Oxygen evolution reaction(OER),a critical half-reaction in photocatalytic overall water splitting for producing hydrogen,is a key step toward sustainable energy conversion.Conventional photocatalysts often suffer from...Oxygen evolution reaction(OER),a critical half-reaction in photocatalytic overall water splitting for producing hydrogen,is a key step toward sustainable energy conversion.Conventional photocatalysts often suffer from limited light absorption and rapid charge recombination,hindering their further applications.To address these challenges,we have designed and synthesized a novel series of self-sensitized metal-organic frameworks(MOFs),Fe_(2)MCDDB(M=Ni,Mn,or Co).By incorporating photosensitive ligands,we have achieved efficient charge separation and promoted the transfer of photogenerated electrons to the active metal sites for water oxidation.Among the series,Fe_(2)NiCDDB exhibits exceptional OER activity,achieving an oxygen evolution rate of 125.3μmol g^(−1)h^(−1)under visible light irradiation.Experimental and theoretical results reveal that the optimized electronic structure and prolonged excited-state lifetime of Fe_(2)NiCDDB contribute to its enhanced catalytic performance.This work provides a promising strategy for designing two-in-one MOF photocatalysts for water oxidation.展开更多
A novel Fe-doping three-dimensional fiower-like Bi_(7)O_(9)I_(3) microspheres with plasmonic Bi and rich surface oxygen vacancies(Fe-Bi/Bi_(7)O_(9)I_(3)/OVs)was prepared as catalysts,and further coupled with natural a...A novel Fe-doping three-dimensional fiower-like Bi_(7)O_(9)I_(3) microspheres with plasmonic Bi and rich surface oxygen vacancies(Fe-Bi/Bi_(7)O_(9)I_(3)/OVs)was prepared as catalysts,and further coupled with natural air diffusion electrode(NADE)to construct the heterogeneous visible-light-driven photoelectro-Fenton(HEVL-PEF)process to enhance the degradation and mineralization of tetracycline(TC).Interfacial≡Fe sites,OVs and Bi metal were simultaneously constructed via Fe doping,which effectively improved visible light absorption and the separation efficiency of photogenerated carriers to further accelerate the transformation of Fe(Ⅲ)to Fe(Ⅱ),achieving Fenton reaction recycling.HE-VL-PEF process could achieve enhanced treatment of pollutants,thanks to the synergistic effect of electro-Fenton(EF)and photo-Fenton(PF).NADE exhibited excellent H_(2)O_(2) electrosynthesis without external oxygen-pumping equipment.Under the irradiation of visible light,Fe-Bi/Bi_(7)O_(9)I_(3)/OVs could achieve more photoelectrons to accelerate the transformation of Fe(Ⅲ)to Fe(Ⅱ)or directly activate H2O2.DFT calculations also clearly demonstrated that except for the fast charge separation and transfer,Fe-Bi/Bi_(7)O_(9)I_(3)/OVs could achieve a faster electron transport between Fe-O,facilitating Fe site acquire more electron.Consequently,the Fe-Bi/Bi_(7)O_(9)I_(3)/OVs in HE-VL-PEF process presented performance superiorities including excellent pollutant removal(91.91%),low electric energy consumption of 66.34 k Wh/kg total organic carbon(TOC),excellent reusability and wide p H adaptability(3–9).展开更多
Storing solar energy in battery systems is crucial to achieving a green and sustainable society.However,the efficient development of photo-enhanced zinc-air batteries(ZABs)is limited by the rapid recombination of phot...Storing solar energy in battery systems is crucial to achieving a green and sustainable society.However,the efficient development of photo-enhanced zinc-air batteries(ZABs)is limited by the rapid recombination of photogenerated carriers on the photocathode.In this work,the visible-light-driven CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst with unique petal-like layer structure was designed and developed,which can be used as air electrode for visible-light-driven ZABs.The superior performance of ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)was mainly attributed to the successful construction of Schottky heterojunction between g-C_(3)N_(4)and carbon nanotubes(CNTs),which accelerates the transfer of electrons from g-C_(3)N_(4)to CoS_(2)/CuS cocatalysts,improves the carrier separation ability,and extends the carrier lifetime.Thereinto,the visible-driven ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst has a power density of 588.90 mW cm^(-2) and a charge-discharge cycle of 643 h under visible light irradiation,which is the highest performance ever reported for photo-enhanced ZABs.More importantly,the charge-discharge voltage drop of ZABs was only 0.54 V under visible light irradiation,which is significantly lower than the voltage drop(0.94 V)in the dark.This study provides a new idea for designing efficient and stable visible-light-driven ZABs cathode catalysts.展开更多
Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniqu...Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniques. The photocatalytic activities of the BiVO4 materials were evaluated for the degradation of Methyl Orange under visible-light irradiation. It is observed that pH value and surfactant exerted a great effect on the morphology and pore structure of the BiVO4 product. Spherical BiVO4 with porous structures, flower-cluster-like BiVO4, and flower-bundle-like BiVO4 were generated hydrothermally at 100°C with poly（vinyl pyrrolidone） （PVP） and urea （pH = 2） and at 160°C with NaHCO3 （pH = 7 and 8）, respectively. The PVP-derived BiVO4 showed much higher surface areas （5.0-8.4 m2/g） and narrower bandgap energies （2.45-2.49 eV）. The best photocatalytic performance of the spherical BiVO4 material with a surface area of 8.4 m2/g was associated with its higher surface area, narrower bandgap energy, higher surface oxygen vacancy density, and unique porous architecture.展开更多
Visible-light-driven photochemical Cadogan-type cyclization has been discovered.The organic D-A type photosensitizer 4 CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermedi...Visible-light-driven photochemical Cadogan-type cyclization has been discovered.The organic D-A type photosensitizer 4 CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermediate that breaks the barriers of deoxygenation in Cadogan reaction and enables a mild metalfree access to carbazoles and related heterocycles.DFT calculation results indicate mildly endergonic formation of the intermediate complex of nitrobiarenes and PPh3,which corresponds with experimental findings regarding reaction temperature.The robust synthetic capacity of the photoredox Cadogan reaction systems has been demonstrated by the viable productivity of a broad range of carbazoles and related N-heterocycles with good tolerance of various functionalities.展开更多
The mass production of urea,the most widely used agricultural fertilizer,usually relies on energy-and carbon-intensive processes.The light-driven synthesis path has great potential for more sustainable techniques to p...The mass production of urea,the most widely used agricultural fertilizer,usually relies on energy-and carbon-intensive processes.The light-driven synthesis path has great potential for more sustainable techniques to produce urea from abundant naturally occurring resources,but this method suffers fromthe use of pure CO_(2)and high-energy-driven forces(high temperature or ultraviolet light).Herein,we present a mild photocatalytic pathway for urea production from diverse nitrogenous species(such as NO3-,NH3,and N2)and diluted CO_(2)using visible light.We designed a palladium(Pd)-doped Schottky heterojunction,composed of graphene and titanium dioxide,as an effective photocatalyst to achieve on-farm urea generation.With the injection of visible-lightgenerated hot electrons from graphene to TiO_(2),the as-integrated Pd(I)centers with a special oxidation state of+1.36 in the TiO_(2)lattice can initiate the universal reaction path of cascade reduction of NO3-/N2 to NH3 and resulting C-N coupling of CO_(2)with as-formed or added NH3 to transform diverse nitrogenous species and CO_(2)into urea.The urea yield over the at.-Pd@TiO_(2)/Gr photocatalyst is 1.62 mmol g-1 h-1 under visible-light irradiation with an apparent quantum yield of 1.05%at 400 nm and 0.39%even at 700 nm.展开更多
In the quest for effective solutions to address Environ.Pollut.and meet the escalating energy demands,heterojunction photocatalysts have emerged as a captivating and versatile technology.These photocatalysts have garn...In the quest for effective solutions to address Environ.Pollut.and meet the escalating energy demands,heterojunction photocatalysts have emerged as a captivating and versatile technology.These photocatalysts have garnered significant interest due to their wideranging applications,including wastewater treatment,air purification,CO_(2) capture,and hydrogen generation via water splitting.This technique harnesses the power of semiconductors,which are activated under light illumination,providing the necessary energy for catalytic reactions.With visible light constituting a substantial portion(46%)of the solar spectrum,the development of visible-light-driven semiconductors has become imperative.Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light.In this comprehensive review,we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media,as well as the remarkable progress made in renewable energy production.Moreover,we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems.Finally,we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain.By unraveling the potential of heterojunction photocatalysts,this reviewcontributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.展开更多
Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups in...Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.展开更多
A novel Ag/g-C_(3)N_(4)/kaolinite composite photocatalyst was fabricated for the first time through a two-step assembly strategy by employing in situ calcination and a photodeposition process.The synthesized Ag/g-C_(3...A novel Ag/g-C_(3)N_(4)/kaolinite composite photocatalyst was fabricated for the first time through a two-step assembly strategy by employing in situ calcination and a photodeposition process.The synthesized Ag/g-C_(3)N_(4)/kaolinite composite reached a higher degradation rate of ibuprofen(IBP)with a reaction rate constant of 0.0113 min^(-1) at an Ag content of 7% under visible-light irradiation,which was approximately 1.87 times that of the Ag/g-C_(3)N_(4) composite.Based on the physicochemical properties,the enhanced photocatalytic activity was attributed to the stronger adsorption property,wider photoresponse range and more efficient separation and transfer of electron-hole pairs.Furthermore,the incorporation of monodispersed Ag nanoparticles onto the g-C_(3)N_(4)/kaolinite sheets provided more reactive sites for the IBP degradation.In addition,according to the EPR study and trapping experiments,it was demonstrated that holes(h^(+))should be the key reactive species.A possible pathway of IBP degradation was also proposed based on the detected intermediates.Overall,the results of this work may facilitate the design of a novel visible-light-driven photocatalyst with a high efficiency that is derived from a natural mineral for environmental remediation.展开更多
Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge ...Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H_(2)O_(2) generation performance.Herein,we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters(AuAg NCs)to polyethyleneimine(PEI)modified C_(3)N_(4)(C3N4-PEI).The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C_(3)N_(4)-PEI,thereby ultimately producing abundant e−for O_(2) reduction under visible light illumination(λ≥400 nm).As a result,the as-designed photocatalyst(C3N4-PEI-AuAg NCs)exhibits excellent photocatalytic activity with an H_(2)O_(2) production capability of 82μM in pure water,which is 3.5 times higher than pristine C_(3)N_(4)(23μM).This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H_(2)O_(2) production.展开更多
Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide （y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40） photocatalysts were fabricated using the dodecylamine-assisted alcohol...Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide （y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40） photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-δS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m^2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi^5＋, Bi^3＋, V^5＋, V^3＋, Fe^3＋, and Fe^2＋ species in y wt.% FeOx/BiVO4-δS0.08. The 1.40 wt.% FeOx/BiVO4-δS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower baudgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-δS0.08.展开更多
Titanium dioxide(TiO2)has garnered attention for its promising photocatalytic activity,energy storage capability,low cost,high chemical stability,and nontoxicity.However,conventional TiO2 has low energy harvesting eff...Titanium dioxide(TiO2)has garnered attention for its promising photocatalytic activity,energy storage capability,low cost,high chemical stability,and nontoxicity.However,conventional TiO2 has low energy harvesting efficiency and charge separation ability,though the recently developed black TiO2 formed under high temperature or pressure has achieved elevated performance.The phase-selectively ordered/disordered blue TiO2(BTO),which has visible-light absorption and efficient exciton disassociation,can be formed under normal pressure and temperature(NPT)conditions.This perspective article first discusses TiO2 materials development milestones and insights of the BTO structure and construction mechanism.Then,current applications of BTO and potential extensions are summarized and suggested,respectively,including hydrogen(H2)production,carbon dioxide(CO2)and nitrogen(N2)reduction,pollutant degradation,microbial disinfection,and energy storage.Last,future research prospects are proposed for BTO to advance energy and environmental sustainability by exploiting different strategies and aspects.The unique NPT-synthesized BTO can offer more societally beneficial applications if its potential is fully explored by the research community.展开更多
In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles（NPs） were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the...In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles（NPs） were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the geothermal water served as the chlorine source. Then the photocatalytic activity was investigated by degradation of 4-Aminobenzoic acid（4-ABA） under visible-light irradiation. It was found that the as-prepared 50 wt% Ag/Ag Cl/WO3 photocatalyst showed the highest photocatalytic efficiency with 25.12 and 3.53 times higher than those of pure WO3 and Ag/Ag Cl, respectively. The active species trapping experiments indicated that h＋and ·O2-were key factors in 4-ABA photodegradation process. The possible plasmonic Z-scheme photocatalytic mechanism of photocatalytic reaction for 4-ABA degradation was proposed based on systematical characterizations. We hope this paper could give new ideas for further exploiting geothermal energy to design and fabricate highly efficient visible-light-driven photocatalysts for environmental remediation.展开更多
Porous hollow microspheres of bismuth vanadate(BiVO_4) were successfully synthesized with the assistances of ethylenediamine tetraacetic(EDTA) and sodium dodecylbenzene sulfonate(SDBS) via hydrothermal method.The as-p...Porous hollow microspheres of bismuth vanadate(BiVO_4) were successfully synthesized with the assistances of ethylenediamine tetraacetic(EDTA) and sodium dodecylbenzene sulfonate(SDBS) via hydrothermal method.The as-prepared BiVO_4 samples were characterized by X-ray diffraction(XRD),field-emission scanning electron microscopy(FE-SEM) and UV-vis diffuse reflectance spectra(DRS).It was found that the ratio of EDTA and SDBS had a significant impact on the crystalline structure,size and morphology of BiVO_4 photocatalyst.The crystal phase could be adjusted by changing the mass ratio of EDTA and SDBS.The photocatalytic activities of different BiVO_4 samples were investigated through the degradation of RhB in the presence of H_2O_2 under visible light irradiation.The results indicated that the photocatalytic performance of the BiVO_4 microstructures was greatly influenced by the porous structure,morphology and band gap.The BiVO_4 sample prepared with the EDTA and SDBS ratio of 2:1 and total amount of 1.5 g have shown superior photocatalytic performance for its unique morphology,good porous structure and low band gap energy.展开更多
Series Bi3NbO7/Bi2Zn（2/3）Nb（4/3）O7 （BN/BZN） composites were synthesized through a facile solid state reaction method. The products were characterized by X-ray diffraction（XRD）, field emission scanning electron...Series Bi3NbO7/Bi2Zn（2/3）Nb（4/3）O7 （BN/BZN） composites were synthesized through a facile solid state reaction method. The products were characterized by X-ray diffraction（XRD）, field emission scanning electron microscopy（FE-SEM） and UV-vis diffuse reflectance spectroscopy（DRS）. When BN： BZN=0.1 mole ratio, the BN/BZN composite showed the best visible-light-driven photocatalytic performance, which decomposed nearly 100% of Rh B（10 ppm, p H=3-4） within 40 min. The results demonstrated that in-situ solid state synthesis of BN/BZN composites could be an efficient strategy to develop new photocatalyst for environmental remediation.展开更多
The rational design of Z-scheme heterojunction photosystems based on covalent organic frameworks(COFs)is a promising strategy for harnessing solar energy for hydrogen conversion.Herein,a direct Z-scheme single-atom ph...The rational design of Z-scheme heterojunction photosystems based on covalent organic frameworks(COFs)is a promising strategy for harnessing solar energy for hydrogen conversion.Herein,a direct Z-scheme single-atom photocatalyst based on COF and metal-organic ring has been constructed through the supramolecular interactions of coral-like COF(S-COF)and photosensitized Pd2L2 type metal-organic ring(MAC-FA1).The MAC-FA1/S-COF heterojunction exhibits good light absorption,efficient charge separation and transfer,slow electron-hole recombination,and highly dispersed Pd active sites,enabling an efficient and stable H_(2) evolution reaction.The optimized 4%MAC-FA1/S-COF achieves an H_(2) evolution rate of 100 mmol g^(−1)h^(−1)within 5 h and obtains a total accumulated turn-over number relative to Pd(TON_(Pd))of 437,685 within 20 h,far superior to S-COF,MAC-FA1,M-5/S-COF,Pd/S-COF,and M-5/Pd/S-COF,which is one of the highest records among COF-based photocatalysts for solar-driven H_(2)evolution.This is the first work to incorporate photosensitized metal-organic rings/cages into porous crystalline COFs to form a supramolecular Z-scheme heterojunction,which has significant potential as a high-performance photocatalyst for solar-driven H_(2)production.展开更多
Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application.In this study,a novel ternary mag...Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application.In this study,a novel ternary magnetic photocatalyst BiVO_(4)/Fe_(3)O_(4)/reduced graphene oxide(BiVO_(4)/Fe_(3)O_(4)/rGO)was synthesized via a facile hydrothermal strategy.The BiVO_(4)/Fe_(3)O_(4) with 0.5 wt%of rGO(BiVO_(4)/Fe_(3)O_(4)/0.5%rGO)exhibited superior activity,degrading greater than 99%Rhodamine B(RhB)after 120 min solar light radiation.The surface morphology and chemical composition of BiVO_(4)/Fe_(3)O_(4)/rGO were studied by scanning electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,UV–visible diffuse reflectance spectroscopy,Fourier transform infrared spectroscopy,and Raman spectroscopy.The free radicals scavenging experiments demonstrated that hole(h^(+))and superoxide radical(O_(2)•^(−))were the dominant species for RhB degradation over BiVO_(4)/Fe_(3)O_(4)/rGO under solar light.The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field.The BiVO_(4)/Fe_(3)O_(4)/rGO composite was easily separated,and the recycled catalyst retained high photocatalytic activity.This study demonstrates that catalyst BiVO_(4)/Fe_(3)O_(4)/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use.The current study provides a possibility for more practical and sustainable photocatalytic process.展开更多
Chlorination has been intensively investigated for use in water disinfection and pollutant elimination due to its efficacy and convenience;however,the generation and transportation of chlorine and hypochlorite are ene...Chlorination has been intensively investigated for use in water disinfection and pollutant elimination due to its efficacy and convenience;however,the generation and transportation of chlorine and hypochlorite are energy-consuming and complicated.In this study,a novel binary photosensitizer consisting of anthraquinone-2-sulfonate(AQ2S)and graphene was synthesized via a p-p stack adsorption method;this compound could allow for the chlorination of organic pollutants using on-site chlorine generation.In this photosensitive degradation process,sulfapyridine(SPY)was selected as a model pollutant and was decomposed by the reactive species(Cl2-,Cland O2-)generated during the photosensitive oxidation of chloride.The synthesized AQ2S/graphene exhibited superior activity,and the degradation rate of SPY was over 90%after 12 h of visible light irradiation with a kinetic constant of 0.2034h1.Results show that 20 mg AQ2S/GR at a 21%weight percentage of AQ2S in a pH 7 SPY solution with 1 mol/L Clachieved the highest kinetics rate at 0.353 h1.Free radical trapping experiments demonstrated that Cl2-and O2-were the dominant species involved in SPY decomposition under solar light.The reusability and stability of this composite were verified by conducting a cycle experiment over five successive runs.The capacity of photodegradation still remained over 90%after these 5 runs.The current study provides an energyefficient and simple-operational approach for water phase SPY control.展开更多
Developing efficient catalysts and photosensitizers is crucial for the construction of effective photocatalytic H2-evolving systems.Here,we report the facile preparation of Coumarin-modified Ir(III)complexes(PS-2 and ...Developing efficient catalysts and photosensitizers is crucial for the construction of effective photocatalytic H2-evolving systems.Here,we report the facile preparation of Coumarin-modified Ir(III)complexes(PS-2 and PS-3)and their utilization as chromophores to drive favorable photocatalytic H2 evolution using Ni-substituted polyoxometalate(Ni_(3)PW_(10))catalyst and triethanolamine(TEOA)as an electron donor.Compared with the commercially available unmodified Ir(III)complex(PS-1),both PS-2 and PS-3 displayed intensive absorption in the range of 400–550 nm with ε_(max) of 110,620 and 91,430 M^(−1) cm6(−1),respectively.Varying the substitutes on the bipyridine ligand affected their physicochemical properties and the corresponding photocatalytic activity dramatically.Under photocatalytic conditions,the quantity of H2 molecules generated by PS-2-and PS-3-containing systems were 13.1 and 2.1 times,respectively,that of the PS-1-containing system.When PS-2 was used as a photosensitizer,the highest turnover number(TON)of 19,739 was obtained versus Ni_(3)PW_(10) catalyst.Various spectroscopic and computational studies have revealed that factors such as strong and broad visible-light-absorbing ability,long-lived triplet state,suitable redox potential,opposed by using polyoxometalate(POM)catalyst,and large highest occupied molecular orbital(HOMO)–lowest unoccupied molecular orbital(LUMO)gap of PS-2 attributed to drastically enhanced photocatalytic activity.展开更多
基金funded by the National Natural Science Foundation of China(22271063 and 22371054)the Foundation of Basic and Applied Basic Research of Guangdong Province(2024A1515010423)+1 种基金Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Z032)Science and Technology Planning Project of Guangdong Province(2021A0505030066).
文摘Oxygen evolution reaction(OER),a critical half-reaction in photocatalytic overall water splitting for producing hydrogen,is a key step toward sustainable energy conversion.Conventional photocatalysts often suffer from limited light absorption and rapid charge recombination,hindering their further applications.To address these challenges,we have designed and synthesized a novel series of self-sensitized metal-organic frameworks(MOFs),Fe_(2)MCDDB(M=Ni,Mn,or Co).By incorporating photosensitive ligands,we have achieved efficient charge separation and promoted the transfer of photogenerated electrons to the active metal sites for water oxidation.Among the series,Fe_(2)NiCDDB exhibits exceptional OER activity,achieving an oxygen evolution rate of 125.3μmol g^(−1)h^(−1)under visible light irradiation.Experimental and theoretical results reveal that the optimized electronic structure and prolonged excited-state lifetime of Fe_(2)NiCDDB contribute to its enhanced catalytic performance.This work provides a promising strategy for designing two-in-one MOF photocatalysts for water oxidation.
基金financially supported by Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)National Key R&D Program International Cooperation Project(No.2021YFE0106500)+3 种基金Natural Science Foundation of China(No.52170085)Fundamental Research Funds for the Central UniversitiesNankai UniversityNational Research Foundation IRGChina/South Africa Research Cooperation Programme(No.132793)。
文摘A novel Fe-doping three-dimensional fiower-like Bi_(7)O_(9)I_(3) microspheres with plasmonic Bi and rich surface oxygen vacancies(Fe-Bi/Bi_(7)O_(9)I_(3)/OVs)was prepared as catalysts,and further coupled with natural air diffusion electrode(NADE)to construct the heterogeneous visible-light-driven photoelectro-Fenton(HEVL-PEF)process to enhance the degradation and mineralization of tetracycline(TC).Interfacial≡Fe sites,OVs and Bi metal were simultaneously constructed via Fe doping,which effectively improved visible light absorption and the separation efficiency of photogenerated carriers to further accelerate the transformation of Fe(Ⅲ)to Fe(Ⅱ),achieving Fenton reaction recycling.HE-VL-PEF process could achieve enhanced treatment of pollutants,thanks to the synergistic effect of electro-Fenton(EF)and photo-Fenton(PF).NADE exhibited excellent H_(2)O_(2) electrosynthesis without external oxygen-pumping equipment.Under the irradiation of visible light,Fe-Bi/Bi_(7)O_(9)I_(3)/OVs could achieve more photoelectrons to accelerate the transformation of Fe(Ⅲ)to Fe(Ⅱ)or directly activate H2O2.DFT calculations also clearly demonstrated that except for the fast charge separation and transfer,Fe-Bi/Bi_(7)O_(9)I_(3)/OVs could achieve a faster electron transport between Fe-O,facilitating Fe site acquire more electron.Consequently,the Fe-Bi/Bi_(7)O_(9)I_(3)/OVs in HE-VL-PEF process presented performance superiorities including excellent pollutant removal(91.91%),low electric energy consumption of 66.34 k Wh/kg total organic carbon(TOC),excellent reusability and wide p H adaptability(3–9).
文摘Storing solar energy in battery systems is crucial to achieving a green and sustainable society.However,the efficient development of photo-enhanced zinc-air batteries(ZABs)is limited by the rapid recombination of photogenerated carriers on the photocathode.In this work,the visible-light-driven CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst with unique petal-like layer structure was designed and developed,which can be used as air electrode for visible-light-driven ZABs.The superior performance of ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)was mainly attributed to the successful construction of Schottky heterojunction between g-C_(3)N_(4)and carbon nanotubes(CNTs),which accelerates the transfer of electrons from g-C_(3)N_(4)to CoS_(2)/CuS cocatalysts,improves the carrier separation ability,and extends the carrier lifetime.Thereinto,the visible-driven ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst has a power density of 588.90 mW cm^(-2) and a charge-discharge cycle of 643 h under visible light irradiation,which is the highest performance ever reported for photo-enhanced ZABs.More importantly,the charge-discharge voltage drop of ZABs was only 0.54 V under visible light irradiation,which is significantly lower than the voltage drop(0.94 V)in the dark.This study provides a new idea for designing efficient and stable visible-light-driven ZABs cathode catalysts.
基金supported by the National Natural Science Foundation of China (No. 20973017, 21077007)the Creative Research Foundation of Beijing University of Technology (No. 00500054R4003, 005000543111501)+2 种基金the HiTech Research and Development Program (863)of China (No. 2009AA063201)the Funding Projectfor Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (No. PHR200907105, PHR201007105,PHR201107104)the Hong Kong Baptist University (FRG2/09-10/023)
文摘Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniques. The photocatalytic activities of the BiVO4 materials were evaluated for the degradation of Methyl Orange under visible-light irradiation. It is observed that pH value and surfactant exerted a great effect on the morphology and pore structure of the BiVO4 product. Spherical BiVO4 with porous structures, flower-cluster-like BiVO4, and flower-bundle-like BiVO4 were generated hydrothermally at 100°C with poly（vinyl pyrrolidone） （PVP） and urea （pH = 2） and at 160°C with NaHCO3 （pH = 7 and 8）, respectively. The PVP-derived BiVO4 showed much higher surface areas （5.0-8.4 m2/g） and narrower bandgap energies （2.45-2.49 eV）. The best photocatalytic performance of the spherical BiVO4 material with a surface area of 8.4 m2/g was associated with its higher surface area, narrower bandgap energy, higher surface oxygen vacancy density, and unique porous architecture.
基金supported by the National Natural Science Foundation of China (No.22071211)the Science and Technology Planning Project of Hunan Province (No.2019RS2039)+1 种基金Hunan Provincial Natural Science Foundation of China (No.2020JJ3032)the Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization。
文摘Visible-light-driven photochemical Cadogan-type cyclization has been discovered.The organic D-A type photosensitizer 4 CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermediate that breaks the barriers of deoxygenation in Cadogan reaction and enables a mild metalfree access to carbazoles and related heterocycles.DFT calculation results indicate mildly endergonic formation of the intermediate complex of nitrobiarenes and PPh3,which corresponds with experimental findings regarding reaction temperature.The robust synthetic capacity of the photoredox Cadogan reaction systems has been demonstrated by the viable productivity of a broad range of carbazoles and related N-heterocycles with good tolerance of various functionalities.
基金supported by the National Natural Science Foundation of China(grant nos.22071146 and 21931005)the Shanghai Science and Technology Committee(grant no.23XD1421800)+1 种基金the Shanghai Shuguang Program(grant no.21SG12)the Shanghai Municipal Science and Technology Major Project.
文摘The mass production of urea,the most widely used agricultural fertilizer,usually relies on energy-and carbon-intensive processes.The light-driven synthesis path has great potential for more sustainable techniques to produce urea from abundant naturally occurring resources,but this method suffers fromthe use of pure CO_(2)and high-energy-driven forces(high temperature or ultraviolet light).Herein,we present a mild photocatalytic pathway for urea production from diverse nitrogenous species(such as NO3-,NH3,and N2)and diluted CO_(2)using visible light.We designed a palladium(Pd)-doped Schottky heterojunction,composed of graphene and titanium dioxide,as an effective photocatalyst to achieve on-farm urea generation.With the injection of visible-lightgenerated hot electrons from graphene to TiO_(2),the as-integrated Pd(I)centers with a special oxidation state of+1.36 in the TiO_(2)lattice can initiate the universal reaction path of cascade reduction of NO3-/N2 to NH3 and resulting C-N coupling of CO_(2)with as-formed or added NH3 to transform diverse nitrogenous species and CO_(2)into urea.The urea yield over the at.-Pd@TiO_(2)/Gr photocatalyst is 1.62 mmol g-1 h-1 under visible-light irradiation with an apparent quantum yield of 1.05%at 400 nm and 0.39%even at 700 nm.
基金supported by the National Natural Science Foundation of China (Nos.52072152 and 51802126)Jiangsu University Jinshan Professor Fund,Jiangsu Specially-Appointed Professor Fund,the Open Fund from Guangxi Key Laboratory of Electrochemical Energy Materials,Zhenjiang“Jinshan Talents”Project 2021,China PostDoctoral Science Foundation (No.2022M721372)+1 种基金the“Doctor of Entrepreneurship and Innovation”in Jiangsu Province (No.JSSCBS20221197)the Postgraduate Research&Practice Innovation Program of Jiangsu Province (No.KYCX22_3645).
文摘In the quest for effective solutions to address Environ.Pollut.and meet the escalating energy demands,heterojunction photocatalysts have emerged as a captivating and versatile technology.These photocatalysts have garnered significant interest due to their wideranging applications,including wastewater treatment,air purification,CO_(2) capture,and hydrogen generation via water splitting.This technique harnesses the power of semiconductors,which are activated under light illumination,providing the necessary energy for catalytic reactions.With visible light constituting a substantial portion(46%)of the solar spectrum,the development of visible-light-driven semiconductors has become imperative.Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light.In this comprehensive review,we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media,as well as the remarkable progress made in renewable energy production.Moreover,we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems.Finally,we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain.By unraveling the potential of heterojunction photocatalysts,this reviewcontributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.
文摘Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.
基金the financial support provided by the Beijing Natural Science Foundation(2202044)the National Postdoctoral Program for Innovative Talents(BX20190370).
文摘A novel Ag/g-C_(3)N_(4)/kaolinite composite photocatalyst was fabricated for the first time through a two-step assembly strategy by employing in situ calcination and a photodeposition process.The synthesized Ag/g-C_(3)N_(4)/kaolinite composite reached a higher degradation rate of ibuprofen(IBP)with a reaction rate constant of 0.0113 min^(-1) at an Ag content of 7% under visible-light irradiation,which was approximately 1.87 times that of the Ag/g-C_(3)N_(4) composite.Based on the physicochemical properties,the enhanced photocatalytic activity was attributed to the stronger adsorption property,wider photoresponse range and more efficient separation and transfer of electron-hole pairs.Furthermore,the incorporation of monodispersed Ag nanoparticles onto the g-C_(3)N_(4)/kaolinite sheets provided more reactive sites for the IBP degradation.In addition,according to the EPR study and trapping experiments,it was demonstrated that holes(h^(+))should be the key reactive species.A possible pathway of IBP degradation was also proposed based on the detected intermediates.Overall,the results of this work may facilitate the design of a novel visible-light-driven photocatalyst with a high efficiency that is derived from a natural mineral for environmental remediation.
基金National Natural Science Foundation of China(21908121,22071127)Taishan Scholar Foundation(tsqn201812074,China)Scientific Research Foundation of Qingdao University of Science and Technology(210/010029031,and 210/010029008).
文摘Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H_(2)O_(2) generation performance.Herein,we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters(AuAg NCs)to polyethyleneimine(PEI)modified C_(3)N_(4)(C3N4-PEI).The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C_(3)N_(4)-PEI,thereby ultimately producing abundant e−for O_(2) reduction under visible light illumination(λ≥400 nm).As a result,the as-designed photocatalyst(C3N4-PEI-AuAg NCs)exhibits excellent photocatalytic activity with an H_(2)O_(2) production capability of 82μM in pure water,which is 3.5 times higher than pristine C_(3)N_(4)(23μM).This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H_(2)O_(2) production.
基金supported by the National Natural Science Foundation of China(No.21077007)the Natural Science Foundation of Beijing Municipality(No.2102008)+3 种基金the Discipline and Postgraduate Education Foundation(No.PXM2013 014204 07 000261,005000542513551)the Creative Research Foundation of Beijing University of Technology(No.00500054R4003,005000543111501)the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality(No.PHR201007105,PHR201107104)the Hong Kong Baptist University for financial support(No.FRG2/09-10/023)
文摘Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide （y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40） photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-δS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m^2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi^5＋, Bi^3＋, V^5＋, V^3＋, Fe^3＋, and Fe^2＋ species in y wt.% FeOx/BiVO4-δS0.08. The 1.40 wt.% FeOx/BiVO4-δS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower baudgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-δS0.08.
基金This work was supported by the Institute for Basic Science(IBS-R011-D1)partially supported by the Korea Evaluation Institute of Industrial Technology(20004627)the INNOPOLIS Foundation(2019-DD-SB-0602).
文摘Titanium dioxide(TiO2)has garnered attention for its promising photocatalytic activity,energy storage capability,low cost,high chemical stability,and nontoxicity.However,conventional TiO2 has low energy harvesting efficiency and charge separation ability,though the recently developed black TiO2 formed under high temperature or pressure has achieved elevated performance.The phase-selectively ordered/disordered blue TiO2(BTO),which has visible-light absorption and efficient exciton disassociation,can be formed under normal pressure and temperature(NPT)conditions.This perspective article first discusses TiO2 materials development milestones and insights of the BTO structure and construction mechanism.Then,current applications of BTO and potential extensions are summarized and suggested,respectively,including hydrogen(H2)production,carbon dioxide(CO2)and nitrogen(N2)reduction,pollutant degradation,microbial disinfection,and energy storage.Last,future research prospects are proposed for BTO to advance energy and environmental sustainability by exploiting different strategies and aspects.The unique NPT-synthesized BTO can offer more societally beneficial applications if its potential is fully explored by the research community.
基金the financial support by the National Natural Science Foundation of China (grant no. 51272107 and 51372118)the Doctor Discipline Special Research Foundation of Chinese Ministry of Education (grant no. 20133219110015)
文摘In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles（NPs） were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the geothermal water served as the chlorine source. Then the photocatalytic activity was investigated by degradation of 4-Aminobenzoic acid（4-ABA） under visible-light irradiation. It was found that the as-prepared 50 wt% Ag/Ag Cl/WO3 photocatalyst showed the highest photocatalytic efficiency with 25.12 and 3.53 times higher than those of pure WO3 and Ag/Ag Cl, respectively. The active species trapping experiments indicated that h＋and ·O2-were key factors in 4-ABA photodegradation process. The possible plasmonic Z-scheme photocatalytic mechanism of photocatalytic reaction for 4-ABA degradation was proposed based on systematical characterizations. We hope this paper could give new ideas for further exploiting geothermal energy to design and fabricate highly efficient visible-light-driven photocatalysts for environmental remediation.
基金National Natural Science Foundations of China(Nos.51178093,51208086)Central University Project,China(No.2232013D3-10)
文摘Porous hollow microspheres of bismuth vanadate(BiVO_4) were successfully synthesized with the assistances of ethylenediamine tetraacetic(EDTA) and sodium dodecylbenzene sulfonate(SDBS) via hydrothermal method.The as-prepared BiVO_4 samples were characterized by X-ray diffraction(XRD),field-emission scanning electron microscopy(FE-SEM) and UV-vis diffuse reflectance spectra(DRS).It was found that the ratio of EDTA and SDBS had a significant impact on the crystalline structure,size and morphology of BiVO_4 photocatalyst.The crystal phase could be adjusted by changing the mass ratio of EDTA and SDBS.The photocatalytic activities of different BiVO_4 samples were investigated through the degradation of RhB in the presence of H_2O_2 under visible light irradiation.The results indicated that the photocatalytic performance of the BiVO_4 microstructures was greatly influenced by the porous structure,morphology and band gap.The BiVO_4 sample prepared with the EDTA and SDBS ratio of 2:1 and total amount of 1.5 g have shown superior photocatalytic performance for its unique morphology,good porous structure and low band gap energy.
基金Funded by the National Natural Science Foundation of China(No.51662005)the Guangxi Natural Science Foundation(No.2014GXNSFFA118004)
文摘Series Bi3NbO7/Bi2Zn（2/3）Nb（4/3）O7 （BN/BZN） composites were synthesized through a facile solid state reaction method. The products were characterized by X-ray diffraction（XRD）, field emission scanning electron microscopy（FE-SEM） and UV-vis diffuse reflectance spectroscopy（DRS）. When BN： BZN=0.1 mole ratio, the BN/BZN composite showed the best visible-light-driven photocatalytic performance, which decomposed nearly 100% of Rh B（10 ppm, p H=3-4） within 40 min. The results demonstrated that in-situ solid state synthesis of BN/BZN composites could be an efficient strategy to develop new photocatalyst for environmental remediation.
基金National Natural Science Foundation Project of China,Grant/Award Numbers:21975291,22171211NSF of Guangdong Province,Grant/Award Numbers:2022A1515011949,2020A1515110474。
文摘The rational design of Z-scheme heterojunction photosystems based on covalent organic frameworks(COFs)is a promising strategy for harnessing solar energy for hydrogen conversion.Herein,a direct Z-scheme single-atom photocatalyst based on COF and metal-organic ring has been constructed through the supramolecular interactions of coral-like COF(S-COF)and photosensitized Pd2L2 type metal-organic ring(MAC-FA1).The MAC-FA1/S-COF heterojunction exhibits good light absorption,efficient charge separation and transfer,slow electron-hole recombination,and highly dispersed Pd active sites,enabling an efficient and stable H_(2) evolution reaction.The optimized 4%MAC-FA1/S-COF achieves an H_(2) evolution rate of 100 mmol g^(−1)h^(−1)within 5 h and obtains a total accumulated turn-over number relative to Pd(TON_(Pd))of 437,685 within 20 h,far superior to S-COF,MAC-FA1,M-5/S-COF,Pd/S-COF,and M-5/Pd/S-COF,which is one of the highest records among COF-based photocatalysts for solar-driven H_(2)evolution.This is the first work to incorporate photosensitized metal-organic rings/cages into porous crystalline COFs to form a supramolecular Z-scheme heterojunction,which has significant potential as a high-performance photocatalyst for solar-driven H_(2)production.
基金supported by the National Nature Science Foundation of China(Grant No.51778175)the State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2021 TS03)_。
文摘Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application.In this study,a novel ternary magnetic photocatalyst BiVO_(4)/Fe_(3)O_(4)/reduced graphene oxide(BiVO_(4)/Fe_(3)O_(4)/rGO)was synthesized via a facile hydrothermal strategy.The BiVO_(4)/Fe_(3)O_(4) with 0.5 wt%of rGO(BiVO_(4)/Fe_(3)O_(4)/0.5%rGO)exhibited superior activity,degrading greater than 99%Rhodamine B(RhB)after 120 min solar light radiation.The surface morphology and chemical composition of BiVO_(4)/Fe_(3)O_(4)/rGO were studied by scanning electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,UV–visible diffuse reflectance spectroscopy,Fourier transform infrared spectroscopy,and Raman spectroscopy.The free radicals scavenging experiments demonstrated that hole(h^(+))and superoxide radical(O_(2)•^(−))were the dominant species for RhB degradation over BiVO_(4)/Fe_(3)O_(4)/rGO under solar light.The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field.The BiVO_(4)/Fe_(3)O_(4)/rGO composite was easily separated,and the recycled catalyst retained high photocatalytic activity.This study demonstrates that catalyst BiVO_(4)/Fe_(3)O_(4)/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use.The current study provides a possibility for more practical and sustainable photocatalytic process.
基金This work was supported by the National Key Research and Development Program of China(2019YFD1100204)the National Nature Science Foundation of China(No.51778175)the Research and Application of Treatment Technology for High Concentration and Refractory Wastewater(Printing and Dyeing,Pharmaceutical,Chemical)GJSZ2021030907-YF.We gratefully acknowledge supports from Heilongjiang Province touyan team.
文摘Chlorination has been intensively investigated for use in water disinfection and pollutant elimination due to its efficacy and convenience;however,the generation and transportation of chlorine and hypochlorite are energy-consuming and complicated.In this study,a novel binary photosensitizer consisting of anthraquinone-2-sulfonate(AQ2S)and graphene was synthesized via a p-p stack adsorption method;this compound could allow for the chlorination of organic pollutants using on-site chlorine generation.In this photosensitive degradation process,sulfapyridine(SPY)was selected as a model pollutant and was decomposed by the reactive species(Cl2-,Cland O2-)generated during the photosensitive oxidation of chloride.The synthesized AQ2S/graphene exhibited superior activity,and the degradation rate of SPY was over 90%after 12 h of visible light irradiation with a kinetic constant of 0.2034h1.Results show that 20 mg AQ2S/GR at a 21%weight percentage of AQ2S in a pH 7 SPY solution with 1 mol/L Clachieved the highest kinetics rate at 0.353 h1.Free radical trapping experiments demonstrated that Cl2-and O2-were the dominant species involved in SPY decomposition under solar light.The reusability and stability of this composite were verified by conducting a cycle experiment over five successive runs.The capacity of photodegradation still remained over 90%after these 5 runs.The current study provides an energyefficient and simple-operational approach for water phase SPY control.
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China(nos.21871025 and 21831001)the Recruitment Program of Global Experts(Young Talents),and the BIT Teli Young Fellow Program.
文摘Developing efficient catalysts and photosensitizers is crucial for the construction of effective photocatalytic H2-evolving systems.Here,we report the facile preparation of Coumarin-modified Ir(III)complexes(PS-2 and PS-3)and their utilization as chromophores to drive favorable photocatalytic H2 evolution using Ni-substituted polyoxometalate(Ni_(3)PW_(10))catalyst and triethanolamine(TEOA)as an electron donor.Compared with the commercially available unmodified Ir(III)complex(PS-1),both PS-2 and PS-3 displayed intensive absorption in the range of 400–550 nm with ε_(max) of 110,620 and 91,430 M^(−1) cm6(−1),respectively.Varying the substitutes on the bipyridine ligand affected their physicochemical properties and the corresponding photocatalytic activity dramatically.Under photocatalytic conditions,the quantity of H2 molecules generated by PS-2-and PS-3-containing systems were 13.1 and 2.1 times,respectively,that of the PS-1-containing system.When PS-2 was used as a photosensitizer,the highest turnover number(TON)of 19,739 was obtained versus Ni_(3)PW_(10) catalyst.Various spectroscopic and computational studies have revealed that factors such as strong and broad visible-light-absorbing ability,long-lived triplet state,suitable redox potential,opposed by using polyoxometalate(POM)catalyst,and large highest occupied molecular orbital(HOMO)–lowest unoccupied molecular orbital(LUMO)gap of PS-2 attributed to drastically enhanced photocatalytic activity.
