Construction of efficient active sites through cyano‐modified graphitic carbon nitride for photocatalytic CO_(2) reduction

The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits moderate photocatalytic activity due to insufficient active sites.In this study,cyano‐modified porous g‐C_(3)N_(4)nanosheets(MCN‐0.5)were synthesized through molecular self‐assembly and alkali‐assisted strategies.The cyano group acted as the active site of the photocatalytic reaction,because the good electron‐withdrawing property of the cyano group promoted carrier separation.Benefiting from the effect of the active sites,MCN‐0.5 exhibited significantly enhanced photocatalytic activity for CO2 reduction under visible light irradiation.Notably,the photocatalytic activity of MCN‐0.5 was significantly reduced when the cyano groups were removed by hydrochloric acid(HCl)treatment,further verifying the role of cyano groups as active sites.The photoreduction of Pt nanoparticles provided an intuitive indication that the introduction of cyano groups provided more active sites for the photocatalytic reaction.Furthermore,the controlled experiments showed that g‐C_(3)N_(4)grafted with cyano groups using melamine as the precursor exhibited enhanced photocatalytic activity,which proved the versatility of the strategy for enhancing the activity of g‐C_(3)N_(4)via cyano group modification.In situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations were used to investigate the mechanism of enhanced photocatalytic activity for CO2 reduction by cyano‐modified g‐C_(3)N_(4).This work provides a promising route for promoting efficient solar energy conversion by designing active sites in photocatalysts.

Photocatalytic activity and kinetics for acid yellow degradation over surface composites of TiO_2-coated activated carbon under different photocatalytic conditions

TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO2 content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO2 particles as well as the mixture of TiO2 powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO2 content in TAs on the degradation rate.

Photocatalytic Characterization of TiO_2 Supported on Active Carbon

The Photocatalytic characterization of TiO2 supported on active carbon was investigated for photocatalytic decomposition of dichloroacetic acid. It was found that TiO2 / AC exhibited a higher photocatalytic activity than pure TiO2. The reason is that active carbon acting as powerful adsorbent supports makes high concentration environments of organic pollutant molecules around TiO2 particles.

Microwave photocatalytic degradation of Rhodamine B using TiO_2 supported on activated carbon:Mechanism implication

The photocatalytic degradation of Rhodamine B （RhB） was carried out using TiO2 supported on activated carbon （TiO2-AC） under microwave irradiation. Composite catalyst TiO2-AC was prepared and characterized using X-ray diffraction （XRD）, transmission electron microscopy （TEM） and Brunauer-Emmett-Teller （BET）. In the process of microwave-enhanced photocatalysis （MPC）, RhB （30 mg/L） was almost completely decoloured in 10 min, and the mineralization efficiency was 96.0% in 20 min. The reaction rate constant of RhB in MPC using TiO2-AC by pseudo first-order reaction kinetics was 4.16 times of that using Degussa P25. Additionally, according to gas chromatography/mass spectrometry （GC/MS） and liquid chromatography/mass spectrometry （LC/MS） identification, the major intermediates of RhB in MPC included two kinds of N-de-ethylation intermediates （N,N-diethyl-N＇-ethyl-rhodamine （DER））, oxalic acid, malonic acid, snccinic acid, and phthalic acid, maleic acid, 3-nitrobenzoic acid, and so on. The degradation of RhB in MPC was mainly attributed to the destruction of the conjugated structure, and then the intermediates transformed to acid molecules which were mineralized to water and carbon dioxide.

Photocatalytic degradation of L- acid by TiO_2 supported on the activated carbon

TiO2 sol was prepared by sol-gel technique with tetrabutyl titanate as precursor. Supported TiO2 catalysts on activated carbon were prepared by soak and sintering method. The aggregation of nano-TiO2 particles can be effectively suppressed by added polyethylene glycol （PEG） as a surface modifier. The average particle diameter of TiO2, specific surface area and absorbability of catalyst can be modified. Based on characteristics of the TiO2 photocatalyst with XRD, specific surface area, adsorption valves of methylene blue and the amount of TiO2 supported on the activated carbon, the photocatalytic degradation of L-acid was studied. The effect of the factors, such as pH of the solution, the initial concentration of L-acid on the photocatalytic degradation of L-acid, were studied also. It was found that when the pH of the solution is 1.95, the amount of photocatalyst is 0.5 g, the concentration of the L-acid solution is 1.34×10^3 mol/L and the illumination time is 7 h, the photocatalytic degradation efficiency of L-acid can reach 89,88%, The catalyst was reused 6 times and its degradation efficiency hardly changed.

Preparation of Nano-TiO_2 Doped with Cerium and Its Photocatalytic Activity

Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and UV/Vis diffuse reflectance spectra （DRS）. The photocatalytic activity was evaluated by photocatalytic degradation of phenol in water. The results of XRD, TEM, and DRS show that pure TiO2 and Ce-doped TiO2 powder crystallines are a mixture of anatase and rutile ; the doping can retard the development of the grain size of TiO2 and decrease the diameter of TiO2 from more than 20 nm of pure TiO2 to about 10 nm; the doped TiO2 can improve the light absorption of TiO2 and suitable doping content tends to move the DRS spectrum of TiO2 towards visible light, but too much doping is not good for the light absorption ability. The results of the photocatalytic experiments show that doping with Ce content of 0.08% -0.4% can increase the photocatalytic activity of TiO2; however, doping with Ce content of 0.5% -2.5% can significantly decrease the photocatalytic activity of TiO2. The favorite doping content is 0.4% in the range of our experiments.

Enhanced visible-light photocatalytic oxidation capability of carbon-doped TiO_2 via coupling with fly ash

A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species generated during the synthesis of the C‐TiO2/FAS composite.A series of analytical techniques,such as scanning electron microscopy(SEM),attenuated total reflection‐Fourier transform infrared(ATR‐FTIR)spectroscopy,X‐ray photoelectron spectroscopy(XPS),and ultraviolet‐visible diffuse reflectance spectroscopy(UV‐Vis DRS),were used to characterize the properties of the prepared samples.The results indicated that C‐TiO2 was successfully coated on the FAS surface.Coupling between C‐TiO2 and FAS resulted in the formation of Si–O–C and Al–O–Ti bonds at their interface.The formation of Si–O–C and Al–O–Ti bonds gave rise to a positive shift of the valence band edge of C‐TiO2 and enhanced its oxidation capability of photogenerated holes as well as photodegradation efficiency of methyl orange.Moreover,the C‐TiO2/FAS photocatalyst exhibited favorable reusability and separability.This work may provide a new route for tuning the electronic band structure of TiO2.

Synthesis of iron(Ⅲ)-doped nanostructure TiO_2/SiO_2 and their photocatalytic activity

Iron（Ⅲ）-doped nanostructure TiO2-coated SiO2 （TiO2/SiO2） particles were prepared using the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized employing the sol-gel method with TiChas a precursor. The samples were characterized by Fourier transform infrared spectroscopy （FTIR）, SEM, EDS, XPS, and XRD. The experimental results show that TiO2 nanopowders on the surface of SiO2 particles are well distributed, the amount of TiO2 is increased with the adding of coating layers, the pure anatase-TiO2 coating layers are synthesized at 500℃, and the photocatalytic activity of Fe^3＋-doped TiO2/SiO2 is higher than that of undoped TiO2/SiO2.

Surface ζ potential and photocatalytic activity of rare earths doped TiO_2

The iso-electric point of different rare earths （La, Ce, Y） doped anatase TiO2 was set out, and three organisms with different sur- face electrical properties （methylene blue trihydrate-positive electricity, methyl orange-negative electricity, methyl red-neutral electricity） were selected as photodegradable models. The result showed that the photocatalytic activity of 0.5wt.%Y ions doped anatase TiO2 was better than those of the others. The relationship between Zeta （ξ） potential and the photocatalytic activity of different RE doped anatase TiO2 were also investigated. The Y-doped anatase TiO2 was found with the special two iso-electric points and three ξ potential values.

Preparation and photocatalytic activity of Cu^(2+)-doped TiO_2/SiO_2

Cu^2＋-doped nanostructured TiO2-coated SiO2 （TiO2/SiO2） particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized by the sol-gel method using TiOSO4 as a precursor. The experimental results showed that TiO2 nanopowders on the surface of SiO2 particles were well distributed and compact. The amount of TiO2 increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550℃. The 2-layer coated TiO2 particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu^2＋-doped TiO2/SiO2 was higher than that ofundoped TiO2/SiO2. The optimum dopant content was about 0.10wt%.

Preparation and Photocatalytic Activity of Ce, H3PW12O40 co-doped TiO2 Hollow Fibers

A series of Ce, H3PW12O40 co-doped TiO2 hollow fibers photocatalysts have been prepared by sol-gel method using ammonium ceric nitrate, H3PW12O40 and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500 ℃ in N2 atmosphere for 2 h. Scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption mea- surements, and UV-Vis spectroscopy are employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photo- catalytic performance of the samples has been studied by photodegradation phenol in water under UV and visible light irradiation. The results show that the TiO2 fiber materials have hollow structures, and the co-doped TiO2 hollow fibers exhibit higher photocatalytic activities for the degradation of phenol than un-doped, single-doped TiO2 hollow fibers under UV and visible light. In addition, the recyclability of co-doped TiO2 fibers is also confirmed that the TiO2 fiber retains ca. 90% of its activity after being used four times. It is shown that the co-doped TiO2 fibers can be activated by visible light and may be potentially applied to the treatment of water contaminated by organic pollutants. The synergistic effect of Ce and H3PW12O40 co-doping plays an important role in improving the photocatalytic activity.

Preparation and photocatalytic activity of Gd-doped TiO_2 nanofibre

In order to realize the photocatalysis of TiO2 in the sunlight and directly apply it to waste water treatment, the Gd-doped TiO2 nanofibre was synthesized using two-step synthesis method as follows: Firstly, potassium carbonate, titanium dioxide and proper gadolinium oxide （dopant） were calcined in the muffle at high temperature and the doped gadolinium K2Ti4O9 fibres were obtained; secondly, the fibre was heated using glycerol as solvent until Gd-doped TiO2 nanofibres were obtained. The synthesized samples were characterized using scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The results show that Gd-doped TiO2 nanofibre heat-treated by glycerol solvent can inhibit the agglomeration, so the grain diameter of the fibre is smaller than that without heat-treated with glycerol. Meanwhile, the diameter of the fibre decreases with the increase of the heating temperature and time. 97% 98% of Gd-doped TiO2 nanofibre is anatase. The photocatalysis results showed that the photocatalysis activity of Gd-doped TiO2 nanofibre is just a little lower than that of TiO2 powder.

Synthesis and Photocatalytic Activity of Fe-doped TiO_2 Supported on Hollow Glass Microbeads

In this paper, Fe-doped TiO_2 photocatalyst supported on hollow glass microbeads(Fe-TiO_2 /beads)is prepared by dip-coating method, which uses hollow glass microbeads as the carriers and tetrabutylorthotitanate [Ti(OC_4H_9)_4] as the raw material. The phase structure, ingredient, morphologies, particle size and shell thickness of the products are characterized by X-ray powder diffraction(XRD), energy-dispersive spectroscopy(EDS) and field emission scanning electron microscope(FESEM). The feasibility of photocatylic degradation of Rhodamine B(Rh B) under illumination of UV-vis light is studied. The results show that the core-shell structure catalyst is composed of Fe-doped anatase TiO_2 and hollow glass microbeads, and the catalytic activity of the TiO_2 is markedly enhanced by Fe ion doping. The optimum concentration of Fe ion is 0.1%(molecular fraction) in the precursor and the photocatalytic activity can be increased to 98% compared with that of the undoped one. The presence of ferrum elements neither influences the transformation of anatase to rutile, nor creates new crystal phases. The possible mechanism of photocatalytic oxidation is also discussed.

Structural Characteristics and Photocatalytic Activity of Ambient Pressure Dried SiO2/TiO2 Aerogel Composites by One-step Solvent Exchange/Surface Modification

An ambient pressure synthesis of SiO2/TiO2 binary aerogel was prepared through the low-cost precursors of titanium tetrachloride（TiCl4） and sodium silicate（Na2O·nSiO2）.After gelation,solvent exchange and surface modification were performed simultaneously and the modified gel was finally dried under ambient pressure.Microstructural analyses by transmission electron microscope（TEM） indicate that fabricated SiO2/TiO2 aerogel composite shows similar sponge-like nanostructure as silica aerogel,and the Brunauer-EmmettTeller（BET） analysis shows that the specific surface area of the composite reaches 605 m^2/g,and the average pore size is 9.7 nm.Such binary aerogel exhibits significant photocatalytic performance in this paper for treating model pollutant of methyl orange（MO）,and the decolorizing efficiency of MO is detected as 84.9%after 210 mins exposure to UV light irradiation.Degraded gel suspends in the water so as to separate from solution for reuse,and after 4 times recycling,70%degradation efficiency can be easily reached when composite catalyzed system is exposed for 210 mins under UV irradiation.

Preparation of spherical activated carbon-supported and Er^(3+):YAlO_3-doped TiO_2 photocatalyst for methyl orange degradation under visible light

In order to develop the high photocatalytic activity of TiO2 under visible light as that under ultraviolet light and make it easy to be separated from treated liquor, a visible light response and spherical activated carbon （SAC） supported photocatalyst doped with upconversion luminescence agent Er3＋：YAlO3 was prepared by immobilizing Er3＋：YAlO3/TiO2, which was obtained by combination of Er3＋：YAlO3 and TiO2 using sol-gel method, on the surface of SAC. The crystal phase composition, surface structure and element distribution, and light absorption of the new photocatalysts were examined by X-ray diffraction （XRD）, energy dispersive X-ray spectra （EDS） analysis, scanning electron microscopy （SEM） and fluorescence spectra analysis （FSA）. The photocatalytic oxidation activity of the photocatalysts was also evaluated by the photodegradation of methyl orange （MO） in aqueous solution under visible light irradiation from a LED lamp （λ400 nm）. The results showed that Er3＋：YAlO3 could perform as the upconversion luminescence agent which converts the visible light up to ultraviolet light. The Er3＋：YAlO3/TiO2 calcinated at 700 °C revealed the highest photocatalytic activity. The apparent reaction rate constant could reach 0.0197 min-1 under visible light irradiation.

Photocatalytic activity of bauxite-tailings supported nano-TiO_2

TiO2/bauxite-tailings （TiO2/BTs） composites were prepared via a chemical liquid deposition method and characterized by X-ray diffractometry （XRD）, scanning electronic microscopy （SEM） and N2 adsorption analysis. The photocatalytic performance of TiO2/BTs composites was evaluated with UV-Vis spectrophotometer following the changes of phenol concentration under different illumination time. Effects of the calcination temperature, the pH and the cycles on the photocatalytic activity of TiO2/BTs composites were investigated. The composites calcined at 500 and 600 ℃ exhibit the best photocatalytic performance, and the phenol degradation ratios reacting for 40 and 160 rain reach 35% and 78% respectively under the same conditions, higher than those of 29% and 76% of the Degussa P25（TiO2）. The ability of TiO2/BTs500 （BTs500 represents bauxite-tailings calcined at 500 ℃） composites to degrade phenol increases with decreasing pH.

Structure and visible photocatalytic activity of nitrogen-doped meso-porous TiO_2 layer on Ti6Al4V substrate by plasma-based ion implantation

The nitrogen-doped porous TiO2 layer on Ti6Al4V substrate was fabricated by plasma-based ion implantation of He, O and N. In order to increase the photodegradation efficiency of TiO2 layer, two methods were used in the process by forming mesopores to increase the specific surface area and by nitrogen doping to increase visible light absorption. Importantly, TiO2 formation, porosity architectures and nitrogen doping can be performed by implantation of He, O and N in one step. After implantation, annealing at 650 ℃ leads to a mixing phase of anatase with a little rutile in the implanted layer. By removing the near surface compact layer using argon ion sputtering, the meso-porous structure was exposed on surfaces. Nitrogen doping enlarges the photo-response region of visible light. Moreover, the nitrogen dose of 8×1015 ion/cm2 induces a stronger visible light absorption. The photodegradation of rhodamine B solution with visible light sources indicates that the mesopores on surfaces and nitrogen doping contribute to an apparent increase of photocatalysis efficiency.

Solvothermal Synthesis and Visible Photocatalytic Activity of Zn0.4Cd0.6S/TiO2/Reduced graphene oxide Nanocomposite

Zn0.4Cd0.6S/TiO2/Reduced graphene oxide(Zn0.4Cd0.6S/TiO2/RGO)nano-photocatalyst was synthe-sized by a facile solvothermal method.During the reaction,TiO2 and Zn0.8Cd0.2S nanoparticles were evenly dispersed across the surface of RGO,which enhanced response to visible light.The photocatalytic activity of as-synthesized Zn0.4Cd0.6S/TiO2/RGO nanocomposite was studied by means of degrading methylene blue(MB)through the irradiation of visible light.Compared with other nanocomposites,the Zn0.4Cd0.6S/TiO2/RGO nanocomposite showed the highest photocatalytic degradation efficiency(96%)and high stability,which was 5.4 times of photodegradation efficiency of pure TiO2.

Construction of electron rich Fe active sites by FeCu alloy anchoring on carbon nitride for photocatalytic nitrogen reduction

Given the clean and inexhaustible solar energy from solar light,photocatalytic ammonia synthesis is extremely appealing.However,high electron-hole recombination rates and insufficient active sites severely limited N2 photoreaction reduction.Herein,we designed and fabricated FeCu alloy nanoparticles anchored on carbon nitride nanosheets with excellent photocatalyt ic ammonia synthesis performance.As a coupler between Fe and carbon nitride,Cu promotes the separation of photogenerated charge carriers in carbon nitride under solar light irradiation,and renters the semiconductor a forceful electron donor for the Fe active sites.The accumulated electrons at Fe sites furtherly facilitated the adsorption and activation of the molecular nitrogen.Besides,the uniform dispersed FeCu alloy nanoparticles were on carbon nitride nanosheets enhanced the stability of photocataly tic nitrogen reduction reaction,making the artificial photocataly tic ammonia synthesis more sustainable for application.This work highlights that a direct electron transfer channel can be used to regulate the photochemical nitrogen fixation network.

Synthesis of CC/BiPO4/Bi2WO6 Composite Material and Its Photocatalytic Performance

Along with the popularity of environmental protection concepts, the environmental treatment of water pollution attracts widespread attention, among which, the research on Bi-based semiconductor photocatalytic degradation technology has made great progress. However, the development of such bismuth-based composites still remains a challenging task due to difficult recovery and low catalytic efficiency. Herein, a novel CC/BiPO4/Bi2WO6 composite was successfully synthesized through two-step hydrothermal method using activated flexible carbon cloth as a substrate. The results of the photocatalytic degradation experiments showed that the obtained CC/BiPO4/Bi2WO6 composites can degrade 92.1% RhB in 60 min under UV-visible light irradiation, which was much higher than that of unloaded BiPO4 (24.4%) and BiPO4/Bi2WO6 (52.9%), exhibiting a better adsorption-photocatalytic degradation performance than BiPO4 and BiPO4/Bi2WO6. Photoluminescence spectra indicated that the improved photocatalytic activity was due to the more effective inhibition of photogenerated carrier complexation. Furthermore, the radical capture experiments confirmed that h+, ·OH and O2- were the main active substances in the photocatalytic degradation process of RhB by the CC/BiPO4/Bi2WO6 composites. More importantly, the prepared CC/BiPO4/Bi2WO6 composite had a simple separation process and good recycling stability, and its photocatalytic degradation efficiency can still reach 53.3% after six cycles of RhB degradation. .