CuO-SiO2气凝胶@TiO2纳米纤维无牺牲剂光催化还原CO2

采用溶胶-凝胶法制备CuO-SiO2复合气凝胶,通过在气凝胶孔道内填充TiCl4,然后将其气相水解,得到了在CuO-SiO2气凝胶表面生长了高结晶度的TiO2纳米纤维(CuO-SiO2@TiO2),纤维直径～16 nm.通过XPS、UPS、UV-Vis DRS、荧光光谱(PL)等表征了材料的结构及光电性能.结果表明,制备的CuO-SiO2@TiO2对可见光有明显吸收,且荧光强度较商用TiO2(P25)大幅降低,光生电子-空穴对更加稳定.再在纳米纤维上负载CuO,所得CuO-SiO2@TiO2/CuO在可见光区的荧光强度进一步增强.以300 W氙灯为光源,分别以CuO-SiO2@TiO2及CuO-SiO2@TiO2/CuO为催化剂,无牺牲剂条件下光催化还原CO2,4 h后甲醇产率分别为1304.0及1589.0μmol/g-cat,转换频率(TOF)分别为0.038及0.046 h–1.循环实验表明,纳米纤维具有较好的光催化稳定性,经过4次光催化循环实验后,CuO-SiO2@TiO2/CuO的保留率～94％,甲醇产率可达1472.0μmol/g-cat,TOF为0.042 h–1.     

Synthesis,characterization, and visible-light photocatalytic activity of transition metals doped ZTO nanoparticles

Transition metals doping has been proved to be a feasible way for tuning the physical properties on the surface and bulk of nanomaterials and also for the good performance in decontamination of emerging pollutants. In this context, doped samples of zinc tin oxide or zinc stannate nanoparticles (ZTO NPs) by several transition metals were synthesized in order to enhance the optical absorbance with the aims of reducing the band gap and therefore ameliorated their photocatalytic activity. They were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy, Raman spectroscopy and photoluminescence. The XRD patterns and the microscopic observations showed the formation of spherical nanoparticles with an average size of about 30 nm and highly pure ZTO phase with an inverse spinel structure. The Raman spectra were dominated by bands relatives to the F2g (2) and A1g symmetries modes of inverse spinel structure. The band gap Eg is estimated to be 3.75 eV for the undoped sample, and 3.67, 3.64, 3.78 and 3.21 eV, for 2% Fe, 2% Mg, 2% Gd, and 2% Mn doped ZTO samples, respectively.Furthermore, the undoped ZTO NPs have the intrinsic problem of recombination of photogenerated charge carriers. We have shown that the reduction of the band gap and oxygen vacancies resulting from the doping effect could be a useful tool for trapping and avoid the recombination of electrons coming from photosensitized rhodamine B (RhB) under visible light irradiation. Owing to the structural advantages and low band gap, 2% Mn doped ZTO NPs, with the kinetic rate constants k of 0.024 min⁻¹, show enhanced performance for the elimination of RhB in aqueous solution compared to undoped and other doped ZTO NPs.     

Microbial coupled photocatalytic fuel cell with a double Z-scheme g-C3N4/ZnO/Bi4O5Br2 cathode for the degradation of different organic pollutants

A novel heterostructure of g-C₃N₄/ZnO/Bi₄O₅Br₂ (ZB-3) was designed, and used in the microbial coupled photocatalytic fuel cell (MPFC). It can effectively improve electron utilization efficiency and pollutant degradation using this double Z-scheme heterojunction structure. The current–time (I–t) curves demonstrated that the current density of ZB-3 was higher than that of ZnO, ZnO/Bi₄O₅Br₂ (ZB-1), g-C₃N₄/ZnO (ZB-2). Electrochemical impedance spectroscopy (EIS) indicated ZB-3 possessed the minimum charge-transfer resistance. This MPFC for degrading rhodamine B (RhB) and tetracycline (TC) under different conditions were developed using these materials. Even in the dark condition, MPFC with g-C₃N₄/ZnO/Bi₄O₅Br₂ demonstrated 93% and 82% degradation efficiency for RhB and TC, respectively. Furthermore, the electron transport mechanism of the MPFC and ZB-3 were proposed. It paves the approach for more efficient pollutant degradation via MFC photocatalysis.     

Microwave-assisted combustion synthesis of ZnAl2O4 and ZnO nanostructure particles for photocatalytic wastewater treatment

ZnAl₂O₄ and ZnO nanostructure particles and in situ crystallization of zinc aluminate and zinc oxide coating layers on sintered α-Al₂O₃ and γ-Al₂O₃ granules by the microwave-assisted combustion method were investigated. For powders, the effects of solution pH value and for coated samples the influence of support type on the structure, microstructure, and photocatalytic activity of powders were studied. Results showed that variation of synthesis pH value caused to considerable change in agglomeration, specific surface area, obtaining up to 88 and 92% yields for zinc aluminate and zinc oxide nanoparticles, respectively. γ-alumina granules were more appropriate supports than the α-alumina ones because of the better photocatalytic activities and lower extent of the attritions for both zinc aluminate and zinc oxide coating layers.     

光敏剂敏化Cu-有机骨架对活性深蓝K-R的高效光催化降解

针对活性染料废水引起的水污染,采用硝酸铜与4,4',4″-[1,3,5-苯基三(酰胺基)]三苯甲酸(H₃L)反应,制备了三维多孔的Cu-有机骨架(Cu-MOF)材料,对染料进行光催化降解。研究了Cu-MOF的热学性能,通过粉末X射线衍射分析确认了其结构特征。通过可见光吸收能力不同的甲基橙(MO)和亚甲基蓝(MB)对Cu-MOF进行敏化,制备了2种复合材料以提升光催化降解效能。研究表明:Cu-MOF及MO-Cu-MOF和MB-Cu-MOF(10 mg) 对40 mL 的34.02 mg/L的活性深蓝K-R的可见光催化降解效率分别为42.4%、76.2%和88.4%,光催化速率常数分别为0.029、0.082、0.122 h^-1,最佳pH值为8;5次光催化循环之后,MB-Cu-MOF对治性深蓝K-R的降解效率仍高达75.1%。     

UV/TiO_2光催化氧化工艺脱汞的试验研究

UV/TiO_2光催化技术在TiO_2催化剂的作用下可将烟气中Hg~0氧化脱除。利用自制的UV/TiO_2氧化试验台研究了影响Hg~0去除率的相关因素,结果表明,在无催化剂和有紫外灯情况下可脱除少量Hg~0;Hg~0去除率随催化剂活性组分含量的增加而上升,但上升速率逐渐下降;在温度(50～200)℃范围内,Hg~0去除率无明显变化;Hg~0去除率随着Hg~0初始浓度的升高逐渐下降;Hg~0去除率随着烟气中氧含量先上升后趋于不变。UV/TiO_2氧化工艺脱汞可为燃煤电厂烟气脱汞提供理论指导。     

Visible light-activated degradation of microcystin-LR by ultrathin g-C3N4 nanosheets-based heterojunction photocatalyst

Microcystins (MCs) is a harmful toxin generated by blue-green algae in water, which has seriously threatened the ecological safety of water and human body. It is urgent to develop new catalysts and techniques for the degradation of MCs. A feasible electrostatic self-assembly method was carried out to synthesize BiVO₄/g-C₃N₄ heterojunction photocatalyst with highly efficient photocatalytic ability, where BiVO₄ nanoplates with exposed {010} facets anchored to the g-C₃N₄ ultrathin nanosheets. The morphology and microstructure of the heterojunction photocatalysts were identified by XRD, SEM, TEM, XPS, and BET. The g-C₃N₄ nanosheets have huge surface area over 200 m²/g and abundant mesoporous ranging from 2-20 nm, which provides tremendous contact area for BiVO₄ nanoplates. Meanwhile, the introduction of BiVO₄ led to red-shift of the absorption spectrum of photocatalyst, which was characterized by UV-vis diffuse reflection spectroscopy (DRS). Compared with pure BiVO₄ and g-C₃N₄, the BiVO₄/g-C₃N₄ heterojunction shows a drastically enhanced photocatalytic activity in degradation of microcystin-LR (MC-LR) in water. The MC-LR could be removed within 15 minutes under the optimal ratio of BiVO₄/g-C₃N₄. The outstanding performance of the photocatalyst is attributed to synergetic effect of interface Z-scheme heterojunction and high active facets {010} of BiVO₄ nanoplates, which provides an efficient transfer pathway to separate photoinduced carriers meanwhile endows the photocatalysts with strong redox ability.     

Enhanced UV- and visible-light driven photocatalytic performances and recycling properties of graphene oxide/ZnO hybrid layers

Light induced catalytic processes have attracted significant attention during the last years for wastewater treatment due to their efficiency in decomposition of organic contaminants. In this study we report the synthesis of graphene oxide (GO)/ZnO hybrid layers with high photocatalytic efficiency using laser radiation. The results show that the hybrid layers exhibit much improved photodecomposition efficiency as compared to pure GO or ZnO both under UV and visible-light irradiation. The enhanced photocatalytic efficiency of the hybrid as compared to the reference pure ZnO and GO layers was attributed to the contribution of GO to the separation and transport of the photogenerated charge carriers. Additionally, under visible light irradiation the organic molecules can act as first sensitizers in the degradation process. The recyclability of the layers was also investigated through repetitive photodegradation cycles under UV- or visible-light irradiation. After consecutive degradation runs, the hybrid photocatalyst layers were still stable and retained high degradation efficiency, ensuring reusability. The photocatalytic activity of the layers was correlated with the gradual change of their chemical structure during consecutive degradation cycles. Owing to the high photodegradation efficiency, reusability, and ease of recovery the synthesised hybrid layers consisting of easily available materials are suitable for environmental purification applications.     

Sonochemical synthesis of PANI-BiVO4-GO semiconductor nanocomposite highly efficient visible-light photocatalytic performance

Abstract

Polyaniline/Bismuth Vanadate/Graphene Oxide (PANI-BiVO₄-GO) or BGPA composite was prepared by sonochemical deposition of bismuth vanadate-graphene oxide (BiVO₄) nanoparticles on the surface of polyaniline (PANI). The best photocatalytic degradation performance was obtained by 5wt% BGPA composites for MB, RhB, and SO dyes, which is approximately 4 times higher than that of 1% BGPA. Meanwhile, the photocatalytic stability of BiVO₄ was significantly improved by introducing PANI into the PANI-BiVO₄-GO composite. The dramatic promotion of the photocatalytic degradation performance and the photocatalytic stability can be attributed to the formation of a heterojunction free electron between PANI and BiVO₄-GO. The existence of those extra free electrons can dramatically enhance the efficiency of the photogenerated electrons, which accelerate the transfer of photogenerated holes from BiVO₄-GO to PANI, and therefore inhibit the self-oxidation of BiVO₄.