This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'g...This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'geometric linearity on their photocatalytic properties.Herein,the Mg O film,obtained by plasma electrolysis of AZ31 Mg alloys,was modified by growing an LDH film,which was further functionalized using cyclic sodium hexametaphosphate(CP)and linear sodium tripolyphosphate(LP).CP acted as an enhancer for flake spacing within the LDH structure,while LP changed flake dispersion and orientation.Consequently,CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis,effectively degrading organic dyes like Methylene blue(MB),Congo red(CR),and Methyl orange(MO).The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules.Furthermore,the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH,leading to its superior photocatalytic performance compared to LP@LDH.Specifically,LP@LDH demonstrated notable degradation efficiencies of 93.02%,92.89%,and 88.81%for MB,MO,and CR respectively,over a 40 min duration.The highest degradation efficiencies were observed in the case of the CP@LDH sample,reporting 99.99%for MB,98.88%for CR,and 99.70%for MO.This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation,offering promising prospects for environmental remediation and water detoxification applications.展开更多
The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)...The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.展开更多
Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are...Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are unable to fully decompose and mineralize plastic waste. Therefore, there is a need to develop an environmentally friendly, innovative and sustainable photocatalytic process that can destroy these wastes with much less energy and chemical consumption. In photocatalysis, various nanomaterials based on wide energy band gap semiconductors such as TiO2 and ZnO are used for the conversion of plastic contaminants into environmentally friendly compounds. In this work, the removal of plastic fragments by photocatalytic reactions using newly developed photocatalytic composites and the mechanism of photocatalytic degradation of microplastics are systematically investigated. In these degradation processes, sunlight or an artificial light source is used to activate the photocatalyst in the presence of oxygen.展开更多
An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a qu...An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.展开更多
This review paper explores the efficacy of magnesium ferrite-based catalysts in photocatalytic degradation of organic contaminates(antibiotic and dyes).We report the influence of different doping strategies,synthesis ...This review paper explores the efficacy of magnesium ferrite-based catalysts in photocatalytic degradation of organic contaminates(antibiotic and dyes).We report the influence of different doping strategies,synthesis methods,and composite materials on the degradation efficiency of these pollutants.Our analysis reveals the versatile and promising nature of magnesium ferrite-based catalysts,offering the valuable insights into their practical application for restoring the environment.Due to the smaller band gap and magnetic nature of magnesium ferrite,it holds the benefit of utilising the broader spectrum of light while also being recoverable.The in-depth analysis of magnesium ferrites'photocatalytic mechanism could lead to the development of cheap and reliable photocatalyst for the wastewater treatment.This concise review offers a thorough summary of the key advancements in this field,highlighting the pivotal role of the magnesium ferrite based photocatalysts in addressing the pressing global issue of organic pollutants in wastewater.展开更多
Defect engineering can give birth to novel properties for adsorption and photocatalysis in the control of antibiotics and heavy metal combined pollution with photocatalytic composites.However,the role of defects and t...Defect engineering can give birth to novel properties for adsorption and photocatalysis in the control of antibiotics and heavy metal combined pollution with photocatalytic composites.However,the role of defects and the process mechanism are complicated and indefinable.Herein,TiO_(2)/CN/3DC was fabricated and defects were introduced into the tripartite structure with separate O_(2)plasma treatment for the single component.We find that defect engineering can improve the photocatalytic activity,attributing to the increase of the contribution from h^(+)and OH.In contrast to TiO_(2)/CN/3DC with a photocatalytic tetracycline removal rate of 75.2%,the removal rate of TC with D-TiO_(2)/CN/3DC has increased to 88.5%.Moreover,the reactive sites of tetracycline can be increased by adsorbing on the defective composites.The defect construction on TiO_(2)shows the advantages in tetracycline degradation and Cu^(2+)adsorption,but also suffers significant inhibition for the tetracycline degradation in a tetracycline/Cu^(2+)combined system.In contrast,the defect construction on graphene can achieve the cooperative removal of tetracycline and Cu^(2+).These findings can provide new insights into water treatment strategies with defect engineering.展开更多
In the pursuit of multifunctional coatings,the controlled growth of materials on stationary platforms holds paramount importance for achieving superior corrosion protection and optimal photocatalytic performance.This ...In the pursuit of multifunctional coatings,the controlled growth of materials on stationary platforms holds paramount importance for achieving superior corrosion protection and optimal photocatalytic performance.This study introduces a cutting-edge approach,intertwining bifunctional metal-organic frameworks(MOFs)seamlessly into defective MgO layers produced by the anodic oxidation of AZ31 alloy.Key metallic oxides of Zn,Sn,and V take center stage as metallic sources for MOF formation,complemented by the organic prowess of L-Tryptophan as anα-amino acid linker.Leveraging the electronic structure of metallic oxides reacting with tryptophan molecules,controlled morphologies with distinct characteristics are induced on the defective surface of the MgO layer,enabling the precise modulation of surface defects.The hybrid composite demonstrates an adaptive microstructure in diverse aqueous environments,offering dual functionality with electrochemical stability and visible light photocatalytic activity for crystal violet degradation.Among the samples,the SnOF complex exhibited remarkable electrochemical stability with a low corrosion current density of 7.50×10^(−10)A·cm^(−2),along with a 94.56%degradation efficiency after 90 min under visible light exposure.The VOF complex,under similar visible light conditions,demonstrated exceptional performance with a higher degradation efficiency of 97.79%and excellent electrochemical stability characterized by a corrosion current density of 3.26×10^(−9)A·cm^(−2).Additionally,Density Functional Theory(DFT)computations shed light on the basic bonding patterns between MOFs and inorganic components,providing electronic understanding of their electrochemical and photocatalytic activities.展开更多
Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical fun...Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.展开更多
Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with...Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.展开更多
Adsorption coupled with photocatalytic degradation is proposed to fulfill the removal and thorough elimination of organic dyes.Herein,we report a facile hydrothermal synthesis of MIL-100(Fe)/GO photocatalysts.The adso...Adsorption coupled with photocatalytic degradation is proposed to fulfill the removal and thorough elimination of organic dyes.Herein,we report a facile hydrothermal synthesis of MIL-100(Fe)/GO photocatalysts.The adsorption and photocatalytic degradation process of methylene blue(MB)on MIL‐100(Fe)/GO composites were systematically studied from performance and kinetic perspectives.A possible adsorption‐photocatalytic degradation mechanism is proposed.The optimized 1M8G composite achieves 95%MB removal(60.8 mg/g)in 210 min and displays well recyclability over ten cycles.The obtained MB adsorption and degradation results are well fitted onto Langmuir isotherm and pseudo‐second order kinetic model.This study shed light on the design of MOFs based composites for water treatment.展开更多
The Nd:TiO_(2 )PEO coatings were formed in a phosphate-based electrolyte with the addition of Nd_(2)O_(3 )under the current density of 150,200,250 and 300 m A/cm^(2).SEM results showed that the micropores decreased on...The Nd:TiO_(2 )PEO coatings were formed in a phosphate-based electrolyte with the addition of Nd_(2)O_(3 )under the current density of 150,200,250 and 300 m A/cm^(2).SEM results showed that the micropores decreased on quantity and increased on scale with the increasing current density.AFM results revealed that the roughness of the coatings increased with the increasing current density.Phase and composition analysis showed that the Nd:TiO_(2) coatings were mainly composed of anatase and rutile phase.And the anatase phase content has reached the maximum value at the current density of 250 m A/cm^(2).XPS results indicated that Ti2p spin-orbit components of the Nd:TiO_(2) coatings are shifted towards higher binding energy,compared with the pure TiO_(2) coating,suggesting that some of the Nd^(3+)ions are combined with TiO_(2) lattice and led to dislocation.Photocatalytic test showed that the photocatalytic activity of Nd:TiO_(2) coatings varied in the same pattern with the anatase content variation in Nd:TiO_(2) coatings.The photocatalytic experiment results show that the photocatalytic activity of Nd:TiO_(2) coatings can be greatly enhanced with moderate amount of Nd^(3+).However,excessive amount of Nd^(3+)does not have an effective impact on the photoctalytic activity improvement.展开更多
A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation abili...A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation ability of all samples was evaluated using methylene blue (MB) as a target contaminant.The band gaps of N-doped samples are all higher than that of pristine ones,which is only 3.12 eV.BET specific surface area S_(BET) and pore volume are increased due to the N doping.And the greater increase of S_(BET),the faster the photodegradation speed of methylene blue on SrMoO_(4).More specifically,the degradation efficiency of MB is improved up to 87%in 100 min.展开更多
Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)...Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.展开更多
Spinning disk reactor(SDR)has emerged as a novel process intensification photocatalytic reactor,and it has higher mass transfer efficiency and photon utilization for the degradation of toxic organic pollutants by adva...Spinning disk reactor(SDR)has emerged as a novel process intensification photocatalytic reactor,and it has higher mass transfer efficiency and photon utilization for the degradation of toxic organic pollutants by advanced oxidation processes(AOPs).In this study,ZnO—TiO_(2)nanocomposites were prepared by solgel method,and coated on the disk of SDR by impregnation-pull-drying-calcination method.The performance of catalyst was characterized by X-ray diffraction,scanning electron microscope,X-ray photoelectron spectroscopy,photoluminescence and ultraviolet—visible diffuse reflectance spectroscopy.Photocatalytic ozonation in SDR was used to remove phenol,and various factors on degradation effect were studied in detail.The results showed that the rate of degradation and mineralization reached 100%and 83.4%under UV light irradiation after 50 min,compared with photocatalysis and ozonation,the removal rate increased by 69.3%and 34.7%,and mineralization rate increased by 56.7%and 62.9%,which indicated that the coupling of photocatalysis and ozonation had a synergistic effect.The radical capture experiments demonstrated that the active species such as photogenerated holes(h^(+)),hydroxyl radicals(·OH),superoxide radical(·O_(2)-)were responsible for phenol degradation,and·OH played a leading role in the degradation process,while h+and·O_(2)^(-)played a non-leading role.展开更多
The photoreduction of CO_(2)into CH_(4)with simultaneous high activity and selectivity is a promising strategy to increase energy supply and alleviate global warming.However,the absence of the active sites that is res...The photoreduction of CO_(2)into CH_(4)with simultaneous high activity and selectivity is a promising strategy to increase energy supply and alleviate global warming.However,the absence of the active sites that is responsible for the adsorption and activation of CO_(2)and the generation of CO and H2via side reactions often lead to poor efficiency and low selectivity of the catalyst.Herein,Cu,Pd,and PdCu metal clusters cocatalyst-anchored defective TiO_(2)nanotubes(Cu/TiO_(2)-SBO,Pd/TiO_(2)-SBO,and Pd1Cu1/TiO_(2)-SBO)were designed via a simple solution impregnation reduction and applied for photocatalytic conversion of CO_(2)to CH_(4).The Pd1Cu1/TiO_(2)-SBO photocatalyst exhibits excellent catalytic performance among the other catalysts for photoreduction of CO_(2)into CH_(4).More interestingly,the product selectivity of CH_(4)reaches up to 100%with a rate of 25μmol g^(-1)h^(-1).In-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)simulations indicate that the main reasons for the high selectivity of CH_(4)are attributed to the PdCu alloy and oxygen vacancies,which jointly enhance the photoinduced carrier separation and lower energy barriers of key intermediates.Moreover,due to the tunable d-band center of the Cu site in the PdCu alloy,the generated intermediates can be well prevented from poisoning and promoted to participate in further reactions.Hopefully,the current study will provide insight into the development of new,highly selective photocatalysts for the visible light-catalytic reduction of CO_(2)into CH_(4).展开更多
Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme hetero...Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2)production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.展开更多
Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)...Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)S_(4)(HVs-ZIS)and CoIn_(2)S_(4)(CIS)via a defect-guided heteroepitaxial growth strategy.The strong interface coupling induces adequate carriers exchanging passageway between HVs-ZIS and CIS,enhancing the internal electric field(IEF)in the ZnIn_(2)S_(4)/CoIn_(2)S_(4)(HVs-ZIS/CIS)heterostructure.The defect structure in HVs-ZIS induces an additional defect level,improving the separation efficiency of photocarriers.Moreover,promoted by the IEF and intimate heterointerface,photogenerated electrons trapped by the defect level can migrate to the valence band of CIS,contributing to massive photogenerated electrons with intense reducibility in HVs-ZIS/CIS.Consequently,the HVs-ZIS/CIS heterostructure performs a boosted H_(2)evolution activity of 33.65 mmol g^(-1)h^(-1).This work highlights the synergistic effects of defect and strong interface coupling in regulating carrier transfer and paves a brave avenue for constructing efficient heterostructure photocatalysts.展开更多
The direct conversion of atmospheric CO_(2) into fuel via photocatalysis exhibits significant practical application value in advancing the carbon cycle.In this study,we established an electro-assisted photocatalytic s...The direct conversion of atmospheric CO_(2) into fuel via photocatalysis exhibits significant practical application value in advancing the carbon cycle.In this study,we established an electro-assisted photocatalytic system with dual compartments and interfaces,and coated Ag nanoparticles on the titanium nanotube arrays(TNTAs)by polydopamine modification.In the absence of sacrificial agent and alkali absorption liquid conditions,the stable,efficient and highly selective conversion of CO_(2) to CO at the gas-solid interface in ambient air was realized by photoelectric synergy.Specifically,with the assistance of potential,the CO formation rates reached 194.9μmol h^(−1) m^(−2) and 103.9μmol h^(−1) m^(−2) under ultraviolet and visible light irradiation,respectively;the corresponding CO_(2) conversion rates in ambient air were 30%and 16%,respectively.The excellent catalytic effect is mainly attributed to the formation of P–N heterojunction during the catalytic process and the surface plasmon resonance effect.Additionally,the introduction of solid agar electrolytes effectively inhibits the hydrogen evolution reaction and improves the electron utilization rate.This system promotes the development of photocatalytic technology for practical applications and provides new insights and support for the carbon cycle.展开更多
Photocatalytic reduction of CO_(2) into fuel represents a promising approach for achieving carbon neutrality,while realizing high selectivity in this process is challenging due to uncontrollable reaction intermediate ...Photocatalytic reduction of CO_(2) into fuel represents a promising approach for achieving carbon neutrality,while realizing high selectivity in this process is challenging due to uncontrollable reaction intermediate and retarded desorption of target products.Engineering the interface microenvironment of catalysts has been proposed as a strategy to exert a significant influence on reaction outcomes,yet it remains a significant challenge.In this study,amino alkylation was successfully integrated into the melem unit of polymeric carbon nitrides(PCN),which could efficiently drive the photocatalytic CO_(2) reduction.Experimental characterization and theoretical calculations revealed that the introduction of amino alkylation lowers the energy barrier for CO_(2) reduction into^(*)COOH intermediate,transforming the adsorption of^(*)COOH intermediate from the endothermic to an exothermic process.Notably,the as-prepared materials demonstrated outstanding performance in photocatalytic CO_(2) reduction,yielding CO_(2)at a rate of 152.8μmol h^(-1) with a high selectivity of 95.4%and a quantum efficiency of 6.6%.展开更多
The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency,thereby boosting the performance of photocatalysts.In this study,BiO_(2-x)nanosheets were synthesized throug...The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency,thereby boosting the performance of photocatalysts.In this study,BiO_(2-x)nanosheets were synthesized through a hydrothermal process and loaded onto NaNbO_(3) microcube to construct a series of BiO_(2-x)/NaNbO_(3) heterojunctions for photocatalytic N_(2) fixation.Results indicated that 2.5%BiO_(2-x)/NaNbO_(3) had the highest photocatalytic performance.The NH_(3) production rate under simulated solar light reached 406.4μmol·L^(-1)·g^(-1)·h^(-1),which reaches 2.6 and 3.8 times that of NaNbO_(3) and BiO_(2-x),respectively.BiO_(2-x)nanosheets primarily act as electron trappers to enhance the separation efficiency of charge carriers.The strong interaction between BiO_(2-x)and NaNbO_(3) facilitates the electron migration between them.Meanwhile,the abundant oxygen vacancies in BiO_(2-x)nanosheets may facilitate the adsorption and activation of N_(2),which may be another possible reason of the high photocatalytic activity of the BiO_(2-x)/NaNbO_(3).This study may offer new insights for the development of semiconductor materials in photocatalytic nitrogen fixation.展开更多
基金the National Research Foundation of Korea(NRF)funded by the Korean Government(MSIT)(No.2022R1A2C1006743)。
文摘This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'geometric linearity on their photocatalytic properties.Herein,the Mg O film,obtained by plasma electrolysis of AZ31 Mg alloys,was modified by growing an LDH film,which was further functionalized using cyclic sodium hexametaphosphate(CP)and linear sodium tripolyphosphate(LP).CP acted as an enhancer for flake spacing within the LDH structure,while LP changed flake dispersion and orientation.Consequently,CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis,effectively degrading organic dyes like Methylene blue(MB),Congo red(CR),and Methyl orange(MO).The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules.Furthermore,the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH,leading to its superior photocatalytic performance compared to LP@LDH.Specifically,LP@LDH demonstrated notable degradation efficiencies of 93.02%,92.89%,and 88.81%for MB,MO,and CR respectively,over a 40 min duration.The highest degradation efficiencies were observed in the case of the CP@LDH sample,reporting 99.99%for MB,98.88%for CR,and 99.70%for MO.This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation,offering promising prospects for environmental remediation and water detoxification applications.
基金the funding support from the National Natural Science Foundation of China(21906072,22006057)the Natural Science Foundation of Jiangsu Province(BK20190982)“Doctor of Mass entrepreneurship and innovation”Project in Jiangsu Province。
文摘The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.
文摘Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are unable to fully decompose and mineralize plastic waste. Therefore, there is a need to develop an environmentally friendly, innovative and sustainable photocatalytic process that can destroy these wastes with much less energy and chemical consumption. In photocatalysis, various nanomaterials based on wide energy band gap semiconductors such as TiO2 and ZnO are used for the conversion of plastic contaminants into environmentally friendly compounds. In this work, the removal of plastic fragments by photocatalytic reactions using newly developed photocatalytic composites and the mechanism of photocatalytic degradation of microplastics are systematically investigated. In these degradation processes, sunlight or an artificial light source is used to activate the photocatalyst in the presence of oxygen.
基金the financial supports from National Natural Science Foundation of China(22172066,22378176)supported by State Key Laboratory of Heavy Oil ProcessingSupported by Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment,Suzhou University of Science and Technology。
文摘An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.
文摘This review paper explores the efficacy of magnesium ferrite-based catalysts in photocatalytic degradation of organic contaminates(antibiotic and dyes).We report the influence of different doping strategies,synthesis methods,and composite materials on the degradation efficiency of these pollutants.Our analysis reveals the versatile and promising nature of magnesium ferrite-based catalysts,offering the valuable insights into their practical application for restoring the environment.Due to the smaller band gap and magnetic nature of magnesium ferrite,it holds the benefit of utilising the broader spectrum of light while also being recoverable.The in-depth analysis of magnesium ferrites'photocatalytic mechanism could lead to the development of cheap and reliable photocatalyst for the wastewater treatment.This concise review offers a thorough summary of the key advancements in this field,highlighting the pivotal role of the magnesium ferrite based photocatalysts in addressing the pressing global issue of organic pollutants in wastewater.
基金support of this research by the National Natural Science Foundation of China(Grant No.51909165,42177438)the Start-up Research Funding of Southwest Jiaotong University(YH1100312372222)+4 种基金the Fundamental Research Funds for the Central Universities(XJ2022003201)Science and Technology Program of Guangzhou(2019050001)National Key Research and Development Program of China(2019YFE0198000)the High-End Foreign Experts Project(G2021030016L)Pearl River Talent Program(2019QN01L951)
文摘Defect engineering can give birth to novel properties for adsorption and photocatalysis in the control of antibiotics and heavy metal combined pollution with photocatalytic composites.However,the role of defects and the process mechanism are complicated and indefinable.Herein,TiO_(2)/CN/3DC was fabricated and defects were introduced into the tripartite structure with separate O_(2)plasma treatment for the single component.We find that defect engineering can improve the photocatalytic activity,attributing to the increase of the contribution from h^(+)and OH.In contrast to TiO_(2)/CN/3DC with a photocatalytic tetracycline removal rate of 75.2%,the removal rate of TC with D-TiO_(2)/CN/3DC has increased to 88.5%.Moreover,the reactive sites of tetracycline can be increased by adsorbing on the defective composites.The defect construction on TiO_(2)shows the advantages in tetracycline degradation and Cu^(2+)adsorption,but also suffers significant inhibition for the tetracycline degradation in a tetracycline/Cu^(2+)combined system.In contrast,the defect construction on graphene can achieve the cooperative removal of tetracycline and Cu^(2+).These findings can provide new insights into water treatment strategies with defect engineering.
基金supported by the National Research Foundation of Korea(NRF)funded by the Korean government(MSIT)(No.2022R1A2C1006743).
文摘In the pursuit of multifunctional coatings,the controlled growth of materials on stationary platforms holds paramount importance for achieving superior corrosion protection and optimal photocatalytic performance.This study introduces a cutting-edge approach,intertwining bifunctional metal-organic frameworks(MOFs)seamlessly into defective MgO layers produced by the anodic oxidation of AZ31 alloy.Key metallic oxides of Zn,Sn,and V take center stage as metallic sources for MOF formation,complemented by the organic prowess of L-Tryptophan as anα-amino acid linker.Leveraging the electronic structure of metallic oxides reacting with tryptophan molecules,controlled morphologies with distinct characteristics are induced on the defective surface of the MgO layer,enabling the precise modulation of surface defects.The hybrid composite demonstrates an adaptive microstructure in diverse aqueous environments,offering dual functionality with electrochemical stability and visible light photocatalytic activity for crystal violet degradation.Among the samples,the SnOF complex exhibited remarkable electrochemical stability with a low corrosion current density of 7.50×10^(−10)A·cm^(−2),along with a 94.56%degradation efficiency after 90 min under visible light exposure.The VOF complex,under similar visible light conditions,demonstrated exceptional performance with a higher degradation efficiency of 97.79%and excellent electrochemical stability characterized by a corrosion current density of 3.26×10^(−9)A·cm^(−2).Additionally,Density Functional Theory(DFT)computations shed light on the basic bonding patterns between MOFs and inorganic components,providing electronic understanding of their electrochemical and photocatalytic activities.
基金the following funding agencies for supporting this work: the National Natural Science Foundation of China (22025502, U23A20552, 22379026, 22222901, 22175022)the Natural Science Foundation of Shanghai (23ZR1407000)the Science and Technology Commission of Shanghai Municipality (21DZ1206800)
文摘Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.
基金supported by the Shandong Provincial Natural Science Foundation(ZR2022ME179,ZR2021QE086)the Shandong Provincial Key Research and Development Program(Public Welfare Science and Technology Research)(2019GGX103010)+2 种基金the Science and Technology Planning Project of Higher School in Shandong Province(J18KA243)the Liaocheng Key Research and Development Program(Policy guidance category)(2022YDSF90)the Liaocheng University High-level Talents&PhD Research Startup Foundation(318051619)。
文摘Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.
基金National Natural Science Foundation of China(Grant No.21902001,22179001)Distinguished Young Research Project of Anhui Higher Education Institution(Grant No.2022AH020007)+1 种基金University Synergy Innovation Program of Anhui Province(Grant No.GXXT-2023-009)Higher Education Natural Science Foundation of Anhui Province(Grant No.2023AH050114).
文摘Adsorption coupled with photocatalytic degradation is proposed to fulfill the removal and thorough elimination of organic dyes.Herein,we report a facile hydrothermal synthesis of MIL-100(Fe)/GO photocatalysts.The adsorption and photocatalytic degradation process of methylene blue(MB)on MIL‐100(Fe)/GO composites were systematically studied from performance and kinetic perspectives.A possible adsorption‐photocatalytic degradation mechanism is proposed.The optimized 1M8G composite achieves 95%MB removal(60.8 mg/g)in 210 min and displays well recyclability over ten cycles.The obtained MB adsorption and degradation results are well fitted onto Langmuir isotherm and pseudo‐second order kinetic model.This study shed light on the design of MOFs based composites for water treatment.
基金Supported by the Open Project Foundation of Industrial Perception and Intelligent Manufacturing Equipment Engineering Research Center of Jiangsu Province (No. ZK220504)the Open Project Foundation of High-tech Key Laboratory of Agricultural Equipment and Intelligence of Jiangsu Province (No. MAET202104)+1 种基金the Open Project Foundation of Jiangsu Wind Power Engineering Technology Center (No. ZK220302)the Qing Lan Project of Jiangsu Province,China。
文摘The Nd:TiO_(2 )PEO coatings were formed in a phosphate-based electrolyte with the addition of Nd_(2)O_(3 )under the current density of 150,200,250 and 300 m A/cm^(2).SEM results showed that the micropores decreased on quantity and increased on scale with the increasing current density.AFM results revealed that the roughness of the coatings increased with the increasing current density.Phase and composition analysis showed that the Nd:TiO_(2) coatings were mainly composed of anatase and rutile phase.And the anatase phase content has reached the maximum value at the current density of 250 m A/cm^(2).XPS results indicated that Ti2p spin-orbit components of the Nd:TiO_(2) coatings are shifted towards higher binding energy,compared with the pure TiO_(2) coating,suggesting that some of the Nd^(3+)ions are combined with TiO_(2) lattice and led to dislocation.Photocatalytic test showed that the photocatalytic activity of Nd:TiO_(2) coatings varied in the same pattern with the anatase content variation in Nd:TiO_(2) coatings.The photocatalytic experiment results show that the photocatalytic activity of Nd:TiO_(2) coatings can be greatly enhanced with moderate amount of Nd^(3+).However,excessive amount of Nd^(3+)does not have an effective impact on the photoctalytic activity improvement.
基金Funded by National Key Research and Development Program of China (No.2021YFA1600203)。
文摘A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation ability of all samples was evaluated using methylene blue (MB) as a target contaminant.The band gaps of N-doped samples are all higher than that of pristine ones,which is only 3.12 eV.BET specific surface area S_(BET) and pore volume are increased due to the N doping.And the greater increase of S_(BET),the faster the photodegradation speed of methylene blue on SrMoO_(4).More specifically,the degradation efficiency of MB is improved up to 87%in 100 min.
基金financial support from the National Natural Science Foundation of China(No.22272038)the Science and Technology Planning Project of Guangzhou City(No.2023A03J0026)。
文摘Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.
基金supported by the National Natural Science Foundation of China(22208328)Fundamental Research Program of Shanxi Province(20210302124618,202203021212134)。
文摘Spinning disk reactor(SDR)has emerged as a novel process intensification photocatalytic reactor,and it has higher mass transfer efficiency and photon utilization for the degradation of toxic organic pollutants by advanced oxidation processes(AOPs).In this study,ZnO—TiO_(2)nanocomposites were prepared by solgel method,and coated on the disk of SDR by impregnation-pull-drying-calcination method.The performance of catalyst was characterized by X-ray diffraction,scanning electron microscope,X-ray photoelectron spectroscopy,photoluminescence and ultraviolet—visible diffuse reflectance spectroscopy.Photocatalytic ozonation in SDR was used to remove phenol,and various factors on degradation effect were studied in detail.The results showed that the rate of degradation and mineralization reached 100%and 83.4%under UV light irradiation after 50 min,compared with photocatalysis and ozonation,the removal rate increased by 69.3%and 34.7%,and mineralization rate increased by 56.7%and 62.9%,which indicated that the coupling of photocatalysis and ozonation had a synergistic effect.The radical capture experiments demonstrated that the active species such as photogenerated holes(h^(+)),hydroxyl radicals(·OH),superoxide radical(·O_(2)-)were responsible for phenol degradation,and·OH played a leading role in the degradation process,while h+and·O_(2)^(-)played a non-leading role.
基金the financial support from the Program for Innovative Research Team in University of Henan Province(21IRTSTHN009)Science and Technology Fund of Henan Province(225200810051)Natural Science Foundation of Henan Province(222300420406)。
文摘The photoreduction of CO_(2)into CH_(4)with simultaneous high activity and selectivity is a promising strategy to increase energy supply and alleviate global warming.However,the absence of the active sites that is responsible for the adsorption and activation of CO_(2)and the generation of CO and H2via side reactions often lead to poor efficiency and low selectivity of the catalyst.Herein,Cu,Pd,and PdCu metal clusters cocatalyst-anchored defective TiO_(2)nanotubes(Cu/TiO_(2)-SBO,Pd/TiO_(2)-SBO,and Pd1Cu1/TiO_(2)-SBO)were designed via a simple solution impregnation reduction and applied for photocatalytic conversion of CO_(2)to CH_(4).The Pd1Cu1/TiO_(2)-SBO photocatalyst exhibits excellent catalytic performance among the other catalysts for photoreduction of CO_(2)into CH_(4).More interestingly,the product selectivity of CH_(4)reaches up to 100%with a rate of 25μmol g^(-1)h^(-1).In-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)simulations indicate that the main reasons for the high selectivity of CH_(4)are attributed to the PdCu alloy and oxygen vacancies,which jointly enhance the photoinduced carrier separation and lower energy barriers of key intermediates.Moreover,due to the tunable d-band center of the Cu site in the PdCu alloy,the generated intermediates can be well prevented from poisoning and promoted to participate in further reactions.Hopefully,the current study will provide insight into the development of new,highly selective photocatalysts for the visible light-catalytic reduction of CO_(2)into CH_(4).
文摘Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2)production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.
基金supported by the National Natural Science Foundation of China(52072196,52002200,52102106,52202262,22379081,22379080)the Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)+1 种基金the Natural Science Foundation of Shandong Province(ZR2020QE063,ZR202108180009,ZR2023QE059)the Project funded by China Postdoctoral Science Foundation(2023M741871)。
文摘Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)S_(4)(HVs-ZIS)and CoIn_(2)S_(4)(CIS)via a defect-guided heteroepitaxial growth strategy.The strong interface coupling induces adequate carriers exchanging passageway between HVs-ZIS and CIS,enhancing the internal electric field(IEF)in the ZnIn_(2)S_(4)/CoIn_(2)S_(4)(HVs-ZIS/CIS)heterostructure.The defect structure in HVs-ZIS induces an additional defect level,improving the separation efficiency of photocarriers.Moreover,promoted by the IEF and intimate heterointerface,photogenerated electrons trapped by the defect level can migrate to the valence band of CIS,contributing to massive photogenerated electrons with intense reducibility in HVs-ZIS/CIS.Consequently,the HVs-ZIS/CIS heterostructure performs a boosted H_(2)evolution activity of 33.65 mmol g^(-1)h^(-1).This work highlights the synergistic effects of defect and strong interface coupling in regulating carrier transfer and paves a brave avenue for constructing efficient heterostructure photocatalysts.
文摘The direct conversion of atmospheric CO_(2) into fuel via photocatalysis exhibits significant practical application value in advancing the carbon cycle.In this study,we established an electro-assisted photocatalytic system with dual compartments and interfaces,and coated Ag nanoparticles on the titanium nanotube arrays(TNTAs)by polydopamine modification.In the absence of sacrificial agent and alkali absorption liquid conditions,the stable,efficient and highly selective conversion of CO_(2) to CO at the gas-solid interface in ambient air was realized by photoelectric synergy.Specifically,with the assistance of potential,the CO formation rates reached 194.9μmol h^(−1) m^(−2) and 103.9μmol h^(−1) m^(−2) under ultraviolet and visible light irradiation,respectively;the corresponding CO_(2) conversion rates in ambient air were 30%and 16%,respectively.The excellent catalytic effect is mainly attributed to the formation of P–N heterojunction during the catalytic process and the surface plasmon resonance effect.Additionally,the introduction of solid agar electrolytes effectively inhibits the hydrogen evolution reaction and improves the electron utilization rate.This system promotes the development of photocatalytic technology for practical applications and provides new insights and support for the carbon cycle.
基金financially supported by the National Natural Science Foundation of China(22309032)the Guangdong Basic and Applied Basic Research Foundation(2022A1515011737)+1 种基金the Science and Technology Program of Guangzhou(2023A04J1395)the GDAS’Project of Science and Technology Development(2021GDASYL-20210102010)。
文摘Photocatalytic reduction of CO_(2) into fuel represents a promising approach for achieving carbon neutrality,while realizing high selectivity in this process is challenging due to uncontrollable reaction intermediate and retarded desorption of target products.Engineering the interface microenvironment of catalysts has been proposed as a strategy to exert a significant influence on reaction outcomes,yet it remains a significant challenge.In this study,amino alkylation was successfully integrated into the melem unit of polymeric carbon nitrides(PCN),which could efficiently drive the photocatalytic CO_(2) reduction.Experimental characterization and theoretical calculations revealed that the introduction of amino alkylation lowers the energy barrier for CO_(2) reduction into^(*)COOH intermediate,transforming the adsorption of^(*)COOH intermediate from the endothermic to an exothermic process.Notably,the as-prepared materials demonstrated outstanding performance in photocatalytic CO_(2) reduction,yielding CO_(2)at a rate of 152.8μmol h^(-1) with a high selectivity of 95.4%and a quantum efficiency of 6.6%.
基金financially supported by the National Natural Science Foundation of China(22172144)Key Research and Development Program of Zhejiang Province(2023C03148)。
文摘The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency,thereby boosting the performance of photocatalysts.In this study,BiO_(2-x)nanosheets were synthesized through a hydrothermal process and loaded onto NaNbO_(3) microcube to construct a series of BiO_(2-x)/NaNbO_(3) heterojunctions for photocatalytic N_(2) fixation.Results indicated that 2.5%BiO_(2-x)/NaNbO_(3) had the highest photocatalytic performance.The NH_(3) production rate under simulated solar light reached 406.4μmol·L^(-1)·g^(-1)·h^(-1),which reaches 2.6 and 3.8 times that of NaNbO_(3) and BiO_(2-x),respectively.BiO_(2-x)nanosheets primarily act as electron trappers to enhance the separation efficiency of charge carriers.The strong interaction between BiO_(2-x)and NaNbO_(3) facilitates the electron migration between them.Meanwhile,the abundant oxygen vacancies in BiO_(2-x)nanosheets may facilitate the adsorption and activation of N_(2),which may be another possible reason of the high photocatalytic activity of the BiO_(2-x)/NaNbO_(3).This study may offer new insights for the development of semiconductor materials in photocatalytic nitrogen fixation.