode of a PEC cell,the photoanode,where the oxygen evolution reaction occurs,should be systematically developed on priority.In particular,WO3 has been identified as one of the most promising photoanode materials owing to its narrow band gap and high valence band position.Its practical implementation,however,is still limited by excessive electron–hole recombination and poor water oxidation kinetics.This review presents the various strategies that have been studied for enhancing the PEC water oxidation performance of WO3,such as controlling the morphology,introducing defects,constructing a heterojunction,loading a cocatalyst,and exploiting the plasmonic effect.In addition,the possible future research directions are presented.展开更多
The effect of chromium doping on the photo- voltaic efficiency of dye-sensitized solar cells （DSSCs） with anodized TiO2 nanotubes followed by an annealing process was investigated. Cr-doped TiO2 nanotubes （CrTNs） ...The effect of chromium doping on the photo- voltaic efficiency of dye-sensitized solar cells （DSSCs） with anodized TiO2 nanotubes followed by an annealing process was investigated. Cr-doped TiO2 nanotubes （CrTNs） with different amounts of chromium were obtained by anodizing of titanium foils in a single-step process using potassium chro- mate as the chromium source. Film features were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, energy-dispersive X-ray spectroscopy （EDX）, and ultraviolet-visible （UV-Vis） spectroscopy. It is clearly seen that highly ordered TiO2 nanotubes are formed in an anodizing solution free of potassium chromate, and with a gradual increase in the potassium chromate concentration, these nanotube structures change to nanoporous and compact films without porosity. The photovoltaic efficiencies of fabricated DSSCs were characterized by a solar cell measurement sys- tem via the photocurrent-voltage （l-V） curves. It is found that the photovoltaic efficiency of DSSCs with CrTNsl sample is improved by more than three times compared to that of DSSCs with undoped TNs. The energy conversion efficiency increases from 1.05 % to 3.89 % by doping of chromium.展开更多
To drive photoelectrochemical water splitting on porous BiVO_(4)photoanode,we herein prepared a carnationlike CuS powder by hydrothermal method and then loaded it onto BiVO_(4)photoelectrode.Expectedly,the CuS/BiVO_(4...To drive photoelectrochemical water splitting on porous BiVO_(4)photoanode,we herein prepared a carnationlike CuS powder by hydrothermal method and then loaded it onto BiVO_(4)photoelectrode.Expectedly,the CuS/BiVO_(4)composite not only presents a higher photocurrent response value at 1.23 V versus RHE(reversible hydrogen electrode)than pure BiVO4 electrode under visible light irradiation,but also exhibits an excellent photoelectrochemical hydrogen production activity in comparison with either the BiVO_(4)or the CuS.The high ameliorated performance of CuS/BiVO4 composite may be due to the strong absorption of visible light and an effective abatement in combination of carriers.These results demonstrate an effective potential approach to design and construct efficient photoelectrochemical(PEC)systems.展开更多
Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode ...Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.展开更多
Photoelectrochemical(PEC)water splitting can convert renewable solar energy into clean hydrogen fuel.Photoelectrodes are the core components of water-splitting cells.In the past 40 years,a series of binary and ternary...Photoelectrochemical(PEC)water splitting can convert renewable solar energy into clean hydrogen fuel.Photoelectrodes are the core components of water-splitting cells.In the past 40 years,a series of binary and ternary transition metal oxides have been investigated as photo-electrode materials for solar water splitting,and numerous studies have been carried out to modify their water-split-ting performances.Although satisfactory transition metal oxide photoelectrode materials have not been found,it is necessary to summarize the recent advancements in tran-sition metal oxide photoelectrode materials to guide future research.In this review,the background and principle of PEC water splitting are introduced.The semiconductor properties and modification progress of typical binary and ternary metal oxide photoanodes and photocathodes for solar water splitting are summarized.Based on the newly developed strategies in recent years,a brief outlook is presented for efficient PEC water splitting using transition metal oxide photoelectrodes.展开更多
We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene h...We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.展开更多
文摘The photoanodic characteristics of layer-structured n-InSe were investigated in polysulfide solution as a solid-liquid junction photoelectro- chemical cell(PEC).A quantum yield approaching about 90% and a photocurrent density as high as 30 mA/cm^2 were obtained.But the stabilization experiment demonstrates that about 8% of the photocurrent is attributed to a photoanodic corrosion ceaction.
基金partly funded by a BIST Ignite Programme grant from the Barcelona Institute of Science and Technology(Code:MOLOPEC)financial support from LICROX and SOREC2 EUFunded projects(Codes:951843 and 101084326)+7 种基金the BIST Program,and Severo Ochoa Programpartially funded by CEX2019-000910-S(MCIN/AEI/10.13039/501100011033 and PID2020-112650RBI00),Fundació Cellex,Fundació Mir-PuigGeneralitat de Catalunya through CERCAfunding from the European Union’s Horizon Europe research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101081441financial support by the Agencia Estatal de Investigación(grant PRE2018-084881)the financial support by from the European Union’s Horizon Europe research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101081441support from the MCIN/AEI JdC-F Fellowship(FJC2020-043223-I)the Severo Ochoa Excellence Postdoctoral Fellowship(CEX2019-000910-S).
文摘This study first demonstrates the potential of organic photoabsorbing blends in overcoming a critical limitation of metal oxide photoanodes in tandem modules:insufficient photogenerated current.Various organic blends,including PTB7-Th:FOIC,PTB7-Th:O6T-4F,PM6:Y6,and PM6:FM,were systematically tested.When coupled with electron transport layer(ETL)contacts,these blends exhibit exceptional charge separation and extraction,with PM6:Y6 achieving saturation photocurrents up to 16.8 mA cm^(-2) at 1.23 VRHE(oxygen evolution thermodynamic potential).For the first time,a tandem structure utilizing organic photoanodes has been computationally designed and fabricated and the implementation of a double PM6:Y6 photoanode/photovoltaic structure resulted in photogenerated currents exceeding 7mA cm^(-2) at 0 VRHE(hydrogen evolution thermodynamic potential)and anodic current onset potentials as low as-0.5 VRHE.The herein-presented organic-based approach paves the way for further exploration of different blend combinations to target specific oxidative reactions by selecting precise donor/acceptor candidates among the multiple existing ones.
基金financially supported by the National Natural Science Foundation of China(No.52173277)the Fundamental Research Funds for the Central Universities of Chang’an University(No.300102299304)+1 种基金the Innovative Research Team for Science and Technology of Shaanxi Province(No.2022TD-04)the open program of Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities(No.2023JXZ03)。
文摘Developing BiVO_(4)photoanode with efficient carrier transfer and fast water oxidation kinetics is the permanent pursuit to achieve the state-of-art solar-driven photoelectrochemical(PEC)water splitting.The capacity to increase the PEC activity of BiVO_(4)by loading oxygen evolution co-catalysts(OECs)has been proven,however it suffers from sluggish charge carriers dynamics brought on by the complicated interface between BiVO_(4)and OECs as well as poor long-term durability.Herein,we connected OECs(NiFeOx)and photoanode with a Al-O bridge for bettering the PEC performance of BiVO_(4).The Al-O bridge served as a channel to extract hole from BiVO_(4)to Ni Fe Ox,thus boosting charge carriers separation and preventing BiVO_(4) from photo-corrosion.The Al-O bridging photoanode(NiFeO_(x)/Al_(2)O_(3)/BiVO_(4))demonstrated a high photocurrent density of 5.87 m A/cm^(2)at 1.23 V vs.RHE and long-term photostability in comparison to Ni Fe Ox/BiVO_(4)photoanode.This study proposes a unique technique to boost charge carriers separation between BiVO_(4) and OECs for high-efficiency solar-driven PEC water splitting.
基金supported by the National Research Foundation of Korea(NRF)funded by the Ministry of Science and Information and Communication Technology(ICT)(NRF-2020M3H4A3106354)Korea Government(MSIT,RS-2023-00213022)the Korea Institution of Science and Technology(KIST)internal projects.
文摘The photochemical conversion of plastic waste into valuable resources under ambient conditions is challenging.Achieving efficient photocatalytic conversion necessitates intimate contact between the photocatalyst and plastic substrate,as water molecules are readily oxidized by photogenerated holes,potentially bypassing the plastic as the electron donor.This study demonstrated a novel strategy for depositing polystyrene(PS)waste onto a photoanode by leveraging its solubility in specific organic solvents,including acetone and chloroform,thus enhancing the interface contact.We used an anodization technique to fabricate a skeleton-like porous tungsten oxide(WO_(3))structure,which exhibited higher durability against detachment from a conductive substrate than the WO_(3) photoanode fabricated using the doctor blade method.Upon illumination,the photogenerated holes were transferred from WO_(3) to PS,promoting the oxidative degradation of plastic waste under ambient conditions.Consequently,the oxidative degradation of PS on the anode side generated carbon dioxide,while the cathodic process produced hydrogen gas through water reduction.Our findings pave the way for sunlight-driven plastic waste treatment technologies that concurrently generate valuable fuels or chemicals and offer the dual benefits of cost savings and environmental protection.
基金The support by the award Program for Minjiang scholar professorship is greatly acknowledgedfinancially supported by the National Natural Science Foundation of China(Nos.21703038,22072025)The financial support from State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Science is acknowledged(No.20240018)。
文摘Atomically precise metal nanoclusters(NCs)have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner,quantum confinement effects,light-harvesting capability and multitude of active sites.Nonetheless,wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan,uncontrollable charge transport pathway,and light-induced poor stability,impeding the construction of robust and stable metal NC-based photosystems.Herein,we report the fabrication of stable alloy(Au_(1-x)Pt_(x))NCs photosystem,for which tailor-made negatively charged l-glutathione(GSH)-capped Au_(1-x)Pt_(x)NCs as the building blocks are controllably deposited on the Bi VO_(4)(BVO)by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes(Au_(1-x)Pt_(x)/BVO).The self-assembled Au_(1-x)Pt_(x)/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Au_(x)/BVO photoanodes,which is caused by the Pt atom doping into the Au_(x)NCs for elevating photosensitivity and boosting the stability.The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation,improving the photostability and accelerating the surface charge transfer kinetics.Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.
基金financially supported by the National Natural Science Foundation of China(No.52372292)Shenzhen Science and Technology Program(No.JCYJ20220530161615035)+1 种基金the Fundamental Research Funds for the Central Universitiesthe International Science and Technology Cooperation Program of Henan Province(No.232102520018).
文摘Solar water splitting is an emerging technology for producing clean and renewable hydrogen fuel from sunlight and water.Among various photoelectrode materials,bismuth vanadate(BiVO_(4))has attracted considerable attention due to its visible light absorption,favorable band edge positions,good chemical stability,and low cost.However,the solar water splitting efficiency of BiVO_(4) photoanodes is still far from satisfactory,mainly because of the low charge carrier mobility,high recombination rate,and slow water oxidation kinetics.In this review,we summarize the recent progress in the synthesis,modification,and application of BiVO_(4)-based photoelectrodes for photoelectrochemical(PEC)water splitting.The working principle of PEC water splitting and the fundamental properties of BiVO_(4) are introduced.Then,the synthesis methods of BiVO_(4) films are reviewed,and the strategies to enhance the PEC properties of BiVO_(4) are critically discussed.Furthermore,the applications of BiVO_(4)-based photoelectrodes in different scenarios are highlighted.Finally,the summary and outlook for the future development of BiVO_(4)-based photoelectrodes for PEC water splitting are presented.
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.
文摘The slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction.A method is proposed to accelerate proton transfer by building up local electric fields.Modifying acetic,ethanedioic and propanetricarboxylic(C_(6)H_(8)O_(6))ligands on BiVO_(4)surface results in a potential difference between BiVO_(4)and ligands that generates a local electric field which serves as a driving force for proton transfer.Among the ligands,carrying the strongest electron-withdrawing ability,the modification of C_(6)H_(8)O_(6) forms the strongest local electric field and leads to the fastest proton transfer and the smallest thermodynamic overpotential.C_(6)H_(8)O_(6)-BiVO_(4)exhibits 3.5 times photocurrent density as high as that of pure BiVO_(4),which is 3.50 mA cm^(-2)at 1.23 VRHE.The onset potential of C_(6)H_(8)O_(6)-BiVO_(4)shifts negatively from 0.70 to 0.38 VRHE.The mechanism for OER transitions from thermodynamically high energy proton-coupled electron transfer to thermodynamically low energy electron transfer as proton transfer is accelerated.
基金supported by the National Natural Science Foundation of China(21832005,22072168,22002175)Major Program of the Lanzhou Institute of Chemical Physics,CAS(No.ZYFZFX-3)+1 种基金Major Science and Technology Projects in Gansu Province(22ZD6GA003)West Light Foundation of The Chinese Academy of Sciences(xbzg-zdsys-202209).
文摘Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seriously limited the overall conversion efficiencies of solar energy to chemical fuels.Herein,we demonstrated a facile and feasible strategy to rationally regulate the coordination environment and electronic structure of surface-active sites on both photoanode and cathode.More specifically,the defect engineering has been employed to reduce the coordination number of ultrathin FeNi catalysts decorated on BiVO4 photoanodes,resulting in one of the highest OER activities of 6.51 mA cm^(−2)(1.23 VRHE,AM 1.5G).Additionally,single-atom cobalt(II)phthalocyanine anchoring on the N-rich carbon substrates to increase Co–N coordination number remarkably promotes CO_(2) adsorption and activation for high selective CO production.Their integration achieved a record activity of 109.4μmol cm^(−2) h−1 for CO production with a faradaic efficiency of>90%,and an outstanding solar conversion efficiency of 5.41%has been achieved by further integrating a photovoltaic utilizing the sunlight(>500 nm).
基金supported by the City University of Hong Kong(9380107 and 7005943)King Abdullah University of Science and Technology,and Agency for Science,Technology and Research(C230415018 and C231218003).
文摘Solar-driven carbon dioxide reduction reaction(CO_(2)RR)provides an oppor tunity to produce value-added chemical feedstocks and fuels.However,achieving efficient and stable photoelectrochemical(PEC)CO_(2)RR into selec tive products is challenging owing to the difficulties associated with the optical and the electrical configuration of PEC devices and electrocatalyst properties.Herein,we construct an efficient,concentrated sunlight-driven CO_(2)RR setup consisting of InGaP/GaAs/Ge triple-junction cell as a photoanode and oxide-derived Au(Ox-Au)as a cathode to perform the unassisted PEC CO_(2)RR.Under one-sun illumination,a maximum operating current density of 11.5 mA cm^(-2) with an impressive Faradaic efficiency(FE)of~98%is achieved for carbon monoxide(CO)production,leading to a solar-to-fuel conversion efficiency of~15%.Under concentrated intensity of 10 sun,the photoanode records a maximum current density of~124 mAcm^(-2) and maintains~60%of FE for CO production.The results demonstrate crucial advancements in usingⅢ-Ⅴbased photoanodes for concentrated PEC CO_(2)RR.
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.
基金Project(21471054)supported by the National Natural Science Foundation of China
文摘A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.
基金supported by the National Basic Research Program of China(2014CB239401)the National Natural Science Foundation of China(51402306+4 种基金5142221021090343)the Deanship of Scientific Research(50-130-35-HiC i)King Abdulaziz UniversitySaudi Arabia~~
文摘A film of mesoporous single-crystal rutile TiO2 rod arrays supported on a transparent conductive glass substrate was synthesized with the assistance of a template layer of closely packed silica nanospheres. This film was used as a photoanode and showed significant improvement for photoelectrochemical water oxidation compared with a reference film of nonporous single-crystal rutile TiO2rod arrays.
基金supported by National Natural Science Foundation of China(Grant no.41506093)
文摘Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for metal to achieve cathodic protection. Comparing with traditional PEC photoanode for water splitting, it requires the photoanode providing a suitable cathodic potential for the metal, instead of pursuit ultimate photon to electric conversion efficiency, thus it is a more possible PEC technology for engineering application. To date, great efforts have been devoted to developing novel n-type semiconductors and advanced modification method to improve the performance on PEC cathodic protection metals. Herein, recent progresses in this field are summarized. We highlight the fabrication process of PEC cathodic protection thin film, various nanostructure controlling, doping, compositing methods and their operation mechanism. Finally, the current challenges and future potential works on improving the PEC cathodic protection performance are discussed.
基金financially supported by the National Natural Science Foundation of China (21808189, 21663027)the Science and Technology Support Project of Gansu Province (1504GKCA027)+2 种基金the Program for Innovative Research Team (NWNULKQN-15-2)the Opening Project of Guangzhou Key Laboratory of Environmental Catalysis and Pollution Control (GKLECPC-12)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education (LYJ18205)~~
文摘Photoelectrochemical(PEC)water splitting capable of reducing and oxidizing water into hydrogen and oxygen in a generation mode of spatial separation has gained extensive popularity.In order to effectively produce hydrogen at the photocathode of a PEC cell,the photoanode,where the oxygen evolution reaction occurs,should be systematically developed on priority.In particular,WO3 has been identified as one of the most promising photoanode materials owing to its narrow band gap and high valence band position.Its practical implementation,however,is still limited by excessive electron–hole recombination and poor water oxidation kinetics.This review presents the various strategies that have been studied for enhancing the PEC water oxidation performance of WO3,such as controlling the morphology,introducing defects,constructing a heterojunction,loading a cocatalyst,and exploiting the plasmonic effect.In addition,the possible future research directions are presented.
基金the financial support from Iranian Nanotechnology Society and Isfahan University of Technology (IUT) Research Council
文摘The effect of chromium doping on the photo- voltaic efficiency of dye-sensitized solar cells （DSSCs） with anodized TiO2 nanotubes followed by an annealing process was investigated. Cr-doped TiO2 nanotubes （CrTNs） with different amounts of chromium were obtained by anodizing of titanium foils in a single-step process using potassium chro- mate as the chromium source. Film features were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, energy-dispersive X-ray spectroscopy （EDX）, and ultraviolet-visible （UV-Vis） spectroscopy. It is clearly seen that highly ordered TiO2 nanotubes are formed in an anodizing solution free of potassium chromate, and with a gradual increase in the potassium chromate concentration, these nanotube structures change to nanoporous and compact films without porosity. The photovoltaic efficiencies of fabricated DSSCs were characterized by a solar cell measurement sys- tem via the photocurrent-voltage （l-V） curves. It is found that the photovoltaic efficiency of DSSCs with CrTNsl sample is improved by more than three times compared to that of DSSCs with undoped TNs. The energy conversion efficiency increases from 1.05 % to 3.89 % by doping of chromium.
基金financially supported by the National Natural Science Foundation of China(Nos.21663027 and 21808189)the Natural Science Foundation of Gansu Province(No.18JR3RA090)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(No.LYJ18205)
文摘To drive photoelectrochemical water splitting on porous BiVO_(4)photoanode,we herein prepared a carnationlike CuS powder by hydrothermal method and then loaded it onto BiVO_(4)photoelectrode.Expectedly,the CuS/BiVO_(4)composite not only presents a higher photocurrent response value at 1.23 V versus RHE(reversible hydrogen electrode)than pure BiVO4 electrode under visible light irradiation,but also exhibits an excellent photoelectrochemical hydrogen production activity in comparison with either the BiVO_(4)or the CuS.The high ameliorated performance of CuS/BiVO4 composite may be due to the strong absorption of visible light and an effective abatement in combination of carriers.These results demonstrate an effective potential approach to design and construct efficient photoelectrochemical(PEC)systems.
文摘Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.
基金financially supported by the National Key R&D Program of China (No. 2018YFE0208500)the National Natural Science Foundation of China (No. 41702037)
文摘Photoelectrochemical(PEC)water splitting can convert renewable solar energy into clean hydrogen fuel.Photoelectrodes are the core components of water-splitting cells.In the past 40 years,a series of binary and ternary transition metal oxides have been investigated as photo-electrode materials for solar water splitting,and numerous studies have been carried out to modify their water-split-ting performances.Although satisfactory transition metal oxide photoelectrode materials have not been found,it is necessary to summarize the recent advancements in tran-sition metal oxide photoelectrode materials to guide future research.In this review,the background and principle of PEC water splitting are introduced.The semiconductor properties and modification progress of typical binary and ternary metal oxide photoanodes and photocathodes for solar water splitting are summarized.Based on the newly developed strategies in recent years,a brief outlook is presented for efficient PEC water splitting using transition metal oxide photoelectrodes.
文摘We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.
