TiO_2-海藻酸钙复合膜的表征、对染料的光催化降解及TiO_2回收

为了解决TiO2纳米粒子难分离,负载的催化剂难回收等问题,首先,将TiO2与海藻酸钠充分混合制成铸膜液,在玻璃板上刮膜,经钙离子交联制备了TiO2-海藻酸钙(T-CA)复合膜。然后,对T-CA复合膜进行了SEM和XRD表征,并研究了T-CA复合膜对染料的光催化降解性能。最后,将T-CA复合膜从染料降解液中取出,浸泡在柠檬酸钠水溶液中,柠檬酸根对钙离子的结合力较强,可使海藻酸盐水凝胶溶解,离心分离TiO2纳米粒子并清洗干燥后,得到了回收TiO2;利用SEM、TEM、FTIR和XRD对回收TiO2进行了表征。结果表明:T-CA复合膜对甲基橙的光催化降解率可达82.37%。回收TiO2与初始的TiO2几乎完全一样,可重新使用且催化能力不变。该方法是一种绿色环保、方便快速的从载体中回收TiO2纳米粒子的方法。     

阳极氧化法制备片状纳米ZnO及其光催化性能

采用阳极氧化法,以锌片为阳极,石墨板为阴极,水/无水乙醇(体积比1∶1)+1.2%氯化铵+不同体积30%双氧水的混合溶液作为电解液,制备了片状纳米ZnO,并利用冷场扫描电镜、X射线衍射和傅里叶红外光谱对试样的形貌、物相和结构进行表征。在紫外灯照射下对10mg/L的苯酚溶液进行光催化降解,考察了片状纳米ZnO的光催化活性。结果表明:当双氧水体积为0.4mL时,可以得到高结晶度、高纯度的片状纳米ZnO,且对苯酚的降解率高达96.37%。     

Bacterial inactivation in water,DNA strand breaking,and membrane damage induced by ultraviolet-assisted titanium dioxide photocatalysis

The effects of UV-assisted TiO₂-photocatalytic oxidation (PCO) inactivation of pathogenic bacteria (Escherichia coli O157:H7, Listeria monocytogenes, Salmonella typhimurium) in a liquid culture using different domains of UV irradiation (A, B and C) were evaluated. Structural changes in super-coiled plasmid DNA (pUC19) and genomic DNA of E. coli were observed using gel electrophoresis to demonstrate the photodynamic DNA strand breaking activity of UV-assisted TiO₂-PCO. Membrane damage in bacterial cells was observed using both a scanning electron microscope (SEM) and a confocal laser scanning microscope (CLSM). Both UVC-TiO₂-PCO and UVC alone resulted in an earlier bactericidal phase (initial counts of approximately 6 log CFU/mL) in 60 s and 90 s, respectively, in liquid culture. UVC-TiO₂-PCO treatment for 6 min converted all plasmid DNA to the linear form; however, under UVC irradiation alone, super-coiled DNA remained. Prolonged UVC-TiO₂-PCO treatment resulted in structural changes in genomic DNA from E. coli. SEM observations revealed that bacteria suffered severe visible cell damage after UVC-TiO₂-PCO treatment for 30–60 min. S. typhimurium cells showed visible damage after 30 min, which was confirmed using CLSM. All treated cells were stained red using propidium iodide under a fluorescent light.     

扩渗温度对TiO_2 NTs/TC4光催化制氢性能的影响

为了提高TiO_2薄膜光催化活性,采用阳极氧化在TC4钛合金表面制备了TiO_2纳米管阵列。利用扫描电镜、X-射线衍射、拉曼谱图、X-射线光电子能谱和紫外可见漫反射光吸收对热扩渗后的阳极化膜层的微观结构进行表征。结果表明:在TC4钛合金的α和β相,氧化膜呈不同的形貌,α相区域纳米管的孔径约为50 nm,β相区域只形成了不规则、大小不均的1~10 nm的小孔。氧化物中V离子的存在对锐钛矿相的生成具有抑制作用,扩渗θ在500和600℃时,膜层中存在少量结晶度不高锐钛矿与金红石相并存的晶体结构。吸附在阳极化膜层表面的碳化物含有石墨相,碳修饰TiO_2纳米管列在可见光区域有很强的光响应区间。在600℃扩渗温度下得到的具有部分石墨化的C修饰V掺杂的TiO_2NTs光催化活性最高,膜层产氢速率为21.25μmol/h。     

N掺杂TiO_2/Ti液膜光催化处理染料废水

以尿素为氮源,采用溶胶-凝胶法制备了N掺杂Ti O2膜电极(N-Ti O2/Ti),并优化了制备条件。结果表明,n(N)∶n(Ti)=0.84∶1、经450℃煅烧2.5 h制得的膜电极光催化性能最佳;与Cu电极组装斜置双极液膜反应器,可见光下考察光催化反应的影响因素。得出最佳降解条件为:初始p H=2.50,废水流量为85 m L/min,Na2SO4质量浓度为0.5 g/L,此条件下处理20 mg/L苋菜红120 min,脱色率可达90.1%;膜电极的重现性与重复性结果表明,6片电极60 min的脱色率为78.1%±4.0%;一片电极经6次循环60 min脱色率比初次减少了7.9%。     

两步机械球磨法制备M/TiO2复合薄膜及光催化性能研究

采用两步机械球磨法制备了M/TiO₂（M = Al、Sn、Zn、Ti）双层复合薄膜,利用光学显微镜和X射线衍射仪分析了涂层的微观结构和相组成,测定了薄膜的光催化性能,研究了过渡层材质以及球磨时间对复合薄膜光催化性能的影响。研究表明,TiO₂粉体在球磨过程中的晶体结构未发生显著变化,保持了良好的光催化活性。金属过渡层Al、Sn以及Zn将显著削弱复合薄膜的光催化活性,Ti是复合薄膜的理想金属过渡层,制备的Ti/TiO₂复合薄膜具有优异的光催化性能。随着第二步球磨时间的延长,Ti/TiO₂复合薄膜的光催化性能逐渐降低,这是由于第二层薄膜表面TiO₂含量降低的原因所致。     

水热法制备3D花球状Bi2SiO5及其光催化油酸酯化反应

化石燃料资源的枯竭和环境污染等问题,使寻找生物燃料等可持续、可再生能源成为世界关注的焦点。本文通过简单水热法制备3D花球状Bi₂SiO₅,并用于在模拟太阳光照射下油酸与甲醇的光催化酯化反应。为了解Bi₂SiO₅催化剂的物理、化学和光学性质,采用X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、高分辨率透射电子显微镜（HRTEM）、氨-程序升温脱附（NH₃-TPD）和紫外-可见漫反射光谱（UV-vis DRS）对其进行表征,且通过傅里叶变换红外光谱（FTIR）分析反应产物成分组成。酯化反应产物油酸甲酯的产率通过¹H NMR进行定量分析,计算过程简单、结果精确可靠。在模拟太阳光照射下,最优反应条件为：醇油比为12∶1、催化剂用量为5%（质量分数）、反应温度为70℃、光照反应时间为6h,油酸甲酯产率为28.8%。核磁共振氢谱（¹H NMR）分析结果显示油酸甲酯选择性高达100%,且催化剂循环3次后油酸甲酯产率仍可达26.8%,稳定性强。电子自旋共振（ESR）测试表明,Bi₂SiO₅光催化酯化反应过程中存在羟基自由基（·OH）和超氧基自由基（·O{}_{\mathrm{2}}^{-}）。基于Bi₂SiO₅首次用于光催化酯化反应,为解释其具有催化活性的原因,提出了其光催化酯化反应机理。     

Photocatalytic degradation of Basic Blue 41 dye under visible light over SrTiO3/Ag3PO4 hetero-nanostructures

In an attempt to develop nanostructured photocatalysts with high performance, SrTiO₃/Ag₃PO₄ hetero-nanostructures were successfully fabricated. The formed binary heterojunctions were composed of SrTiO₃ nanotubes prepared using liquid-phase deposition, and Ag₃PO₄ nanoparticles prepared using a sol–gel method. Synthesis details, including morphology, structure, and optical properties of the prepared photocatalysts, were characterized and comparatively discussed. The results showed that at an optimal ratio of SrTiO₃ to Ag₃PO₄ (20–80), the photocatalytic degradation of Basic Blue 41 under 80-min visible light irradiation is the maximum amount of 99%, which is about 4.4 and 1.5 times higher than that of pristine SrTiO₃ nanorods and Ag₃PO₄ nanoparticles, respectively. It can be due to the synergistic effect of two materials that provide high light absorption and charge carriers’ separation. Finally, a detailed possible mechanism for enhancing the photocatalytic activity of the SrTiO₃/Ag₃PO₄ hetero-nanostructures was proposed.     

Investigation of the effect of ytterbium doping on photoluminescence and photocatalytic activity of Li4Ti5O12

This work reports the combined effect of the morphology and crystallization to investigate the role of Yb³⁺ as an additive in Li₄Ti₅O₁₂ crystals on its photocatalytic and photoluminescence (PL) properties. With the pure phase, the synthesized samples have a spherical morphology and spherical structure with good crystallinity and uniform particle size distribution. Li₄Ti₅O₁₂ doped with ytterbium (Yb³⁺), were obtained by a new optimized hydrothermal approach. The crystal properties and surface morphology of the synthesized compounds were examined by X-ray diffraction method and field emission scanning electron microscopy. Bond structures and surface areas were investigated by Fourier transform infrared spectroscopy and Brunauer-Emmett-Teller analyses. Finally, the excitation and emission spectra were obtained by a PL spectrophotometer. The PL results show that room-temperature PL of Yb³⁺ doped Li₄Ti₅O₁₂ phosphor has an emission peak at 710 nm which can be attributed to Li₄Ti₅O12 crystal defect emission. Moreover, it has been found that Yb doping resulted in enhancement of photocatalytic activity, evaluated by monitoring the degradation of methylene blue solution. Note that, 0.01% Yb doped lithium titania phosphor exhibited excellent photocatalytic activity.     

Newly-modeled graphene-based ternary nanocomposite for the magnetophotocatalytic reduction of CO2 with electrochemical performance

The development of CO₂ into hydrocarbon fuels has emerged as a green method that could help mitigate global warning. The novel structured photocatalyst is a promising material for use in a photocatalytic and magneto-electrochemical method that fosters the reduction of CO₂ by suppressing the recombination of electron−hole pairs and effectively transferring the electrons to the surface for the chemical reaction of CO₂ reduction. In our study, we have developed a novel-structured AgCuZnS₂–graphene–TiO₂ to analyze its catalytic activity toward the selective evolution of CO₂. The selectivity of each nanocomposite substantially enhanced the activity of the AgCuZnS₂–graphene–TiO₂ ternary nanocomposite due to the successful interaction, and the selectivity of the final product was improved to a value 3 times higher than that of the pure AgCuZnS₂ and 2 times higher than those of AgCuZnS₂–graphene and AgCuZnS₂–TiO₂ under ultra-violet (UV)-light (λ = 254 nm) irradiation in the photocatalytic process. The electrochemical CO₂ reduction test was also conducted to analyze the efficacy of the AgCuZnS₂–graphene–TiO₂ when used as a working electrode in laboratory electrochemical cells. The electrochemical process was conducted under different experimental conditions, such as various scan rates (mV·s^–1), under UV-light and with a 0.07 T magnetic-core. The evolution of CO₂ substantially improved under UV-light (λ = 254 nm) and with 0.07 T magnetic-core treatment; these improvements were attributed to the facts that the UV-light activated the electron-transfer pathway and the magnetic core controlled the pathway of electron-transmission/prevention to protect it from chaotic electron movement. Among all tested nanocomposites, AgCuZnS₂–graphene–TiO₂ absorbed the CO₂ most strongly and showed the best ability to transfer the electron to reduce the CO₂ to methanol. We believe that our newly-modeled ternary nanocomposite opens up new opportunities for the evolution of CO₂ to methanol through an electrochemical and photocatalytic process.