Efficient removal of Cr(VI) by a 3D Z-scheme TiO2-ZnxCd1-xS graphene aerogel via synergy of adsorption and photocatalysis under visible light

Efficient and robust photocatalysts for environmental pollutants removal with outstanding stability have great significance. Herein, we report a kind of three dimensional (3D) photocatalyst presented as Z-scheme heterojunction, which combining TiO 2 and Zn x Cd 1- x S with graphene aerogel to contrast TiO 2 -Zn x Cd 1- x S graphene aerogel (TSGA, x = 0.5) through a moderate hydrothermal process. The as-prepared Z-scheme TSGA was used to remove aqueous Cr(VI) via a synergistic effect of adsorption and visible light photocatalysis. The adsorption equilibrium can be reached about 40 min, then after about 30 min irradiation under visible light (wavelength ( λ) > 420 nm) the removal rate of Cr(VI) almost reached 100%, which is much better than the performance of pristine TiO 2 and Zn 0.5 Cd 0.5 S, as well as TiO 2 graphene aerogel (TGA) and Zn 0.5 Cd 0.5 S graphene aerogel (SGA). The virulent Cr(VI) was reduced to Cr(III) with hypotoxicity after photocatalysis on TSGA, meanwhile the as-synthesized TSGA presented a good stability and reusability. The reduced graphene oxide (rGO) sheets between TiO 2 and Zn 0.5 Cd 0.5 S played a role as charge transfer mediator, promoting the photoinduced electrons transfer and photocatalysis ability of TSGA was enhanced significantly. Hence,such photocatalyst exhibits a potential application on removing heavy metals with high efficiency and stability from polluted aqueous environment.     

TiO2光催化剂载体及提高其光催化活性的研究进展

光催化技术是一种新型的绿色环保技术,TiO2是光催化反应中的一种研究较为广泛的光催化剂,其在污水处理以及空气净化等领域具有广泛的应用前景。文章综述了TiO2作为光催化剂的研究现状,着重介绍了TiO2光催化剂载体的研究及TiO2的改性研究。并结合我们在TiO2载体以及提高其催化活性方面所作的一些研究工作,提出一些看法。     

Construction of vesicle CdSe nano-semiconductors photocatalysts with improved photocatalytic activity: Enhanced photo induced carriers separation efficiency and mechanism insight

Visible-light-driven photocatalysis as a green technology has attracted a lot of attention due to its potential applications in environmental remediation. Vesicle Cd Se nano-semiconductor photocatalyst are successfully prepared by a gas template method and characterized by a variety of methods. The vesicle Cd Se nano-semiconductors display enhanced photocatalytic performance for the degradation of tetracycline hydrochloride, the photodegradation rate of78.824% was achieved by vesicle Cd Se, which exhibited an increase of 31.779% compared to granular Cd Se. Such an exceptional photocatalytic capability can be attributed to the unique structure of the vesicle Cd Se nano-semiconductor with enhanced light absorption ability and excellent carrier transport capability. Meanwhile, the large surface area of the vesicle Cd Se nano-semiconductor can increase the contact probability between catalyst and target and provide more surface-active centers. The photocatalytic mechanisms are analyzed by active species quenching. It indicates that h+and UO_2~-are the main active species which play a major role in catalyzing environmental toxic pollutants. Simultaneously, the vesicle Cd Se nano-semiconductor had high efficiency and stability.     

Removal of hexavalent chromium from water by Z-scheme photocatalysis using TiO2 (rutile) nanorods loaded with Au core–Cu2O shell particles

All-solid-state Z-scheme photocatalysts, containing Cu₂O, TiO₂ (rutile), and Au as the electron mediator, were prepared and applied to the reduction of Cr(VI) in aqueous solutions. The Cu₂O–Au–TiO₂ composites were prepared by loading Au core–Cu₂O shell hemisphere particles on TiO₂ (rutile) nanorods using a two-step photocatalytic deposition process. Under ultraviolet–visible (UV–vis) light illumination, the Cu₂O–Au–TiO₂ composites exhibited higher photocatalytic Cr(VI) reduction activities than those exhibited by single TiO₂ (rutile) and Cu₂O. In this reaction, a precipitate containing Cr, which was considered to be Cr(OH)₃, was deposited site-selectively on the Au core–Cu₂O shell particles of the composites, indicating that the reduction site of the composite was Cu₂O, and the reaction proceeded according to the Z-scheme. The Cu₂O–Au–TiO₂ composites also exhibited photocatalytic activity under visible light illumination. The oxidation state of Cu in the Cu₂O–Au–TiO₂ composite gradually changed from Cu(I) to Cu(II) during the photocatalytic Cr(VI) reduction. However the composite maintained its high photocatalytic performance even after oxidation. The role of Au in the Cu₂O–Au–TiO₂ composite was examined by comparing the properties of the Cu₂O–Au–TiO₂ composite with those of the Cu₂O–TiO₂ composite prepared via direct Cu₂O deposition on TiO₂.     

环境治理中光催化剂的失活与再生

催化剂失活是影响光催化过程用于污染治理经济实用的关键因素。对近几年来国内外环境污染控制中光催化剂的失活现象及其原因进行了综述．分析了液相和气相光催化反应体系中催化剂失活后再生的方法．特别是对气相光催化反应中水蒸汽的影响进行了讨论。     

Fe/Si/TiO2三元复合光催化剂的性能研究

用溶胶-凝胶法制备了Fe/Si/TiO2三元复合光催化剂,利用X射线衍射(XRD)和紫外-可见漫反射光谱(DRS)对样品进行了分析表征,并以甲基橙为模拟污染物,考察了其光催化活性.结果表明,Fe/Si/TiO2三元复合光催化剂与TiO2相比,光催化活性明显提高;当煅烧温度为900℃、添加Fe的摩尔分数为0.050%时,光催化活性最佳.     

Remediation of a chlorinated aromatic hydrocarbon in water by photoelectrocatalysis

Photoelectrocatalysis driven by visible light offers a new and potentially powerful technology for the remediation of water contaminated by organo-xenobiotics. In this study, the performance of a visible light-driven photoelectrocatalytic (PEC) batch reactor, applying a tungsten trioxide (WO₃) photoelectrode, to degrade the model pollutant 2,4-dichlorophenol (2,4-DCP) was monitored both by toxicological assessment (biosensing) and chemical analysis. The bacterial biosensor used to assess the presence of toxicity of the parent molecule and its breakdown products was a multicopy plasmid lux-marked E. coli HB101 pUCD607. The bacterial biosensor traced the removal of 2,4-DCP, and in some case, its toxicity response suggests the identification of transient toxic intermediates. The loss of the parent molecule, 2,4-DCP determined by HPLC, corresponded to the recorded photocurrents. Photoelectrocatalysis offers considerable potential for the remediation of chlorinated hydrocarbons, and that the biosensor based toxicity results identified likely compatibility of this technology with conventional, biological wastewater treatment.     

Efficient photocatalysis of tetracycline hydrochloride (TC-HCl) from pharmaceutical wastewater using AgCl/ZnO/g-C3N4 composite under visible light: Process and mechanisms

AgCl/ZnO/g-C₃N₄, a visible light activated ternary composite catalyst, was prepared by combining calcination, hydrothermal reaction and in-situ deposition processes to treat/photocatalyse tetracycline hydrochloride (TC-HCl) from pharmaceutical wastewater under visible light. The morphological, structural, electrical, and optical features of the novel photocatalyst were characterized using scanning electron microscopy (SEM), UV-visible light absorption spectrum (UV–Vis DRS), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and transient photocurrent techniques. All analyses confirmed that the formation of heterojunctions between AgCl/ZnO and g-C₃N₄ significantly increase electron-hole transfer and separation compared to pure ZnO and g-C₃N₄. Thus, AgCl/ZnO/g-C₃N₄ could exhibit superior photocatalytic activity during TC-HCl assays (over 90% removal) under visible light irradiation. The composite could maintain its photocatalytic stability even after four consecutive reaction cycles. Hydrogen peroxide (H₂O₂) and superoxide radical (^·O₂) contributed more than holes (h⁺) and hydroxyl radicals (^·OH) to the degradation process as showed by trapping experiments. Liquid chromatograph-mass spectrometer (LC-MS) was used for the representation of the TC-HCl potential degradation pathway. The applicability and the treatment potential of AgCl/ZnO/g-C₃N₄ against actual pharmaceutical wastewater showed that the composite can achieve removal efficiencies of 81.7%, 71.4% and 69.0% for TC-HCl, chemical oxygen demand (COD) and total organic carbon (TOC) respectively. AgCl/ZnO/g-C₃N₄ can be a prospective key photocatalyst in the field of degradation of persistent, hardly-degradable pollutants, from industrial wastewater and not only.     

Mitigating phytotoxicity of tetracycline by metal-free 8-hydroxyquinoline functionalized carbon nitride photocatalyst

Photooxidative removal of pharmaceuticals and organic dyes is an effective way to eliminate growing micropollutants. However, photooxidation often results in byproducts as secondary hazardous substances such as phytotoxins. Herein, we found that photooxidation of common antibiotic tetracycline hydrochloride (TCH) over a metal-free 8-hydroxyquinoline (8-HQ) functionalized carbon nitride (CN) photocatalyst significantly reduces the TCH phytotoxic effect. The phytotoxicity test of photocatalytic treated TCH-solution evaluated towards seed growth of Cicer arietinum plant model endowed natural root and shoot growth. This study highlights the conceptual insights in designing of metal-free photocatalyst for environmental remediation.     

纳米TiO2光催化降解技术在污水处理中的应用

光催化技术是一种新兴的高效节能现代污水处理技术，目前大部分还处于实验研究阶段。本文介绍了TiO2光催化降解水中有机物的机理以及pH值、载体、外加氧化剂等对其光催化活性的影响，TiO2光催化剂的表面修饰及与其它技术的联用情况。讨论了光电催化、太阳能利用等对光催化领域的推动作用，并指出在该领域的研究中存在问题和发展方向。