Enhanced photocatalytic activity of rGO/TiO2 for the decomposition of formaldehyde under visible light irradiation

Due to the low concentration of indoor air contaminants,photocatalytic technology shows low efficiency for indoor air purification.The application of TiO_2 for photocatalytic removal of formaldehyde is limited,because TiO_2 can only absorb ultraviolet(UV) light.Immobilization of TiO_2 nanoparticles on the surface of graphene can improve the visible light photocatalytic activity and the adsorption capacity.In this study,rGO(reduced graphene oxide)/TiO_2 was synthesized through a hydrothermal method using titanium tetrabutoxide and graphene oxide as precursors,and was used for the degradation of low concentration formaldehyde in indoor air under visible light illumination.Characterization of the crystalline structure and morphology of rGO/TiO_2 revealed that most GO was reduced to rGO during the hydrothermal treatment,and anatase TiO_2 nanoparticles(with particle size of 15–30 nm) were dispersed well on the surface of the rGO sheets.rGO/TiO_2 exhibited excellent photocatalytic activity for degradation of formaldehyde in indoor air and this can be attributed to the role of rGO,which can act as the electron sink and transporter for separating photo-generated electron–hole pairs through interfacial charge transfer.Furthermore,rGO could adsorb formaldehyde molecules from air to produce a high concentration of formaldehyde on the surface of rGO/TiO_2.Under visible light irradiation for 240 min,the concentration of formaldehyde could be reduced to 58.5 ppbV.rGO/TiO_2 showed excellent moisture-resistance behavior,and after five cycles,r GO/TiO_2 maintained high photocatalytic activity for the removal of formaldehyde(84.6%).This work suggests that the synthesized rGO/TiO_2 is a promising photocatalyst for indoor formaldehyde removal.     

Visible light driven mineralization of spiramycin over photostructured N-doped TiO2 on up conversion phosphors

A novel visible light-active photocatalyst formulation(NdT/OP) was obtained by supporting N-doped TiO_2(NdT) particles on up-conversion luminescent organic phosphors(OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon(TOC) of aqueous solution,and CO and CO_2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO_2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity(58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support",able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.     

Preparations of TiO2 film coated on foam nickel substrate by sol-gel processes and its photocatalytic activity for degradation of acetaldehyde

Anatase TiO2 films were successfully prepared on foam nickel substrates by sol-gel technique using tetrabutyl titanate as precursor. The characteristics of the TiO2 films were investigated by XPS, XRD, FE-SEM, TEM and UV-Vis absorption spectra. The photocatalytic activities of TiO2 films were investigated by photocatalytic degradation reactions of gaseous acetaldehyde, an indoor pollutant, under ultraviolet light irradiation. It was found that Ni^2＋ doping into TiO2 films due to the foam nickel substrates resulted in the extension of absorption edges of TiO2 films from UV region to visible light region. The pre-heating for foam nickel substrates resulted in the formation of NiO layer, which prevented effectively the injection of photogenerated electrons from TiO2 films to metal nickel. The TiO2 films displayed high photocatalytic activity for the degradation of acetaldehyde, and were enhanced by calcining the substrates and coating TiO2 films repeatedly. The high activity was mainly attributed to the improvement of the characteristics of substrate surface and the increase of active sites on photocatalyst.     

Photocatalytic degradation of aqueous Methyl Orange using nitrogen-doped TiO2 photocatalyst prepared by novel method of ultraviolet-assisted thermal synthesis

A nitrogen-doped titanium dioxide composite photocatalyst(N–TiO_2) with heterojunction structures is synthesized by three different approaches: a novel UV-assisted thermal synthesis, annealing, and microwave technique. Photocatalytic activities of synthesized photocatalysts are evaluated by the degradation of Methyl Orange under ultraviolet light types A(UV-A), B(UV-B), and C(UV-C), visible light, and direct sunlight irradiation. Results show that by using N–TiO_2 photocatalyst prepared by the UV-assisted thermal synthesis and annealing, the degradation increases by 16.5% and 20.4%, respectively, compared to that by bare TiO_2. The best results are obtained at a nitrogen to TiO_2 mass ratio of 0.15(N:TiO_2). The enhancement of the photocatalytic activity observed in the visible range is mainly attributed to the increasing separation rate of photogenerated charge carriers. The novel UV-assisted thermal synthesis has produced encouraging results as a preparation method for the nitrogen-doped TiO_2 photocatalyst; thus, further studies are recommended for process optimization, immobilization, and scale-up to evaluate its applicability in wastewater treatment.     

Preparation of Ti species coating hydrotalcite by chemical vapor deposition for photodegradation of azo dye

TiO_2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve its photocatalytic activity, the Ti-coating Mg Al hydrotalcite(Ti–Mg Al–LDH) was prepared by chemical vapor deposition(CVD) method.Response surface method(RSM) was employed to evaluate the effect of Ti species coating parameters on the photocatalytic activity, which was found to be affected by the furnace temperature, N2 flow rate and influx time of precursor gas. Application of RSM successfully increased the photocatalytic efficiency of the Ti–Mg Al–LDH in methylene blue photodegradation under UV irradiation, leading to improved economy of the process.According to the results from X-ray diffraction, scanning electron microscopy, Brunner–Emmet–Teller and Barrett–Joyner–Hallender, thermogravimetric and differential thermal analysis, UV–vis diffuse reflectance spectra analyses, the Ti species(TiO_2or/and Ti~(4+)) were successfully coated on the Mg Al–LDH matrix. The Ti species on the surface of the Ti–Mg Al–LDH lead to a higher photocatalytic performance than commercial TiO_2-P25. The results suggested that CVD method provided a new approach for the industrial preparation of Ti-coating Mg Al–LDH material with good photocatalytic performances.     

Application of Ag/AgBr/GdVO4 composite photocatalyst in wastewater treatment

Ag/AgBr/GdVO_4 composite photocatalysts were designed and synthesized in this paper.The physical and chemical structures, as well as optical properties of the synthesized composite were investigated via XRD, XPS, TEM, and UV–vis. It is found that the composite showed a ternary heterojunction structure of Ag, Ag Br and GdVO_4. Meanwhile, it has a high intensity of light current, indicating its high separation efficiency of electron and hole.Photocatalytic oxidation of rhodamine B(RhB) under visible light irradiation was performed to investigate the activity of the Ag/Ag Br/GdVO_4 composite. Result indicates that it shows excellent photocatalytic activity. Under visible light irradiation for 12 min, about 80% of Rh B(30 μmol/L) was degraded. The degradation rate is estimated to be 0.253 min1, which is three times higher than that of pure AgBr. The high photoactivity can be ascribed to the synergetic effect of Ag Br, GdVO_4, and Ag nanoparticle in separation of electron–hole pairs.     

Pd-MnO2 nanoparticles/TiO2 nanotube arrays (NTAs) photo-electrodes photo-catalytic properties and their ability of degrading Rhodamine B under visible light

Pd-MnO_2/TiO_2 nanotube arrays(NTAs) photo-electrodes were successfully fabricated via anodization and electro deposition subsequently; the obtained Pd-MnO_2/TiO_2 NTAs photo electrodes were analyzed by scanning electron microscopy(SEM), X-ray diffraction(XRD) and characterized accordingly. Moreover, the light harvesting and absorption properties were investigated via ultraviolet–visible diffuse reflectance spectrum(DRS); photo degradation efficiency was investigated via analyzing the photo catalytic degradation of Rhodamine B under visible illumination(xenon light). The performed analyses illustrated that Pd-MnO_2 codoped particles were successfully deposited onto the surface of the TiO_2 nanotube arrays;DRS results showed significant improvement in visible light absorption which was between400 and 700 nm. Finally, the photo catalytic degradation efficiency results of the designated organic pollutant(Rhodamine B) illustrated a superior photocatalytic(PC) efficiency of approximately 95% compared to the bare TiO_2 NTAs, which only exhibited a photo catalytic degradation efficiency of approximately 61%, thus it indicated the significant enhancement of the light absorption properties of fabricated photo electrodes and their yield of UOH radicals.     

Synthesis and enhanced visible-light responsive of C,N,S-tridoped TiO2 hollow spheres

C,N,S-tridoped TiO2 hollow spheres （labeled as C,N,S-THs） were synthesized using carbon spheres as template and C,N,S-tridoped TiO2 nanoparticles as building blocks. The structure and physicochemical properties of the catalysts were characterized by X- ray diffraction （XRD）, scanning electron microscopy （SEM）, UV-Vis diffuse reflectance spectrum （DRS）, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy （XPS） and Photoluminescence emission spectroscopy （PL）. The results showed that the hollow spheres had average diameter of about 200 nm and the shell thickness was about 20 nm. The tridoped TiO2 hollow spheres exhibited strong absorption in the visible-light region. C,N,S-tridoped could narrow the band gap of the THs by mixing the orbit O 2p with C 2p, N 2p and S 3p orbits and shift its optical response from ultraviolet （UV） to the visible-light region. PL analysis indicated that the electron-hole recombination rate of TiO2 hollow spheres had been effectively inhibited when doped with C, N and S elements. The photocatalytic activities of the samples were evaluated for the degradation of X-3B （Reactive Brilliant Red dye, C.I. Reactive Red 2） aqueous solution under visible-light （λ 〉 420 nm） irradiation. It was found that the C,N,S-tridoped TiO2 hollow spheres indicated higher photocatalytic activity than commercial P25 and the undoped counterpart photocatalyst.     

In-situ synthesis of TiO2 rutile/anatase heterostructure by DC magnetron sputtering at room temperature and thickness effect of outermost rutile layer on photocatalysis

TiO_2 rutile/anatase heterostructure thin films with varying rutile thickness have been in-situ synthesized via DC magnetron sputtering with Ar gas at room temperature. The crystal texture, surface morphology, energy gap and optical properties of the films have been investigated by X-ray diffraction meter, grazing incidence X-ray diffraction meter, Raman spectroscopy, scanning electron microscopy, and UV–visible spectrophotometer, which indicates that the rutile/anatase heterostructure films are successfully fabricated. The further degradation experiments display that the photocatalytic activity can be dramatically affected by the thickness of the outmost rutile layer and the 100 nm thickness exhibits the best performance in all of the TiO_2 thin films. With the increase of the outmost rutile layer, the optical band gap of TiO_2 film displays a systematic decrease slightly. However,the change in photocatalytic activity does not coincide with that in the band gap. The photoresponse and electrochemical properties of the thin films have been characterized to understand the mechanism of the varied photocatalytic activity.     

Visible light induced photodegradation of organic pollutants on nitrogen and fluorine co-doped TiO2 photocatalyst

The nitrogen and fluorine co-doped TiO2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetrabutyl titanate with ammonium fluoride. Nitrogen and fluorine co-doping causes the absorption edge of TiO2 to shift to a lower energy region.The photocatalytic activity of co-doped TiO2 with anatase phases was found to be 2.4 times higher than that of the commercial TiO2 photocatalyst Degussa P‘25 for phenol decomposition under visible light irradiation. The co-doped TiO2 powders only contain anatase phases even at 1000%. Apparently, ammonium fluoride added retarded phase transformation of the TiO2 powders from anatase to futile.The substitutional fluorine and interstitial nitrogen atoms in co-doped TiO2 polycrystalline powder were responsible for the vis light response and caused the absorption edge of TiO2 to shift to a lower energy region.     

Photo-catalytic reduction of carbon dioxide with in-situ synthesized CoPc/TiO2 under visible light irradiation

CO₂ is photo-catalytically reduced to produce formic acid, methanol, formaldehyde in an aqueous solution using visible light irradiation and in-situ synthesized CoPc/TiO₂. CoPc/TiO₂ nano-composite is in-situ synthesized through the annulations of 1,2-dicyanobenzene on the surface of TiO₂ with Co(II) as template. The prepared catalysts are characterized by means of XRD, DTA–TG, UV–vis and FT-IR methods. The photo-catalytic activity of these catalysts under visible light is discussed. The experimental results indicate that cobalt-phthalocyanine (CoPc) and TiO₂ are indeed synthesized by the in-situ method. Under the visible light irradiation, CoPc molecules are excited first and the excited electrons are injected into the conduction band of TiO₂, then the separation of electron–hole pairs is increased so that the photo-catalytic efficiency is increased. The results show that the in-situ CoPc/TiO₂ out performed physical absorbed CoPc/TiO₂. The total organic carbon (TOC) yield of 0.7 wt.% in-situ CoPc/TiO₂ is 1714.9 μmol/g catal. following 10 h of visible light illumination. The yield is much higher than those of TiO₂ and physical absorbed CoPc/TiO₂.     

Simultaneous removal of arsenic and antimony from mining wastewater using granular TiO2: Batch and field column studies

Coexisting arsenic (As) and antimony (Sb) in mining wastewater is a common and great concern. On-site simultaneous removal of As and Sb from mining wastewater was achieved by using a reusable granular TiO₂ column in this study. To evaluate the accuracy of the scale-up procedure, As and Sb adsorption from wastewater was studied in both large (600 g TiO₂) and small columns (12 g TiO₂) based on the proportional diffusivity rapid small-scale column tests (PD-RSSCTs) design. The comparable As and Sb breakthrough curves obtained from small and large columns confirmed the accuracy of the PD-RSSCT theory in the design of large-scale columns. Meanwhile, the consistent As and Sb adsorption results from batch and column experiments suggested that TiO₂ adsorption for As and Sb can be predicted from bench-scale tests. Charge distribution multi-site complexation (CD-MUSIC) and one-dimensional transport modeling integrated in the PHREEQC program were performed to study the adsorption behaviors of As and Sb on the TiO₂ surface. Coexisting ions, such as Ca^2 +, Mg^2 +, and Si^4 +, play an important role in As and Sb adsorption, and the breakthrough curves were well simulated after considering the compound ion effects. The results from this study highlight the surface reactions of As and Sb on TiO₂ and provide a practical way for on-site remediation of industrial wastewater.     

Effects of surfactants on the combined toxicity of TiO2 nanoparticles and cadmium to Escherichia coli

The combined ecological toxicity of TiO₂ nanoparticles (nano-TiO₂) and heavy metals has been paid more attention. As the common pollutants in water environment, surfactants could affect the properties of nanoparticles and heavy metals, and thus further influence the combined toxicity of nano-TiO₂ and heavy metals. In this study, the effects of sodium dodecyl benzene sulfonate (SDBS) and Tween 80 on the single and combined toxicities of Cd^2 + and nano-TiO₂ to Escherichia coli (E. coli) were examined, and the underlying influence mechanism was further discussed. The results showed both SDBS and Tween 80 enhanced the toxicity of Cd^2 + to E. coli in varying degrees. The reaction of SDBS and Cd^2 + could increase the outer membrane permeability and the bioavailability of Cd, while Tween 80 itself could enhance the outer membrane permeability. The combined toxicity of nano-TiO₂ and Cd^2 + to E. coli in absence of surfactant was antagonistic because of the adsorption of Cd^2 + to nano-TiO₂ particles. However, in the presence of SDBS, both SDBS and nano-TiO₂ influenced the toxicity of Cd^2 +, and also SDBS could adsorb to nano-TiO₂ by binding to Cd^2 +. The combined toxicity was reduced at Cd^2 + lower than 4 mg/L and enhanced at Cd^2 + higher than 4 mg/L under multiple interactions. Tween 80 enhanced the combined toxicity of nano-TiO₂ and Cd^2 + by increasing the outer membrane permeability. Our study firstly elucidated the effects of surfactants on the combined toxicity of nano-TiO₂ and Cd^2 + to bacteria, and the underlying influencing mechanism was proposed.     

Toward chemical-free reclamation of biologically pretreated greywater: solar photocatalytic oxidation with powdered activated carbon

Heterogeneous photocatalytic oxidation is a water reclamation technology which avoids chemical consumption and can be powered by solar radiation. Because this generally sustainable process is of limited efficiency for the treatment of biologically pretreated greywater, it was combined with activated carbon adsorption. The effluent of a constructed wetland for treatment of separately collected greywater was subjected to photocatalytic oxidation using the photocatalyst titanium dioxide (TiO₂) “P25” in both the absence and the presence of powdered activated carbon (PAC). Photocatalytic oxidation alone with UV fluences of about 10 Wh L^?1 was not capable of reducing total organic carbon (TOC) from an initial concentration of 5.5 mg L^?1 safely below 2 mg L^?1 as a prerequisite for high-quality water reuse purposes. However, when PAC was added, TOC concentrations subsequent to photocatalytic oxidation were less than 2 mg L^?1 even after reusing the TiO₂/PAC mixture 10 times. PAC addition is estimated to reduce the insolation area necessary to achieve this target by solar photocatalytic oxidation of biologically treated greywater by a factor 7. This combination process represents an innovative chemical-free technology within wastewater reuse schemes.     

上转换发光剂掺杂纳米TiO2的制备及可见光降解乙基紫的研究

合成了一种新型含有稀土金属Er的上转换发光剂40CdF₂·60BaF₂·1.6Er₂O₃,此上转换发光剂在488 nm可见光的激发下,产生了5个波长均小于387 nm的上转换紫外光发射峰.采用超声波分散的方法制备出了上转换发光剂掺杂的纳米TiO₂可见光光催化剂.利用X-射线衍射(XRD)及透射电镜(TEM)对催化剂进行了表征.以乙基紫染料为研究对象,研究了在(三基色灯下发出的)可见光的照射下该可见光光催化剂的催化降解性能,并与未掺杂的纳米TiO₂粉末的催化性能进行了对比.结果表明,作为掺杂成分的上转换发光剂可有效地将可见光转化为紫外光并被纳米TiO₂粉末吸收利用,在可见光照射12.0 h后乙基紫降解率达到了99.68%,大大高于未掺杂纳米TiO2时的降解率.     

Protecting the photosynthetic performance of snap bean under free air ozone exposure

Tropospheric ozone(O_3) is a major air pollutant and causes serious injury to vegetation. To protect sensitive plants from O_3 damage, several agrochemicals have been assessed,including cytokinin(e.g., kinetin, KIN) and ethylenediurea(EDU) with cytokinin-like activity.In higher plant, leaves are primarily injured by O_3 and protective agrochemicals are often applied by leaf spraying. To our knowledge, the mitigating abilities of EDU and KIN have not been compared directly in a realistic setup. In the present research, impacts of elevated O3(2 × ambient O_3, 24 hr per day, for 8 days) on an O_3 sensitive line(S156) of snap bean(Phaseolus vulgaris), which is often used for biomonitoring O_3 pollution, were studied in a free air controlled exposure system. The day before starting the O_3 exposure, plants were sprayed with a solution of EDU(300 ppm), KIN(1 mmol/L) or distilled water, to compare their protective abilities. The results demonstrated that 2 × ambient O_3 inhibited net photosynthetic rate and stomatal conductance, increased the minimal fluorescence yield of the dark-adapted state, decreased the maximal quantum yield of PSII photochemistry, and led to visible injury. KIN and EDU alleviated the reduction of the photosynthetic performance, and visible injury under O_3 fumigation. The plants sprayed with EDU showed greater ability to mitigate the O_3 damage than those sprayed with KIN. Chlorophyll fluorescence imaging may have detected more precisely the differences in O_3 response across the leaf than the conventional fluorometer.     

An innovative approach to minimize excess sludge production in sewage treatment using integrated bioreactors

The present investigation deals with an application of integrated sequential oxic and anoxic bioreactor(SOABR) and fluidized immobilized cell carbon oxidation(FICCO) reactor for the treatment of domestic wastewater with minimum sludge generation. The performance of integrated SOABR-FICCO system was evaluated on treating the domestic wastewater at hydraulic retention time(HRT) of 3 hr and 6 hr for 120 days at organic loading rate(OLR)of 191 ± 31 mg/(L·hr). The influent wastewater was characterized by chemical oxygen demand(COD) 573 ± 93 mg/L; biochemical oxygen demand(BOD5) 197 ± 35 mg/L and total suspended solids(TSS) 450 ± 136 mg/L. The integrated SOABR-FICCO reactors have established a significant removal of COD by 94% ± 1%, BOD5 by 95% ± 0.6% and TSS by 95% ± 4% with treated domestic wastewater characteristics COD 33 ± 5 mg/L; BOD59 ± 0.8 mg/L and TSS 17 ± 9 mg/L under continuous mode of operation for 120 days. The mass of dry sludge generated from SOABR-FICCO system was 22.9 g/m~3. The sludge volume index of sludge formed in the SOABR reactor was 32 mL/g and in FICCO reactor it was 46 mL/g. The sludge formed in SOABR and FICCO reactor was characterized by TGA, DSC and SEM analysis. Overall, the results demonstrated that the integrated SOABR-FICCO reactors substantially removed the pollution parameters from domestic wastewater with minimum sludge production.     

可见光响应漂浮式微球光催化剂及其光降解模拟海水中苯酚

为了将光催化技术应用于有机物污染海水的治理,本文首先利用水热还原得到了具有可见光响应的还原商用P25光催化剂,而后将还原后的P25作为活性组分负载在透明的有机玻璃空心微球表面,制成漂浮式微球光催化剂.还原后的P25的表征结果表明,水热条件下金属还原作用会将P25中少量Ti~(4+)还原成Ti~(3+),同时催化剂表面还形成了无序化-内部结晶的核壳结构.这两种结构变化都会显著拓展还原P25催化剂的可见光响应.含苯酚模拟污染海水的光降解实验发现,降解低浓度苯酚时,漂浮型微球光催化剂显示了优异的降解效率,降解5 h的去除率达到了95%以上.由于还原P25光催化剂的稳定性并且漂浮式微球光催化剂能简易回收,在多次重复实验中微球光催化剂都可以保持较高的催化活性.     

Photocatalytic degradation of dichlorvos using TiO2 supported on hollow glass microbeads

In this paper, a method for TiO₂ supported on hollow glass microbeads was described and the feasibility of photocatalytic degradation of dichlorvos using supported TiO₂(TiO₂/beads) was studied. The results showed that 1.0×10^-4 mol.dm^-3 of dichlovos could be completely photocatalytically degraded into PO₄^3- after 120 min illumination with a 375 W medium pressure mercury lamp. The effects of the amount of TiO₂/beads and concentration of Cu²⁺ on the photocatalytic degradation were also investigated. Some intemediate products of photocatalytic degradation of dichlorvos were detected.