过氧化氢(H_(2)O_(2))是一种重要的化工产品,广泛应用于污水处理、消毒杀菌和印染漂白等领域.在蒽醌法生产H_(2)O_(2)的过程中,易产生有毒气体并存在爆炸危险.因此,仅利用水、氧气和太阳光即可在合适的光催化剂上生成H_(2)O_(2)的光催...过氧化氢(H_(2)O_(2))是一种重要的化工产品,广泛应用于污水处理、消毒杀菌和印染漂白等领域.在蒽醌法生产H_(2)O_(2)的过程中,易产生有毒气体并存在爆炸危险.因此,仅利用水、氧气和太阳光即可在合适的光催化剂上生成H_(2)O_(2)的光催化技术备受关注.本课题组报道了通过酸碱自组装法制备的四(4-羧基苯基)卟啉(SA-TCPP)光催化剂,用于生产H_(2)O_(2).该催化剂克服了大部分H_(2)O_(2)光催化剂存在的需要牺牲剂、活性低和光利用率不足等问题,但其性能仍受限于较高的复合率.晶面调控已被证实是改善许多无机催化剂电荷复合的有效策略,然而,对于有机光催化剂,关于暴露晶面与其活性关系的研究仍然较少.本文采用溶解-重结晶法在水和三种有机溶剂的混合物中成功合成了三种具有不同暴露晶面的卟啉光催化剂.即利用卟啉在有机溶剂和水中的溶解度差异,将卟啉先溶解在四氢呋喃(THF)、甲醇(MeOH)或乙二醇(EG)溶液中,随后在水溶液中重新结晶.X射线衍射、高分辨率透射电子显微镜及晶面模拟模型图的结果表明,三种催化剂具有相同的晶体结构,但分别暴露了(400)、(022)和(020)晶面.通过紫外分光光度计测量这些催化剂在氙灯(λ≥420 nm)照射下的光催化活性,结果表明,具有(400)暴露面的卟啉光催化剂的H_(2)O_(2)生产速率最高,可达29.33 mmol L h^(-1)g^(-1),分别是具有(022)暴露面和(020)暴露面的卟啉光催化剂的2.7倍和4.1倍,约是已报道的SA-TCPP光催化剂的1.3倍.通过紫外漫反射、莫特肖特基曲线分析以及LED灯照射下的光催化活性测试,排除了光吸收能力对这三种卟啉光催化剂活性的影响.开尔文探针力显微镜、光生电流密度谱图、晶面模拟模型图和密度泛函理论计算结果表明,活性的差异主要归因于(400)表面暴露的高羧基含量所引发的强内建电场,并且在该暴露面上的内建电场方向有利于空穴从吡咯氮向羧基碳的跃迁,因此阻碍了电荷的快速重组,促进了富有挑战性的水氧化过程,而(020)面由于暴露了最多的吡咯氮和最少的羧基碳,其产生的内建电场强度最弱,且内建电场方向阻碍了空穴向羧基碳的跃迁,因此H_(2)O_(2)生产速率最低.综上所述,本工作通过晶面调控产生强内建电场以加速空穴的迁移,降低了电子空穴复合速率,实现了高H_(2)O_(2)生产速率,为更高效的有机光催化剂的设计和开发提供了新思路.展开更多
Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uni...Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.展开更多
Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high...Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.展开更多
Recently,defect architectured photocatalysis is proved to be the most versatile choice for high solar to chemical energy conversion processes.Defect engineering strategies are of great demand to effectively tune the e...Recently,defect architectured photocatalysis is proved to be the most versatile choice for high solar to chemical energy conversion processes.Defect engineering strategies are of great demand to effectively tune the electronic microstructure and surface morphologies of semiconductors to boost charge carrier concentration and extend light harvesting capability.This review provides a comprehensive insight to various kinds of defects along with their synthesis procedures and controlling mechanism to uplift photocatalytic activity.In addition,the contribution made by defects and material optimization techniques toward electronic band structure of the photocatalyst,the optimal concentration of defects,the key adsorption processes,charge distribution,and transfer dynamics have been explained in detail.Further,to clarify the relationship between photocatalytic activity and defect states in real,a comprehensive outlook to the versatile photocatalytic applications has been presented to highlight current challenges and future applications.Defect engineering therefore stands as the next step toward advancement in the design and configuration of modern photocatalysts for high efficiency photocatalysis.展开更多
Surface hybrid inorganic semiconductors photocatalysts withπconjugated structure have recently been widely used in the field of photocatalytic environmental remediation and energy conversion.Surface hybridization is ...Surface hybrid inorganic semiconductors photocatalysts withπconjugated structure have recently been widely used in the field of photocatalytic environmental remediation and energy conversion.Surface hybridization is considered to be an efficient way to significantly enhance the photocatalytic activity by several times,completely inhibit photocorrosion of inorganic photocatalysts and expand the spectral response range of photocatalysts.This review provides a comprehensive overview of the surface hybridization definition,the principle of enhancing photocatalytic performance and the control factors of surface hybridization to promote photoactivity.Summarize the preparation and structural identification method of the surface hybrid photocatalyst.Special emphasis is placed on the various photocatalytic system construction of surface hybridization.The development of surface hybrid photocatalysts for pollutant degradation and energy conversion are further presented.Finally,the challenges and future development prospects of surface hybridization in photocatalysis are discussed.We hope this critical review can provide a clear picture of the state-of-the-art achievements and facilitate the applications of surface hybrid photocatalysts in environmental remediation and energy conversion.展开更多
Photocatalytic water splitting based on semiconductor photocatalysts is a promising approach for producing carbon‐neutral,sustainable,and clean H_(2) fuel.Cocatalyst loading,which is an appealing strategy,has been ex...Photocatalytic water splitting based on semiconductor photocatalysts is a promising approach for producing carbon‐neutral,sustainable,and clean H_(2) fuel.Cocatalyst loading,which is an appealing strategy,has been extensively employed to improve the photocatalytic efficiency semiconductors.In view of the high cost and rare preservation of noble metal cocatalysts that significantly hinder their utilization for large‐scale energy production,various cocatalysts comprising earth‐abundant ele‐ments have been developed as noble‐metal‐free candidates using different methods to boost pho‐tocatalytic water splitting.Among these preparation strategies,photodeposition has attracted tre‐mendous attention in the deposition of earth‐abundant cocatalysts owing to its simplicity and mod‐erate availability,improved interfacial charge separation and transfer,and abundant active sites on the surface.In this review,we first summarize the deposition principles,deposition advantages,categories of cocatalysts,roles of cocatalysts,influencing factors,modification strategies,and design considerations in the photodeposition of earth‐abundant cocatalysts.The photodeposited earth‐abundant cocatalysts for the photocatalytic H_(2) evolution half reaction,photocatalytic O_(2) evo‐lution half reaction,and overall photocatalytic water splitting are discussed.Finally,some perspec‐tives on the challenges and possible future directions for the photodeposition of earth‐abundant cocatalysts in photocatalytic water splitting are presented.展开更多
The active sites of monodisperse transition metal Ni-clusters were anchored on carbon nitride(CN)by an in situ photoreduction deposition method to promote the efficient separation of photogenerated charges and achieve...The active sites of monodisperse transition metal Ni-clusters were anchored on carbon nitride(CN)by an in situ photoreduction deposition method to promote the efficient separation of photogenerated charges and achieve high-efficiency photocatalytic activity for hydrogen evolution.The Ni-cluster/CN exhibited a photocatalytic hydrogen production rate of 16.5 mmol·h^(-1)·g^(-1) and a total turnover frequency(TOF(H_(2)))value of 461.14 h^(-1).X-ray absorption spectroscopy based on synchrotron radiation indicated that CN had two reaction centers to form stable interface interactions with monodispersed Ni-clusters,in which carbon can act as an electron acceptor,while nitrogen can act as an electron donor.Meanwhile,the hybrid electronic structure of the Ni-cluster/CN system was constructed,which was favorable for photocatalytic activity for hydrogen production.An in-depth understanding of the interfacial interaction between CN and Ni-clusters will have important reference significance on the mechanistic study of development based on the cocatalyst.展开更多
The hydrogen abstraction reaction of methanol with fluorine atoms can produce HF and CH_(3)O or CH_(2)OH radicals,which are important in the environment,combustion,radiation,and interstellar chemistry.In this work,the...The hydrogen abstraction reaction of methanol with fluorine atoms can produce HF and CH_(3)O or CH_(2)OH radicals,which are important in the environment,combustion,radiation,and interstellar chemistry.In this work,the dynamics of this typical reaction is investigated by the quasi-classical trajectory method based on a recently developed globally accurate full-dimensional potential energy surface.Particularly,the vibrational state distributions of the polyatomic products CH_(3)O and CH_(2)OH are determined by using the normal mode analysis method.It is found that CH_(3)O and CH_(2)OH are dominantly populated in the ground state when the reactants are at the ground ro-vibrational state.The OH stretching mode,torsional mode,H_(2)CO out-of-plane bending mode and their combination bands in the CH_(2)OH product can be effectively excited once the OH stretching mode of the reactant CH_(3)OH is excited to the first vibrationally excited state.Most of the available energy flows into the HF vibrational energy and the translational energy in both channels,while the radical products,CH_(3)O or CH_(2)OH,receive a small amount of energy,consistent with experiment,which is an indication of its spectator nature.展开更多
The anodic electrooxidation of ethanol to value-added acetate is an excellent example of replacing the oxygen evolution reaction to promote the cathodic hydrogen evolution reaction and save energy.Herein,we present a ...The anodic electrooxidation of ethanol to value-added acetate is an excellent example of replacing the oxygen evolution reaction to promote the cathodic hydrogen evolution reaction and save energy.Herein,we present a colloidal strategy to produce Ni-Fe bimetallic alloy nanoparticles(NPs)as efficient electrocatalysts for the electrooxidation of ethanol in alkaline media.Ni-Fe alloy NPs deliver a current density of 100 mA·cm^(-2) in a 1.0 M KOH solution containing 1.0 M ethanol merely at 1.5 V vs.reversible hydrogen electrode(RHE),well above the performance of other electrocatalysts in a similar system.Within continuous 10 h testing at this external potential,this electrode is able to produce an average of 0.49 mmol·cm^(-2)·h^(-1) of acetate with an ethanol-to-acetate Faradaic efficiency of 80%.A series of spectroscopy techniques are used to probe the electrocatalytic process and analyze the electrolyte.Additionally,density functional theory(DFT)calculations demonstrate that the iron in the alloy NPs significantly enhances the electroconductivity and electron transfer,shifts the rate-limiting step,and lowers the energy barrier during the ethanol-to-acetate reaction pathway.展开更多
Antibiotics are a widely used and effective treatment for bacterial infections.However,bacteria can gradually evolve during infection,leading to developing resistance to antibiotics,which renders previously effective ...Antibiotics are a widely used and effective treatment for bacterial infections.However,bacteria can gradually evolve during infection,leading to developing resistance to antibiotics,which renders previously effective treatments ineffective.Finding a useful and convenient manner to treat bacterial infections is a great challenge.Here,we report a flexible hydrogen-bond-bridged phosphorene film with photodynamic antibacterial properties and excellent mechanical properties,fabricated from electrochemical exfoliation of black phosphorus(BP).When illuminated under 700 nm light,the hydrogen bond-bridged phosphorene flexible film is capable of converting ground-state triplet oxygen(O_(2))into excited-state singlet oxygen(^(1)O_(2)),destroying the structure of the membrane of Staphylococcus aureus,and eventually leading to bacterial death,via breaking the C=C of unsaturated fatty acids within the bacterial cell membrane after the reaction between^(1)O_(2)and unsaturated fatty acids,thus realizing a highly efficient antibacterial approach,which is supported by gas chromatography-mass spectrometry(GC-MS)technique.This work establishes an effective phototherapy platform for treating bacterial traumatic infections.展开更多
Numerous bismuth-based semiconductors(BBSs)with sophisticated and desirable structures used as photocatalysts for efficient photocatalytic degradation of water organic contaminants have attracted considerable attentio...Numerous bismuth-based semiconductors(BBSs)with sophisticated and desirable structures used as photocatalysts for efficient photocatalytic degradation of water organic contaminants have attracted considerable attention.However,regulating the crystal phases and phase transition of BBSs for promoted photocatalytic performance is ignored.Herein,the unique crystal structure and band structure features of each typical BBSs,and the vital roles on phase controlling of each phase were systematically presented based on the classification of BBSs.Notably,the critical factors for the phase transition of BBSs and intrinsic driving forces endowed by phases of BBSs for enhanced photocatalytic performance of organic contaminants removal were also elucidated.This review will provide systematical guidelines and horizons for regulating the crystal phase and phase transition of BBSs,promoting photocatalytic degradation and mineralization of organic contaminants.展开更多
Renewable-energy-driven nitrate(NO_(3)^(−))electroreduction to ammonia(NH_(3))(NERA)has been an attractive technology for decarbonizing NH_(3)production and wastewater treatment.Improving NERA efficiency requires elec...Renewable-energy-driven nitrate(NO_(3)^(−))electroreduction to ammonia(NH_(3))(NERA)has been an attractive technology for decarbonizing NH_(3)production and wastewater treatment.Improving NERA efficiency requires electrocatalysts that are earth-abundant and show fantastic performance.Here we report a semiempirical activity descriptor of eg occupancy(of surface B-site cations)for identifying inexpensive perovskite oxides with extremely high efficacy toward NERA.We establish the descriptor by systematic investigations of more than 10 perovskite oxides.These investigations demonstrate that their intrinsic NERA activities display a volcano-shaped dependence on eg occupancy and the optimized intrinsic activities are accessible at near-1 eg occupancies.This could plausibly be attributed to the favorable overlaps between surface adsorbates and vertically-oriented eg orbitals.More importantly,utilizing this descriptor,we predict a highly active,selective,and durable NERA electrocatalyst with a composition of Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF).Because of its close-to-1 e_(g)occupancy(i.e.~1.2),the BSCF features a superior NH_(3)production rate of 0.12 g·h^(−1)·mg_(cat.)^(−1)(Faradaic efficiency of 97.8%)that is at top of the volcano plot,and substantially outperforms most NERA electrocatalysts reported in literature.展开更多
Herein,a series of three-dimensionally ordered macroporous(3DOM)Bi_(4)O_(5)Br_(2)photocatalysts with different macropore sizes were successfully fabricated via a polymethyl methacrylate(PMMA)template method.The photoc...Herein,a series of three-dimensionally ordered macroporous(3DOM)Bi_(4)O_(5)Br_(2)photocatalysts with different macropore sizes were successfully fabricated via a polymethyl methacrylate(PMMA)template method.The photocatalytic activity for phenol degradation over 3DOM Bi_(4)O_(5)Br_(2)first increased and then decreased with the rise in macropore size.Specifically,3DOM Bi_(4)O_(5)Br_(2)-255(macropore diameter ca.170 nm)exhibits the best photocatalytic activity in the static system,which is about 4.5,7.3,and 11.9 times higher than those of bulk Bi_(4)O_(5)Br_(2),Bi_(2)WO_(6),and g-C_(3)N_(4),respectively.Meanwhile,high phenol conversion(75%)is also obtained over 3DOM Bi_(4)O_(5)Br_(2)-255 in the flow system under full spectrum irradiation.Furthermore,3DOM Bi_(4)O_(5)Br_(2)-255 also shows strong mineralization capacity owing to the downward shift of valance band position(0.15 V)as compared with Bi_(4)O_(5)Br_(2).Total organic carbon(TOC)removal rate over 3DOM Bi_(4)O_(5)Br_(2)-255(62%)is much higher than that of Bi_(4)O_(5)Br_(2)(17%).The enhancement in photocatalytic performance of 3DOM Bi_(4)O_(5)Br_(2)-255 is attributable to its better phenol adsorption,O_(2)activation,and charge separation and transfer abilities.This work combines the advantages of 3D structure and surface dangling bonds,providing new possibilities for designing highly efficient photocatalysts for pollutants removal.展开更多
Microenvironments of the catalytic center,which play a vital role in adjusting electrocatalytic CO_(2) reduction reaction(ECO_(2) RR)activity,have received increasing attention during the past few years.However,contro...Microenvironments of the catalytic center,which play a vital role in adjusting electrocatalytic CO_(2) reduction reaction(ECO_(2) RR)activity,have received increasing attention during the past few years.However,controllable microenvironment construction and the effects of multi-microenvironment variations for improving ECO_(2) RR performance remain unclear.Herein,we summarize the representative strategies for tuning the catalyst and local microenvironments to enhance ECO_(2) RR selectivity and activity.The multifactor synergetic effects of microen-vironment regulation for enhancing CO_(2) accessibility,stabilizing key intermediates,and improving the performance of ECO_(2) RR catalysts are discussed in detail,as well as perspectives on the challenges when investigating ECO_(2) RR microenvironments.We anticipate that the discussions in this review will inspire further research in microenvironment engineering to accelerate the development of the ECO 2 RR for practical application.展开更多
Environmental pollution is a major challenge faced by human beings, and is becoming more serious due to increasing urbanization and industrialization. Catalysis is the key technology for environmental remediation. As...Environmental pollution is a major challenge faced by human beings, and is becoming more serious due to increasing urbanization and industrialization. Catalysis is the key technology for environmental remediation. As a “green” technology, photocatalysis and ambient catalysis could offer numerous opportunities to realize environmental remediation under mild reaction conditions with low energy input. Over the past two decades, great advances have been made on the design and synthesis of the photocatalysts and ambient catalysts, precise control of catalyst active sites, and the mechanistic understanding on the catalytic process for environmental remediation.展开更多
omprehensive Summary Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl s...omprehensive Summary Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes.However,the important reactions have never been realized in aromatic metallacycles.Herein,we present the first carbonylation reactions of metallaaromatics,specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne.During the carbonylation process,the electronic and steric properties of nucleophiles are regarded as critical factors.The alcohols with bulky substituents(isopropanol)require more reaction time and tert-butyl alcohol is inert in the reaction.Comparatively,amines,being stronger nucleophiles,exhibit divergent behaviors.Bulky amines undergo aminocarbonylation,whereas small amines prefer direct nucleophilic additions.Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction.According to these observations,a divergent pathway for the reaction is proposed.Furthermore,the photophysical properties of these carbonyl-functionalized osmapentalene complexes are studied,and the maximum absorption peak of compound with a carboxylic group exhibits a significant red-shift due to the smaller HOMO-LUMO gap.These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl-functionalized metallacycles.展开更多
As a two-dimensional(2D) material, polymeric carbon nitride(g-C_3N_4) nanosheet holds great potentials in environmental purification and solar energy conversion. In this review, we summarized latest progress in the op...As a two-dimensional(2D) material, polymeric carbon nitride(g-C_3N_4) nanosheet holds great potentials in environmental purification and solar energy conversion. In this review, we summarized latest progress in the optimization of photocatalytic performance in 2D g-C_3N_4. Some of the latest structural engineering methods were summed up, where the relevant influences on the behaviors of photoinduced species were emphasized. Furthermore, the construction strategies for band structure modulation and charge separation promotion were then discussed in detail. A brief discussion on the opportunity and challenge of 2D g-C_3N_4-based photocatalysis are presented as the conclusion of this review.展开更多
The hybridization of graphene with Bi_(2)WO_(6)photocatalysts was employed to enhance the photocatalytic activity.The photocatalytic activity enhancements were dependent on the amount of graphene and it was found that...The hybridization of graphene with Bi_(2)WO_(6)photocatalysts was employed to enhance the photocatalytic activity.The photocatalytic activity enhancements were dependent on the amount of graphene and it was found that the optimal hybridized amount of graphene was about 1.5 wt%,which was close to the monolayer dispersing of graphene on Bi_(2)WO_(6)surface.Up to four times of the photocatalytic activity was enhanced by the hybridization of graphene,compared with that of pristine Bi_(2)WO_(6).The enhancement mechanism of the photocatalytic activity was attributed to the higher separation efficiency and the inhibition of recombination of photoinduced electron-hole pairs.The electronic interaction was verified by the photoelectrochemical measurements.展开更多
A self-assembled perylene diimide(SA-PDI)film was prepared on an indium-tin-oxide(ITO)substrate and acted as a photoanode for the photoelectrocatalytic(PEC)degradation of some emerging contaminants under visible light...A self-assembled perylene diimide(SA-PDI)film was prepared on an indium-tin-oxide(ITO)substrate and acted as a photoanode for the photoelectrocatalytic(PEC)degradation of some emerging contaminants under visible light irradiation(λ>420 nm)and applied voltage.Due to the synergistic effect,the photocatalytic degradation rate by the SA-PDI film under visible light irradiation and an applied voltage of 2.1 V was 2.72 times and 14.5 times those of the PC and EC processes,respectively.The visible light irradiation not only generated a promoting effect on electrocatalytic(EC)oxidation at potentials above1.2 V but also generated many more h+ for promoting the electrocatalytic oxidation of phenol.Furthermore,an applied voltage above 1.2 V could effectively improve the separation rate of electrons from the SA-PDI electrodes to the Pt electrodes,and then,much more ·O2-and ·OH could be generated for improving the photocatalytic(PC)oxidation efficiency.Therefore,the h+,·OH and ·O2-could improve the synergistic effect of phenol oxidation during the PEC process.Moreover,the SA-PDI film appeared to have satisfactory stability in the PEC process.The SA-PDI film was also proven to be effective for two other contaminants,namely,2,4-dichlorophenol,and ciprofloxacin.展开更多
Herein,microtubular nanoporous g-C3N4(TPCN)with hierarchical structure and nitrogen defects was prepared via a facile self-templating approach.On one hand,the hexagonal tubular structure can facilitate the light refle...Herein,microtubular nanoporous g-C3N4(TPCN)with hierarchical structure and nitrogen defects was prepared via a facile self-templating approach.On one hand,the hexagonal tubular structure can facilitate the light reflection/scattering,provide internal/external active sites,and endow the electron with oriented transfer channels.The well-developed nanoporosity can result in large specific surface area and abundant accessible channels for charge migration.On the other hand,the existence of nitrogen vacancies can improve the light harvesting(>450 nm)and prompt charge separation by acting as the shallow charge traps.More NHxgroups in g-C3N4 framework can promote the interlayer charge transport by generating hydrogen-bonding interaction between C3N4 layers.Therefore,TPCN possessed highly efficient visible photocatalytic performances to effectively inactivate Escherichia coli(E.coli)cells and thoroughly mineralize organic pollutants.TPCN with the optimum bactericidal efficiency can completely inactivated5×10^6 cfu mL^-1 of E.coli cells after 4 h of irradiation treatment,while about 74.4%of E.coli cells were killed by bulk g-C3N4(BCN).Meanwhile,the photodegradation rate of TPCN towards methylene blue,amaranth,and bisphenol A were almost 3.1,2.5 and 1.6 times as fast as those of BCN.Furthermore,h^+and·O2^- were the reactive species in the photocatalytic process of TPCN system.展开更多
文摘过氧化氢(H_(2)O_(2))是一种重要的化工产品,广泛应用于污水处理、消毒杀菌和印染漂白等领域.在蒽醌法生产H_(2)O_(2)的过程中,易产生有毒气体并存在爆炸危险.因此,仅利用水、氧气和太阳光即可在合适的光催化剂上生成H_(2)O_(2)的光催化技术备受关注.本课题组报道了通过酸碱自组装法制备的四(4-羧基苯基)卟啉(SA-TCPP)光催化剂,用于生产H_(2)O_(2).该催化剂克服了大部分H_(2)O_(2)光催化剂存在的需要牺牲剂、活性低和光利用率不足等问题,但其性能仍受限于较高的复合率.晶面调控已被证实是改善许多无机催化剂电荷复合的有效策略,然而,对于有机光催化剂,关于暴露晶面与其活性关系的研究仍然较少.本文采用溶解-重结晶法在水和三种有机溶剂的混合物中成功合成了三种具有不同暴露晶面的卟啉光催化剂.即利用卟啉在有机溶剂和水中的溶解度差异,将卟啉先溶解在四氢呋喃(THF)、甲醇(MeOH)或乙二醇(EG)溶液中,随后在水溶液中重新结晶.X射线衍射、高分辨率透射电子显微镜及晶面模拟模型图的结果表明,三种催化剂具有相同的晶体结构,但分别暴露了(400)、(022)和(020)晶面.通过紫外分光光度计测量这些催化剂在氙灯(λ≥420 nm)照射下的光催化活性,结果表明,具有(400)暴露面的卟啉光催化剂的H_(2)O_(2)生产速率最高,可达29.33 mmol L h^(-1)g^(-1),分别是具有(022)暴露面和(020)暴露面的卟啉光催化剂的2.7倍和4.1倍,约是已报道的SA-TCPP光催化剂的1.3倍.通过紫外漫反射、莫特肖特基曲线分析以及LED灯照射下的光催化活性测试,排除了光吸收能力对这三种卟啉光催化剂活性的影响.开尔文探针力显微镜、光生电流密度谱图、晶面模拟模型图和密度泛函理论计算结果表明,活性的差异主要归因于(400)表面暴露的高羧基含量所引发的强内建电场,并且在该暴露面上的内建电场方向有利于空穴从吡咯氮向羧基碳的跃迁,因此阻碍了电荷的快速重组,促进了富有挑战性的水氧化过程,而(020)面由于暴露了最多的吡咯氮和最少的羧基碳,其产生的内建电场强度最弱,且内建电场方向阻碍了空穴向羧基碳的跃迁,因此H_(2)O_(2)生产速率最低.综上所述,本工作通过晶面调控产生强内建电场以加速空穴的迁移,降低了电子空穴复合速率,实现了高H_(2)O_(2)生产速率,为更高效的有机光催化剂的设计和开发提供了新思路.
基金supported by the National Natural Science Foundation of China(21707052)Jiangsu Agriculture Science and Technology Innovation Fund(CX(18)2025)+1 种基金Fundamental Research Funds for the Central Universities(JUSRP11905 and JUSRP51714B)Key Research and Development Program of Jiangsu Province(BE2017623)~~
文摘Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.
基金This project was supported financially by the National Natural Science Foundation of China(21908079,21902009,21707052)Natural Science Foundation of Jiangsu Province(BK20201345)+3 种基金the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF2005)Startup Funding at Jiangnan University(1045210322190170,1045281602190010,1042050205204100)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108)Fundamental Research Funds for the Central Universities(JUSRP11905,JUSRP52004B).
文摘Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.
基金financialy supported by National Natural Science Foundation of China (22002142)China Postdoctoral Science Foundation (2019M652570, 2019M650172 and 2020T130605)+1 种基金Support Plan for College Science and Technology Innovation Team of Henan Province (No. 16IRTSTHN001)the Science & Technology Innovation Talent Plan of Henan Province (No. 174200510018)
文摘Recently,defect architectured photocatalysis is proved to be the most versatile choice for high solar to chemical energy conversion processes.Defect engineering strategies are of great demand to effectively tune the electronic microstructure and surface morphologies of semiconductors to boost charge carrier concentration and extend light harvesting capability.This review provides a comprehensive insight to various kinds of defects along with their synthesis procedures and controlling mechanism to uplift photocatalytic activity.In addition,the contribution made by defects and material optimization techniques toward electronic band structure of the photocatalyst,the optimal concentration of defects,the key adsorption processes,charge distribution,and transfer dynamics have been explained in detail.Further,to clarify the relationship between photocatalytic activity and defect states in real,a comprehensive outlook to the versatile photocatalytic applications has been presented to highlight current challenges and future applications.Defect engineering therefore stands as the next step toward advancement in the design and configuration of modern photocatalysts for high efficiency photocatalysis.
基金This study was partly supported by the National Natural Science Foundation of China(No.21872077,21673126,21761142017,21621003)Collaborative Innovation Centre for Regional Environmental Quality。
文摘Surface hybrid inorganic semiconductors photocatalysts withπconjugated structure have recently been widely used in the field of photocatalytic environmental remediation and energy conversion.Surface hybridization is considered to be an efficient way to significantly enhance the photocatalytic activity by several times,completely inhibit photocorrosion of inorganic photocatalysts and expand the spectral response range of photocatalysts.This review provides a comprehensive overview of the surface hybridization definition,the principle of enhancing photocatalytic performance and the control factors of surface hybridization to promote photoactivity.Summarize the preparation and structural identification method of the surface hybrid photocatalyst.Special emphasis is placed on the various photocatalytic system construction of surface hybridization.The development of surface hybrid photocatalysts for pollutant degradation and energy conversion are further presented.Finally,the challenges and future development prospects of surface hybridization in photocatalysis are discussed.We hope this critical review can provide a clear picture of the state-of-the-art achievements and facilitate the applications of surface hybrid photocatalysts in environmental remediation and energy conversion.
文摘Photocatalytic water splitting based on semiconductor photocatalysts is a promising approach for producing carbon‐neutral,sustainable,and clean H_(2) fuel.Cocatalyst loading,which is an appealing strategy,has been extensively employed to improve the photocatalytic efficiency semiconductors.In view of the high cost and rare preservation of noble metal cocatalysts that significantly hinder their utilization for large‐scale energy production,various cocatalysts comprising earth‐abundant ele‐ments have been developed as noble‐metal‐free candidates using different methods to boost pho‐tocatalytic water splitting.Among these preparation strategies,photodeposition has attracted tre‐mendous attention in the deposition of earth‐abundant cocatalysts owing to its simplicity and mod‐erate availability,improved interfacial charge separation and transfer,and abundant active sites on the surface.In this review,we first summarize the deposition principles,deposition advantages,categories of cocatalysts,roles of cocatalysts,influencing factors,modification strategies,and design considerations in the photodeposition of earth‐abundant cocatalysts.The photodeposited earth‐abundant cocatalysts for the photocatalytic H_(2) evolution half reaction,photocatalytic O_(2) evo‐lution half reaction,and overall photocatalytic water splitting are discussed.Finally,some perspec‐tives on the challenges and possible future directions for the photodeposition of earth‐abundant cocatalysts in photocatalytic water splitting are presented.
文摘The active sites of monodisperse transition metal Ni-clusters were anchored on carbon nitride(CN)by an in situ photoreduction deposition method to promote the efficient separation of photogenerated charges and achieve high-efficiency photocatalytic activity for hydrogen evolution.The Ni-cluster/CN exhibited a photocatalytic hydrogen production rate of 16.5 mmol·h^(-1)·g^(-1) and a total turnover frequency(TOF(H_(2)))value of 461.14 h^(-1).X-ray absorption spectroscopy based on synchrotron radiation indicated that CN had two reaction centers to form stable interface interactions with monodispersed Ni-clusters,in which carbon can act as an electron acceptor,while nitrogen can act as an electron donor.Meanwhile,the hybrid electronic structure of the Ni-cluster/CN system was constructed,which was favorable for photocatalytic activity for hydrogen production.An in-depth understanding of the interfacial interaction between CN and Ni-clusters will have important reference significance on the mechanistic study of development based on the cocatalyst.
基金supported by the National Natural Science Foundation of China(No.21973009 to Jun Li)the Chongqing Municipal Natural Science Foundation(No.cstc2019jcyj-msxm X0087 to Jun Li)the support from the Talent Introduction Project of Hubei Polytechnic University(No.21xjz01R)。
文摘The hydrogen abstraction reaction of methanol with fluorine atoms can produce HF and CH_(3)O or CH_(2)OH radicals,which are important in the environment,combustion,radiation,and interstellar chemistry.In this work,the dynamics of this typical reaction is investigated by the quasi-classical trajectory method based on a recently developed globally accurate full-dimensional potential energy surface.Particularly,the vibrational state distributions of the polyatomic products CH_(3)O and CH_(2)OH are determined by using the normal mode analysis method.It is found that CH_(3)O and CH_(2)OH are dominantly populated in the ground state when the reactants are at the ground ro-vibrational state.The OH stretching mode,torsional mode,H_(2)CO out-of-plane bending mode and their combination bands in the CH_(2)OH product can be effectively excited once the OH stretching mode of the reactant CH_(3)OH is excited to the first vibrationally excited state.Most of the available energy flows into the HF vibrational energy and the translational energy in both channels,while the radical products,CH_(3)O or CH_(2)OH,receive a small amount of energy,consistent with experiment,which is an indication of its spectator nature.
基金supported by the Natural Science Foundation of Sichuan Province(No.2022NSFSC1229)the open project from Hebei Key Laboratory of Photoelectric Control on Surface and Interface(No.ZD2022003)+3 种基金J.S.L.thanks the project funded by China Postdoctoral Science Foundation(project No.2023MD734228)It was also supported by the European Regional Development Funds and by the Spanish Ministerio de Ciencia e Innovación through the project COMBENERGY(No.PID2019-105490RB-C32)Y.Y.Y.acknowledges funding from the National Natural Science Foundation of China(NSFC,No.22172121)the Fundamental Research Funds for the Central Universities,Southwest Minzu University(No.xiao2021102).
文摘The anodic electrooxidation of ethanol to value-added acetate is an excellent example of replacing the oxygen evolution reaction to promote the cathodic hydrogen evolution reaction and save energy.Herein,we present a colloidal strategy to produce Ni-Fe bimetallic alloy nanoparticles(NPs)as efficient electrocatalysts for the electrooxidation of ethanol in alkaline media.Ni-Fe alloy NPs deliver a current density of 100 mA·cm^(-2) in a 1.0 M KOH solution containing 1.0 M ethanol merely at 1.5 V vs.reversible hydrogen electrode(RHE),well above the performance of other electrocatalysts in a similar system.Within continuous 10 h testing at this external potential,this electrode is able to produce an average of 0.49 mmol·cm^(-2)·h^(-1) of acetate with an ethanol-to-acetate Faradaic efficiency of 80%.A series of spectroscopy techniques are used to probe the electrocatalytic process and analyze the electrolyte.Additionally,density functional theory(DFT)calculations demonstrate that the iron in the alloy NPs significantly enhances the electroconductivity and electron transfer,shifts the rate-limiting step,and lowers the energy barrier during the ethanol-to-acetate reaction pathway.
基金the National Natural Science Foundation of China(Nos.22171158 and 22136002)the Tribology Science Fund of the State Key Laboratory of Tribology(No.SKL TKF20B18).
文摘Antibiotics are a widely used and effective treatment for bacterial infections.However,bacteria can gradually evolve during infection,leading to developing resistance to antibiotics,which renders previously effective treatments ineffective.Finding a useful and convenient manner to treat bacterial infections is a great challenge.Here,we report a flexible hydrogen-bond-bridged phosphorene film with photodynamic antibacterial properties and excellent mechanical properties,fabricated from electrochemical exfoliation of black phosphorus(BP).When illuminated under 700 nm light,the hydrogen bond-bridged phosphorene flexible film is capable of converting ground-state triplet oxygen(O_(2))into excited-state singlet oxygen(^(1)O_(2)),destroying the structure of the membrane of Staphylococcus aureus,and eventually leading to bacterial death,via breaking the C=C of unsaturated fatty acids within the bacterial cell membrane after the reaction between^(1)O_(2)and unsaturated fatty acids,thus realizing a highly efficient antibacterial approach,which is supported by gas chromatography-mass spectrometry(GC-MS)technique.This work establishes an effective phototherapy platform for treating bacterial traumatic infections.
基金supported by the National Science Foundation of China(22306018,22136002,22302114)Natural Science Foundation of Hunan Province(2023JJ30074)+3 种基金National Key Research and Development Project of China(2020YFA0710304)Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality(BK20220023)Changsha UniversityTsinghua University。
文摘Numerous bismuth-based semiconductors(BBSs)with sophisticated and desirable structures used as photocatalysts for efficient photocatalytic degradation of water organic contaminants have attracted considerable attention.However,regulating the crystal phases and phase transition of BBSs for promoted photocatalytic performance is ignored.Herein,the unique crystal structure and band structure features of each typical BBSs,and the vital roles on phase controlling of each phase were systematically presented based on the classification of BBSs.Notably,the critical factors for the phase transition of BBSs and intrinsic driving forces endowed by phases of BBSs for enhanced photocatalytic performance of organic contaminants removal were also elucidated.This review will provide systematical guidelines and horizons for regulating the crystal phase and phase transition of BBSs,promoting photocatalytic degradation and mineralization of organic contaminants.
基金the National Natural Science Foundation of China(No.52102258)the Taishan Scholars Program(No.tsqn202306309)+2 种基金Natural Science Foundation of Shandong Province(No.ZR2023YQ012)Natural Science Foundation of Jiangsu Province(No.BK20210447)the Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality(No.BK20220023).
文摘Renewable-energy-driven nitrate(NO_(3)^(−))electroreduction to ammonia(NH_(3))(NERA)has been an attractive technology for decarbonizing NH_(3)production and wastewater treatment.Improving NERA efficiency requires electrocatalysts that are earth-abundant and show fantastic performance.Here we report a semiempirical activity descriptor of eg occupancy(of surface B-site cations)for identifying inexpensive perovskite oxides with extremely high efficacy toward NERA.We establish the descriptor by systematic investigations of more than 10 perovskite oxides.These investigations demonstrate that their intrinsic NERA activities display a volcano-shaped dependence on eg occupancy and the optimized intrinsic activities are accessible at near-1 eg occupancies.This could plausibly be attributed to the favorable overlaps between surface adsorbates and vertically-oriented eg orbitals.More importantly,utilizing this descriptor,we predict a highly active,selective,and durable NERA electrocatalyst with a composition of Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF).Because of its close-to-1 e_(g)occupancy(i.e.~1.2),the BSCF features a superior NH_(3)production rate of 0.12 g·h^(−1)·mg_(cat.)^(−1)(Faradaic efficiency of 97.8%)that is at top of the volcano plot,and substantially outperforms most NERA electrocatalysts reported in literature.
基金This work was supported by the National Natural Science Foundation of China(Nos.22206102,21872077,and 21621003)the National Key Research and Development Program of China(No.2020YFA0710304)the China Postdoctoral Science Foundation(No.2021M700078).
文摘Herein,a series of three-dimensionally ordered macroporous(3DOM)Bi_(4)O_(5)Br_(2)photocatalysts with different macropore sizes were successfully fabricated via a polymethyl methacrylate(PMMA)template method.The photocatalytic activity for phenol degradation over 3DOM Bi_(4)O_(5)Br_(2)first increased and then decreased with the rise in macropore size.Specifically,3DOM Bi_(4)O_(5)Br_(2)-255(macropore diameter ca.170 nm)exhibits the best photocatalytic activity in the static system,which is about 4.5,7.3,and 11.9 times higher than those of bulk Bi_(4)O_(5)Br_(2),Bi_(2)WO_(6),and g-C_(3)N_(4),respectively.Meanwhile,high phenol conversion(75%)is also obtained over 3DOM Bi_(4)O_(5)Br_(2)-255 in the flow system under full spectrum irradiation.Furthermore,3DOM Bi_(4)O_(5)Br_(2)-255 also shows strong mineralization capacity owing to the downward shift of valance band position(0.15 V)as compared with Bi_(4)O_(5)Br_(2).Total organic carbon(TOC)removal rate over 3DOM Bi_(4)O_(5)Br_(2)-255(62%)is much higher than that of Bi_(4)O_(5)Br_(2)(17%).The enhancement in photocatalytic performance of 3DOM Bi_(4)O_(5)Br_(2)-255 is attributable to its better phenol adsorption,O_(2)activation,and charge separation and transfer abilities.This work combines the advantages of 3D structure and surface dangling bonds,providing new possibilities for designing highly efficient photocatalysts for pollutants removal.
基金This research was supported by the Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality(BK20220023)National Natural Science Foun-dation of China(21902009)Startup Funding at Jiangnan University.
文摘Microenvironments of the catalytic center,which play a vital role in adjusting electrocatalytic CO_(2) reduction reaction(ECO_(2) RR)activity,have received increasing attention during the past few years.However,controllable microenvironment construction and the effects of multi-microenvironment variations for improving ECO_(2) RR performance remain unclear.Herein,we summarize the representative strategies for tuning the catalyst and local microenvironments to enhance ECO_(2) RR selectivity and activity.The multifactor synergetic effects of microen-vironment regulation for enhancing CO_(2) accessibility,stabilizing key intermediates,and improving the performance of ECO_(2) RR catalysts are discussed in detail,as well as perspectives on the challenges when investigating ECO_(2) RR microenvironments.We anticipate that the discussions in this review will inspire further research in microenvironment engineering to accelerate the development of the ECO 2 RR for practical application.
文摘Environmental pollution is a major challenge faced by human beings, and is becoming more serious due to increasing urbanization and industrialization. Catalysis is the key technology for environmental remediation. As a “green” technology, photocatalysis and ambient catalysis could offer numerous opportunities to realize environmental remediation under mild reaction conditions with low energy input. Over the past two decades, great advances have been made on the design and synthesis of the photocatalysts and ambient catalysts, precise control of catalyst active sites, and the mechanistic understanding on the catalytic process for environmental remediation.
基金supported by the National Natural Science Foundation of China(Nos.92156021,22350009,22101115 and 22371111)Financial Support for Outstanding Talents Training Fund in Shenzhen,the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)+1 种基金high level of special funds(G03050k003)Introduction of Major Talent Projects in Guangdong Province(No.2019CX01C079).
文摘omprehensive Summary Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes.However,the important reactions have never been realized in aromatic metallacycles.Herein,we present the first carbonylation reactions of metallaaromatics,specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne.During the carbonylation process,the electronic and steric properties of nucleophiles are regarded as critical factors.The alcohols with bulky substituents(isopropanol)require more reaction time and tert-butyl alcohol is inert in the reaction.Comparatively,amines,being stronger nucleophiles,exhibit divergent behaviors.Bulky amines undergo aminocarbonylation,whereas small amines prefer direct nucleophilic additions.Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction.According to these observations,a divergent pathway for the reaction is proposed.Furthermore,the photophysical properties of these carbonyl-functionalized osmapentalene complexes are studied,and the maximum absorption peak of compound with a carboxylic group exhibits a significant red-shift due to the smaller HOMO-LUMO gap.These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl-functionalized metallacycles.
基金supported by the National Natural Science Foundation of China (21437003, 21673126, 21621003, 21761142017)the Youth Innovation Promotion Association of CAS (2017493)Young Elite Scientist Sponsorship Program by CAST and Collaborative Innovation Center for Regional Environmental Quality
文摘As a two-dimensional(2D) material, polymeric carbon nitride(g-C_3N_4) nanosheet holds great potentials in environmental purification and solar energy conversion. In this review, we summarized latest progress in the optimization of photocatalytic performance in 2D g-C_3N_4. Some of the latest structural engineering methods were summed up, where the relevant influences on the behaviors of photoinduced species were emphasized. Furthermore, the construction strategies for band structure modulation and charge separation promotion were then discussed in detail. A brief discussion on the opportunity and challenge of 2D g-C_3N_4-based photocatalysis are presented as the conclusion of this review.
基金the National Natural Science Foundation of China(20925725)the Fundamental Research Funds for the Central Universities(2011QN138)State Key Laboratory of New Ceramic and Fine Processing Tsinghua University.
文摘The hybridization of graphene with Bi_(2)WO_(6)photocatalysts was employed to enhance the photocatalytic activity.The photocatalytic activity enhancements were dependent on the amount of graphene and it was found that the optimal hybridized amount of graphene was about 1.5 wt%,which was close to the monolayer dispersing of graphene on Bi_(2)WO_(6)surface.Up to four times of the photocatalytic activity was enhanced by the hybridization of graphene,compared with that of pristine Bi_(2)WO_(6).The enhancement mechanism of the photocatalytic activity was attributed to the higher separation efficiency and the inhibition of recombination of photoinduced electron-hole pairs.The electronic interaction was verified by the photoelectrochemical measurements.
基金partly supported by the National Natural Science Foundation of China (21673126, 21437003, 21761142017, and 21621003)Collaborative Innovation Center for Regional Environmental Quality
文摘A self-assembled perylene diimide(SA-PDI)film was prepared on an indium-tin-oxide(ITO)substrate and acted as a photoanode for the photoelectrocatalytic(PEC)degradation of some emerging contaminants under visible light irradiation(λ>420 nm)and applied voltage.Due to the synergistic effect,the photocatalytic degradation rate by the SA-PDI film under visible light irradiation and an applied voltage of 2.1 V was 2.72 times and 14.5 times those of the PC and EC processes,respectively.The visible light irradiation not only generated a promoting effect on electrocatalytic(EC)oxidation at potentials above1.2 V but also generated many more h+ for promoting the electrocatalytic oxidation of phenol.Furthermore,an applied voltage above 1.2 V could effectively improve the separation rate of electrons from the SA-PDI electrodes to the Pt electrodes,and then,much more ·O2-and ·OH could be generated for improving the photocatalytic(PC)oxidation efficiency.Therefore,the h+,·OH and ·O2-could improve the synergistic effect of phenol oxidation during the PEC process.Moreover,the SA-PDI film appeared to have satisfactory stability in the PEC process.The SA-PDI film was also proven to be effective for two other contaminants,namely,2,4-dichlorophenol,and ciprofloxacin.
基金financially supported by the National Natural Science Foundation of China(No.21707052)the Jiangsu Agriculture Science and Technology Innovation Fund(No.CX(18)2025)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.JUSRP11905 and JUSRP51714B)the Key Research and Development Program of Jiangsu Province(No.BE2017623)。
文摘Herein,microtubular nanoporous g-C3N4(TPCN)with hierarchical structure and nitrogen defects was prepared via a facile self-templating approach.On one hand,the hexagonal tubular structure can facilitate the light reflection/scattering,provide internal/external active sites,and endow the electron with oriented transfer channels.The well-developed nanoporosity can result in large specific surface area and abundant accessible channels for charge migration.On the other hand,the existence of nitrogen vacancies can improve the light harvesting(>450 nm)and prompt charge separation by acting as the shallow charge traps.More NHxgroups in g-C3N4 framework can promote the interlayer charge transport by generating hydrogen-bonding interaction between C3N4 layers.Therefore,TPCN possessed highly efficient visible photocatalytic performances to effectively inactivate Escherichia coli(E.coli)cells and thoroughly mineralize organic pollutants.TPCN with the optimum bactericidal efficiency can completely inactivated5×10^6 cfu mL^-1 of E.coli cells after 4 h of irradiation treatment,while about 74.4%of E.coli cells were killed by bulk g-C3N4(BCN).Meanwhile,the photodegradation rate of TPCN towards methylene blue,amaranth,and bisphenol A were almost 3.1,2.5 and 1.6 times as fast as those of BCN.Furthermore,h^+and·O2^- were the reactive species in the photocatalytic process of TPCN system.
