TiO_2/Fe-杭锦2~#土催化剂光催化降解废水中乙酸的研究

首先采用离子交换法制得Fe-杭锦2#土,以其为载体使用溶胶-凝胶法制备了TiO_2/Fe-杭锦2#土负载型光催化剂,并通过X射线粉末衍射(XRD)、氮气吸附脱附(N2-BET)、固体紫外可见漫反射(UV-Vis DRS)、X射线光电能谱(XPS)和扫描电子显微镜(SEM)分析等对催化剂进行了表征.以光催化降解乙酸为探针反应,考察了Ti的负载量、光源、光照时间、催化剂用量和反应温度等反应条件对催化剂催化性能的影响.实验结果表明,对于浓度为100 mg·L-1的乙酸溶液,选用氧化钛负载量为20%的光催化剂、300 W汞灯为光源、反应温度为50℃、反应时间为6 h、催化剂用量为50 g·L~(-1)时,对乙酸的光催化降解效果相对最优,降解率达到78.30%.     

Pd/MCM-41催化剂的制备及其光催化苯羟基化的研究

以酸化高岭土为原料,采用水热法在碱性介质中制得MCM-41分子筛.以此分子筛为载体制备了负载型Pd催化剂并对载体和催化剂进行了氮气吸附脱附、X射线粉末衍射和透射电镜等表征.研究其在光催化苯羟基化反应中的催化性能,考察了Pd的负载量、氧化剂的用量、不同光源及光照时间等反应条件对催化剂催化性能的影响,以及催化剂的回收重复利用率.结果表明以H_2O_2为氧化剂时,在汞灯照射下,Pd/MCM-41催化剂对苯羟基化反应表现出了良好的催化性能.     

介孔TiO2的水热法制备及其光催化性能

以二钛酸钾(K2Ti2O5)经离子交换得到的无定形水合二钛酸(H2Ti2O5·xH2O)为原料,与葡萄糖溶液在220℃下进行水热反应,再在空气中520℃焙烧,制备出介孔TiO2.用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附、透射电子显微镜(TEM)等技术对样品进行了表征.结果表明,该介孔TiO2具有微米级棒状或针状形貌,晶粒大小为12.3 nm,比表面积为106 m2·g-1,孔容为0.31 cm3·g-1,孔径为8.06 nm,焙烧处理后晶型仍是锐钛矿相.水热生成的碳抑制了晶粒的团聚生长和晶型的转变,提高了介孔TiO2的热稳定性.甲基橙降解实验评价了介孔TiO2的光催化性能,结果发现其活性与商用TiO2催化剂P25相当,而其较大的粒径更容易回收再利用.以碘化钾为探针反应,表明介孔TiO2的光催化机制以光生空穴氧化为主.     

介孔TiO2的水热法制备及其光催化性能

以二钛酸钾(K2Ti2O5)经离子交换得到的无定形水合二钛酸(H2Ti2O5·xH2O)为原料, 与葡萄糖溶液在220 ℃下进行水热反应, 再在空气中520 ℃焙烧, 制备出介孔TiO2. 用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附、透射电子显微镜(TEM)等技术对样品进行了表征. 结果表明, 该介孔TiO2具有微米级棒状或针状形貌, 晶粒大小为12.3 nm, 比表面积为106 m2·g-1, 孔容为0.31 cm3·g-1, 孔径为8.06 nm, 焙烧处理后晶型仍是锐钛矿相. 水热生成的碳抑制了晶粒的团聚生长和晶型的转变, 提高了介孔TiO2的热稳定性. 甲基橙降解实验评价了介孔TiO2的光催化性能, 结果发现其活性与商用TiO2催化剂P25相当, 而其较大的粒径更容易回收再利用. 以碘化钾为探针反应, 表明介孔TiO2的光催化机制以光生空穴氧化为主.     

Cu/Ni助催化剂对TiO2光催化制取苯酚性能的影响

以TiO₂纳米粒子为主催化剂,采用"浸渍-还原法"构筑了铜、镍共负载的二氧化钛基光催化系统。以苯为起始原料,H₂O₂为氧化剂,研究了Cu/Ni助催化剂对TiO₂可见光催化制取苯酚性能的影响并对Cu/Ni助催化剂的作用机制进行了探讨。结果表明,在可见光照射下,纯TiO₂纳米粒子对苯氧化制取苯酚反应没有催化活性。铜、镍的引入可以明显地增强Ti₀₂可见光催化制取苯酚的活性。当使用负载有铜、镍的TiO₂作为催化剂时,苯酚的产率可达到18%。结果还表明Cu、Ni之间存在着很强的协同作用。在该协同作用下,Cu、Ni共负载的TiO₂纳米粒子表现出了较单一金属负载的TiO₂纳米粒子高得多的光催化活性。     

Cu/Ni助催化剂对TiO2光催化制取苯酚性能的影响

以TiO₂纳米粒子为主催化剂, 采用“浸渍-还原法”构筑了铜、镍共负载的二氧化钛基光催化系统。以苯为起始原料, H₂O₂为氧化剂, 研究了Cu/Ni助催化剂对TiO₂可见光催化制取苯酚性能的影响并对Cu/Ni助催化剂的作用机制进行了探讨。结果表明, 在可见光照射下, 纯TiO₂纳米粒子对苯氧化制取苯酚反应没有催化活性。铜、镍的引入可以明显地增强TiO₂可见光催化制取苯酚的活性。当使用负载有铜、镍的TiO₂作为催化剂时, 苯酚的产率可达到18%。结果还表明Cu、Ni之间存在着很强的协同作用。在该协同作用下, Cu、Ni共负载的TiO₂纳米粒子表现出了较单一金属负载的TiO₂纳米粒子高得多的光催化活性。     

高热稳定性有序介孔TiO_2/活性炭制备及其孔-孔协同光催化性能

以十六烷基三甲基溴化铵(CTAB)表面活性剂和钛酸四丁酯分别为造孔模板和钛源,通过超声辅助溶剂挥发自组装技术制备有序介孔氧化钛(ordered mesoporous Ti O2,OMPT)及其活性炭负载体(ordered mesoporous Ti O2/AC,OMPTA).为探讨OMPTA结构与性能之间的关系,采用超声辅助溶胶-凝胶技术合成了无孔氧化钛/活性炭(nonporous Ti O2/AC,NPTA)负载体,利用热重-差热(TG-DTA)、X射线衍射(XRD)、氮气吸附-解吸、透射电子显微镜(TEM)和紫外漫反射(DRS)等手段对制备材料结构进行表征.以酸性红B(acid red B,ARB)的光催化降解为探针实验,评价OMPTA的光催化性能和使用寿命,提出了孔-孔协同光催化扩增机制,并探讨了催化条件(染料浓度、催化剂浓度和溶液p H)对协同扩增效果的影响.结果表明:相对于纯OMPT,OMPTA具有晶粒生长的高活化能、较小的粒径尺寸和对有序介孔结构的高热稳定性,这归功于活性炭的吸附力和非晶相层对晶粒生长的阻碍作用.由于孔-孔协同光催化扩增效应,导致OMPTA在NPTA、OMPT-AC、OMPT、P25和NPT中具有更高的催化活性.热处理温度强烈影响OMPTA的光催化活性,其中OMPTA-500具有最高的光催化活性,这归功于其具备完善的结晶性、相对高浓度的羟基和Ti3+离子.同时,OMPTA-500在重复使用过程中也具有很高的光催化性能.当使用OMPTA-500为催化剂对ARB降解时,最佳的催化条件为催化剂浓度1 g/L,ARB浓度15 mg/L,p H 5.     

Cu掺杂对介孔VOx-TiO2催化苯羟基化制苯酚的影响

将Cu作为第二金属,制备了不同Cu掺杂量的和不同温度下焙烧的双金属改性的Cu/VOx-TiO2复合催化剂,并用于液相苯直接羟基化制苯酚反应中.固定钒的含量为4.3%,合成了一系列不同Cu掺杂量(w=0.29%~2.5%)的催化剂,并在不同的温度下(350~650°C)进行了焙烧.利用X射线衍射、N2吸附-脱附、扫描电镜、透射电镜、H2程序升温还原以及X射线光电子能谱对催化剂进行了表征.结果表明,加入Cu后催化剂仍保持有序的介孔结构,并且有效地促进了VOx物种在载体TiO2上的分散和VOx物种的还原,同时提高了催化剂的热稳定性,其中Cu以+2价的形态存在于催化剂中.另外,考察了催化剂用量,反应温度等对苯羟基化反应性能的影响.     

几种载体载Ni催化剂上苯直接羟基化制备苯酚的研究

本文利用浸渍法制备了一系列不同载体的镍基催化剂,并将其用于苯的羟基化反应.用等离子原子直读光谱、粉末X射线衍射分析、比表面测试等对所制备的催化剂进行了表征.发现在所制备的催化剂中,以γ-Al2O3为载体的Ni1.7/γ-Al2O3 催化剂在苯的羟基化反应中具有相对较好的催化活性和选择性,而在Ni/TiO2和Ni/NaX上,则苯酚的深度氧化严重.     

纳米TiO2-SnO2介孔材料的制备及其对含氰废水的光催化降解性能

以TiCl4和SnCl4为原料,采用直接水解常压液相反应合成出了纳米TiO2-SnO2复合介孔材料.利用XRD和TEM及漫反射谱等对样品进行了表征,并研究了纳米TiO2-SnO2复合介孔材料对含氰废水的光催化降解性能.结果表明,纳米TiO2与SnO2复合后,导致材料的光谱响应拓宽;此种催化剂在日光灯下比在紫外灯下对废水中CN-的降解效果要好.     

苯直接一步氧化合成苯酚

苯直接一步氧化合成苯酚是开辟苯酚合成路线具有挑战性的热点课题之一.近年来研究和开发了以N2O、H2O2和O23种不同氧化剂体系为核心和主流的苯氧化合成苯酚路线.本文详细综述了目前3种不同氧化体系的研究进展和趋势,分析了各种合成路线的特点和工业应用前景.以N2O为氧化剂合成苯酚路线,技术趋于成熟,但N2O来源受限而影响其经济性和推广应用;以H2O2为氧化剂合成苯酚路线,是环境友好过程,有开发潜力,但技术还很不成熟,而且也因H2O2价格昂贵带来了经济成本问题;以O2为氧化剂、氢气为还原剂体系合成苯酚路线,是环境清洁可持续发展制备路线,具有很好的开发潜力,此外无机膜催化合成苯酚路线也更具吸引力.     

纳米孔碳负载Fe3O4催化剂上苯直接羟基化制苯酚

Fe3O4/CMK-3 was prepared by impregnation and used as a catalyst for the direct hydroxylation of benzene to phenol with hydro-gen peroxide. The iron species in the prepared catalyst was Fe3O4 because of the partial reduction of iron(III) to iron(II) on the surface of CMK-3. The high catalytic activity of the catalyst arises from the formation of Fe3O4 on the surface of CMK-3 and the high selectivity for phenol is attributed to the consumption of excess hydroxyl radicals by CMK-3. The effect of temperature,re...     

可见光下改性的纳米孔二氧化硅(LUS-1)光催化苯直接羟基化合成苯酚(英文)

Fe-g-C3N4-LUS-1 was prepared by the thermal decomposition of dicyandiamide inside the pores of LUS-1 under an inert atmosphere.It was used as a photocatalyst for the hydroxylation of benzene to phenol in sunlight.The catalysts were characterized by Fourier transform infrared spectroscopy,N2 adsorption-desorption,X-ray diffraction,and scanning electron microscopy.In Fe-g-C3N4-LUS-1,a single layer of graphitic carbon nitride(g-C3N4) was formed on the surface of LUS-1.The photocatalytic activity of the iron containing g-C3N4 based catalysts was investigated,and the catalytic activity was remarkably enhanced when the reaction condition was changed from dark to sunlight.The best result was obtained with 20%Fe-g-C3N4-LUS-1 in sunlight.     

Pyridine-H5PMo10V2O40 hybrid catalysts for liquid-phase hydroxylation of benzene to phenol with molecular oxygen

Pyridine(Py)-modified Keggin-type vanadium-substituted heteropoly acids (Py _n PMo₁₀V₂O₄₀, n=1 to 5) were prepared by a precipitation method as organic/inorganic hybrid catalysts for direct hydroxylation of benzene to phenol in a pressured batch reactor and their structures were detected by FT-IR. Among various catalysts, Py₃PMo₁₀V₂O₄₀ exhibits the highest catalytic activity (yield of phenol, 11.5%), without observing the formation of catechol, hydroquinone and benzoquinone in the reaction with 80 vol% aqueous acetic acid, molecular oxygen and ascorbic acid used as the solvent, oxidant and reducing reagent, respectively. Influences of reaction temperature, reaction time, oxygen pressure, amount of ascorbic acid and catalyst on yield of phenol were investigated to obtain the optimal reaction conditions for phenol formation. Pyridine can greatly promote the catalytic activity of the Py-free catalyst (H₅PMo₁₀V₂O₄₀), mostly because the organic π electrons in the hybrid catalyst may extend their conjugation to the inorganic framework of heteropoly acid and dramatically modify the redox properties, at the same time, pyridine adsorbed on heteropoly acids can promote the effect of “pseudo-liquid phase”, thus accounting for the enhancement of phenol yield. Supported by the National Natural Science Foundation of China (Grant Nos. 20476046 and 20776069) and the “Qinglan” Project of Jiangsu Province for Young Researchers     

Photocatalytic decomposition of phenol over a novel kind of loaded photocatalyst of TiO2/activated carbon/silicon rubber film

A novel kind of loaded photocatalyst TiO₂/activated carbon/silicon rubber film that can photodegrade organic pollutants in dilute aqueous solution effectively is reported in this paper. Activated carbon is used as adsorbant and silicon rubber film as support. Compared with powdered TiO₂ catalyst this preparation procedure leads to a highly active and easily separable immobilized hybrid catalyst composed of 90 wt.% TiO₂ and 10 wt.% activated carbon in the photodegradation of phenol under UV irradiation. This revised version was published online in June 2006 with corrections to the Cover Date.     

以双氧水或氧气为氧化剂的苯羟基化制苯酚的催化反应机理

C—H键的活化是有机合成中最重要的科学问题之一。以环境友好的双氧水或者氧气为氧化剂的苯羟基化制备苯酚的反应,不仅涉及苯环的$\text C_{\text s \text p^{2}}— \text H $活化这一基础问题,还涉及双氧水或氧气的活化,以及双氧水的分解、苯酚的深度氧化等副反应,几十年来一直是有机合成领域的一大挑战。更重要的是,在大力倡导绿色化工的背景之下,该反应愈加受到工业界的青睐,期望它能够取代异丙苯法成为苯酚生产的绿色新工艺。本文以苯羟基化制备苯酚的催化反应机理为线索,综述近年来金属基催化剂以及处于起步阶段的非金属催化剂的最新研究进展,着重从自由基机理和非自由基机理两个方面详细归纳分析催化剂的组成结构与其反应的活性和选择性之间的构效关系,并就该领域未来的发展动向及需要关注的问题给出了展望和建议,期望有助于深化对催化机理的认识,并为进一步研发更高活性和稳定性的苯羟基化催化剂提供有益借鉴。      

Effect of ZSM-11 crystallinity on its catalytic performance in benzene to phenol oxidation with nitrous oxide

Evolution of ZSM-11 zeolite crystal and pore structure has been studied at 150°C depending on the synthesis time. The amorphous gel was shown to be catalytically inert over the whole induction period, which precedes the crystallization process. The concentration of active sites and the catalytic activity in the oxidation of benzene to phenol is related to the zeolite structure formation and the increasing degree of crystallinity.     

Organic–inorganic hybrid of anchored dicationic ionic liquid on Al‐MCM‐41‐phosphovanadomolybdate toward selective oxidation of benzene to phenol

A phosphovanadomolybdate hybridized with an anchored dicationic ionic liquid on Al‐MCM‐41 was prepared through the anion exchange and characterized by ¹H and ¹³C NMR, FTIR, UV–Vis, XRD, XPS, TGA, TEM, FESEM, ICP‐OES and BET techniques. The obtained data demonstrated that the composite is a porous material with the high surface area and also having a large pore volume which are 405 m² g^?1 and 0.616 cm³ g^?1 respectively. The prepared composite has shown an acceptable catalytic activity for converting benzene selectively to phenol with hydrogen peroxide as eco‐friendly oxidant. Under the optimized reaction conditions, the hybrid catalyst resulted in phenol yield of 14.8% with 100% selectivity and a TOF value of 20.0 h^?1. The catalyst also revealed a desired recovery and reusability. The efficient performance of the composite is related to the textural and polyoxometalate properties.     

Pyridine-H_5PMo_(10)V_2O_(40) hybrid catalysts for liquid-phase hydroxylation of benzene to phenol with molecular oxygen

Pyridine(Py)-modified Keggin-type vanadium-substituted heteropoly acids(PynPMo10V2O40,n=1 to 5) were prepared by a precipitation method as organic/inorganic hybrid catalysts for direct hydroxylation of benzene to phenol in a pressured batch reactor and their structures were detected by FT-IR.Among various catalysts,Py3PMo10V2O40 exhibits the highest catalytic activity(yield of phenol,11.5%),without observing the formation of catechol,hydroquinone and benzoquinone in the reaction with 80 vol% aqueous acetic ...