Highly photocatalytically active cobalt-doped ZnO （ZnO：Co） nanorods have been prepared by a facile hydrothermal process. X-ray diffraction, X-ray photoelectron spectroscopy, Raman scattering and UV-vis diffuse refl...Highly photocatalytically active cobalt-doped ZnO （ZnO：Co） nanorods have been prepared by a facile hydrothermal process. X-ray diffraction, X-ray photoelectron spectroscopy, Raman scattering and UV-vis diffuse reflectance spectroscopy confirmed that the dopant ions substitute for some of the lattice zinc ions, and furthermore, that Co〉 and Co〉 ions coexist. The as-prepared ZnO：Co samples have an extended light absorption range compared with pure ZnO and showed highly efficient photocatalytic activity, only requiring 60 rain to decompose -93% of alizarin red dye under visible light irradiation （λ 〉 420 nm）, The photophysical mechanism of the visible photocatalytic activity was investigated with the help of surface photovoltage spectroscopy. The results indicated that a strong electronic interaction between the Co and ZnO was present, and that the incorporation of Co promoted the charge separation and enhanced the charge transfer ability and, at the same time, effectively inhibited the recombination of photogenerated charge carriers in ZnO, resulting in high visible light photocatalytic activity.展开更多
Silica gel-supported Fe(II) (SiOFe) was prepared and used for heterogeneous degradation of sulforho-damine B (SRB) and 2,4-dichlorophenol (DCP) under visible irradiation (λ > 420 nm) as an effective catalyst. UVvi...Silica gel-supported Fe(II) (SiOFe) was prepared and used for heterogeneous degradation of sulforho-damine B (SRB) and 2,4-dichlorophenol (DCP) under visible irradiation (λ > 420 nm) as an effective catalyst. UVvisible spectra, and infrared Spectrophotometry (IR), fluorescence, total organic carbon (TOC) and electron spin resonance (ESR) measurements were employed to analyze the photoreaction products. The results showed that SRB could be efficiently degraded by SiOFe/H2O2 system under visible irradiation with 100% decolorization and 72.3% TOC removal after 180 min illumination. The results of ESR and fluorescence measurements indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) generated in the system.展开更多
The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is high...The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.展开更多
Nanoflower-like ZnO-C_(3)N_(4) thin film with a porous net structure was successfully synthesized by a simple chemical corrosion method.The prepared ZnOC_(3)N_(4) thin films presented remarkable photocatalytic activit...Nanoflower-like ZnO-C_(3)N_(4) thin film with a porous net structure was successfully synthesized by a simple chemical corrosion method.The prepared ZnOC_(3)N_(4) thin films presented remarkable photocatalytic activities for the degradation of methyl orange under visible light irradiation,and more than 90%methyl orange was removed from water by ZnO-C_(3)N_(4) composite.Meanwhile,the ZnO-C_(3)N_(4) composite presented an enhanced photocatalytic stability.The loading content of C_(3)N_(4) had a great effect on the photocatalytic performance.Moreover,the photocatalytic activities were higher in acidic media than those in alkaline conditions.The adsorption of methyl orange was enhanced,and the recombination of photogenerated electrons and holes was suppressed with a suitable content of C_(3)N_(4).However,too much loading content of C_(3)N_(4) resulted in a poor dispersion of C_(3)N_(4) as the aggregated C_(3)N_(4) can behave as recombination centers.In addition,the prepared ZnO-C_(3)N_(4) thin film can be used for the water splitting in water-methanol system under simulated solar light irradiation.展开更多
The performance of Mn-TiO2/sepiolite photocatalysts prepared by the solgel method and calcinated at different temperatures was studied in the photocatalytic degradation of direct fast emerald green dye under visible l...The performance of Mn-TiO2/sepiolite photocatalysts prepared by the solgel method and calcinated at different temperatures was studied in the photocatalytic degradation of direct fast emerald green dye under visible light irradiation,and a series of analytical techniques such as XRD,SEM,FTIR,TG-DSC,XPS,UV-vis-DRS and Raman spectroscopy were used to characterize the morphology,structure and optical properties of the photocatalysts.It is found that the anatase TiO2 was formed in all photocatalysts.Mn4+might incorporate into the lattice structure of TiO2 and partially replace Ti4+,thus causing the defects in the crystal structure and the broadening of the spectral response range of TiO2.At the same time,TiO2 particles were dispersed on the surface of the sepiolite,which immobilized TiO2 particles with sepiolite via the bond of Ti-O-Si.Mn-TiO2/sepiolite calcined at 400°C exhibits the highest photocatalytic activity and the degradation rate of direct fast emerald green is up to 98.13%.Meanwhile,it also shows good stability and universality.展开更多
Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental research and industrial production of fine chemicals.However,the employment of stoichiometric strong oxidizing or red...Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental research and industrial production of fine chemicals.However,the employment of stoichiometric strong oxidizing or reducing reagents(e.g.,K_(2)Cr_(2)O_(7) and LiAlH_(4))and harsh reaction conditions(e.g.,high temperature and pressure)always leads to the products of overreaction and other by-product residues(e.g.,salt and acid waste).Thus the poor control of product selectivity and tremendous energy consumption result in the urgent demand to develop novel technologies for heterogeneous catalysis.Given the current global theme of development in CO_(2) reduction and sustainable energy utilization,one promising protocol is heterogeneous photocatalysis.It enables sustainable solar-to-chemical energy conversion under mild conditions(e.g.,room temperature,ambient pressure,and air as the oxidant)and offers unique reaction pathways for improved selectivity control.To accurately tailor the selectivity of desired products,the electronic structure(e.g.,positions of valence-band maximum and conduction-band minimum),geometric structure(e.g.,nanorod,nanosheet,and porous morphology),and surface chemical micro-environment(e.g.,vacancy sites and co-catalysts)of heterogeneous photocatalysts require rational design and construction.In this review,we will briefly analyze some effective photocatalytic systems with the excellent regulation ability of product selectivity in organic transformations(mainly oxidation and reduction types)under visible light irradiation,and put forward opinions on the optimal fabrication of nanostructured photocatalysts to realize selective organic synthesis.展开更多
The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production ...The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production of DFF from HMF has attracted tremendous attention. Herein, the MoS_(2)/CdIn_(2)S_(4)(MC)flower-like heterojunctions were prepared and considered as photocatalysts for selective oxidation of HMF into DFF under visible-light irradiation in aqueous solution. Results demonstrated MoS_(2) in MC heterojunction could promote the separation of photoexcited electron-hole pairs, while the amount of MoS_(2) dropping was proved influenced on the photocatalytic performance. 80.93% of DFF selectivity was realized when using 12.5% MC as photocatalyst. In addition, the MC catalyst also showed great potential in transformation of other biomass derived benzyl-and furyl-alcohols. The catalytic mechanism suggested that ·O_(2)^(-) was the decisive active radical for HMF oxidation. Therefore, the MC heterojunction could be applied in photocatalytic conversion of biomass to valuable chemicals under ambient condition.展开更多
Exfoliation of bulk graphitic carbon nitride(g‐C3N4)into two‐dimensional(2D)nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g‐C3N4 nanosheets(CN)have larger spe...Exfoliation of bulk graphitic carbon nitride(g‐C3N4)into two‐dimensional(2D)nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g‐C3N4 nanosheets(CN)have larger specific surface areas and more reaction sites.In addition,poly‐o‐phenylenediamine(PoPD)can improve the electrical conductivity and photocatalytic activity of semiconductor materials.Here,the novel efficient composite PoPD/AgCl/g‐C3N4 nanosheets was first synthesized by a precipitation reaction and the photoinitiated polymerization approach.The obtained photocatalysts have larger specific surface areas and could achieve better visible‐light response.However,silver chloride(AgCl)is susceptible to agglomeration and photocorrosion.The PoPD/AgCl/CN composite exhibits an extremely high photocurrent density,which is three times that of CN.Obviously enhanced photocatalytic activities of PoPD/AgCl/g‐C3N4 are revealed through the photodegradation of tetracycline.The stability of PoPD/AgCl/CN is demonstrated based on four cycles of experiments that reveal that the degradation rate only decreases slightly.Furthermore,.O2^-and h+are the main active species,which are confirmed through a trapping experiment and ESR spin‐trap technique.Therefore,the prepared PoPD/AgCl/CN can be considered as a stable photocatalyst,in which PoPD is added as a charge carrier and acts a photosensitive protective layer on the surface of the AgCl particles.This provides a new technology for preparing highly stable composite photocatalysts that can effectively deal with environmental issues.展开更多
A novel mixed-valence,ring-shaped multinuclear Mn-containing polyoxometalate,[H_(2)N(CH_(3))_(2)]_(15) NaH8-[Mn^(Ⅲ) 3MnIV(μ3-O)_(3)(OAc)PO4(B-α-PW_(9)O_(34))]_(4)·36H_(2)O(1)was made and systematically charact...A novel mixed-valence,ring-shaped multinuclear Mn-containing polyoxometalate,[H_(2)N(CH_(3))_(2)]_(15) NaH8-[Mn^(Ⅲ) 3MnIV(μ3-O)_(3)(OAc)PO4(B-α-PW_(9)O_(34))]_(4)·36H_(2)O(1)was made and systematically characterized using various spectroscopic and computational techniques.Its polyoxoanion can be described as a tetramer made of four[Mn^(Ⅲ) 3MnIV(μ3-O)3(OAc)(B-α-PW_(9)O_(34))]_(3)−({Mn^(Ⅲ) 3Mn^(IV)(PW_(9))})clusters and four PO_(4) linkers.展开更多
Graphitic carbon nitride(g-C_(3)N_(4)) is a fascinating photocatalyst for solar energy utilization in photo-catalysis.Nevertheless,it often suffers from moderate photo-catalytic activity due to its low specific surfac...Graphitic carbon nitride(g-C_(3)N_(4)) is a fascinating photocatalyst for solar energy utilization in photo-catalysis.Nevertheless,it often suffers from moderate photo-catalytic activity due to its low specific surface area and fast recombination rate of photogenerated electrons upon photo-excitation.Herein,we overcome the bottlenecks by constructing a porous g-C_(3)N_(4) nanosheet(PCNS)through a simple thermal oxidation etching method.Benefited from its porous layer structure,the obtained PCNS exhibits large specific surface area,efficient separation of photogenerated charge carriers,as well as high exposure of active sites.As a result,it is robust and universal in visible light-driven dehydrogenation of alcohols in water under oxidant-free condition.Almost quantitative yields(>99%)of various valuable carbonyl compounds were obtained over PCNS,while bulk g-C_(3)N_(4) was far less efficient.Moreover,the photo-catalyst was highly stable and could be facilely recovered from the aqueous system for efficient reuse.The easy preparation and excellent performance made PCNS a promising and competitive photocatalyst for the solar applications.展开更多
The chemistry of alkoxy radicals was extensively explored during the period of 1960s to 1990s,but it has remained dormant for the past few decades.Recently,alkoxy radicals attract the attentions again,because new meth...The chemistry of alkoxy radicals was extensively explored during the period of 1960s to 1990s,but it has remained dormant for the past few decades.Recently,alkoxy radicals attract the attentions again,because new methods for generating alkoxy radical species have emerged.These newly developed methods are mainly based on the photolysis by visible light under mild conditions,thus allowing for new transformations of the carbon-centered radical species that are generated from theβ-scission or hydrogen abstraction of the alkoxy radicals.展开更多
We report a new and simple preparation method of the visible light responsive Titanium dioxide (TiO2) photocatalytic films using sol-gel method and ultraviolet light (UV) irradiation. Proposed films were prepared on f...We report a new and simple preparation method of the visible light responsive Titanium dioxide (TiO2) photocatalytic films using sol-gel method and ultraviolet light (UV) irradiation. Proposed films were prepared on fused silica plates using titanium tetra-isopropoxide, urea, 2-methoxyethanol, water and UV irradiation. The 650°C-annealed films were carbon-containing anatase type TiO2, not carbon-doped ones. The prepared films absorbed visible light with wavelengths longer than 400 nm. Also, organic dyes were effectively photodegradated by visible light irradiation in the presence of these films.展开更多
Gd-doped PbMoO_(4) nanoparticles were prepared by a refluxing method at 80℃ for 2 h.Effect of molar content of Gd dopant on phase,morphology and optical properties was studied.The as-prepared Gddoped PbMoO_(4) sample...Gd-doped PbMoO_(4) nanoparticles were prepared by a refluxing method at 80℃ for 2 h.Effect of molar content of Gd dopant on phase,morphology and optical properties was studied.The as-prepared Gddoped PbMoO_(4) samples can be indexed to pure tetragonal PbMoO_(4) phase.The particles size of PbMoO_(4) is decreased with increasing in the molar content of Gd dopant from 15.20±3.04 nm for pure PbMoO_(4) to 8.72±1.53 nm for 5 mol% Gd-doped PbMoO_(4).The absorption of 5 mol% Gd-doped PbMoO_(4) nanoparticles shows red-shift caused by lattice distortion of PbMoO_(4).The photocatalytic performance of 5 mol% Gddoped PbMoO_(4) nanoparticles shows the highest degradation of rhodamine B(RhB) of 97.92% under UV radiation and 67.65% under visible radiation because Gd^(3+) dopant as an electron acceptor plays the role in enhancing the separation of electron-hole pair.展开更多
A photoinduced reaction of potassium alkyltrifluoroborates,sulfur dioxide,and para-quinone methides under visible light irradiation at room temperature is developed,giving rise to diarylmethyl alkylsulfones in moderat...A photoinduced reaction of potassium alkyltrifluoroborates,sulfur dioxide,and para-quinone methides under visible light irradiation at room temperature is developed,giving rise to diarylmethyl alkylsulfones in moderate to good yields.This reaction works well under photocatalysis with a broad substrate scope by using DABCO·(SO_(2))_(2)as the source of sulfur dioxide.Mechanistic study shows that this transformation is initiated by alkyl radicals generated in situ from potassium alkyltrifluoroborates in the presence of photocatalyst.The subsequent insertion of sulfur dioxide and radical 1,6-addition of para-quinone methides with alkylsulfonyl radical intermediates afford the corresponding diarylmethyl alkylsulfones.展开更多
Nonylphenol(NP)residues,as a typical endocrine disrupting chemical(EDC),frequently exist in sewage,surface water,groundwater and even drinking water,which poses a serious threat to human health due to its bioaccumulat...Nonylphenol(NP)residues,as a typical endocrine disrupting chemical(EDC),frequently exist in sewage,surface water,groundwater and even drinking water,which poses a serious threat to human health due to its bioaccumulation.In order to remove NP,a series of MIL-100(Fe)/Zn Fe_(2)O_(4)/flake-like porous carbon nitride(MIL/ZC)was synthesized through in-situ synthesis at room temperature.High performance of ternary MIL/ZC is used to degrade NP under visible light irradiation.The results show that 30MIL/ZC2(20 wt.%Zn Fe_(2)O_(4))ternary composite had the best photocatalytic activity(99.84%)when the dosage was 30 mg.Further mechanism analysis shows that the excellent photocatalytic activity of 30MIL/ZC2could be ascribed to the double charge transfer process between flake-like porous carbon nitride(PCN)and other catalysts in the ternary heterojunction,and the separation of photogenerated electron-hole pairs was more effective.In addition,the 30MIL/ZC2 also showed high stability after five cycles of the photodegradation reaction.Furthermore,the active substance(·O_(2)^(-))was considered to be the main active substance in the NP degradation process.Based on the research results,the possible photocatalytic reaction mechanism of 30MIL/ZC2ternary composite was proposed and discussed in detail.展开更多
Unique multiple heterojunction of Pt-BiOBr/TiO2 nanotube arrays（Pt-BiOBr/TNTAs） was achived by successively loading both Pt nanoparticles（NPs） and BiOBr nanoflkes（NFs） on surface of ordered and spaced TiO2 nanot...Unique multiple heterojunction of Pt-BiOBr/TiO2 nanotube arrays（Pt-BiOBr/TNTAs） was achived by successively loading both Pt nanoparticles（NPs） and BiOBr nanoflkes（NFs） on surface of ordered and spaced TiO2 nanotubes（NTs） using anodization followed by solvothermal and sequential chemical bath deposition（S-CBD） method. The fabricated Pt-Bi OBr/TNTAs were fully characterized, and the photocatalytic（PC） activity and stability of PtBiOBr/TNTAs toward degradation of methyl orange（MO） under visible-light irradiation（λ＆gt;400 nm） were evaluated. The results reveal that multiple heterostructures of Pt/TiO2, Pt/BiOBr and BiOBr/TiO2 are constructed among TNTAs substrate, Pt NPs and BiOBr NFs, and the hybrid Pt-BiOBr/TNTAs catalyst exhibits remarkable visible-light PC activity, favourable reusability and long-term stability. The combined effect of several factors may contribute to the remarkable PC performance, including strong visible-light absorption by both Pt NPs and BiOBr NFs, lower recombination rate of photo-generated electrons and holes attributed to the multiple heterojunction, microstructures for facile light injection and adsorption as well as efficient mass transport, and larger specific surface area for enhancing light absorption, increasing the effective contact area between the absorbed dye molecules and catalyst and benefiting the molecule transport of reactants or products.展开更多
A metal-free and environmentally friendly aerobic aromatization photosensitized by organic dye eosin Y bis(tetrabutyl ammonium salt)(TBA-eosinY)has been developed.With the aid of K_(2)CO_(3),the aerobic catalytic syst...A metal-free and environmentally friendly aerobic aromatization photosensitized by organic dye eosin Y bis(tetrabutyl ammonium salt)(TBA-eosinY)has been developed.With the aid of K_(2)CO_(3),the aerobic catalytic system converts 1,4-dihydropyridines to their corresponding pyridine derivatives efficiently under visible light irradiation(λ=450 nm)at room temperature.展开更多
基金Acknowledgements We are grateful to the National Basic Research Program of China （973 Program, No. 2007CB613303） for financial support. This work was also supported by the National Natural Science Foundation of China （No. 20873053）.
文摘Highly photocatalytically active cobalt-doped ZnO （ZnO：Co） nanorods have been prepared by a facile hydrothermal process. X-ray diffraction, X-ray photoelectron spectroscopy, Raman scattering and UV-vis diffuse reflectance spectroscopy confirmed that the dopant ions substitute for some of the lattice zinc ions, and furthermore, that Co〉 and Co〉 ions coexist. The as-prepared ZnO：Co samples have an extended light absorption range compared with pure ZnO and showed highly efficient photocatalytic activity, only requiring 60 rain to decompose -93% of alizarin red dye under visible light irradiation （λ 〉 420 nm）, The photophysical mechanism of the visible photocatalytic activity was investigated with the help of surface photovoltage spectroscopy. The results indicated that a strong electronic interaction between the Co and ZnO was present, and that the incorporation of Co promoted the charge separation and enhanced the charge transfer ability and, at the same time, effectively inhibited the recombination of photogenerated charge carriers in ZnO, resulting in high visible light photocatalytic activity.
基金the National Natural Science Foundation of China (Grant Nos. 50639070 and 20373074)the Youth Outstanding Foundation of Hubei Province of China (Grant No. 2005ABB030)the Natural Science Research Plan Project of Education Office of Hubei Province of China (Grant No. 2004Z001)
文摘Silica gel-supported Fe(II) (SiOFe) was prepared and used for heterogeneous degradation of sulforho-damine B (SRB) and 2,4-dichlorophenol (DCP) under visible irradiation (λ > 420 nm) as an effective catalyst. UVvisible spectra, and infrared Spectrophotometry (IR), fluorescence, total organic carbon (TOC) and electron spin resonance (ESR) measurements were employed to analyze the photoreaction products. The results showed that SRB could be efficiently degraded by SiOFe/H2O2 system under visible irradiation with 100% decolorization and 72.3% TOC removal after 180 min illumination. The results of ESR and fluorescence measurements indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) generated in the system.
文摘The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.
基金financially supported by the National Natural Science Foundation of China(No.51574071)。
文摘Nanoflower-like ZnO-C_(3)N_(4) thin film with a porous net structure was successfully synthesized by a simple chemical corrosion method.The prepared ZnOC_(3)N_(4) thin films presented remarkable photocatalytic activities for the degradation of methyl orange under visible light irradiation,and more than 90%methyl orange was removed from water by ZnO-C_(3)N_(4) composite.Meanwhile,the ZnO-C_(3)N_(4) composite presented an enhanced photocatalytic stability.The loading content of C_(3)N_(4) had a great effect on the photocatalytic performance.Moreover,the photocatalytic activities were higher in acidic media than those in alkaline conditions.The adsorption of methyl orange was enhanced,and the recombination of photogenerated electrons and holes was suppressed with a suitable content of C_(3)N_(4).However,too much loading content of C_(3)N_(4) resulted in a poor dispersion of C_(3)N_(4) as the aggregated C_(3)N_(4) can behave as recombination centers.In addition,the prepared ZnO-C_(3)N_(4) thin film can be used for the water splitting in water-methanol system under simulated solar light irradiation.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(Grant No.21406184)the Foundation of Youth Science and Technology Innovation Team of Sichuan Province(Grant No.2015TD0007).
文摘The performance of Mn-TiO2/sepiolite photocatalysts prepared by the solgel method and calcinated at different temperatures was studied in the photocatalytic degradation of direct fast emerald green dye under visible light irradiation,and a series of analytical techniques such as XRD,SEM,FTIR,TG-DSC,XPS,UV-vis-DRS and Raman spectroscopy were used to characterize the morphology,structure and optical properties of the photocatalysts.It is found that the anatase TiO2 was formed in all photocatalysts.Mn4+might incorporate into the lattice structure of TiO2 and partially replace Ti4+,thus causing the defects in the crystal structure and the broadening of the spectral response range of TiO2.At the same time,TiO2 particles were dispersed on the surface of the sepiolite,which immobilized TiO2 particles with sepiolite via the bond of Ti-O-Si.Mn-TiO2/sepiolite calcined at 400°C exhibits the highest photocatalytic activity and the degradation rate of direct fast emerald green is up to 98.13%.Meanwhile,it also shows good stability and universality.
基金This work was supported by the National Key R&D Program of China(No.2020YFA0406103)the National Natural Science Foundation of China(NSFC)(Nos.21725102 and 91961106)+1 种基金the Dalian National Laboratory for Clean Energy(DNL)Cooperation Fund,Chinese Academy of Sciences(CAS)(No.DNL201922)the startup grant from University of Science and Technology of China(USTC)(No.KY2260080010).
文摘Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental research and industrial production of fine chemicals.However,the employment of stoichiometric strong oxidizing or reducing reagents(e.g.,K_(2)Cr_(2)O_(7) and LiAlH_(4))and harsh reaction conditions(e.g.,high temperature and pressure)always leads to the products of overreaction and other by-product residues(e.g.,salt and acid waste).Thus the poor control of product selectivity and tremendous energy consumption result in the urgent demand to develop novel technologies for heterogeneous catalysis.Given the current global theme of development in CO_(2) reduction and sustainable energy utilization,one promising protocol is heterogeneous photocatalysis.It enables sustainable solar-to-chemical energy conversion under mild conditions(e.g.,room temperature,ambient pressure,and air as the oxidant)and offers unique reaction pathways for improved selectivity control.To accurately tailor the selectivity of desired products,the electronic structure(e.g.,positions of valence-band maximum and conduction-band minimum),geometric structure(e.g.,nanorod,nanosheet,and porous morphology),and surface chemical micro-environment(e.g.,vacancy sites and co-catalysts)of heterogeneous photocatalysts require rational design and construction.In this review,we will briefly analyze some effective photocatalytic systems with the excellent regulation ability of product selectivity in organic transformations(mainly oxidation and reduction types)under visible light irradiation,and put forward opinions on the optimal fabrication of nanostructured photocatalysts to realize selective organic synthesis.
基金funded by the National Key Research and Development Program of China ( 2018YFB1501704)the National Natural Science Foundation of China (22078018)the Beijing Natural Science Foundation (2222016)。
文摘The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production of DFF from HMF has attracted tremendous attention. Herein, the MoS_(2)/CdIn_(2)S_(4)(MC)flower-like heterojunctions were prepared and considered as photocatalysts for selective oxidation of HMF into DFF under visible-light irradiation in aqueous solution. Results demonstrated MoS_(2) in MC heterojunction could promote the separation of photoexcited electron-hole pairs, while the amount of MoS_(2) dropping was proved influenced on the photocatalytic performance. 80.93% of DFF selectivity was realized when using 12.5% MC as photocatalyst. In addition, the MC catalyst also showed great potential in transformation of other biomass derived benzyl-and furyl-alcohols. The catalytic mechanism suggested that ·O_(2)^(-) was the decisive active radical for HMF oxidation. Therefore, the MC heterojunction could be applied in photocatalytic conversion of biomass to valuable chemicals under ambient condition.
基金supported by the National Natural Science Foundation of China(21576125,21776117)the China Postdoctoral Science Foundation(2017M611716,2017M611734)+1 种基金the Six talent peaks project of Jiangsu Province(XCL-014)the Zhenjiang Science&Technology Program(SH2016012)~~
文摘Exfoliation of bulk graphitic carbon nitride(g‐C3N4)into two‐dimensional(2D)nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g‐C3N4 nanosheets(CN)have larger specific surface areas and more reaction sites.In addition,poly‐o‐phenylenediamine(PoPD)can improve the electrical conductivity and photocatalytic activity of semiconductor materials.Here,the novel efficient composite PoPD/AgCl/g‐C3N4 nanosheets was first synthesized by a precipitation reaction and the photoinitiated polymerization approach.The obtained photocatalysts have larger specific surface areas and could achieve better visible‐light response.However,silver chloride(AgCl)is susceptible to agglomeration and photocorrosion.The PoPD/AgCl/CN composite exhibits an extremely high photocurrent density,which is three times that of CN.Obviously enhanced photocatalytic activities of PoPD/AgCl/g‐C3N4 are revealed through the photodegradation of tetracycline.The stability of PoPD/AgCl/CN is demonstrated based on four cycles of experiments that reveal that the degradation rate only decreases slightly.Furthermore,.O2^-and h+are the main active species,which are confirmed through a trapping experiment and ESR spin‐trap technique.Therefore,the prepared PoPD/AgCl/CN can be considered as a stable photocatalyst,in which PoPD is added as a charge carrier and acts a photosensitive protective layer on the surface of the AgCl particles.This provides a new technology for preparing highly stable composite photocatalysts that can effectively deal with environmental issues.
基金supported by National Natural Science Foundation of China(NSFCnos.21831001,21571016,91122028,20725101,and 21871025).
文摘A novel mixed-valence,ring-shaped multinuclear Mn-containing polyoxometalate,[H_(2)N(CH_(3))_(2)]_(15) NaH8-[Mn^(Ⅲ) 3MnIV(μ3-O)_(3)(OAc)PO4(B-α-PW_(9)O_(34))]_(4)·36H_(2)O(1)was made and systematically characterized using various spectroscopic and computational techniques.Its polyoxoanion can be described as a tetramer made of four[Mn^(Ⅲ) 3MnIV(μ3-O)3(OAc)(B-α-PW_(9)O_(34))]_(3)−({Mn^(Ⅲ) 3Mn^(IV)(PW_(9))})clusters and four PO_(4) linkers.
基金financial support provided by the National Natural Science Foundation of China(21676078)the Natural Science Foundation of Hunan Province for Distinguished Young Scholar(2016JJ1013)+1 种基金Scientific Research Fund of Hunan Provincial Education Department(19A323)Science and Technology Planning Project of Hunan Province(2018TP1017)。
文摘Graphitic carbon nitride(g-C_(3)N_(4)) is a fascinating photocatalyst for solar energy utilization in photo-catalysis.Nevertheless,it often suffers from moderate photo-catalytic activity due to its low specific surface area and fast recombination rate of photogenerated electrons upon photo-excitation.Herein,we overcome the bottlenecks by constructing a porous g-C_(3)N_(4) nanosheet(PCNS)through a simple thermal oxidation etching method.Benefited from its porous layer structure,the obtained PCNS exhibits large specific surface area,efficient separation of photogenerated charge carriers,as well as high exposure of active sites.As a result,it is robust and universal in visible light-driven dehydrogenation of alcohols in water under oxidant-free condition.Almost quantitative yields(>99%)of various valuable carbonyl compounds were obtained over PCNS,while bulk g-C_(3)N_(4) was far less efficient.Moreover,the photo-catalyst was highly stable and could be facilely recovered from the aqueous system for efficient reuse.The easy preparation and excellent performance made PCNS a promising and competitive photocatalyst for the solar applications.
基金The project is supported by NSFC(91956104),BNLMS,and Laboratory for Synthetic Chemistry and Chemical Biology of Health@InnoHK of ITC,HKSAR.
文摘The chemistry of alkoxy radicals was extensively explored during the period of 1960s to 1990s,but it has remained dormant for the past few decades.Recently,alkoxy radicals attract the attentions again,because new methods for generating alkoxy radical species have emerged.These newly developed methods are mainly based on the photolysis by visible light under mild conditions,thus allowing for new transformations of the carbon-centered radical species that are generated from theβ-scission or hydrogen abstraction of the alkoxy radicals.
文摘We report a new and simple preparation method of the visible light responsive Titanium dioxide (TiO2) photocatalytic films using sol-gel method and ultraviolet light (UV) irradiation. Proposed films were prepared on fused silica plates using titanium tetra-isopropoxide, urea, 2-methoxyethanol, water and UV irradiation. The 650°C-annealed films were carbon-containing anatase type TiO2, not carbon-doped ones. The prepared films absorbed visible light with wavelengths longer than 400 nm. Also, organic dyes were effectively photodegradated by visible light irradiation in the presence of these films.
基金supported by Center of Excellence in Materials Science and Technology,Chiang Mai University,Thailand。
文摘Gd-doped PbMoO_(4) nanoparticles were prepared by a refluxing method at 80℃ for 2 h.Effect of molar content of Gd dopant on phase,morphology and optical properties was studied.The as-prepared Gddoped PbMoO_(4) samples can be indexed to pure tetragonal PbMoO_(4) phase.The particles size of PbMoO_(4) is decreased with increasing in the molar content of Gd dopant from 15.20±3.04 nm for pure PbMoO_(4) to 8.72±1.53 nm for 5 mol% Gd-doped PbMoO_(4).The absorption of 5 mol% Gd-doped PbMoO_(4) nanoparticles shows red-shift caused by lattice distortion of PbMoO_(4).The photocatalytic performance of 5 mol% Gddoped PbMoO_(4) nanoparticles shows the highest degradation of rhodamine B(RhB) of 97.92% under UV radiation and 67.65% under visible radiation because Gd^(3+) dopant as an electron acceptor plays the role in enhancing the separation of electron-hole pair.
基金Financial support from the National Natural Science Foundation of China(Nos.22007017 and 21871053)the Talents'Startup Fund of Gannan Medical University(No.QD201831)+3 种基金the Education Bureau of Jiangxi Province(No.GJJ190799)the Research Fund of Gannan Medical University(No.ZD201905)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01005)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2020ZD04)。
文摘A photoinduced reaction of potassium alkyltrifluoroborates,sulfur dioxide,and para-quinone methides under visible light irradiation at room temperature is developed,giving rise to diarylmethyl alkylsulfones in moderate to good yields.This reaction works well under photocatalysis with a broad substrate scope by using DABCO·(SO_(2))_(2)as the source of sulfur dioxide.Mechanistic study shows that this transformation is initiated by alkyl radicals generated in situ from potassium alkyltrifluoroborates in the presence of photocatalyst.The subsequent insertion of sulfur dioxide and radical 1,6-addition of para-quinone methides with alkylsulfonyl radical intermediates afford the corresponding diarylmethyl alkylsulfones.
基金supported by the National Natural Science Foundation of China(No.21477050)the International Scientific and Technological Cooperation in Changzhou(No.CZ20140017)+2 种基金Postgraduate Research Innovation Project of Jiangsu Province(Nos.KYCX20_2561,KYCX20_2598)the Jiangsu Planned Projects for Postdoctoral Research Funds(No.2019K112)the Jiangsu Province subsidizes the recruitment of postdoctoral personnel(No.2019Z143)。
文摘Nonylphenol(NP)residues,as a typical endocrine disrupting chemical(EDC),frequently exist in sewage,surface water,groundwater and even drinking water,which poses a serious threat to human health due to its bioaccumulation.In order to remove NP,a series of MIL-100(Fe)/Zn Fe_(2)O_(4)/flake-like porous carbon nitride(MIL/ZC)was synthesized through in-situ synthesis at room temperature.High performance of ternary MIL/ZC is used to degrade NP under visible light irradiation.The results show that 30MIL/ZC2(20 wt.%Zn Fe_(2)O_(4))ternary composite had the best photocatalytic activity(99.84%)when the dosage was 30 mg.Further mechanism analysis shows that the excellent photocatalytic activity of 30MIL/ZC2could be ascribed to the double charge transfer process between flake-like porous carbon nitride(PCN)and other catalysts in the ternary heterojunction,and the separation of photogenerated electron-hole pairs was more effective.In addition,the 30MIL/ZC2 also showed high stability after five cycles of the photodegradation reaction.Furthermore,the active substance(·O_(2)^(-))was considered to be the main active substance in the NP degradation process.Based on the research results,the possible photocatalytic reaction mechanism of 30MIL/ZC2ternary composite was proposed and discussed in detail.
基金supported by the National Natural Science Foundation of China(Nos.51402078 and 51302060)Anhui Provincial Natural Science Foundation(No.1408085QE85)the Young Scholar Enhancement Foundation(Plan B)of Hefei University of Technology in China(No.JZ2016HGTB0711)
文摘Unique multiple heterojunction of Pt-BiOBr/TiO2 nanotube arrays（Pt-BiOBr/TNTAs） was achived by successively loading both Pt nanoparticles（NPs） and BiOBr nanoflkes（NFs） on surface of ordered and spaced TiO2 nanotubes（NTs） using anodization followed by solvothermal and sequential chemical bath deposition（S-CBD） method. The fabricated Pt-Bi OBr/TNTAs were fully characterized, and the photocatalytic（PC） activity and stability of PtBiOBr/TNTAs toward degradation of methyl orange（MO） under visible-light irradiation（λ＆gt;400 nm） were evaluated. The results reveal that multiple heterostructures of Pt/TiO2, Pt/BiOBr and BiOBr/TiO2 are constructed among TNTAs substrate, Pt NPs and BiOBr NFs, and the hybrid Pt-BiOBr/TNTAs catalyst exhibits remarkable visible-light PC activity, favourable reusability and long-term stability. The combined effect of several factors may contribute to the remarkable PC performance, including strong visible-light absorption by both Pt NPs and BiOBr NFs, lower recombination rate of photo-generated electrons and holes attributed to the multiple heterojunction, microstructures for facile light injection and adsorption as well as efficient mass transport, and larger specific surface area for enhancing light absorption, increasing the effective contact area between the absorbed dye molecules and catalyst and benefiting the molecule transport of reactants or products.
基金We are grateful for financial support from the National Natural Science Foundation of China(21172102)the Ministry of Science and Technology of China(2013CB834804)the Fundamental Research Funds for the Central Universities(lzujbky-2013-47).
文摘A metal-free and environmentally friendly aerobic aromatization photosensitized by organic dye eosin Y bis(tetrabutyl ammonium salt)(TBA-eosinY)has been developed.With the aid of K_(2)CO_(3),the aerobic catalytic system converts 1,4-dihydropyridines to their corresponding pyridine derivatives efficiently under visible light irradiation(λ=450 nm)at room temperature.
