介孔TiO2-SiO2的制备及光催化降解黑液的影响因素

以钛酸四丁酯（TBOT）为钛源，正硅酸乙酯（TEOS）为硅源，三嵌段共聚物（P125）为模板剂，溶胶-凝胶法合成了具有不同钛硅摩尔比的介孔TiO2-SiO2，用小角X射线衍射（SAXRD）、X射线粉末衍射（XRD）、透射电子显微镜（TEM）、红外（FT-IR）等分析手段对产物结构和光学性能进行了表征。考察了催化剂的种类、光照时间、催化剂的用量、初始pH、通氧方式等对降解制浆黑液的影响因素。结果表明：介孔TiO2-SiO2（Ti／Si=100：1）具有较高的催化活性，在催化剂用量为1．5g／L、初始pH=6、连续通氧条件下降解效果最佳，光照反应12h后，黑液CODCr及色度的去除率分别达94．9％和97．6％．     

DRIFT study on cerium-tungsten/titania catalyst for selective catalytic reduction of NOx with NH3

CeO(2)/TiO(2) and CeO(2)-WO(3)/TiO(2) catalysts prepared by impregnation method assisted with ultrasonic energy were investigated on the selective catalytic reduction (SCR) of NO(x) (NO and NO(2)) by NH(3). The catalytic activity of 10% CeO(2)/TiO(2) (CeTi) was greatly enhanced by the addition of 6% WO(3) in the broad temperature range of 200-500 °C, the promotion mechanism was proposed on basis of the results of in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH(3) was introduced into both catalysts preadsorbed with NO + O(2), SCR would not proceed except for the reaction between NO(2) and ammonia. For CeO(2)/TiO(2) catalysts, coordinated NH(3) linked to Lewis acid sites were the main adsorbed ammonia species. When NO + O(2) was introduced, all the ammonia species consumed rapidly, indicating that these species could react with NO(x) effectively. Two different reaction routes, L-H mechanism at low temperature (<200 °C) and E-R mechanism at high temperatures (>200 °C), were presented for SCR reaction over CeO(2)/TiO(2) catalyst. For CeO(2)-WO(3)/TiO(2) catalysts, the Lewis acid sites on Ce(4+) state could be converted to Br?nsted acid sites due to the unsaturated coordination of Ce(n+) and W(n+) ions. When NO + O(2) was introduced, the reaction proceeded more quickly than that on CeO(2)/TiO(2). The reaction route mainly followed E-R mechanism in the temperature range investigated (150-350 °C) over CeO(2)-WO(3)/TiO(2) catalysts. Tungstation was beneficial for the formation of Ce(3+), which would influence the active sites of the catalyst and further change the mechanisms of SCR reaction. In this way, the cooperation of tungstation and the presence of Ce(3+) state resulted in the better activity of CeO(2)-WO(3)/TiO(2) compared to that of CeO(2)/TiO(2).     

TiO_2-SiO_2复合溶胶的制备及性能

以正硅酸乙酯、钛酸丁酯为原料,采用溶胶-凝胶法制备TiO2-SiO2复合溶胶,研究Ti/Si摩尔比和乙醇稀释倍数对复合溶胶密度、固含量、折射率、黏度及凝胶时间的影响.结果表明,随着Ti/Si摩尔比和乙醇稀释倍数的增大,复合溶胶的黏度、固含量、密度和折射率随之减小,凝胶时间延长.SiO2-TiO2复合溶胶的最佳Ti/Si摩尔比为3,EtOH稀释倍数为5.     

TiO2/SiO2的制备与光催化降解甲基橙

为了探讨Ti02晶粒形貌对光催化过程的作用规律,研究吸附法和浸渍法制备的TiO2光催化剂降解甲基橙的过程,并考察制备反应条件对催化剂形貌和活性的影响.通过剖析反应的基本过程后得出,扩散过程与表面反应过程耦合,催化剂活性与甲基橙浓度的相对高低决定反应过程的控制步骤,从而对表观级数产生影响.在催化剂活性的考评中发现,低Ti含量以及小粒径情况下影响光催化的关键因素是晶型,其次为含量、粒径.吸附法制备的光催化剂Ti含量高,粒径小,可控性好,具有比浸渍法制备的材料更好的催化性能.随着水量的增加,吸附相反应技术的优势越来越显著.     

Photocatalytic oxidation and decomposition of acetic acid on titanium silicalite

Transient reaction of adsorbed monolayers of acetic acid was used to characterize the photocatalytic properties of titanium silicalite zeolites (TS-1). The TS-1 zeolites having Si/Ti ratios of 5, 12.5, and 50 are effective catalysts at room temperature for both photocatalytic oxidation (PCO) and decomposition (PCD) of acetic acid. The rates of PCO are higher than the rates of PCD for each catalyst. Acetic acid oxidized photocatalytically in 0.2% O2 to form gas-phase CO2 and CH4 and adsorbed H2O on the TS-1 catalysts, whereas no CH4 formed on Degussa P25 TiO2. Isotope labeling showed that, on both TiO2 and TS-1 catalysts, the alpha-carbon formed CO2 whereas the beta-carbon formed CH4 and CO2. The rates of oxidation of the two carbons have different dependencies on UV intensity. The catalysts with higher Si/Ti ratios adsorbed significantly more acetic acid, and the PCO rates per gram of titanium are highest on the TS-1 catalyst with the lowest Ti content, apparently because a larger fraction of the Ti atoms are surface atoms on this catalyst. During PCD in an inert atmosphere, CO2, CH4, and C2H6 formed on TiO2 and on the catalyst with a Si/Ti ratio of 5, but C2H6 was not detected on the other catalysts. The CO2/CH4 selectivity during PCD increased with increasing Si/Ti ratio. The first step in PCO and PCD on TS-1 catalysts appears to be similar and involves formation of a CH3 radical.     

Impact of interactions between metal oxides to oxidative reactivity of manganese dioxide

Manganese oxides typically exist as mixtures with other metal oxides in soil-water environments; however, information is only available on their redox activity as single oxides. To bridge this gap, we examined three binary oxide mixtures containing MnO(2) and a secondary metal oxide (Al(2)O(3), SiO(2) or TiO(2)). The goal was to understand how these secondary oxides affect the oxidative reactivity of MnO(2). SEM images suggest significant heteroaggregation between Al(2)O(3) and MnO(2) and to a lesser extent between SiO(2)/TiO(2) and MnO(2). Using triclosan and chlorophene as probe compounds, pseudofirst-order kinetic results showed that Al(2)O(3) had the strongest inhibitory effect on MnO(2) reactivity, followed by SiO(2) and then TiO(2). Al(3+) ion or soluble SiO(2) had comparable inhibitory effects as Al(2)O(3) or SiO(2), indicating the dominant inhibitory mechanism was surface complexation/precipitation of Al/Si species on MnO(2) surfaces. TiO(2) inhibited MnO(2) reactivity only when a limited amount of triclosan was present. Due to strong adsorption and slow desorption of triclosan by TiO(2), precursor-complex formation between triclosan and MnO(2) was much slower and likely became the new rate-limiting step (as opposed to electron transfer in all other cases). These mechanisms can also explain the observed adsorption behavior of triclosan by the binary oxide mixtures and single oxides.     

纳米TiO2/SiO2涂布颜料的制备及其喷墨打印性能的研究

用溶胶-凝胶法制备了纳米TiO2/SiO2复合材料,用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和红外光谱(FT-IR)对其结构进行了表征。FT-IR光谱、TEM和SEM谱图分析表明,TiO2与SiO2基质之间存在着Ti—O—Si键,纳米TiO2/SiO2粒子形状基本为球形,粒径大小为20~50 nm。将纳米TiO2/SiO2复合材料用作喷墨打印涂布颜料,能够改善纸页平滑度、吸收性能、提高图像打印和印刷质量。     

用吸附相反应技术制备弱光响应的铈掺杂TiO2复合光催化剂

为拓展多相光催化的实际应用和满足环境治理的严格要求,利用吸附相反应技术设计并制备了弱紫外光响应高效的TiO2 多组分催化剂。借助透射电子显微镜、高分辨率透射电子显微镜和X 射线衍射分析了不同焙烧温度下铈离子掺杂量对催化剂形貌的影响,并结合光致发光光谱和弱光降解甲基橙过程,探索了催化剂结构变化对光生载流子复合率和弱光催化活性的影响。结果表明,当掺杂量较低（小于0.10%）时,铈离子掺入引起TiO2 晶格膨胀,从而引入光生载流子的浅能级捕获中心,提升了催化活性;在较高掺杂量（0.20% 以上）时, 铈离子掺入抑制了TiO2 结晶,催化剂中大量无定形TiO2 严重抑制了其活性;焙烧温度越高,铈离子掺杂量对催化剂结构和活性的影响越显著;降解高浓度甲基橙时,催化性能最好的催化剂的活性是商用P 25 的2 倍多。     

锦纶织物的SiO2/TiO2复合水溶胶超亲水整理

以钛酸四丁酯和正硅酸乙酯为前驱体,水为溶剂制备SiO2/TiO2复合水溶胶,并以浸渍法对锦纶织物进行超亲水抗静电整理.以接触角、感应电压和半衰期为评价依据,研究织物经SiO2/TiO2复合水溶胶整理后的亲水抗静电性能.试验表明,随着复合水溶胶中Si/(Si+ Ti)的比例增大,整理织物的亲水性和抗静电性均呈现先增强后减弱的趋势;当Si/(Si+Ti)比例为0.89和0.91时,经复合水溶胶整理的锦纶织物呈现超亲水性.     

ZrO2-modified mesoporous nanocrystalline TiO2-xNx as efficient visible light photocatalysts

Mesoporous nanocrystalline TiO2-xNx and TiO2-xNx/ZrO2 visible-light photocatalysts have been prepared by a sol-gel method. The photocatalysts were characterized by XRD, N2 adsorption-desorption, TEM, XPS, UV/Vis, and IR spectroscopy. The photocatalytic activity of the samples was evaluated by the decomposition of ethylene in air under visible light (lambda > 450 nm) illumination. Results revealed that nitrogen was doped into the lattice of TiO2 by the thermal treatment of NH3-adsorbed TiO2 hydrous gels, converting the TiO2 into a visible-light responsive catalyst. The introduction of ZrO2 into TiO2-xNx considerably inhibits the undesirable crystal growth during calcination. Consequently, the ZrO2-modified TiO2-xNx displays higher porosity, higher specific surface area, and an improved thermal stability over the corresponding unmodified TiO2-xNx samples.     

固体酸SO42-/TiO2-ZrO2催化制备乙酰丙酸的研究

以蔗糖为原料,固体SO42-/TiO2-ZrO2为催化剂,以水为溶剂制备乙酰丙酸。研究了浸渍用硫酸浓度和催化剂焙烧温度对催化剂活性的影响,并探讨了不同反应条件及催化剂重复使用次数对乙酰丙酸得率的影响。用XRD和NH3-TPD对使用前后的催化剂的结构和酸性进行了表征。实验结果表明,1.0 mol/L硫酸浓度浸渍,550℃焙烧3 h的催化剂活性较强。在催化剂投加量为1.0 g,反应温度为190℃的条件下反应1 h,乙酰丙酸摩尔得率高达50.0%。回收的SO42-/TiO2-ZrO2催化剂焙烧后在多次重复使用过程中仍然表现出较好的催化活性。     

Influence of preparation method on morphology and photocatalysis activity of nanostructured TiO2

Supported TiO2 photocatalysts on aerosol silica were prepared by adsorption phase reaction technique (APRT) and impregnation method (IMP) under different water concentrations. Energy dispersive X-ray microanalysis indicated that Ti concentration in samples prepared by both methods increased with the content of water rising. There was a sharp increase in Ti content curve of APRT samples, while Ti concentration of IMP samples changed slowly. The grain size of TiO2 by APRT was below 6 nm and TiO2 particles dispersed uniformly on surface of silica. But the size of TiO2 by IMP was larger than 20 nm and the number of large particles increased rapidly when water concentration increased. The photocatalysis activity of as-prepared catalysts was characterized by methyl-orange photodegradation. The results showed that APRT photocatalysts had higher photocatalysis activity than IMP photocatalysts. Ti concentration and TiO2 crystalline form were two factors which affected photocatalysis activity the most. The grain size of TiO2 had little influence on photocatalysis activity, which might be counteracted by the decrease of anastase TiO2.     

Alkali metal poisoning of a CeO2-WO3 catalyst used in the selective catalytic reduction of NOx with NH3: an experimental and theoretical study

The alkali metal-induced deactivation of a novel CeO(2)-WO(3) (CeW) catalyst used for selective catalytic reduction (SCR) was investigated. The CeW catalyst could resist greater amounts of alkali metals than V(2)O(5)-WO(3)/TiO(2). At the same molar concentration, the K-poisoned catalyst exhibited a greater loss in activity compared with the Na-poisoned catalyst below 200 °C. A combination of experimental and theoretical methods, including NH(3)-TPD, DRIFTS, H(2)-TPR, and density functional theory (DFT) calculations, were used to elucidate the mechanism of the alkali metal deactivation of the CeW catalyst in SCR reaction. Experiments results indicated that decreases in the reduction activity and the quantity of Br?nsted acid sites rather than the acid strength were responsible for the catalyst deactivation. The DFT calculations revealed that Na and K could easily adsorb on the CeW (110) surface and that the surface oxygen could migrate to cover the active tungsten, and then inhibit the SCR of NO(x) with ammonia. Hot water washing is a convenient and effective method to regenerate alkali metal-poisoned CeW catalysts, and the catalytic activity could be recovered 90% of the fresh catalyst.     

Propene poisoning on three typical Fe-zeolites for SCR of NOχ with NH₃: from mechanism study to coating modified architecture

Application of Fe-zeolites for urea-SCR of NO(x) in diesel engine is limited by catalyst deactivation with hydrocarbons (HCs). In this work, a series of Fe-zeolite catalysts (Fe-MOR, Fe-ZSM-5, and Fe-BEA) was prepared by ion exchange method, and their catalytic activity with or without propene for selective catalytic reduction of NO(x) with ammonia (NH(3)-SCR) was investigated. Results showed that these Fe-zeolites were relatively active without propene in the test temperature range (150-550 °C); however, all of the catalytic activity was suppressed in the presence of propene. Fe-MOR kept relatively higher activity with almost 80% NO(x) conversion even after propene coking at 350 °C, and 38% for Fe-BEA and 24% for Fe-ZSM-5 at 350 °C, respectively. It was found that the pore structures of Fe-zeolite catalysts were one of the main factors for coke formation. As compared to ZSM-5 and HBEA, MOR zeolite has a one-dimensional structure for propene diffusion, relatively lower acidity, and is not susceptible to deactivation. Nitrogenated organic compounds (e.g., isocyanate) were observed on the Fe-zeolite catalyst surface. The site blockage was mainly on Fe(3+) sites, on which NO was activated and oxidized. Furthermore, a novel fully formulated Fe-BEA monolith catalyst coating modified with MOR was designed and tested, the deactivation due to propene poisoning was clearly reduced, and the NO(x) conversion reached 90% after 700 ppm C(3)H(6) exposure at 500 °C.     

固体酸SO4^2-／TiO2-ZrO2催化制备乙酰丙酸的研究

以蔗糖为原料,固体SO4^2＋／TiO2．ZrO2为催化剂,以水为溶剂制备乙酰丙酸。研究了浸渍用硫酸浓度和催化剂焙烧温度对催化制活性的影响,并探讨了不同反应条件及催化剂重复使用次数对乙酰丙酸得率的影响。用XRD和NH3-TPD对使用前后的催化剂的结构和酸性进行了表征。实验结果表明,1．0mol／L硫酸浓度浸渍,550℃焙烧3h的催化剂活性较强。在催化剂投加量为1．0g,反应温度为190℃的条下反应1h,乙酰丙酸摩尔得率高达50．0％。回收的SO4^2-TiO2-ZrO2催化剂焙烧后在多次重复使用过程中仍然表现出较好的催化活性。     

Development of an E-H2O2/TiO2 photoelectrocatalytic oxidation system for water and wastewater treatment

In this study, an innovative E-H2O2/TiO2 (E-H2O2 = electrogenerated hydrogen peroxide) photoelectrocatalytic (PEC) oxidation system was successfully developed for water and wastewater treatment. A TiO2/Ti mesh electrode was applied in this photoreactor as the anode to conduct PEC oxidation, and a reticulated vitreous carbon (RVC) electrode was used as the cathode to electrogenerate hydrogen peroxide simultaneously. The TiO2/Ti mesh electrode was prepared with a modified anodic oxidation process in a quadrielectrolyte (H2SO4-H3PO4-H2O2-HF) solution. The crystal structure, surface morphology, and film thickness of the TiO2/Ti mesh electrode were characterized by X-ray diffraction and scanning electron microscopy. The analytical results showed that a honeycomb-type anatase film with a thickness of 5 microm was formed. Photocatalytic oxidation (PC) and PEC oxidation of 2,4,6-trichlorophenol (TCP) in an aqueous solution were performed under various experimental conditions. Experimental results showed that the TiO2/Ti electrode, anodized in the H2SO4-H3PO4-H2O2-HF solution, had higher photocatalytic activity than the TiO2/Ti electrode anodized in the H2SO4 solution. It was found that the maximum applied potential would be around 2.5 V, corresponding to an optimum applied current density of 50 microA cm(-2) under UV-A illumination. The experiments confirmed that the E-H2O2 on the RVC electrode can significantly enhance the PEC oxidation of TCP in aqueous solution. The rate of TCP degradation in such an E-H2O2-assisted TiO2 PEC reaction was 5.0 times that of the TiO2 PC reaction and 2.3 times that of the TiO2 PEC reaction. The variation of pH during the E-H2O2-assisted TiO2 PEC reaction, affected by individual reactions, was also investigated. It was found that pH was well maintained during the TCP degradation in such an E-H2O2/TiO2 reaction system. This is beneficial to TCP degradation in an aqueous solution.     

混凝-光催化联用技术处理制浆中段废水的研究——TiO2-SiO2光催化剂的制备

以钛酸丁酯、正硅酸乙酯、无水乙醇等为原料,采用Sol-Gel法制备TiO2-SiO2光催化剂,通过单因素实验得到最佳制备工艺条件为:n(钛酸丁酯)∶n(正硅酸乙酯)为2.33∶1,煅烧温度为600℃,煅烧时间为3 h,反应溶液pH值为3。当进水CODCr为379.5 mg/L,TiO2-SiO2光催化剂的投加量为0.5 g/L,紫外光照时间为3 h时,出水CODCr为67.8 mg/L。TiO2-SiO2光催化剂颗粒大小为100～500 nm,具有较高的催化活性和稳定性,可以多次重复使用。对比实验表明,TiO2-SiO2处理制浆中段废水的效率比TiO2高。     

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.     

Photooxidation of atmospheric alcohols on laboratory proxies for mineral dust

We have used a novel photochemical Knudsen cell reactor to investigate the uptake and phototransformation of some atmospherically important trace organics on TiO(2) and TiO(2)-SiO(2) mixed films. Illumination of TiO(2) films led to an enhanced uptake of isopropanol and n-propanol and the concurrent production of gas-phase acetone and propionaldehyde, respectively, with high efficiency. Acetone production from isopropanol on illuminated TiO(2) films displayed a significant enhancement in the presence of cosorbed AgNO(3) or KNO(3). Uptake of cyclohexene by TiO(2) films required the presence of both nitrate anion and light. The wavelength and substrate (TiO(2) vs SiO(2)) dependence of the nitrate-induced enhancement in uptake indicates that it was not caused by direct photolysis of nitrate anion. We propose a 2-fold role for nitrate anion in the present experiments: first, as an electron trapping agent that activates the TiO(2) surface toward photooxidation; second, as suggested by our results for cyclohexene, as a source of reactive nitrate radical at the TiO(2) surface. These observations suggest that mineral dust containing photoactive components may catalyze the transformation of photochemically inactive organic compounds into species that absorb in the actinic region.     

二氧化硅接枝杨梅单宁用于水体中Cu2+的吸附去除

采用微乳法制备了氨基化二氧化硅(NH2-SiO2),并通过Mannich反应将杨梅单宁(bayberry tannin)接枝到氨基化二氧化硅表面制备了一种新型的吸附剂,即二氧化硅接枝杨梅单宁(SiO2-BT)。对SiO2-BT吸附剂进行了红外光谱(FTIR)和X射线光电子能谱(XPS)分析,并系统的研究了该吸附剂对水溶液中Cu2+的吸附特性,包括pH的影响?吸附动力学?吸附等温线?共存离子的影响和解吸性能。结果表明:SiO2-BT能有效去除水溶液中的Cu2+,30℃时平衡吸附容量达到28.1 mg/g,且随着温度的升高吸附容量增大。SiO2-BT对Cu2+的吸附动力学符合拟一级速率方程,吸附平衡符合Langmuir方程。此外,SiO2-BT对Cu2+的吸附具有吸附速率快?吸附容量大且易于解吸的特点,可用于水体中Cu2+的吸附去除。