TiO2-V2O5纳米纤维光催化氧化烟气中的Hg0

对静电纺丝法制备的TiO₂和TiO₂-V₂O₅纳米纤维进行光催化脱除模拟烟气中Hg⁰的研究。对纳米纤维进行了SEM、TEM、XRD、BET和UV-Vis检测。结果表明TiO₂-V₂O₅纳米纤维为锐钛矿,V₂O₅高度分散在TiO₂中。纤维直径在200 nm左右,由粒径为10 nm左右的微粒组成。掺杂V₂O₅后,纤维的吸光范围扩大,在可见光范围内的吸光度比纯TiO₂时有了很大提高。实验研究了不同光照条件、V₂O₅的掺杂量和循环次数对脱汞的影响,分析了TiO₂-V₂O₅催化脱汞的机理。当V₂O₅的质量含量为3%时,TiO₂-V₂O₅在可见光下的脱汞率可达到66%,比纯TiO₂时的7%有了显著提高;纤维的脱汞性能稳定,多次循环后紫外光和可见光下的脱汞率仍分别保持在80%和65%左右。电子的跃迁和电子、空穴的快速分离是TiO₂-V₂O₅在可见光下脱汞率提高的主要原因。     

溶胶-凝胶原位合成宽活性温度V2O5/TiO2脱硝催化剂

利用溶胶-凝胶技术原位合成一系列不同V₂O₅担载量的V₂O₅/TiO₂催化剂,通过BET、XRD、NH₃-TPD及紫外-可见光等手段对催化剂进行表征。结果表明：制备的催化剂均具有介孔结构,V₂O₅在TiO₂表面高度分散,且存在3种典型的酸性位。通过选择性催化还原反应对V₂O₅/TiO₂催化剂进行活性评价,结果显示随着V₂O₅含量的增加,NO转化率大于75%的温度窗口向低温方向偏移,含10% （质量分数）V₂O₅的催化剂的NO转化率为80%的温度窗口最宽为200～450℃,240℃时20 h连续实验表现出稳定的抗硫抗水性能。结合紫外-可见光谱分析,揭示了钒掺杂所形成的单聚和低聚钒酸盐为催化剂的活性组分。     

V2O5-MoO3/TiO2 催化剂的NOx选择性催化还原及SO2氧化活性

采用浸渍法以TiO₂为载体制备V₂O₅-MoO₃/TiO₂ 选择性催化还原催化剂,研究V₂O₅和MoO₃负载量对于催化剂选择性催化还原反应及SO₂氧化活性的影响,并考察氧含量、氨氮物质的量比和反应空速对3%V₂O₅-6%MoO₃/TiO₂催化剂选择性催化还原脱硝活性的影响。结果表明,随着催化剂中V₂O₅负载质量分数增加,V₂O₅-MoO₃/TiO₂ 催化剂的选择性催化还原活性和SO₂氧化活性均呈上升趋势。MoO₃的负载对催化剂的SO₂氧化活性有明显抑制作用。MoO₃负载质量分数超过9%,制备的催化剂既保持较高的低温选择性催化还原活性,又使选择性催化还原反应中的SO₂转化率小于1%。     

含Nb2O5非晶光子结构色釉的制备及其色彩调控机制

在Na₂O–K₂O–MgO–CaO–Al₂O₃–SiO₂系陶瓷釉中，通过引入2%～7%(质量分数)的Nb₂O₅，制备出蓝、青色的非晶光子结构色釉。采用紫外–可见反射光谱、Fourier变换红外光谱、扫描电子显微镜、透射电子显微镜等研究Nb₂O₅加入量对釉色、分相结构及元素分布的影响，并揭示其对非晶光子结构色的调控机制。结果表明：随着Nb₂O₅加入量的增多，釉中[NbO₄]四面体转变为[NbO₆]八面体，其作为网络修饰体存在于釉中，使得高温下釉熔体的黏度降低，分相液滴长大。并且，富集于分相液滴中的Nb元素提高了其与基相的相对折射率差，促使非晶光子结构色的波长向长波方向移动，釉色由蓝色向青色发展。     

氧化铁对SiO2-Al2O3-CaO-Na2O-B2O3釉系统的显微结构和釉面呈色影响

在SiO₂-Al₂O₃-CaO-Na₂O-B₂O₃多元釉系统中以氧化铁作为变量，研究不同氧化铁添加量对于硼硅酸盐系统的釉层显微结构、釉色等的影响。结果表明：氧化铁的加入使得釉层结构改变，进而形成了釉面颜色变化。在没有氧化铁加入时，硼硅酸盐釉系统形成分相，产生200 nm左右的富B球形液滴和富Si连续相，在米氏散射作用下釉面呈现乳浊白色；少量氧化铁的加入导致釉熔体分相结构改变，富B相球形液滴尺寸减小，入射光在釉层被散射，在离子着色的作用下釉面呈现棕黄色；随着氧化铁的增加，球形液滴的尺寸继续减小，铁离子浓度在釉层不断聚集增大，入射光在釉层被大量的消耗，最终使得釉面呈黑色；当氧化铁添加量过多时，大量六边形赤铁矿α-Fe₂O₃晶体从釉层析出且呈不规则取向排列，形成“金星闪耀”的釉面效果。     

花型结晶釉的制备及显微结构表征

针对传统结晶釉产品普遍存在的烧成温度高、保温时间长、连续化生产难等问题,以钾长石、方解石、氧化锌、玻璃粉为主要原料,在1 220 ℃成功烧成K₂O-Na₂O-CaO-ZnO-SiO₂-Al₂O₃系陶胎结晶釉,重点研究了窑炉冷却制度和着色剂对釉面效果的影响。结果表明:冷却过程中,1 100 ℃“定点保温”3 h,2%(质量分数)NiO和2%(质量分数)CuO的着色剂组合可使陶胎釉面呈现直径约4.5 cm、白色花边、绿色内簇的花状粗晶;在速率为125 ℃/h的“缓速冷却”制度下,可生成内部绿色放射状晶簇、宏观尺寸约8 mm、美观自然且边界清晰的“梅花状”晶体。采用场发射扫描电镜(FESEM)、能谱仪(EDS)、XRD等分析对典型“梅花状”晶体的显微结构、化学组成等进行了表征,发现其内部存在着六边形柱状、针状等同晶异构硅锌矿晶体。六边形柱状晶体主要聚集在“梅花”中心,由于垂直釉面方向空间受限而长大缓慢,其尺寸普遍在2 μm左右;针状晶体主要平行于釉面并向“花瓣”放射生长。底釉非晶玻璃相中存在大量纳米级分相微球结构,呈现出豆绿乳浊效果。Fe₂O₃、CuO、MnO、NiO的两两组合可使陶胎釉面呈现窑变多色的釉面结晶效果,其中Fe₂O₃与MnO,以及NiO与CuO的着色组合效果最佳。     

V2O5/（TiO2-SiO2）脱硝催化剂新型制备工艺及性能研究

将偏钒酸铵和羟丙基甲基纤维素搅拌混溶制备滴胶液,以自制的7孔圆柱蜂窝钛硅复合氧化物为载体,采用滴胶涂覆法制备了V₂O₅/（TiO₂-SiO₂）脱硝催化剂。通过X射线衍射（XRD）、程序升温还原（H₂-TPR）、比表面积分析（BET）和催化剂评价等方法对制备的脱硝催化剂进行分析表征。考察了五氧化二钒在钛硅复合氧化物载体上的分布、五氧化二钒涂覆量等对催化剂性能的影响,并就反应温度、反应空速、氨与一氧化氮物质的量比等条件对脱硝催化剂活性的影响进行了研究。实验结果表明,使用五氧化二钒涂覆量为1.2%（质量分数）的V₂O₅/（TiO₂-SiO₂）脱硝催化剂,在反应温度为320 ℃、空速为10 000 h^-1、氨与一氧化氮物质的量比为1.2条件下进行脱硝活性实验,一氧化氮转化率达到93.0%。经与工业脱硝催化剂对比实验表明,制备的V₂O₅/（TiO₂-SiO₂）脱硝催化剂性能优良,并且降低了钒的使用量,节约了生产成本,减少了环境污染。     

青釉制备及其影响因素的研究

以钠长石、偏高岭土、方解石、石英粉为釉用原料，氧化铁为着色剂，在高岭土坯体上采用热化学反应法成功制备了青瓷乳浊釉面。研究了Si/Al比、RO/R₂O比、Fe₂O₃加入量、烧结温度对青瓷釉面以及釉面/坯体结构的影响。利用XRD、SEM、EDS、光学显微镜对所制备的青瓷釉面物相组成与显微结构进行了表征。结果表明，当Si/Al比为9.136～10.456、RO/R₂O比为5时，烧结温度1320℃，保温3 h时可制备出光滑无裂纹、具有乳浊性能的青瓷釉面。当Fe₂O₃的加入量为1.0%～1.5%(wt)时，青瓷釉面呈粉青色，随着Fe₂O₃的加入量增加到2.5%～3.5%(wt)时，青瓷釉面逐渐变成豆青色。坯体中的Al³⁺扩渗到釉层中形成钙长石晶须，使青瓷釉面具有乳浊性能。     

甲醇直接氧化合成二甲氧基甲烷催化剂的研究

二甲氧基甲烷是重要的有机化工原料,在溶剂、化工中间体、制氢和燃料添加剂等领域应用广泛,以甲醇为原料一步合成二甲氧基甲烷是C1化工的研究新热点。以TiO₂为载体,通过负载V₂O₅并采用Ti(SO₄)₂改性制备V₂O₅/TiO₂-SO₄^2-催化剂,在温度（135～150） ℃、V（CH₃OH）∶V（O₂）∶V（N₂）=1∶（1.5～4）∶（7～20）和原料气流量(5 000～8 000) mL·(g·h)^-1条件下,将甲醇直接氧化合成二甲氧基甲烷。结果表明,甲醇转化率为48%,二甲氧基甲烷选择性为80%。     

钨对VOx/TiO2催化燃烧氯苯的作用

采用等体积浸渍法（VO_x和WO_x的添加采用共浸渍）制备不同钨添加量的VO_x-WO_x/TiO₂（VW/Ti）催化剂。采用XRD和EDS对VW/Ti催化剂样品进行表征，并考察催化剂催化燃烧氯苯的活性。结果表明，钨添加前，VO_x/TiO₂催化剂中TiO₂以锐钛矿相和金红石相共存，锐钛矿相为主要晶相，同时还存在V₂O₅晶相；添加一定量钨后，催化剂中TiO₂金红石相和V₂O₅晶相消失，W与Ti质量比0.024时，催化剂中活性组分VO_x在载体TiO₂表面分散最均匀，催化活性最高，T₅₀和T₉₀分别为226.72 ℃和298.67 ℃。W与Ti质量比0.12时，出现WO₃晶相，催化活性略降。因此，适量添加钨不仅可以抑制TiO₂由锐钛矿相向金红石相转变，还可以促进活性组分VO_x在载体上的分散，进而改善催化剂催化降解氯苯的活性。     

金属光泽釉内墙砖烧成制度优化

采用钾长石、玻璃粉、石灰石、石英、氧化锌、硼酸为主要原料,添加氧化铜、二氧化锰、五氧化二钒等金属氧化物析晶剂,制备具有金属光泽的内墙砖,考察了烧成制度对金属光泽釉的影响,并进行了优化。采用XRD,SEM等检测设备对金属光泽釉的物相组成和晶体形貌进行了表征,揭示了性能与结构之间的关系。     

SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures

To get the low temperature sulfur resistant V₂O₅/TiO₂ catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V₂O₅/TiO₂ catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V₂O₅/TiO₂ catalysts showed high catalytic activity for NH₃ selective catalytic reduction (NH₃-SCR) of NO_x carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V₂O₅/TiO₂ > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V₂O₅/TiO₂ for maximum NO_x conversion, which also showed high resistance to SO₂ in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V₂O₅/TiO₂ and compared with commercial W(10%)V₂O₅/TiO₂ catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V₂O₅/TiO₂ catalyst with temperature was observed. SO₂ deactivation experiments were carried out for Sb(2%)/V₂O₅/TiO₂ and W(10%)/V₂O₅/TiO₂ at a temperature of 230 °C for 90 h, resulted Sb(2%)/V₂O₅/TiO₂ was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V₂O₅/TiO₂ than Sb(2%)/V₂O₅/TiO₂ catalyst.     

3-甲基吡啶一步气相氧化合成烟酸的V2O5/TiO2催化剂研究进展

烟酸作为重要的化工和医药中间体广泛应用于不同领域.相较于传统工艺,3-甲基吡啶气相一步催化氧化合成烟酸的方法具有成本低、污染低、产品质量高等优点,展现出良好的应用前景.目前V₂O₅/TiO₂系列催化剂在3-甲基吡啶的氧化反应中表现出了良好的氧化活性.本文主要分析了催化剂表面的VO_x结构,并概述了载体、制备方法、负载量、焙烧过程和助剂掺杂对结构的影响,探讨催化剂中各组分之间的相互作用,根据相关文献推测3-甲基吡啶氧化的反应机理.但该类催化剂仍然存在反应速率和选择性较低、温度窗口窄、反应过程中放出的热量对催化剂的影响等一些技术问题.文章从催化剂的开发和反应器的设计两方面进行了展望.     

Improvement of response characteristics of TiO2 humidity sensors by simultaneous addition of Li2O and V2O5

Porous TiO₂ ceramics were prepared by adding various amounts of Li₂O and V₂O₅ and the humidity sensitivity of the resulting ceramics was investigated by means of electrical measurements, scanning electron microscopy and mercury intrusion porosimetry. Simultaneous addition of Li₂O and V₂O₅ to TiO₂ enabled sintering at temperatures as low as 700 °C and also decreased the impedance of the ceramics. Furthermore, in the ceramics including these additives simultaneously, excellent humidity sensitivity as well as good response characteristics were observed. The microstructures of these ceramics depended on the firing temperature and the amount and ratio of Li₂O/V₂O₅, and optimum humidity sensitivity was observed for the sample including both 0.25 mol% Li₂O and 0.75 mol% V₂O₅ fired at 700 °C. These results indicated that the humidity sensitivity and its response characteristics were closely related to the microstructure, and that improving the uniformity of microstructure is important for improving humidity sensitivity and its response characteristics.     

Effect of promoters including tungsten and barium on the thermal stability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3

The effect of tungsten and barium on the thermal stability of V₂O₅/TiO₂ catalyst for NO reduction by NH₃ was examined over a fixed bed flow reactor system. The activity of V₂O₅/sulfated TiO₂ catalyst gradually decreased with respect to the thermal aging time at 600 °C. The addition of tungsten to the catalyst surface significantly enhanced the thermal stability of V₂O₅ catalyst supported on sulfated TiO₂. On the basis of Raman and XRD measurements, the tungsten on the catalyst surface was identified as suppressing the progressive transformation of monomeric vanadyl species into crystalline V₂O₅ and of anatase into rutile phase of TiO₂. However, the NO removal activity of V₂O₅/sulfated TiO₂ catalyst including barium markedly decreased after a short aging time, 6 h at 600 °C. This may be due to the transformation of vanadium species to inactive V–O–Ba compound by the interaction with BaO which was formed by the decomposition of BaSO₄ on the catalyst surface at high reaction temperature of 600 °C. The addition of SO₂ to the feed gas stream could partly restore the NO removal activity of thermally aged V₂O₅/sulfated TiO₂ catalyst containing barium.     

Boosting low-temperature selective catalytic reduction of NO with NH3 of V2O5/TiO2 catalyst via B-doping

A series of B-doped V₂O₅/TiO₂ catalysts has been prepared the by sol-gel and impregnation methods to investigate the influence of B-doping on the selective catalytic reduction (SCR) of NO_x with NH₃. X-ray diffraction, Brunauer-Emmett-Teller specific surface area, scanning electron microscope, X-ray photoelectron spectroscopy, temperature-programmed reduction of H₂ and temperature-programmed desorption of NH₃ technology were used to study the effect of the B-doping on the structure and NH₃-SCR activity of V₂O₅/TiO₂ catalysts. The experimental results demonstrated that the introduction of B not only improved the low-temperature SCR activity of the catalysts, but also broadened the activity temperature window. The best SCR activity in the entire test temperature range is obtained for VTiB_2.0 with 2.0% doping amount of B and the NO_x conversion rate is up to 94.3% at 210 ℃. The crystal phase, specific surface area, valence state reducibility and surface acidity of the active components for the as-prepared catalysts are significantly affected by the B-doping, resulting in an improved NH₃-SCR performance. These results suggest that the V₂O₅/TiO₂ catalysts with an appropriate B content afford good candidates for SCR in the low temperature window.     

Factors controlling the selectivity of V2O5 supported catalysts in the oxidative dehydrogenation of propane

The surface properties of a series of V₂O₅ catalysts supported on different oxides (Al₂O₃, H–Na/Y zeolite, MgO, SiO₂, TiO₂ and ZrO₂) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH₃ adsorption. In the case of the V₂O₅/SiO₂ system TEM images evidenced the presence of V₂O₅ crystallites, whereas such segregated phase was not observed for the other samples. VO_x species resulted widely spread on the surface of Al₂O₃, H–Na/Y zeolite, MgO and SiO₂, whereas on TiO₂ and ZrO₂ they are assembled in a layer covering almost completely the support. Furthermore, evidences for the presence in this layer of V–OH Brønsted acid sites close to the active centres were found. It is proposed that propene molecules primarily produced by oxydehydrogenation of propane can be adsorbed on this acid centres and then undergo an overoxidation by reaction with redox centres in the neighbourhood. This features could account for the low selectivity of V₂O₅/TiO₂ and V₂O₅/ZrO₂ catalysts.     

Effects of microwaves on selective oxidation of toluene to benzoic acid over a V2O5/TiO2 system

Two series of catalysts, V₂O₅/TiO₂ and modified V₂O₅/TiO₂, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V₂O₅/TiO₂. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V₂O₅/TiO₂ with MoO₃, WO₃, Nb₂O₅ or Ta₂O₅, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed.     

Ag-Fe_2O_3-V_2O_5/TiO_2催化剂制备及其甲基吡啶催化氧化脱甲基性能

针对甲基吡啶氧化脱甲基反应,以TiO_2为载体经浸渍法制备Ag-Fe_2O_3-V_2O_5/TiO_2催化剂,结合结构表征和催化剂性能评价,考察制备条件对其催化甲基吡啶氧化脱甲基性能的影响。结果表明,通过Fe_2O_3改性可以提高Ag-V_2O_5/TiO_2催化剂对3-甲基吡啶氧化脱甲基化反应的催化性能,其作用主要是抑制V_2O_5团聚,促进V物种的分散。同时,锐钛矿相TiO_2载体表面B酸中心有利于催化3-甲基吡啶脱甲基,提高产物吡啶选择性。经实验优化,Ag-Fe_2O_3-V_2O_5/TiO_2催化剂适宜制备条件为:焙烧温度450℃、焙烧时间4 h、V_2O_5和Ag的负载质量分数分别为15%和1.5%、Fe与V物质的量比1∶2。在优化条件下,吡啶收率与选择性最高可达到62.97%和78.75%。