Cu/TiO_(2) Photocatalysts for CO_(2) Reduction: Structure and Evolution of the Cocatalyst Active Form

Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.

Mg-doped SrTaO_(2)N as a visible-light-driven H_(2)-evolution photocatalyst for accelerated Z-scheme overall water splitting

Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.

Construction of direct-Z-scheme heterojunction photocatalyst of g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)composite and its degradation behavior for dyes of Rhodamine B

Direct-Z-scheme g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)photocatalyst with giant internal electric field was prepared by onestep aqueous sonication self-assembly method using g-C_(3)N_(4)and MXene of Ti_(3)C_(2)as the source materials.The chemical composition and structure of the catalysts was characterized by FT-IR,XRD,SEM,TEM,and XPS.The XPS characterization indicated that Ti_(3)C_(2)was partially oxidized to TiO_(2)during the composite process.As a result,an efficient direct-Z-scheme heterojunction structure consisting of the g-C_(3)N_(4)and TiO_(2)with Ti_(3)C_(2)as an electron bridge was constructed.The photocatalytic performance of the prepared catalysts was evaluated by degrading the Rhodamine B(RhB)wastewater.Compared with the single g-C_(3)N_(4),the g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)composite photocatalyst exhibited efficient and stable photocatalytic degradation ability,with a degradation efficiency as high as 99.2%for RhB under optimal conditions(2%Ti_(3)C_(2),pH=3).The high degradation performance of g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)for RhB was attributed to the combination of Ti_(3)C_(2),TiO_(2),and g-C_(3)N_(4)components,forming a direct-Z-scheme heterojunction with a high-speed electron transport channel structure.The role of Z-scheme heterojunctions in electron transport is verified by photoelectrochemical characterization,along with photoluminescence(PL).Our research provides a simple method to design photocatalysts by constructing direct-Z-scheme electron transport channels for highly efficient treatment of dye wastewater.

TiO2-PES Fibrous Composite Material for Ammonia Removal Using UV-A Photocatalyst

This study focused on the development and characterization of TiO2-PES composite fibers with varying TiO2 loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO2 nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO2 composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO2 composite fibers as promising photocatalysts for ammonia removal in water treatment applications.

Recent progress in research and design concepts for the characterization,testing,and photocatalysts for nitrogen reduction reaction

The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.

Recent advances in bismuth-based photocatalysts:Environment and energy applications

Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalytic performance.Among them,Bi-based photocatalysts have become one of the most popular research topics due to their suitable band gaps,unique layered structures,and physicochemical properties.In this review,Bi-based photocatalysts(BiOX,BiVO_(4),Bi_(2)S_(3),Bi_(2)MoO_(6),and other Bi-based photocatalysts)have been summarized in the field of photocatalysis,including their applications of the removal of organic pollutants,hydrogen production,oxygen production etc.The preparation strategies on how to improve the photocatalytic performance and the possible photocatalytic mechanism are also summarized,which could supply new insights for fabricating high-efficient Bi-based photocatalysts.Finally,we summarize the current challenges and make a reasonable outlook on the future development direction of Bi-based photocatalysts.

A Metal-free Polyimide Photocatalyst for the Oxidation of Amines to Imines

Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride(PMDA) and various diamine monomers(melamine(MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 ℃/min(MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.

Waste fly ash-ZnO as a novel sunlight-responsive photocatalyst for dye discoloration

Treating waste with a waste material using freely available solar energy is the most effective way towards sustainable future.In this study,a novel photocatalyst,partly derived from waste material from the coal industry,was developed.Fly ash hybridized with ZnO(FAeZn)was synthesized as a potential photocatalyst for dye discoloration.The synthesized photocatalyst was characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,and ultravioletevisible/near infra-red spectroscopy.The photocatalytic activity was examined with the discoloration of methylene blue used as synthetic dye wastewater.All the experiments were performed in direct sunlight.The photocatalytic performance of FAeZn was found to be better than that of ZnO and the conventionally popular TiO2.The LangmuireHinshelwood model rate constant values of ZnO,TiO2,and FAeZn were found to be 0.016 min1,0.017 min1,and 0.020 min1,respectively.There were two reasons for this:(1)FAeZn was able to utilize both ultraviolet and visible parts of the solar spectrum,and(2)its BrunauereEmmetteTeller surface area and porosity were significantly enhanced.This led to increased photon absorption and dye adsorption,thus exhibiting an energy-efficient performance.Therefore,FAeZn,partly derived from waste,can serve as a suitable material for environmental remediation and practical solar energy applications.

Recycling Spent LiCoO_(2)Battery as a High-efficient Lithiumdoped Graphitic Carbon Nitride/Co_(3)O_(4)Composite Photocatalyst and Its Synergistic Photocatalytic Mechanism

The ever-increasing quantity of spent lithium-ion batteries(LIBs)is both a potential environmental pollutant and a valuable resource.The spent LIBs recycling mainly aimed at the separation of valuable elements.Some issues still exist in these processes such as high energy consumption and complex separation procedures.This study avoided element separation and proposed a facile approach to transform spent LiCoO_(2) electrode into a lithium(Li)-doped graphitic carbon nitride(g-C_(3)N_(4))/Co_(3)O_(4) composite photocatalyst through one-pot in situ thermal reduction.During the thermal process,melamine served as the reductant for LiCoO_(2) decomposition and the raw material for g-C_(3)N_(4) production.Li was in situ doped in g-C_(3)N_(4) and the generated Co_(3)O_(4) was in situ integrated,forming a Li-doped g-C_(3)N_(4)/Co_(3)O_(4) composite photocatalyst.This special composite exhibited an enhanced photocatalytic performance,and its photocatalytic H2 production and RhB degradation rates were 8.7 and 6.8 times higher than those of g-C_(3)N_(4).The experiments combined with DFT calculation revealed that such enhanced photocatalytic efficiency was ascribed to the synergy effect of Li doping and Co_(3)O_(4) integrating,which extended the visible light absorption(450-900 nm)and facilitated the charge transfer and separation.This study transforms waste into a high-efficient catalyst,realizing high-valued utilization of waste and environmental protection.

Synthesis of AgCl/Ti_(3)C_(2)@TiO_(2)Ternary Composite Photocatalysts for Photocatalytic Oxidation of 1,4-Dihydropyridine and Tetracycline Hydrochloride

AgCl/Ti_(3)C_(2)@TiO_(2)ternary composites were prepared to form a heterojunction structure between AgCl and TiO_(2)and introduce Ti3C2 as a cocatalyst.The as-prepared AgCl/Ti_(3)C_(2)@TiO_(2)composites showed higher photocatalytic activity than pure AgCl and Ti_(3)C_(2)@TiO_(2)for photooxidation of a 1,4-dihydropyridine derivative(1,4-DHP)and tetracycline hydrochloride(TCH)under visible light irradiation(λ>400 nm).The photocatalytic activity of AgCl/Ti_(3)C_(2)@TiO_(2)composites depended on Ti_(3)C_(2)@TiO_(2)content,and the catalytic activity of the optimized samples were 6.9 times higher than that of pure AgCl for 1,4-DHP photodehydrogenation and 7.3 times higher than that of Ti_(3)C_(2)@TiO_(2)for TCH photooxidation.The increased photocatalytic activity was due to the formation of a heterojunction structure between AgCl and TiO_(2)and the introduction of Ti3C2 as a cocatalyst,which lowered the internal resistance,sped up the charge transfer,and increased the separation efficiency of photogenerated carries.Photogenerated holes and superoxide radical anions were the major active species in the photocatalytic process.

Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts

With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4）. The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation（λ≥ 400 nm）. In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.

Preparation and characterization of ternary magnetic g-C_3N_4 composite photocatalysts for removal of tetracycline under visible light

A stable PNIPAM/Fe_3O_4/g-C_3N_4 composite photocatalyst was designed and prepared by a thermal photoinitiation technology.The structure and properties of the materials were characterized and the composite photocatalyst was found to show good stability for tetracycline degradation.The sample not only retained the magnetic properties of Fe_3O_4,allowing it to be recycled,but its photocatalytic properties could also be changed by controlling the temperature of the reaction system.The degradation intermediate products of tetracycline were further investigated by MS.This work provides a new facile strategy for the development of intelligent and recyclable photocatalytic materials.

Research progress of Ag_3PO_4-based photocatalyst: Fundamentals and performance enhancement

Ag3PO4 is found to be a highly efficient photocatalyst and receives great attention. The high activity of the photocatalyst is credited to the intrinsic electronic structure. The morphology control and nano-composite fabrication are used to improve the performance and practicability. This paper reviews the structure, properties and some theoretical aspects of Ag3PO4 single crystal. Also, the major strategies, namely the morphology control and hetero-nanostructure construction, as ways to improve the performance of Ag3PO4-based photocatalysts, are summarized with the aid of some typical instances.

Visible-Light Activities of Erbium Doped BiVO4 Photocatalysts

Er-doped BiVO4 composite photocatalyst was hydrothermal synthesized and characterized by X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray Spectroscopy, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectra techniques. The activity of the catalyst was determined by oxidative decomposition of methyl orange in aqueous solution under visible-light irradiation. X-ray photoelectron spectroscopy and energy-dispersive X-ray Spectroscopy analysis revealed that the doped Er existed in the form of Er2O3. It also showed that the Er doping can enhance the visible-light absorption abilities of catalysts and their visible-light-driven photocatalytic activities in comparison with those of pure BiVO4.

Visible light induced photodegradation of organic pollutants on nitrogen and fluorine co-doped TiO_2 photocatalyst

The nitrogen and fluorine co doped TiO 2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetra butyl titanate with ammonium fluoride. Nitrogen and fluorine co doping causes the absorption edge of TiO 2 to shift to a lower energy region. The photocatalytic activity of co doped TiO 2 with anatase phases was found to be 2 4 times higher than that of the commercial TiO 2 photocatalyst Degussa P25 for phenol decomposition under visible light irradiation. The co doped TiO 2 powders only contain anatase phases even at 1000℃. Apparently, ammonium fluoride added retarded phase transformation of the TiO 2 powders from anatase to rutile. The substitutional fluorine and interstitial nitrogen atoms in co doped TiO 2 polycrystalline powder were responsible for the vis light response and caused the absorption edge of TiO 2 to shift to a lower energy region.

Preparation and characterization of visible-light-active nitrogen-doped TiO_2 photocatalyst

A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO_4)_2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wavelength. The crystal structure of anatase was characterized by XRD. The structure analysis result of X-ray fluorescence(XRF) shows that doped-nitrogen was presented in the sample. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants. The photocatalytic activities of samples were increasing gradually with calcination temperature from 400℃ to 700℃ under UV irradiation. It can be seen that the degradation of methyl orange follows zero-order kinetics. However, the calcination temperatures have no significant influence on the degradation of phenol under sunlight. The N-doped catalyst shows higher activity than the bare one under solar irradiation.

TiO_2/polyaniline composites:An efficient photocatalyst for the degradation of methylene blue under natural light

Polyaniline （PAn） sensitized nanocrystalline TiO2 composites （TiO2/PAn） were successfully prepared and used as an efficient photocatalyst for the degradation of dye methylene blue （MB）. The results showed that PAn was able to sensitize TiO2 efficiently and the composite photocatalyst could be activated by absorbing both the ultraviolet and visible light （λ： 190 ～ 800 nm）, whereas pure TiO2 absorbed ultraviolet light only （λ 〈 380 nm）. Under the irradiation of natural light, MB could be degraded more efficiently on the TiO2/PAn composites than on the TiO2 Furthermore, it could be easily separated from the solution by simple sedimentation.

Photocatalytic remediation ofγ-hexachlorocyclohexane contaminated soils using TiO_2 and montmorillonite composite photocatalyst

TiO2 and montmorillonite composite photocatalysts were prepared and applied in degrading γ-hexachlorocyclohexane （γ-HCH） in soils. After being spiked with γ-HCH, soil samples loaded with the composite photocatalysts were exposed to UV-light irradiation. The results indicated that the photocatalytic activities of the composite photocatalysts varied with the content of TiO2 in the order of 10%〈70%〈50% 〈30%, Moreover, the photocatalytic activity of the composite photocatalysts with TiO2 content 30% was higher than that of the pure P25 with the same mass of TiO2. The strong adsorption capacity of the composite photocatalysts and quantum size effect may contribute to its increased photocatalytic activities. In addition, effect of dosage of composite photocatalysts and soil pH on γ-HCH photodegradation was investigated. Pentachlorocyclohexene, trichlorocyclohexene, and dichlorobenzene were detected as photodegradation intermediates, which were gradually degraded with the photodegradation evolution.

Efficient removal of ammonia with a novel graphene-supported BiFeO_3 as a reusable photocatalyst under visible light

Graphene‐supported BiFeO3 (rG‐BiFeO3) was synthesized by the hydrothermal method and used for the efficient removal of ammonia under visible light. X‐ray diffraction, transmission electron microscopy,Fourier transform infrared spectroscopy, Raman spectroscopy, and ultraviolet‐visiblediffuse reflectance spectroscopy were conducted to characterize the rG‐BiFeO3. The specific surfacearea of the rG‐BiFeO3 catalyst was 48.6 m2/g, larger than that of BiFeO3 (21.0 m2/g). When used as aheterogeneous photocatalyst, rG‐BiFeO3 achieved 91.20% degradation of a NH3‐N solution (50mg/L) at pH = 11 under visible‐light irradiation in the absence of hydrogen peroxide. The degradationof ammonia followed pseudo‐first‐order kinetics, and the catalyst retained high photocatalyticactivity after seven reaction cycles. Study of the mechanism showed that the holes, superoxide anion radicals, and hydroxyl radicals, arising from the synergy between graphene and BiFeO3, oxidized NH3 directly to N2.

Preparation and characterization of the TiO_2-V_2O_5 photocatalyst with visible-light activity

Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method. The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level. The binary sol was then intercalated into interspaces of polyaniline （PANI） by means of in-situ polymerization of aniline. Conglomeration of the TiO2-V2O5 dusters during the calcination process was avoided because of the wrap of polyaniline. The surface mor- phology, the crystal phases, the structure, and the absorption spectra of （PANI）,/TiO2-V2O5 and the composite catalyst were studied using SEM, XRD, FT-IR, and UV-Vis. The photoactivity of the prepared catalyst under UV and visible light irradiation were evaluated by decolorization of methylene blue （MB） solution. The results showed that the composite catalyst displayed a homogeneous anatase phase, and the vanadium pentoxide species was highly dispersed in the TiO2 phase. The composite catalyst responded to visible light because of the narrowed band gap. In this study, the catalyst with the sol volume ratio of TiO2： V2O5 = 10：1 presented the best photocatalytic activity.