微波助离子液体中Y掺杂TiO_2光催化剂制备及微波强化光催化活性

在微波助离子液体介质中制备稀土元素Y掺杂改性TiO_2光催化剂,以提高催化剂的光催化降解活性,用XRD、SEM和BET等测试手段对催化剂结构进行表征;以甲基橙溶液和苯酚溶液为模拟污染物,分别在紫外光照(UV)和微波辐射-紫外光照(MW-UV)条件下考察TiO_2-Y催化剂的光催化活性;以对苯二甲酸作为荧光探针利用荧光技术检测TiO_2-Y催化剂表面所产生的羟基自由基,并对光催化降解反应进行动力学分析,探索了光催化降解反应机理.实验结果表明,通过优化反应条件后制得的TiO_2-Y催化剂具有较高光催化活性和热稳定性,在UV和UV-MW条件下降解甲基橙和苯酚溶液1.5h后,甲基橙降解率分别为98.3%和99.5%,苯酚降解率分别为97.5%和98.2%.荧光光谱分析表明,TiO_2-Y在MW-UV条件下产生的羟基自由基比UV条件下要多,因而微波辐照具有强化TiO_2-Y降解模拟污染物的作用;反应动力学数据分析表明,TiO_2-Y光催化降解甲基橙溶液反应呈现一级反应动力学规律,其表观速率常数K最大值为0.051 9min-1.     

氟铌酸钾的低温固相法合成及其对甲基橙的光催化降解性能

以草酸铌、草酸钾和氟化钾为原料,采用改进的固相法在较低温度(600℃)下合成了层状K2NbO3F;测定了其对甲基橙光催化降解的催化作用,并基于紫外-可见漫反射光谱分析和X射线衍射分析初步探讨了甲基橙在自然光照条件下的光催化反应过程及降解机理.结果表明,合成的K2NbO3F与微量H2O2作用后,在自然光照条件下几乎可以使甲基橙染料完全降解;当反应温度为45℃,催化剂投加量为1g/L,H2O2用量为0.33%(体积分数)时,2h内可将初始浓度为15mg/L的甲基橙溶液几乎完全降解.就甲基橙的光催化降解机理而言,·OH自由基在其降解过程中起重要作用.     

微波超声强化银掺杂TiO_2催化剂光催化活性的研究

在[Bmim]PF6离子液体介质中,用溶胶凝胶-微波干燥法制备银掺杂TiO_2光催化剂TiO_2-Ag.以甲基橙为有机污染物,用微波超声组合仪分别在微波(MW)、紫外(UV)、紫外-微波(UV-MW)和超声-紫外-微波(UT-UV-MW)4种条件下降解甲基橙溶液,考察银掺杂对催化剂降解甲基橙的影响,以提高催化剂光催化性能.分别用X射线衍射分析(XRD)、扫描电子显微镜(SEM)、能谱分析(EDS)、热重-差示扫描量热分析(TG-DSCDTG)、固体紫外可见分析(Uv-vis)和红外分析(IR)对TiO_2-Ag催化剂进行测试表征.结果表明,优化条件下制备TiO_2-Ag催化剂在UV、UV-MW和UT-UV-MW条件下降解甲基橙35 min后,甲基橙的降解率分别为88.05%、93.98%和99.84%;降解甲基橙55min后,甲基橙的降解率分别为98.79%、99.05%和99.90%.在UTUV-MW条件下降解25min后,降解率接近100%.表明TiO2-Ag催化剂具有较高的光催化降解活性,微波超声协同作用加快光催化降解反应进行.催化剂的结构分析表明,银掺杂抑制了二氧化钛晶相的转变,使相变温度升高,稳定性增强;同时,催化剂向可见光区扩宽了光响应范围,提高了量子效率,从而光催化性能得以提高.     

共沉淀法制备稀土Ce掺杂的纳米ZnO及其光催化降解染料的性能

以六水合硝酸锌和六水合硝酸铈?髥为原料,通过共沉淀法制备了一系列稀土Ce掺杂的纳米ZnO,并采用X射线粉末衍射(XRD)、傅里叶红外光谱(IR)、扫描电镜(SEM)、X射线能谱分析(EDS)、紫外可见漫反射光谱对其进行了全面表征。部分样品还通过X射线光电子能谱(XPS)和光致荧光光谱(PL)进行了进一步分析。分别在日光和紫外光条件下,对这一系列Ce掺杂的ZnO进行了光催化降解亚甲基蓝的性能研究,得出当Ce的掺杂量为3%(n/n)时(ZnO-3%Ce),其光催化活性最佳,光催化降解亚甲基蓝的效率均超过98%。选取ZnO-3%Ce作为催化剂,分别进一步考察其在日光和紫外光下对罗丹明B和甲基橙的光催化降解性能。研究结果表明,ZnO-3%Ce在日光和紫外光下均表现出较好的光催化降解效果,体现出良好的光降解普适性。日光下光降解效率顺序为:亚甲基蓝>罗丹明B>甲基橙,而紫外光下降解效率顺序为:罗丹明B>亚甲基蓝>甲基橙。最后,我们研究了催化剂ZnO-3%Ce的循环利用及稳定性性能。实验结果表明:该催化剂循环使用3次之后,光催化效率仍然稳定在97%以上,并且其结构和组成保持不变,体现出优异的稳定性和应用前景。     

CNTs/TiO2多孔复合膜的组装及光催化性能

提出了一种在掺氟的SnO2(FTO)导电玻璃上组装碳纳米管(CNTs)/Fe-Ni/TiO2多孔复合膜光催化剂的新方法.采用喷涂热解法(SPD)将掺杂镍和铁的含有嵌段聚合物P123的二氧化钛前驱体溶胶涂覆在FTO导电玻璃上,制备Fe-Ni/TiO2多孔膜,再采用化学气相沉积法(CVD)在Fe-Ni/TiO2膜上原位生长CNTs,得到CNTs/Fe-Ni/TiO2多孔复合膜光催化剂.CNTs/Fe-Ni/TiO2复合膜具有多级孔结构特征,在TiO2表面原位生长的CNTs不但具有较好的石墨化结构,且CNTs较均匀地分布在整个膜层的孔中.考察了CNTs/Fe-Ni/TiO2复合膜光催化剂的结构和性能,并通过降解甲基橙溶液评价了复合膜的光催化活性.结果表明,CNTs的复合及铁和镍的掺杂等改性显著提高了TiO2膜材料的光催化活性.     

ZnO纳米管的光学性质及其对甲基橙降解的光催化活性

以十二烷基硫酸钠为模板剂采用水热法合成了ZnO纳米管,以尿素和ZnSO4为原料制备了ZnO纳米颗粒,并应用透射电镜、x射线衍射、光致发射光谱、拉曼光谱、比表面积测定、傅里叶红外光谱和紫外-可见漫反射光谱等技术对样品进行了表征.结果表明,ZnO纳米管的比表面积较大,在λ≈650nm的可见光波段ZnO纳米管开始出现吸收峰,而ZnO纳米颗粒在可见光波段几乎没有吸收.ZnO纳米管和纳米颗粒在紫外光照射下均对甲基橙有降解作用,其中ZnO纳米管的光催化活性较高.随着催化剂用量的增加和光照时间的延长,甲基橙降解率逐渐提高;甲基橙浓度的增大使甲基橙降解率降低.     

H_2O_2处理H_3PW_6Mo_6O_(40)/ZrO_2-SiO_2光催化降解甲基橙

采用浸渍法制备了H_3PW_6Mo_6O_(40)/ZrO_2-SiO_2催化剂,用H_2O_2进行敏化处理,并通过FT-IR、XRD对其进行了表征。探讨了该催化剂对甲基橙溶液的催化降解活性,较系统地研究了溶液的初始浓度、溶液的pH、催化剂用量对光催化降解甲基橙的影响。研究发现:H_3PW_6Mo_6O_(40)/ZrO_2-SiO_2对甲基橙有良好的降解效果。在甲基橙溶液初始浓度为10mg·L~(-1),溶液pH为2.5,催化剂用量为溶液总质量0.5%的条件下光照2.5h,甲基橙的降解率达到91.1%。H_3PW_6Mo_6O_(40)/ZrO_2-SiO_2催化剂光催化降解甲基橙溶液为一级动力学反应。     

磷钨酸对甲基橙光催化降解的初步研究

在自制的光化学反应器中,以紫外灯为光源,以磷钨酸为光催化剂,研究了其对模拟甲基橙染料废水的光催化脱色降解的影响。实验结果表明,催化剂加入量、溶液初始浓度、不同光强度是影响催化降解效果的重要因素。最佳催化条件为20 mg/L的甲基橙溶液在紫外灯(16W)辐射下,光催化剂磷钨酸用量为1.5 g/L。     

异质结型AgBr/CuO光催化剂的合成、 光催化活性及再生

采用沉淀法制备了具有p-n异质结结构的AgBr/CuO可见光催化剂, 对其结构进行了表征, 通过甲基橙溶液的降解率评价了AgBr/CuO的光催化活性, 并通过活性物种测试及能带结构分析推测了其光催化机理, 采用3%(质量分数)溴水对使用后的AgBr/CuO进行了再生处理. 结果表明, 在可见光照射下, 0.1 g AgBr/CuO光催化剂30 min对甲基橙溶液(初始浓度为15 mg/L)的降解率高达92%, 远高于同等条件下的AgBr. AgBr/CuO光催化活性提高的原因是AgBr与CuO的复合一方面使催化剂的禁带宽度变宽, 提高了光生电子与光生空穴的氧化还原能力; 另一方面, 在两者之间形成了p-n型异质结结构, 有利于光生电子的转移及光生电子与空穴的分离. 采用绿色环保的溴水再生法可显著恢复催化剂的光催化活性.     

异质结型AgBr/CuO光催化剂的合成、光崔化活性及再生

采用沉淀法制备了具有p-n异质结结构的AgBr/CuO可见光催化剂,对其结构进行了表征,通过甲基橙溶液的降解率评价了AgBr/CuO的光催化活性,并通过活性物种测试及能带结构分析推测了其光催化机理,采用3％(质量分数)溴水对使用后的AgBr/CuO进行了再生处理.结果表明,在可见光照射下,0.1gAgBr/CuO光催化剂30 min对甲基橙溶液(初始浓度为15 mg/L)的降解率高达92％,远高于同等条件下的AgBr.AgBr/CuO光催化活性提高的原因是AgBr与CuO的复合一方面使催化剂的禁带宽度变宽,提高了光生电子与光生空穴的氧化还原能力;另一方面,在两者之间形成了p-n型异质结结构,有利于光生电子的转移及光生电子与空穴的分离.采用绿色环保的溴水再生法可显著恢复催化剂的光催化活性.     

Cu2O/ZnO的形貌可控制备及光催化性能

以CuSO₄和ZnCl₂为原料, 采用温和的液相还原法制备得到Cu₂O/ZnO微米结构高效光催化剂. 研究了不同[Cu²⁺]/[Zn²⁺]比条件下所得Cu₂O/ZnO复合物的形貌和光催化活性. 通过5.5 h的光照, Cu₂O/ZnO光催化剂对甲基橙染料的降解率为(77.5±0.1)%. 将多形貌Cu₂O/ZnO复合物作为阳极, 铂片作为对电极, 中间注入甲基橙溶液, 组装“三明治”结构拟电池, 研究了复合物的光降解机制.     

球磨法制备复合光催化剂Bi12TiO20/ZnO及其光催化性能

本文用水作为分散介质,采用球磨法掺杂一定量的Bi₁₂TiO₂₀于ZnO中制备复合光催化剂Bi₁₂TiO₂₀/ZnO. 利用UV-Vis、XRD和SEM等仪器对样品进行了分析与表征. 通过对甲基橙的氧化来研究其光催化活性. 结果表明,光催化剂Bi₁₂TiO₂₀/ZnO对甲基橙氧化的催化活性高于氧化锌的催化活性.当Bi₁₂TiO₂₀的掺杂量为0.5%(质量分数),球磨时间为12 h,焙烧温度为300℃时,光照20 min后,复合光催化剂Bi₁₂TiO₂₀/ZnO对甲基橙的降解率可达到95.2%.     

Fe_3O_4/SrTiO_3复合光催化剂降解甲基橙

用共沉淀法制备了SrTiO3光催化剂及Fe3O4/SrTiO3复合光催化剂.通过紫外-可见漫反射光谱、XRD、SEM-EDX对其进行表征,以甲基橙为探针分子考察其光催化性能.结果表明,适量Fe3O4的掺入可明显提高Sr-TiO3光催化剂对可见光的吸收,从而增强其光催化性能;在光降解甲基橙的反应中,掺杂10%Fe3O4的SrTiO3光催化剂其催化活性是纯SrTiO3光催化剂的两倍.     

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 spectrometer, and X-ray photoelectron spectrThe 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.     

Synthesis of Nano‐Sized Zinc Oxide Photocatalyst by Combustion Method

The objective of this research was to use combustion synthesis to create a nano‐sized ZnO photocatalyst using citric acid as the fuel and zinc nitrate as the oxidant. The starting materials were mixed in a stoichiometric ratio, and a slurry precursor with high homogeneity was formed. The precursor was ignited at room temperature, resulting in dry, loose, and voluminous ZnO powders. The powders, characterized by SEM, TEM and XRD, showed a particle size range of 40 to 80 nm with a wurtzite structure. The ZnO powders were introduced as a photocatalyst for the degradation of methyl orange, which was adopted as a model compound. UV light (6W) was used as the irradiation source to induce synthesized ZnO powders to perform catalytic activity. The photocatalytic reaction was executed in 40 mL of a 10 ppm methyl orange aqueous solution under 254 nm UV illumination. In this work, it was observed that both UV light and ZnO powders are needed for the photocatalytic reaction. In addition, it was found that increasing the amount of ZnO powder present in the MO (methyl orange‐C₁₄H₁₄N₃NaO₃S) solution did not correlate directly with an increase in photocatalytic ability. It was found that the scattering problem of UV light also needs to be considered. The optimized photocatalytic degradation ratio in this work reached 92.7%.     

Preparation,characterization and activity evaluation of p–n junction photocatalyst p-NiO/n-ZnO

In this paper, p–n junction photocatalyst NiO/ZnO was prepared by the sol–gel method using Ni (NO₃)₂ and zinc acetate as the raw materials. The structural and optical properties of the p–n junction photocatalyst NiO/ZnO were characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, UV–Vis diffuse reflection spectrum (DRS) and the fluorescence emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇ ²⁻ and photocatalytic oxidation of methyl orange (MO). The results showed that the photocatalytic activity of the p–n junction photocatalyst NiO/ZnO is much higher than that of ZnO on the photocatalytic reduction of Cr₂O₇ ²⁻. However, the photocatalytic activity of the photocatalyst is much lower than that of ZnO on the photocatalytic oxidation of methyl orange. Namely, the p–n junction photocatalyst NiO/ZnO has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. The heat treatment condition also influences the photocatalytic activity strongly, and the best preparation condition is about 400 °C for 2 h. Effect of the heat treatment condition on the photocatalytic activity of the photocatalyst was also investigated. The mechanisms of influence on the photocatalytic activity were discussed by the p–n junction principle.     

NiO亚微米球的制备及其光催化性质

在混合溶剂体系中,通过简单的二步方法成功合成了NiO亚微米球。第一步,以Ni(CH3COO)2和精氨酸为主要反应物,160℃溶剂热反应8 h制备出前驱体;第二步,煅烧前驱体成功合成了NiO产物。利用X射线粉末衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),热重分析(TGA)等手段对产物进行了表征。在紫外光照射下,研究不同光催化剂对甲基橙溶液降解效果。结果表明,NiO亚微米球在紫外光照射条件下对甲基橙溶液有光降解作用。     

Synthesis of an Ag–ZnO nanocomposite catalyst for visible light-assisted degradation of a textile dye in aqueous solution

The photocatalytic activity of silver-deposited ZnO in the photodegradation of methyl orange (MO) was investigated. The as-prepared photocatalysts were characterized by X-ray diffraction, UV–visible diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The results showed that the silver-deposited ZnO had a visible light plasmon absorption band. The photocatalytic degradation experiment revealed that the catalytic efficiency of the Ag–ZnO composite in the degradation of MO was greater than that of pure ZnO samples. This study shows that the degradation process is dominated by the Ag–ZnO photocatalytic system, complying with a pseudo-first-order rate law. Under the experimental conditions, approximately 65.0% dye removal was achieved within 100 min.     

Z型复合催化剂g-C3N4/Vo-ZnO光催化活性的研究

随着科学技术的不断进步和经济的快速发展,人类对自然资源的需求量越来越大,在开发利用自然资源的同时,大量的有机污染物也随之进入自然环境.这些物质不仅污染环境、破坏生态,更对人类的生活和健康带来了巨大的威胁.研究证实,半导体光催化剂在光照条件下可以破坏有机污染物的分子结构,最终将其氧化降解成CO2、H2O或其它不会对环境产生二次污染的小分子,从而净化水质.近年来,有关光催化降解有机污染物的报道日益增多. ZnO作为一种广泛研究的光催化降解材料,因其无毒、低成本和高效等特点而具有一定的应用前景.但是ZnO较大的禁带宽度(3.24 eV)导致其只能吸收紫外光部分,而对可见光的吸收效率很小,极大地制约了其实际应用.除此之外, ZnO受光激发产生的电子-空穴分离效率较低、光催化过程中的光腐蚀严重也是制约其实际应用的重要因素.为了提高ZnO的光催化活性和稳定性,本文合成了用g-C3N4修饰的氧空位型ZnO(g-C3N4/Vo-ZnO)复合催化剂,在有效调控ZnO半导体能带结构的同时,通过负载一定量的g-C3N4以降低光生电子-空穴对的复合速率和反应过程中ZnO的光腐蚀,增强催化剂的光催化活性和稳定性.本文首先合成前驱体Zn(OH)F,然后焙烧三聚氰胺和Zn(OH)F的混合物得到g-C3N4/Vo-ZnO复合催化剂,并采用电子顺磁共振波谱(EPR)、紫外-可见光谱(UV-vis)、高分辨透射电镜(HRTEM)和傅里叶变换红外光谱(FT-IR)等表征了它们的结构及其性质. EPR结果表明,ZnO焙烧后具有一定浓度的氧空位,导致其禁带宽度由3.24 eV降至3.09 eV,因而提高了ZnO对可见光的吸收效率. UV-vis结果显示, Vo-ZnO复合g-C3N4后对可见光的吸收显著增强. HRTEM和FT-IR结果均表明, g-C3N4纳米片和Vo-ZnO颗粒之间通过共价键形成了强耦合,这对g-C3N4/Vo-ZnO复合催化剂中光生载流子的传送和光生电子-空穴对的有效分离起到重要作用.可见光催化降解甲基橙(MO)和腐殖酸(HA)的实验进一步证明, g-C3N4/Vo-ZnO复合材料具有较好的光催化活性,优于单一的g-C3N4或Vo-ZnO材料.同时还发现, g-C3N4的负载量对光催化活性有显著影响,当氮化碳的负载量为1 wt%时,所制材料具有最高的光催化活性：可见光照射60 min后,MO降解率可达到93%, HA降解率为80%.复合材料光催化活性的增强一方面是因为氧空位的形成减小了ZnO的禁带宽度,使得ZnO对可见光的吸收能力大大增强;另一方面, g-C3N4和Vo-ZnO的能带符合了Z型催化机理所需的有效能带匹配,使得光生电子-空穴对得到了有效的分离,从而提高了光催化活性.降解MO的循环实验表明, g-C3N4/Vo-ZnO催化剂具有很好的稳定性且不容易发生光腐蚀.与此同时,我们对比了用不同方法制备的g-C3N4/ZnO材料的催化性能.结果显示,本文制备的g-C3N4/Vo-ZnO复合材料具有更好的降解效率.总体而言,对于降解有机污染物, g-C3N4/Vo-ZnO可能是一个更为有效可行的催化体系.此外,本文也为设计与制备其他新型光催化剂提供了一条新的思路.     

Photocatalytic degradation of methyl orange over metalloporphyrins supported on TiO2 Degussa P25

The photocatalytic activity of meso-tetraphenylporphyrins with different metal centers (Fe, Co, Mn and Cu) adsorbed on TiO(2) (Degussa P25) surface has been investigated by carrying out the photodegradation of methyl orange (MO) under visible and ultraviolet light irradiation. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV (DRS-UV-vis) and infrared spectra. Copper porphyrin-sensitized TiO(2) photocatalyst (CuP-TiO(2)) showed excellent activity for the photodegradation of MO whether under visible or ultraviolet light irradiation. Natural Bond Orbital (NBO) charges analysis showed that methyl orange ion is adsorbed easier by CuP-TiO(2) catalyst due to the increase of induced interactions.