Design of graphene-based TiO2 photocatalysts—a review

There is a recent increase in the interest of designing high-performance photocatalysts using graphene-based materials. This review gathers some important aspects of graphene?CTiO₂, graphene oxide?CTiO₂, and reduced graphene oxide?CTiO₂ composites, which are of especial relevance as next generation photocatalysts. The methods used for the preparation of these materials, the associated mechanistic fundamentals, and the application of graphene-based composites on the photocatalytic degradation of pollutants are reviewed. Some structural, textural, and chemical properties of these materials and other photo-assisted applications, such as hydrogen production from water splitting and dye-sensitized solar cells, are also briefly included.     

Review on synthesis of three-dimensional graphene skeletons and their absorption performance for oily wastewater

Water pollution is a global environmental problem that affects the ecosystem severely. Treatment of oily wastewater and organic pollutants is a major challenge that waits to be solved as soon as possible. Adsorbing is one of the most effective strategies to deal with this problem. Three-dimensional (3D) porous adsorbents made of graphene or graphene-based nanomaterials skeletons had attracted more attention in wastewater treatment because of their large surface area, high porosity, low density, high chemical/thermal stability, and steady mechanical properties, which allow different pollutants to easily access and diffuse into 3D networks of adsorbents. This work presents an extensive summarization of recent progress in the synthesis methodologies and microstructures of 3D graphene foams and 3D graphene-based foams and highlights their adsorption performance for oils and organic solvents. Advantages and disadvantages of various preparation strategies are compared and the corresponded structures of these skeletons are studied in detail. Furthermore, the effects of the structures on oil-adsorption properties are analyzed and some data and parameters of the oil-adsorption properties are listed and studied for easier comparison. At last, the future research directions and technical challenges are prospected, which is hoped that the researchers will be inspired to develop the new graphene-based adsorbents.

     

光催化-膜分离三相流化床循环反应装置处理酸性红B废水

耦合光催化氧化和有机膜分离技术,设计了一种新型光催化氧化-有机膜分离三相流化床循环反应装置（循环反应装置）;并对循环反应装置光催化降解酸性红B时的影响因素进行了研究。结果表明,减小膜出水通量和降低酸性红B废水浓度均有利于膜出水降解率的提高;循环反应装置中废水降解率随光催化反应器底部曝气量的增加而先增加再降低,膜分离器中废水降解率的波动则随曝气量的增加而总是在增大,其最佳曝气量为1．00m^3／h;光催化反应器中多光源布置有利于循环反应装置的稳定运行;循环反应装置可有效地处理酸性红B废水。     

Solar photocatalysis for treatment of Acid Yellow-17 (AY-17) dye contaminated water using Ag@TiO2 core–shell structured nanoparticles

Wastewater released from textile industries causes water pollution, and it needs to be treated before discharge to the environment by cost effective technologies. Solar photocatalysis is a promising technology for the treatment of dye wastewater. The Ag@TiO₂ nanoparticles comprising of Ag core and TiO₂ shell (Ag@TiO₂) have unique photocatalytic property of inhibition of electron–hole recombination and visible light absorption, which makes it a promising photocatalyst for use in solar photocatalysis and with higher photocatalytic rate. Therefore, in the present work, the Ag@TiO₂ nanoparticles synthesized by one pot method with postcalcination step has been used for the degradation of Acid Yellow-17 (AY-17) dye under solar light irradiation. The Ag@TiO₂ nanoparticles were characterized using thermogravimetric–differential thermal analysis, X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. The catalyst has been found to be very effective in solar photocatalysis of AY-17, as compared to other catalysts. The effects of pH, catalyst loading, initial dye concentration, and oxidants on photocatalysis were also studied. The optimized parameters for degradation of AY-17 using Ag@TiO₂ were found to be pH?3, dye/catalyst ratio of 1:10 (g/g), and 2 g/L of (NH₄)₂S₂O₈ as oxidant. Efficient decolorization and mineralization of AY-17 was achieved. The kinetics of color, total organic carbon, and chemical oxygen demand removal followed the Langmuir–Hinshelwood model. Ag@TiO₂ catalyst can be reused thrice without much decline in efficiency. The catalyst exhibited its potential as economic photocatalyst for treatment of dye wastewater.     

Nanomaterials photocatalytic activities for waste water treatment: a review

Water is necessary for the survival of life on Earth. A wide range of pollutants has contaminated water resources in the last few decades. The presence of contaminants incredibly different dyes in waste, potable, and surface water is hazardous to environmental and human health. Different types of dyes are the principal contaminants in water that need sudden attention because of their widespread domestic and industrial use. The toxic effects of these dyes and their ability to resist traditional water treatment procedures have inspired the researcher to develop an eco-friendly method that could effectively and efficiently degrade these toxic contaminants. Here, in this review, we explored the effective and economical methods of metal-based nanomaterials photocatalytic degradation for successfully removing dyes from wastewater. This study provides a tool for protecting the environment and human health. In addition, the insights into the transformation of solar energy for photocatalytic reduction of toxic metal ions and photocatalytic degradation of dyes contaminated wastewater will open a gate for water treatment research. The mechanism of photocatalytic degradation and the parameters that affect the photocatalytic activities of various photocatalysts have also been reported.

     

TiO2光催化剂在污水处理中的应用

在污水处理方面TiO2光催化剂以其独特的氧化活性、光学性能和无机化能力引起了人们极大的关注.对TiO2光催化原理、农药、染料和环境荷尔蒙等有机污染物的分解,提高催化效率的方法以及其实用技术等方面,分别作了综合评述.     

Enhanced photocatalytic activity using GO/TiO<Subscript>2</Subscript> catalyst for the removal of DCA solutions

This work aimed to optimize high-performance photocatalysts based on graphene oxide/titanium dioxide (GO/TiO₂) nanocomposites for the effective degradation of aqueous pollutants. The catalytic activity was tested against the degradation of dichloroacetic acid (DCA), a by-product of disinfection processes that is present in many industrial wastewaters and effluents. GO/TiO₂ photocatalysts were prepared using three different methods, hydrothermal, solvothermal, and mechanical, and varying the GO/TiO₂ ratio in the range of 1 to 10%. Several techniques were applied to characterize the catalysts, and better coupling of GO and TiO₂ was observed in the thermally synthesized composites. Although the results obtained for DCA degradation showed a coupled influence of the composite preparation method and its composition, promising results were obtained with the photocatalysts compared to the limited activity of conventional TiO₂. In the best case, corresponding to the composite synthesized via hydrothermal method with 5% of GO/TiO₂ weight ratio, an enhancement of 2.5 times of the photocatalytic degradation yield of DCA was obtained compared to bare TiO₂, thus opening more efficient ways to promote the application of photocatalytic remediation technologies.     

Fabrication of cerium titanate cellulose fiber nanocomposite materials for the removal of methyl orange and methylene blue from polluted water by photocatalytic degradation

In this study, cellulose fibers (Cf), extracted from sunflower seed husk, and different molar ratios of cerium titanate (Ce-Ti) NPs were prepared from sunflower seed husk extract by a green biosynthesis approach. Cf and Ce-Ti NPs were reacted via cross-linking reaction to synthesize a novel nanocomposite photocatalyst of Ce-Ti/Cf. Using Fourier-transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM-EDX) spectroscopy, all manufactured materials were characterized. The results obtained from FTIR and EDX analyses indicated that Cf and its nanocomposites (0.1 Ce-Ti/Cf, 0.3 Ce-Ti/Cf, and 0.5 Ce-Ti/Cf) were successfully prepared by harnessing biomass extract from sunflower seed husk. Furthermore, XRD revealed that the degree of crystallinity of the nanocomposites was enhanced by increasing the molar ratios of the Ce-Ti NPs. The photocatalytic activity of as-fabricated 0.1 Ce-Ti/Cf, 0.3 Ce-Ti/Cf, and 0.5 Ce-Ti/Cf nanocomposite samples was investigated on methylene blue (MB) and methyl orange (MO) dyes as model organic compounds found in wastewaters. The effects of dose, contact time, and pH on the photocatalytic activity of the synthesized nanocomposites, the photodegradation kinetic parameters of MB, and MO degradation with/without the addition of H₂O₂ were also studied. The results revealed that high photodegradation efficiency could be obtained as the ratio of TiO₂ in the Ce-Ti nanocomposite formula increases. Moreover, after sunlight irradiation, the adsorption capacity and the dye decomposition ratio significantly increase during the early contact time and reach equilibrium at about 240 and 120 min for 0.5 Ce-Ti/Cf nanocomposite photocatalyst in the absence and presence of hydrogen peroxide, respectively. In light of the obtained results and the practical wastewater treatment study conducted, the prepared photocatalyst from Ce-Ti/Cf nanocomposites could be a promising material for treating dye wastewater especially collected from Egypt.

     

Titania-supported silver-based bimetallic nanoparticles as photocatalysts

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag–Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO₂-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO₂). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.     

Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

Performance evaluation and application of surface-molecular-imprinted polymer-modified TiO2 nanotubes for the removal of estrogenic chemicals from secondary effluents

The removal of estrogenic chemicals during wastewater reclamation has been a great concern. Current advanced treatment processes are inefficient for the removal of estrogenic chemicals from secondary effluents of municipal wastewater treatment plants (WWTPs) due to the coexistence of other pollutants with less environmental significance which are also removed simultaneously. The search for highly selective and low-cost removal methods is warranted. Therefore, surface-molecular-imprinted polymer-modified TiO₂ nanotube (S-MIP-TiO₂ NT) photocatalysts were fabricated, characterized, and tested for the removal of estrogenic pollutants from wastewater in this study for the first time. Scanning electron microscopy and Fourier-transform infrared spectroscopy studies showed that the TiO₂ NTs (with an average diameter of 60 nm) were successfully imprinted with functional groups (i.e., carboxyl). The adsorption selectivity and photocatalytic activity of the S-MIP-TiO₂ NTs towards template compound (17β-estradiol, E2) were improved, compared with neat TiO₂ NTs. Interestingly, S-MIP-TiO₂ NTs exhibited higher adsorption intensity and photocatalytic selectivity at low concentrations (from 10 ng/L to 100 μg/L, as normal estrogenic chemical concentrations in secondary effluents) of E2 than that at high concentrations (from 10 to 1,000 mg/L). It was also found that some representative estrogenic chemicals and estrogenic activity could be selectively and rapidly removed from secondary effluents of municipal wastewater treatment plants using S-MIP-TiO₂ NTs as photocatalysts. In addition, S-MIP-TiO₂ NT photocatalysts exhibited excellent regeneration characteristics. Photocatalytic treatment using S-MIP-TiO₂ NTs could be a promising approach for the effective removal of estrogenic chemicals from secondary effluents of municipal WWTPs.     

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

Photocatalytic reduction of carbon dioxide to methanol and formic acid by graphene-TiO2

Graphene-TiO₂ was obtained by reduction of graphite oxide by the hydrothermal method. Using photocatalytic activity to reduce carbon dioxide to methanol and formic acid was investigated in this study. The results show that the graphene loading affects the absorption of light in the visible light region. A larger surface area can also improve the catalytic activity. The largest yield of methanol and formic acid, under light of 365 nm, can reach 160 and 150 μmol g^?1, respectively, with 8.5% graphene loading. An increase in graphene loading can enhance photocatalytic performance, but too much will also decrease the reduction efficiency by shielding the light from reaching the catalytic surface. The effect of pH was also investigated. The mechanism of the reaction was also discussed in this study.

Implications: Graphene-TiO₂ hybrids were prepared by the hydrothermal method. Surface area and visible light adsorption increased with the graphene loading. Increased graphene loading improved the methanol and formic acid production. Too much graphene loading will decrease the reduction efficiency. The effect of pH shows that the HCO₃^? species prefers the formation of formic acid. The mechanism of the reaction was also discussed in this study.     

Recent developments in MnO2-based photocatalysts for organic dye removal: a review

The textile industry consumes a large volume of organic dyes and water. These organic dyes, which remained in the effluents, are usually persistent and difficult to degrade by conventional wastewater treatment techniques. If the wastewater is not treated properly and is discharged into water system, it will cause environmental pollution and risk to living organisms. To mitigate these impacts, the photo-driven catalysis process using semiconductor materials emerges as a promising approach. The semiconductor photocatalysts are able to remove the organic effluent through their mineralization and decolorization abilities. Besides the commonly used titanium dioxide (TiO₂), manganese dioxide (MnO₂) is a potential photocatalyst for wastewater treatment. MnO₂ has a narrow bandgap energy of 1~2 eV. Thus, it possesses high possibility to be driven by visible light and infrared light for dye degradation. This paper reviews the MnO₂-based photocatalysts in various aspects, including its fundamental and photocatalytic mechanisms, recent progress in the synthesis of MnO₂ nanostructures in particle forms and on supporting systems, and regeneration of photocatalysts for repeated use. In addition, the effect of various factors that could affect the photocatalytic performance of MnO₂ nanostructures are discussed, followed by the future prospects of the development of this semiconductor photocatalysts towards commercialization.

     

多相光催化在水污染治理中的应用

多相光催化过程是近年来日益引起重视的污染治理新技术，具有适用范围广、可使污染物彻底破坏、适用于低浓污染物治理等优点，本文对国外近年有关多相光催化在水污染治理中应用的研究结果进行了总结，包括各种有机污染物的氧化及各种无机离子的治理，并讨论了多相光催化过程的优点及实用性。     

NORMACAT project: normalized closed chamber tests for evaluation of photocatalytic VOC treatment in indoor air and formaldehyde determination

Background, aim

The aims of the NORMACAT project are: to develop tools and unbiased standardized methods to measure the performance and to validate the safety of new materials and systems integrating photocatalysis, to develop new photocatalytic media with higher efficiency and to give recommendations aimed at improving the tested materials and systems.

Method

To achieve this objective, it was necessary to design standardized test benches and protocols to assess photocatalytic efficiency of materials or systems used in the treatment of volatile organic compounds (VOCs) and odour under conditions close to applications. The tests are based on the validation of robust analytical methods at the parts per billion by volume level that not only follow the disappearance of the initial VOCs but also identify the secondary species and calculate the mineralization rates.

Results

The first results of inter-laboratory closed chamber tests, according to XP B44-013 AFNOR standard, are described. The photocatalytic degradation of mixtures of several defined pollutants under controlled conditions (temperature, relative humidity, initial concentration) was carried out in two independent laboratories with the same photocatalytic device and with various analytical procedures. Comparison of the degradation rate and of the mineralization efficiency allowed the determination of the clean air delivery rate in both cases. Formaldehyde was the only by-product detected during photocatalytic test under standardized experimental conditions. The concentration of transient formaldehyde varied according to the initial VOC concentration. Moreover the photocatalytic reaction rate of formaldehyde in mixture with other pollutants was analysed. It was concluded that formaldehyde concentration did not increase with time.

Conclusion??perspective

This type of experiment should allow the comparison of the performances of different photoreactors and of photocatalytic media under controlled and reproducible conditions against mixtures of pollutants including formaldehyde.     

Effect of water composition on the photocatalytic removal of pesticides with different TiO2 catalysts

The objective of this work is double—firstly to explore the photocatalytic efficiency of five different commercial TiO₂ catalysts in the photodegradation of a mixture of pesticides classified by the EU as priority pollutants and secondly to analyze the correlation between their physicochemical properties and the inhibition of the studied photocatalytic process when natural water was employed. Photocatalytic efficiencies when ultrapure water was used seem to point out that surface area was not a prerequisite for the photodegradation of the selected mixture of pesticides. On the other hand, significant differences in total organic carbon (TOC) conversions were obtained with the two studied water compositions. On one side, Evonik materials appear to be mostly inhibited when natural water was employed, whereas on the other, it should be remarked that anatase Sigma-Aldrich (SA) and, particularly, Hombikat UV100 (HBK) materials presented a very limited photo-efficiency inhibition or even a higher initial rate of TOC removal when a natural water matrix was used, probably due to their specific surface properties (PZC, S _BET). Therefore, heterogeneous photocatalysis has proved to be a promising technology for the degradation of the selected mixture of pesticides where the final photo-efficiency of the five commercial titania catalysts studied here responds to a complex balance between its surface and structural properties.     

光磁耦合废水处理工艺条件的优化研究

以Fe3O4/TiO2作为磁性光催化剂,采用光磁耦合技术处理模拟印染废水。利用统计学方法对光磁耦合废水处理的影响因素进行了探讨和分析,考察了磁场强度、磁性光催化剂投加量、pH值和光照时间对光磁耦合废水处理的影响。通过Design-Expert 7.0.0软件分析得到最佳工艺条件:磁场强度73.95 mT,磁性光催化剂投加量1.13 g/L,模拟废水pH值13,光照时间120 min。在最佳工艺条件下进行实验,脱色率为88.60%。     

纳米TiO2改性可见光催化降解有机物研究进展

光催化降解水中有机污染物是一项颇有发展前途的废水处理技术.目前主要的研究工作由紫外光逐步向可见光催化方向发展,使这项技术向实用性又迈进了一步.系统介绍了纳米TiO2的光催化降解有机污染物的原理,光催化处理水的现状,并从离子掺杂、表面光敏化和分子筛负载几个方面综述了可见光化的研究现状和发展方向.     

无机离子对光催化水处理过程影响的研究进展

无机离子在自然水体和生产废水中广泛存在。在不同的反应体系,无机离子对光催化反应的影响不同。深入了解无机离子对光催化水处理过程的影响有助于研究光催化反应的机制,增强金属离子与有机污染物光催化反应的协同作用,提高光催化反应的效率。