Photocatalytic Activity of Nanosized ZnWO4 Prepared by the Sol-gel Method

Nanosized ZnWO4 photocatalysts were successfully synthesized via the sol-gel process in a temperature range of 450-800 ℃.The grain size,crystal size,and crystallinity of ZnWO4 particles increased with the increase of calcination temperature and prolonging calcination time.The photocatalytic activity was measured for the degradation of an aqueous Rhodamine-B(RhB)solution and gaseous formaldehyde(FAD).With the increase of calcination temperature and time,the activities increased to a maximum and then decreased.ZnWO4 photocatalyst prepared at 550 ℃ for 10 h showed the highest activity,which is similar to the photocatalytic activity of P25TiO2 for the degradation of gaseous FAD.High crystallinity,large surface area,and good dispersion are responsible for the high photocatalytic performance of the prepared ZnWO4.     

超细钨酸锌纳米棒的制备及其光催化性能

在含有溴化十六烷基三甲基铵(CTAB)的水溶液中,通过水热法制备了超细钨酸锌（ZnWO4）纳米棒。 用X射线衍射、扫描电子显微镜和紫外可见漫反射光谱表征了所制备的样品。 在汞灯照射下,通过降解甲基橙（MO）检测了超细ZnWO4纳米棒的光催化活性。 结果表明,在CTAB胶束作用下,ZnWO4纳米棒更细更长,超细ZnWO4纳米棒光催化活性比普通ZnWO4纳米棒更强,在同样条件下,前者对MO的降解率为90.2%,后者为50%。     

NaOH溶液中CdS纳米棒的水热合成

在NaOH溶液中水热合成了CdS纳米棒, 并探讨了NaOH溶液浓度和反应时间对CdS纳米棒形貌及晶体结构的影响及其可能的生长机理和母液循环可行性. 用粉末X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 高分辨透射电子显微镜(HRTEM)和选区电子衍射(SAED)对CdS纳米棒进行了表征, 并考察了其在可见光照射下光催化降解亚甲基蓝的活性. 结果表明, NaOH溶液是形成棒状形貌的关键因素. 在最优实验条件下, 可获得六方纤锌矿结构CdS纳米棒, 直径约200 nm, 长度可达4 μm. 该纳米棒具有良好的可见光光催化活性.     

磷酸铋纳米棒的可控合成及其光催化性能

采用水热法合成了形貌可控的磷酸铋纳米棒光催化剂,并以亚甲基蓝(MB)为探针研究了其光催化活性.利用粉末X射线衍射(XRD),透射电镜(TEM)和紫外-可见漫反射光谱(UV-VisDRS)对产物进行了表征.研究发现甘油含量、水热时间、水热温度及前驱体浓度会影响磷酸铋纳米棒的形貌及结构.甘油含量和前驱体浓度主要影响产物形貌.随着甘油含量的增加,产物的长径比先增大后减小.前驱体浓度越低,所得BiPO4纳米棒的尺寸越小,长径比越大.水热时间短时,产物结晶度差,且为六方相,时间延长后转化为单斜相.水热温度过低或过高均不利于完美晶体的形成,160°C时产物的结晶度最高.实验结果表明:BiPO4纳米棒在紫外光下具有良好的光催化性能,其光催化活性受长径比和尺寸大小影响的总体趋势是长径比越大,尺寸越小,其光催化活性越强.结晶度对BiPO4的光催化性能影响较大,结晶度越高,其光催化活性越好.单斜相BiPO4的光催化活性较六方相的强.     

反应条件对ZnWO4纳米棒的形貌和光致发光性能的影响

采用水热法合成了ZnWO4纳米棒, 并用扫描电镜(SEM)、透射电镜(TEM)和粉末X射线衍射(XRD)等技术对产物进行了表征. 实验结果表明, 反应溶液的pH值和反应时间是影响ZnWO4纳米棒形成的重要因素. 研究了不同反应条件下制备的ZnWO4纳米晶的光致发光性能.     

Synthesis of hexagonal BaTa2O6 nanorods and influence of defects on the photocatalytic activity

Hexagonal barium tantalate (BaTa2O6) nanorods were synthesized by a hydrothermal method based on the reaction of concentrated Ba(OH)2 solution and Ta2O5. BaTa2O6 samples show a uniform cylindrical structure with diameters of 5-30 nm and the lengths of 50-200 nm. The formation of BaTa2O6 nanorods follows a dissolution-recrystallization mechanism and is governed by hydrothermal temperature and time. BaTa2O6 nanorod samples prepared at 270 degrees C for 72 h have exhibited the highest photocatalytic activity in the degradation of Rhodamine B (RhB) in aqueous solution under UV radiation. Hydrogen-related defects were detected in BaTa2O6 nanorods, which originate from the oxygen octahedron. The number of defects was dependent on the hydrothermal temperature, and the photocatalytic activities of BaTa2O6 nanorods increase with the decrease of defect amounts. On the basis of the experiment results, the difference in photocatalytic activities for samples is mainly caused by lattice defects, which can act as inactivation centers.     

氧化铈形貌对Au/CeO2催化剂催化氧化CO反应活性的影响

采用水热合成法制备了形貌规则的纳米氧化铈颗粒,分别为棒状、立方体和多面体,通过溶胶沉积法将金颗粒沉积到不同形貌氧化铈表面制得了Au/CeO2催化剂.考察了催化剂载体的不同形貌对CO催化氧化反应活性的影响.实验结果表明,棒状(110 100)和多面体(111 100)氧化铈作为载体时的催化剂活性比立方体(100)作为载体时的活性高.在低温段,多面体氧化铈作为载体的催化剂表现出较高活性,而在高温范围,棒状氧化铈作为载体的催化剂的催化活性最好.     

Photocatalytic Degradation of 2-Propanol and Phenol Using Au Loaded MnWO4 Nanorod Under Visible Light Irradiation

Single crystalline MnWO₄ nanorod has been prepared by low temperature hydrothermal reaction at 180 °C. The prepared MnWO₄ possesses band gap of 2.63 eV. Photochemical decomposition method has been followed to disperse Au nanoparticles onto MnWO₄ nanorod. The prepared Au loaded MnWO₄ nanorod demonstrated greatly enhanced photocatalytic activity in decomposing 2-propanol and evolving CO₂ in gas phase and phenol in aqueous phase compared to bare MnWO₄ and commercial TiO₂ nanoparticles (Degussa P25) under visible light (λ ≥ 420 nm) irradiation. The Au loading was optimized to 3.79 wt% for the highest efficiency. The enhanced photocatalytic activity originates from the absorption of visible light by MnWO₄ as well as the introduction of nanoparticulate Au on the surface of MnWO₄ as cocatalyst to impede the recombination of photogenerated charge-carriers.     

钛酸纳米管前驱体水热制备TiO2：水热媒介对结晶度及光催化活性的影响

以钛酸纳米管为先驱体,180℃24 h同一水热条件下,利用H2O、HNO3、KBF4以及HNO3+KBF4的4种水热媒介溶液,制备了高结晶度高光催化活性的TiO2,并研究了水热媒介对TiO2结晶度、表面羟基和光催化活性的影响。通过扫描电镜(SEM)、X射线衍射(XRD)、红外测试(FTIR)、X射线光电子能谱(XPS)、紫外可见漫反射吸收光谱(UV-Vis)进行了结构表征。光催化活性通过降解甲基橙溶液进行了评价。结果表明,与其他3种媒介相比,HNO3+KBF4溶液为水热媒介制备的锐钛矿晶型TiO2,结晶度高,表面羟基含量高,因此,呈现高的光催化活性。     

Large‐Scale Production of Hierarchical TiO2 Nanorod Spheres for Photocatalytic Elimination of Contaminants and Killing Bacteria

We report a facile non‐hydrothermal method for the large‐scale production of hierarchical TiO₂ nanorod spheres for the photocatalytic elimination of contaminants and killing bacteria. Crescent Ti/RF spheres were prepared by deliberately adding titanium trichloride (TiCl₃) to the reaction of resorcinol (R) and formaldehyde (F) in an open reactor under heating and stirring. The hierarchical TiO₂ nanorod spheres were obtained by calcining the crescent Ti/RF spheres in a furnace in air to burn off the RF spheres. This method has many merits, such as large‐scale production, good crystallisation of TiO₂, and good reproducibility, all of which are difficult to realise by conventional hydrothermal methods. The calcination temperature plays a significant role in influencing the morphology, crystallisation, porosity, Brunauer–Emmett–Teller (BET) specific surface area, and hierarchy of the TiO₂ nanorod spheres, thus resulting in different photocatalytic performances under UV light and solar light irradiation. The experimental results have demonstrated that the hierarchical TiO₂ nanorod spheres obtained after calcination of the crescent Ti/RF spheres at different temperatures displayed similar photocatalytic activities under irradiation with UV light. We attribute this to a balance of opposing effects of the investigated factors. A higher calcination temperature leads to greater light absorption capability of the TiO₂ nanorod spheres, thus resulting in higher photocatalytic antibacterial activity under solar light irradiation. It is also interesting to note that the hierarchical TiO₂ nanorod spheres displayed intrinsic antibacterial activity in the absence of light irradiation, apparently because their sharp outward spikes can easily pierce and penetrate the walls of bacteria. In this study, the sharpest hierarchical TiO₂ nanorod spheres were obtained after calcination at 500 °C, and these exhibited the highest antibacterial activity without light irradiation. A higher calcination temperature proved detrimental to the sharpness of the TiO₂ nanorods, thus reducing their intrinsic antibacterial activity.     

Formation of ZSM-22 zeolite catalytic particles by fusion of elementary nanorods

An ZSM-22 aluminosilicate zeolite was synthesized using the hydrothermal gel method at 150 degrees C. Products obtained after different synthesis times were characterized using various techniques and catalytic testing. Massive formation of ZSM-22 nanocrystals occurs after only a short synthesis time, appearing as isolated rods with a cross section of 12+/-4 nm. Nanorods have aluminum enriched at their external surface. Later in the crystallization process nanorods align and fuse sideways, whereby the external surface is systematically converted into an internal micropore surface. The formation of aluminum bearing micropores by the joining of nanorod surfaces is responsible for the enhanced catalytic activity. For this, the zeolite synthesis of nanoscale crystallites is ineffective for enhancing catalytic activity.     

水热pH值对溴氧化铋组成、形貌及光催化性能的影响

通过调节pH值一步水热法制备溴氧化铋光催化剂,并利用X射线衍射（XRD）、扫描电镜（SEM）、紫外-可见漫反射光谱（UV-vis DRS）和固体荧光光谱（PL）等方法对其进行表征。在可见光（γ>420 nm）照射下,通过对水溶液中罗丹明B,甲基橙和苯酚的降解效果来评价溴氧化铋的光催化活性。结果表明,由于B9提高了对可见光的吸收以及电子-空穴对的分离效率,B9具有最好的光催化活性,同时探索水热pH值对制备溴氧化铋的形貌和组成的影响,并说明了不同水热pH值下溴氧化铋的合成过程。     

形貌可控ZnO微纳米结构的水热合成及光催化性能

以乙醇胺为辅助溶剂,采用水热合成法,制备了花状、梭状和剑状的ZnO微纳米结构。采用扫描电镜(SEM)、X射线衍射(XRD)、光致发光光谱(PL)和拉曼光谱等测试手段对样品的形貌、结构、晶相等进行了表征。结果表明所有样品均为六方纤锌矿结构ZnO;其形貌和结晶度可通过改变物质的量的配比nZn2+/nOH-来调控。探讨了反应物配比对产物形貌结构的影响,乙醇胺对不同形貌ZnO的制备起到至关重要作用。以亚甲基蓝为目标降解物,采用紫外-可见吸收光谱(UV-Vis)并结合低温氮吸附-脱附比表面测试(BET),研究了花状、梭状和剑状ZnO的光催化活性。结果表明,与商用ZnO相比,制备的ZnO具有更好的光催化活性;样品催化活性与其比表面积不成正比,具有最小比表面积的花状ZnO拥有最好的光催化活性,这可能是由于其低的结晶度和特殊的花状形貌所致。     

形貌可控ZnO微纳米结构的水热合成及光催化性能

以乙醇胺为辅助溶剂,采用水热合成法,制备了花状、梭状和剑状的ZnO微纳米结构。采用扫描电镜（SEM）、Ｘ射线衍射（XRD）、光致发光光谱（PL）和拉曼光谱等测试手段对样品的形貌、结构、晶相等进行了表征。结果表明所有样品均为六方纤锌矿结构ZnO;其形貌和结晶度可通过改变物质的量的配比n_Zn²⁺/n_OH^-来调控。探讨了反应物配比对产物形貌结构的影响,乙醇胺对不同形貌ZnO的制备起到至关重要作用。以亚甲基蓝为目标降解物,采用紫外-可见吸收光谱（UV-Vis）并结合低温氮吸附-脱附比表面测试（BET）,研究了花状、梭状和剑状ZnO的光催化活性。结果表明,与商用ZnO相比,制备的ZnO具有更好的光催化活性;样品催化活性与其比表面积不成正比,具有最小比表面积的花状ZnO拥有最好的光催化活性,这可能是由于其低的结晶度和特殊的花状形貌所致。     

高活性钒酸铋的尿素沉淀法控制合成及其光催化活性增强机制研究

通过普通尿素沉淀法、超声协助和水热尿素法合成出高结晶度的单斜晶白钨矿型的钒酸铋粉末。利用XRD、SEM、DRS等手段分别对合成材料的晶型、微观形貌及光物理性质等进行研究。结果表明3种方法均能得到结晶度较高的钒酸铋颗粒,但微观形貌上有较大差异。在可见光下对难生化降解的红色染料FN-3G的降解效果表明,所合成的三种BiVO₄样品的光催化性能均较好,超声协助法和水热法合成的样品光催化活性增强的机制主要归因于结晶度的提高和比表面积的增大。结晶度的提高可降低电子和空穴复合几率,从而增强光电转换效率;而比表面积的增大主要提高了染料分子的吸附能力。     

纳米二氧化钛的制备及其光催化性能

分别采用水热法和溶胶-凝胶法制备了TiO2纳米粉体;利用X射线衍射仪和扫描电镜分析了两种方法制备的TiO2粉体的形貌和晶体结构,并测定了纳米TiO2粉体对罗丹明B的光催化降解活性.结果表明:采用水热法制备的TiO2纳米粉体含有锐钛矿相和金红石相,粒径较小,大约为50nm,而且分散均匀,光催化性能良好;采用溶胶-凝胶法制备的TiO2粉体经过550℃煅烧后仍然为锐钛矿相,而且粒径较大,大约为80nm.     

Mesoporous MnO2 synthesized by hydrothermal route for electrochemical supercapacitor studies

Poorly crystalline mesoporous MnO₂, which is suitable for supercapacitor studies, is synthesized from neutral KMnO₄ aqueous solution by hydrothermal route. But it requires a high temperature (180 °C) and also a long reaction time (24 h). Addition of a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123), which is generally used as a soft template for the synthesis of nano-structured porous materials, reduces the hydrothermal temperature to 140 °C and also reaction time to 2 h. When the reaction time is increased, the product morphology changes from nanoparticles to nanorods with a concomitant decrease in BET surface area. Also, the product tends to attain crystallinity. The electrochemical capacitance properties of MnO₂ synthesized under varied hydrothermal conditions are studied in 0.1 M Na₂SO₄ electrolyte. A specific capacitance of 193 F?g^?1 is obtained for the mesoporous MnO₂ sample consisting of nanoparticle and nanorod mixed morphology synthesized in 6 h using P123 at 140 °C.     

铋掺杂二氧化钛纳米颗粒的制备及其可见光催化性能

采用水热法,以纳米管钛酸为前驱物制备了Bi掺杂的TiO₂,并利用X射线衍射、透射电子显微镜、X射线光电子能谱、紫外-可见漫反射光谱等手段对样品进行了表征. 以甲基橙的光催化降解为模型反应评价了样品的可见光催化性能. 结果表明,Bi离子并没有进入TiO₂的晶格中,而是以BiOCl的形式存在. 所制得的BiOCl/TiO₂复合物对甲基橙降解表现出较优越的可见光催化活性;当Bi/Ti摩尔比为1%,水热温度为130℃时,所制催化剂的光催化性能最佳,并对光催化活性提高的机理进行了讨论. 同时,该催化剂对4-氯苯酚降解也表现出较高的光催化性能.     

煅烧温度对阳极氧化WO3多孔薄膜的形貌及光电化学性能的影响

采用一步式阶跃电压加压方法,在NH4F/(NH4)2SO4电解质溶液中对W片进行阳极氧化处理制备了WO3多孔薄膜,通过后续热处理温度的控制,制备了性能规律性变化的WO3多孔纳米薄膜材料.用场发射扫描电镜(FE-SEM)、X射线衍射(XRD)分析等手段考察了热处理温度对氧化钨晶体结构和形貌影响的规律,在450°C以下的煅烧温度下,薄膜保持50-100nm孔径;通过对光电化学性质、光催化降解甲基橙动力学行为的研究,考察了不同热处理温度对WO3多孔薄膜光电转换性能影响的规律.研究表明,450°C煅烧处理后的WO3薄膜在500W氙灯光源照射及1.2V偏压下,光电流密度达到5.11mA·cm-2;340及400nm单色光辐射下光电转换效率(IPCE)值分别达到87.4%及22.1%.电化学交流阻抗谱显示,450°C煅烧处理后的WO3薄膜表现出最佳的导电率及最小的界面电荷转移电阻.实验结果证明,高结晶度的多孔结构是WO3薄膜具有高光电转换效率的主要因素,控制热处理温度是实现薄膜具有高孔隙率、完整结晶度、低电阻的重要手段.     

核壳结构CdS/ZnS微米球表面处理与光催化制氢性能的关系

具有高活性和稳定性的半导体光催化材料是太阳能光催化制氢领域的研究热点,其中CdS胶体颗粒催化剂因其合适的禁带宽度和带边位置以及较低的原料价格而广受关注.但它在水溶液中不稳定,易受光腐蚀,因而限制了其应用.目前人们致力于用各种方法提高其稳定性,包括各种纳米结构的应用、复合其他催化剂材料以及不同晶相结构复合.ZnS是一种宽禁宽半导体,禁带宽度为3.6 eV,常被用来与CdS形成固溶体调控其能带结构,从而提高其性能和稳定性.其中核壳结构CdS/ZnS异质结具有骑跨型(I型)能带结构,具有特殊的光学和电学性质,在量子点LED和量子点生物荧光显示剂方面获得关注和应用,同时也显示了良好的光催化性能.研究人员对核壳结构CdS/ZnS异质结材料中ZnS壳层厚度对其光学性能包括荧光效率等的影响进行了研究,然而ZnS壳层厚度、颗粒尺寸及其表面处理对光催化性能影响方面的报道很少.本文发展了一种简易的两步法,制备了核壳结构CdS/ZnS微米球光催化剂.首先采用超声喷雾热分解法制备CdS微米球,然后以水浴法在CdS微米球上生长ZnS壳层.采用扫描电镜(SEM)、X射线衍射(XRD)、紫外-可见吸收光谱(UV-vis)和透射电镜(TEM)对所得样品进行了表征.SEM和TEM结果显示,所得微米球为完整包裹的球形核壳结构;XRD表征证实CdS核与ZnS壳层皆为六角相晶型;光催化性能表征结果显示,该样品的光催化制氢性能远高于单独的CdS微米球以及同法所制的ZnS微米球.通过改变前驱液浓度(Zn源浓度分别为0.2,0.3和0.5 mol/L)获得了三种不同厚度的核壳结构CdS/ZnS微米球,X射线荧光光谱结果证实了其壳层厚度成功调控.UV-vis结果发现,其吸收边由内核CdS决定,受壳层厚度的影响不大.光致荧光发射光谱分析发现,随着壳层厚度的增加,其540 nm处的CdS带边发射峰强度逐渐增大.这可能是由于ZnS壳层对CdS表面缺陷的钝化作用降低了其非辐射复合过程,从而提高了荧光发光效率.光催化制氢性能结果表明,前驱液浓度为0.3 mol/L时合成的核壳结构CdS/ZnS微米球的产氢效率最高.为了进一步提高其光催化效率,采用氮气中高温热处理、水热二次硫化法以及两者共用三种方式对性能最优的微米球进行改性,获得了三种核壳结构CdS/ZnS样品.结果发现,这些改性方法未影响其吸收边,但水热二次硫化法处理以及两者共用处理的样品在540 nm处的光致荧光发射峰强度明显高于未处理的和高温热处理的样品,证实水热二次硫化法处理可以有效地消除其表面缺陷,减少非辐射复合.XRD结果表明其晶型没有发生变化.TEM表征发现,经高温热处理后其壳层发生重结晶,形成颗粒包裹形貌,而经水热二次硫化法处理后其壳层同样发生重结晶,但包裹颗粒的尺寸明显更小.光催化性能测试表明,处理后样品的光催化性能皆优于未处理样品,其中两者共用法处理的样品产氢性能和稳定性最高.