载银纳米TiO_2光催化降解水中有机污物

以TiOSO4和TiOCl2 为原料 ,合成出锐钛相和金红石相的相对含量分别约为 85 %和 1 5 %的纳米TiO2 光降解催化剂。在纳米TiO2 表面担载质量分数为 0 5 %的银后 ,不但能较好地提高催化活性和使用寿命 ,而且表现出特有的絮凝作用 ,使催化剂易于分离 ,达到多次循环使用的目的。对光催化降解活性黑模拟污水 ,以及蒽醌类染料、糖厂等实际污水发现 ,这种纳米TiO2 具有活性高、寿命较长的特点 ,且能多次循环使用 ,降低了处理污水的成本。

可见光催化降解水中邻苯二甲酸二异辛酯的研究

邻苯二甲酸二异辛酯(DEHP)是环境激素类物质的一种,在环境中该物质持久存在不易分解,对人体健康造成严重危害,因此研究其废水降解具有重要的意义。以氙灯作为可见光光源,纳米CuPcTs/TiO2为催化剂,在可见光照射下较系统地考察了催化剂的活性、初始溶液的pH值、催化剂用量、光照时间等因素,对水溶液中DEHP光催化降解进行了研究。结果表明在pH=5,催化剂用量为0.4 g/L,光照时间为50 min,初始浓度为10 mg/L的DEHP水溶液降解速率为最佳,降解率达到93.6%,并证明了只有在催化剂和光源协同作用时,水中DEHP才可获得较快的降解。

聚丙烯酰胺的处理方法研究进展

降解聚丙烯酰胺(PAM)的机理是将难降解的水溶性高分子长链聚合物分解为小分子物质。介绍了近年来国内聚丙烯酰胺的降解技术研究进展,包括生物降解、化学降解和物理降解三个方向,对这些方法做了比较,并对今后研究方法提出建议:在聚丙烯酰胺的降解机理、降解率的因素及高效催化剂方面需要进一步研究。

Synthesis of Cu2O/Ag Composite with Visible Light Photocatalytic Degradation Activity for in situ SERS Analysis

A multifunctional Cu2O/Ag micro-nanocomposite, which has the characteristics of high cat- alytic activities under the visible light and high surface-enhanced Raman scattering （SERS） activity, was fabricated via a facile method and employed for the in situ SERS monitoring of the photocatalytic degradation reaction of crystal violet. Through the variation of the AgNO3 concentration, Ag content on the Cu2O template can be controllably tuned, which has great influence on the SERS effect. The results indicate that Ag nanopartieles form on the Cu2O nanoframes to obtain the Cu2O/Ag nanoeomposite, which can act as an excellent bifunetional platform for in situ monitoring of photocatalytic degradation of organic pollutions by SERS.

Novel visible-light-responding InVO_4-Cu_2O-TiO_2 ternary nanoheterostructure: Preparation and photocatalytic characteristics

A novel visible-light-responding InVO4-Cu2O-TiO2 ternary nanoheterostructure was designed on the basis of the strategy of energy gap engineering and prepared through ordinary wet chemistry methods. The as-prepared nanoheterostructure was characterized by X-ray powder diffraction（XRD）, transmission electron microscopy（TEM）, high-resolution transmission electron microscopy（HRTEM） and diffuse reflectance ultraviolet-visible spectroscopy（UV-vis/DRS）. The TEM and HRTEM images of 10%InVO4-40%Cu2O-50%TiO2 confirm the formation of nanoheterostructures resulting from contact of the nanosized TiO2, Cu2O and InVO4 in the size of 5–20 nm in diameter. The InVO4-Cu2O-TiO2 nanoheterostructure, when compared with TiO2, Cu2O, InVO4, InVO4-TiO2 and Cu2O-TiO2, shows significant enhancement in the photocatalytic performance for the degradation of methyl orange（MO） under visible-light irradiation. With a 9 W energy-saving fluorescent lamp as the visible-light source, the MO degradation rate of 10%InVO4-40%Cu2O-50%TiO2 reaches close to 90% during 5 h, and the photocatalytic efficiency is maintained at over 90% after six cycles. This may be mainly ascribed to the matched bandgap configurations of TiO2, Cu2O and InVO4, and the formations of two p-n junctions by the p-type semiconductor Cu2O with the n-type semiconductors TiO2 and InVO4, all of which favor spatial photogenerated charge carrier separation. The X-ray photoelectron spectroscopy（XPS） characterization for the used 10%InVO4-40%Cu2O-50%TiO2 reveals that only a small shakeup satellite peak appears for Cu（II） species, implying bearable photocorrosion of Cu2O. This work could provide new insight into the design and preparation of novel visible-light-responding semiconductor composites.

Preparation of amphiphilic TiO_2 Janus particles with highly enhanced photocatalytic activity

Stearic-acid-modified TiO2 (STA-TiO2) particles were prepared via the impregnation approach and used as a precursor for preparing TiO2 Janus particles. The morphology, structure, and properties of the TiO2 Janus particles were characterized using Fourier-transform infrared spectroscopy, ultraviolet- visible diffuse reflectance spectroscopy, thermogravimetric analysis, fluorescence microscopy, high-resolution transmission electron microscopy, contact angle analysis, dynamic light scattering, biological microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy measurements. The results show that TiO2 Janus particles can be successfully prepared via toposelective surface modification. STA grafted on the surface of TiO2 enhances its hydrophobicity, promotes charge separation, and improves its adsorption capacity for organic compounds. The TiO2 Janus particles strongly adsorb on an oil-water interface to form a stable Pickering emulsion. The degradation rates of high-concentration kerosene and nitrobenzene wastewaters when the photocatalyst is pure TiO2, STA-TiO2, or TiO2 Janus particles are discussed and compared. The degradation rates were determined using an ultraviolet-visible spectrophotometer. It was found that the Pickering emulsion stabilized by the TiO2 Janus particles exhibited the best photocatalytic performance;these Janus particles show promising potential for catalytic application.

Hydrogen producing water treatment through mesoporous TiO2 nanofibers with oriented nanocrystals

The development of well-defined TiO2 nanoarchitectures is a versatile strategy to achieve high-efficiency photocatalytic performance.In this study,mesoporous TiO2 nanofibers consisting of oriented nanocrystals were fabricated by a facile vapothermal-assisted topochemical transformation of preformed H-titanate nanobelts.The vapothermal temperature is crucial in tuning the microstructures and photocatalytic redox properties of the resulting mesoporous TiO2 nanofibers.The microstructures were characterized with XRD,TEM,XPS and nitrogen adsorption-desorption isotherms,etc.The photocatalytic activities were evaluated by photocatalytic oxidation of organic pollutant(Rhodamine B as an example)as well as photocatalytic reduction of water to generate hydrogen(H2).The nanofibers vapothermally treated at 150°C showed the highest photocatalytic activity in both oxidation and reduction reactions,2 times higher than that of P25.The oriented alignment and suitable mesoporosity in the resulting nanofiber architecture were crucial for enhancing photocatalytic performances.The oriented alignment of anisotropic anatase nanocrystals shall facilitate faster vectorial charge transportation along the nanofibers architecture.And,the suitable mesoporosity and high surface area would also effectively enhance the mass exchange during photocatalytic reactions.We also demonstrate that efficient energy-recovering photocatalytic water treatments could be accomplished by a cascading oxic-anoxic process where the dye is degraded in the oxic phase and hydrogen is generated in the successive anoxic phase.This study showcases a novel and facile method to fabricate mesoporous TiO2 nanofibers with high photocatalytic activity for both clean energy production and environmental purification.

Enhanced visible photocatalytic activity of TiO_2 hollow boxes modified by methionine for RhB degradation and NO oxidation

Hierarchical TiO2 hollow nanoboxes(TiO2‐HNBs)assembled from TiO2 nanosheets(TiO2‐NSs)show improved photoreactivity when compared with the building blocks of discrete TiO2‐NSs.However,TiO2‐HNBs can only be excited by ultraviolet light.In this paper,visible‐light‐responsive N and S co‐doped TiO2‐HNBs were prepared by calcining the mixture of cubic TiOF2 and methionine(C5H11NO2S),a N‐and S‐containing biomacromolecule.The effect of calcination temperature on the structure and performance of the TiO2‐HNBs was systematically studied.It was found that methionine can prevent TiOF2‐to‐anatase TiO2 phase transformation.Both N and S elements are doped into the lattice of TiO2‐HNBs when the mixture of TiOF2 and methionine undergoes calcination at 400°C,which is responsible for the visible‐light response.When compared with that of pure 400°C‐calcined TiO2‐HNBs(T400),the photoreactivity of 400°C‐calcined methionine‐modified TiO2‐HNBs(TM400)improves 1.53 times in photocatalytic degradation of rhodamine‐B dye under visible irradiation(?>420 nm).The enhanced visible photoreactivity of methionine‐modified TiO2‐HNBs is also confirmed by photocatalytic oxidation of NO.The successful doping of N and S elements into the lattice of TiO2‐HNBs,resulting in the improved light‐harvesting ability and efficient separation of photo‐generated electron‐hole pairs,is responsible for the enhanced visible photocatalytic activity of methionine‐modified TiO2‐HNBs.The photoreactivity of methionine modified TiO2‐HNBs remains nearly unchanged even after being recycled five times,indicating its promising use in practical applications.

In-situ transformation of Bi_2WO_6 to highly photoreactive Bi_2WO_6@Bi_2S_3 nanoplate via ion exchange

As a two dimensional(2D)visible‐light‐responsive semiconductor photocatalyst,the photoreactivity of Bi2WO6 is not high enough for practical application owing to its limited response to visible light and rapid recombination of photogenerated electron‐hole pairs.In this paper,2D core‐shell structured Bi2WO6@Bi2S3 nanoplates were prepared by calcination of a mixture of Bi2WO6(1.3 g)and a certain amount of Na2S·9H2O(0–3.0 g)at 350°C for 2 h.The reactivity of the resulting photocatalyst materials was evaluated by photocatalytic degradation of Brilliant Red X‐3B(X3B),an anionic dye,under visible light irradiation(?>420 nm).As the amount of Na2S·9H2O was increased from 0 to 1.5 g,the degradation rate constant of X3B sharply increased from 0.40×10?3 to 6.6×10?3 min?1.The enhanced photocatalytic activity of Bi2WO6@Bi2S3 was attributed to the photosensitization of Bi2S3,which greatly extended the light‐responsive range from the visible to the NIR,and the formation of a heterojunction,which retarded the recombination rate of photogenerated electron‐hole pairs.However,further increases in the amount of Na2S·9H2O(from 1.5 to 3.0 g)resulted in a decrease of the photocatalytic activity of the Bi2WO6@Bi2S3 nanoplates owing to the formation of a photo‐inactive NaBiS2 layer covering the Bi2WO6 surface.

Synthesis and Photocatalytic Activity of One-dimensional ZnO-Zn2SnO4 Mixed Oxide Nanowires

Mixed oxide photocatalysts, ZnO-Zn2SnO4 （ZnO-ZTO） nanowires with different sizes were prepared by a simple thermal evaporation method. The ZnO-ZTO nanowires were characterized with a scanning electron microscope, X-ray diffraction, high-resolution transmission electron microscopy, energy-dispersive spectrom- eter, and X-ray photoelectron spectra. The photocatalytic activity of the ZnO-ZTO mixed nanowires were studied by observing the photodegradation behaviors of methyl orange aqueous solution. The results suggest that the ZnO-ZTO mixed oxide nanowires have a higher photocatalytic activity than pure ZnO and Zn2SnO4 nanowires. The photocatalyst concentration in the solution distinctly affects the degradation rate, and our results show that higher photodegradation efficiency can be achieved with a smaller amount of ZnO-ZTO nanowire catalyst, as compared to the pure ZnO and ZTO nanowires. Moreover, the photocatalytic activity can also be enhanced by reducing the average diameter of the nanowires. The activity of pure ZnO and ZTO nanowires are also enhanced by physically mixing them. These results can be explained by the synergism between the two semiconductors.

High photocatalytic activities of zinc oxide nanotube arrays modified with tungsten trioxide nanoparticles

Well‐aligned zinc oxide(ZnO)nanotube arrays loaded with tungsten trioxide(WO3)nanoparticles were synthesized by a process involving chemical bath deposition in combination with pyrolysis.The prepared ZnO–WO3composites were characterized by X‐ray diffraction,energy dispersive spectrometer,field emission scanning electron microscopy,X‐ray photoelectron spectroscopy,photoluminescence spectroscopy,Fourier transform infrared spectroscopy and UV–vis diffuse reflectance spectroscopy.The photocatalytic activities of the ZnO–WO3composite photocatalysts with different WO3contents for the degradation of the herbicide chlorinated phenoxyacetic acid(MCPA‐Na)under simulated sunlight irradiation were systematically evaluated.It was found that the WO3content had a great effect on the photocatalytic activity of the ZnO–WO3composites.The composite with3%WO3showed the highest photocatalytic activity,with a degradation rate of chlorinated phenoxyacetic acid of98.5%after200min with20mg of photocatalyst.This photodegradation rate was about twice that of the pristine ZnO nanotube array.The recombination of photogenerated electrons and holes was increasingly suppressed with the addition of WO3to ZnO.The high relative content of defects on the surface of the ZnO–WO3composites was beneficial to their photocatalytic activity in the degradation of chlorinated phenoxyacetic acid.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalysts toward artificial carbon cycling

Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.

Visible light-responsive carbon-decorated p-type semiconductor CaFe_2O_4 nanorod photocatalyst for efficient remediation of organic pollutants

We report the fabrication and photocatalytic property of a composite of C/CaFe2O4nanorods(NRs)in an effort to reveal the influence of carbon modification.It is demonstrated that the photocatalytic degradation activity is dependent on the mass ratio of C to CaFe2O4.The optimal carbon content is determined to be58wt%to yield a methylene blue(MB)degradation rate of0.0058min.1,which is4.8times higher than that of the pristine CaFe2O4NRs.The decoration of carbon on the surface of CaFe2O4NRs improves its adsorption capacity of the MB dye,which is specifically adsorbed on the surface as a monolayer according to the adsorption isotherm analysis.The trapping experiments of the reactive species indicate that superoxide radicals(.O2)are the main active species responsible for the removal of MB under visible‐light irradiation.Overall,the unique feature of carbon coating enables the efficient separation and transfer of photogenerated electrons and holes,strengthens the adsorption capacity of MB,and improves the light harvesting capability,hence enhancing the overall photocatalytic degradation of MB.

Facile synthesis and photoelectrochemical properties of novel TiN/C3N4/CdS nanotube core/shell arrays

Recently, the g-C3N4-based heterojunctions have been widely investigated for their greatly enhanced photogenerated carrier separation efficiency. However, most studies are based on the study of g-C3N4 powders. In this study, a novel TiN/C3N4/CdS nanotube arrays core/shell structure is designed to improve the photoelectrochemical catalytic performance of the g-C3N4-based heterojunctions. Among them, TiN nanotube arrays do not respond to simulated solar light, and thus only serve as an excellently conductive nanotube arrays backbone for supporting g-C3N4/CdS heterojunctions. g-C3N4 prepared by simple liquid atomic layer deposition, which possesses appropriate energy band position, mainly acts as the electron acceptor to transport and separate electrons. Deposited CdS quantum dots obtained by successive ionic layer adsorption reaction can effectively absorb visible light and thus act as a light absorber. The TiN/C3N4/CdS nanotube arrays core/shell structure could be verified by X-ray diffractions, Raman spectra, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy elemental mappings and X-ray photoelectron spectroscopy. Compared with TiN/C3N4 nanotube arrays, the TiN/C3N4/CdS samples greatly improve the photoelectrochemical performance, which can be evaluated by photoelectrochemical tests and photoelectrochemical catalytic degradation. Especially, the optimized photocurrent density of TiN/C3N4/CdS has almost 120 times improvement on TiN/C3N4 at 0 V bias under simulated sunlight, which can be ascribed to the effective expansion of the light absorption range and separation of electron-hole pairs.

Studies of Photocatalytic Kinetics on the Degradation of Bisphenol A （BPA） by Immobilized ZnO Nanoparticles in Aerated Photoreactors

The photocatalytic kinetics of BPA （4, 4＇-isopropylidenediphenol）, a representative endocrine disruptor, was explored using immobilized ZnO nanoparticles as a photocatalyst in a laboratory scale photocatalytic reactor. The conditions of photocatalytic degradation were optimized. Direct photocatalytic degradation of BPA was undertaken in an aqueous solution containing ZnO nanoparticles under the optimized experimental conditions. The effects of various factors, such as initial BPA concentrations, initial pH values and various anions （CI, NO3, COa2, SO42-, HCO3＂） were investigated. In the case of the nanoparticles derived films, the photocatalytic efficiency was found not to be remarkably related with the calcination temperature employed in the coating process. Screen-printed ZnO nanoparticles films obtained in the optimal processing conditions showed that the photocatalytic activity is comparable to ZnO nanoparticles in aqueous suspensions. Over 90% degradation efficiency of BPA was achieved under the optimum conditions. The degradation rates in all photocatalytic experiments were linear with the degradation efficiencies of BPA by regression analysis （r ≥ 0.99）. The results showed that the degradation kinetics of BPA in the reactor with immobilized nano-ZnO film as photocatalyst was in agreement with a pseudo-first order rate law.

ZnO nanopowders and their excellent solar light/UV photocatalytic activity on degradation of dye in wastewater

Low-cost and scalable preparation,high photocatalytic activity,and convenient recycle of Zn O nanopowders(NPs)would determine their practical application in purifying wastewater.In this contribution,ZnO NPs were scalably synthesized via the simple reaction of Zn powder with H_2O vapor in autoclave.The structural,morphological and optical properties of the samples were systematically characterized by X-ray diffraction,scanning electron microscopy,Fourier transform infrared spectra,transmission electron microscopy,Micro-Raman,photoluminescence,and ultraviolet-visible spectroscopy.The as-prepared Zn O NPs are composed of nanoparticles with 100–150 nm in diameter,and have a small Brunauer-Emmett-Teller surface area of 6.85 m^2/g.The formation of Zn O nanoparticles is relative to the peeling of H_2 release.Furthermore,the product has big strain-stress leading to the red-shift in the band gap of product,and shows a strong green emission centered at 515 nm revealing enough atomic defects in Zn O NPs.As a comparison with P25,the obtained dust gray Zn O NPs have a strong absorbance in the region of 200–700 nm,suggesting the wide wave-band utilization in sunlight.Based on the traits above,the Zn O NPs show excellent photocatalytic activity on the degradation of rhodamine B(Rh-B)under solar light irradiation,close to that under UV irradiation.Importantly,the Zn O NPs could be well recycled in water due to the quick sedimentation in themselves in solution.The low-cost and scalable preparation,high photocatalytic activity,and convenient recycle of Zn O NPs endow themselves with promising application in purifying wastewater.

Development of cation exchanger-based nano-CdS hybrid catalyst for visible-light photodegradation of rhodamine B from water

A new polymeric nanocomposite photocatalyst A15-CdS with large spherical beads (0.70-0.80 mm in diameter) was fabricated for efficient Rhodamine B (RhB) photodegradation with facile separation during cyclic runs,and photocorrosion,a congenital drawback of CdS,was successfully inhibited for A15-CdS.The nanocomposite catalyst was obtained by impregnating CdS nanoparticles within porous polymeric cation exchanger A15 through a facile inner-surface deposition.CdS nanoparticles (<20 nm) immobilized in A15 were deliberately distributed within an outside ring-like region of 40-50 m in depth,which is dominant for photoreaction because visible light is not expected to permeate through the inner region of nontransparent A15.As expected,efficient RhB photodegradation by A15-CdS was achieved under visible light irradiation,and large-size A15-CdS beads are expected to result in their facile separation from solution for repeated use.More significantly,negligible photocorrosion for the hybrid catalyst A15-CdS was demonstrated by the constant photodegradation efficiency and negligible CdS loss during five-cycle runs.The results indicated that nano-CdS immobilization within A15 would greatly improve the applicability of CdS nanoparticles in practical environmental remediation.