表面酸性对Ni/SiO_2-Al_2O_3催化剂催化1,4-丁炔二醇高压加氢性能的影响

通过浸渍法分别在Al(OH)_3和Al_2O_3中引入SiO_2,经焙烧后制备具有不同表面酸性质的SiO_2-Al_2O_3载体,以上述SiO_2-Al_2O_3及Al_2O_3为载体,采用等体积浸渍法制备Ni负载量为15%的Ni/SiO_2-Al_2O_3催化剂(分别为Ni/SA-1和Ni/SA-2)与Ni/Al_2O_3.采用N2物理吸附、Py-FTIR、NH3-TPD、XRD、H2-TPR和H2-TPD手段对催化剂进行表征,考察了表面酸性质对催化剂催化1,4-丁炔二醇高压加氢性能的影响.结果表明,SiO_2引入方式会影响Ni/Al_2O_3催化剂表面酸性质及活性组分Ni在载体表面的分散行为.在Al(OH)3中引入SiO_2时,Ni/SA-1催化剂不仅活性组分具有高分散度,而且表面具有丰富的L酸位点,L酸位点与Ni活性中心协同作用有效提高了催化剂的高压加氢性能.而在Al_2O_3中直接引入SiO_2时,SiO_2覆盖了Al_2O_3表面的L酸位点,催化剂活性组分分散度较低,表现出低的加氢活性.     

基于Cu-Fc配位聚合物衍生的Pt-Cu/CuxFeyO@C催化1,4-丁炔二醇加氢性能研究

1,4-丁烯二醇是精细化工领域的重要中间体,有着广泛的应用.采用异丙醇还原氯铂酸制备Pt纳米颗粒,并通过浸渍法将其负载于1,1’-二茂铁二羧酸(Fc)与CuCl_2·2H_2O水热法合成的Cu-Fc配位聚合物,干燥焙烧后制备得到Pt-Cu/Cu_xFe_yO@C催化剂,利用XRD、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重分析仪(TG)、N_2吸附脱附仪等表征手段对所制备的催化剂进行表征,对比了催化剂焙烧前后加氢效果,并考察了催化剂与底物的物质的量之比对1,4-丁炔二醇加氢制备1,4-丁烯二醇的影响.结果表明,以焙烧后制备的5%Pt-Cu/Cu_xFe_yO@C催化剂,在n催化剂∶n原料=1∶2 000,温度为120℃,H_2压力为4 MPa,反应时间为30 min的条件下,加氢反应的转化率为100%,生成1,4-丁烯二醇选择性为96.1%.     

不同金属负载对Cr/Al2O3-TiO2催化剂结构及氧化NO性能的影响

采用溶胶-凝胶法和浸渍法制备Cr/Al_2O_3-TiO_2催化剂,在考察不同Cr负载量的基础上,研究不同金属负载与焙烧温度对Cr/Al_2O_3-TiO_2催化剂结构与性能影响。程序升温氧化(TPO)结果表明,当Cr负载量为10%(w/w)时具有较好的催化活性;不同金属负载Cr/Al_2O_3-TiO_2时,负载Co及在焙烧温度为550℃时催化剂具有较好的活性。通过程序升温还原(H_2-TPR)表征发现,Co的负载使催化剂的低温氧化还原能力逐渐提高,表明Co-Cr具有较好的协同催化作用。X射线光电子能谱(XPS)表征表明,Co增加了Cr~(6+)和表面吸附氧(O_β)含量,随着焙烧温度的升高(450～550℃),晶格氧不断向催化剂表面流动,表面化学吸附氧O_β比例逐渐增加,导致催化活性不断升高,说明Cr~(6+)和O_β是催化氧化NO的重要活性物种。     

水热改性对铝基载体孔结构及异丁烷脱氢性能的影响

分别以两种水热介质对γ-Al_2O_3载体进行水热改性,并将改性后的载体负载CrO_x后应用于异丁烷催化脱氢,考察了水热温度对载体物化性质以及水热改性对催化脱氢性能的影响。通过XRD、N_2吸附-脱附及H_2-TPR对载体结构进行表征。结果表明,水热改性使γ-Al_2O_3发生再水合过程,焙烧后,结晶度变好,活性组分与载体的相互作用增加,CrO_x/Al_2O_3催化剂的异丁烷脱氢性能得到改善。以盐溶液水热改性载体,140℃处理4h,CrO_x/Al_2O_3催化剂表现出较好的异丁烷脱氢性能,10h内异丁烷脱氢平均转化率为43.04%,平均选择性86.34%,失活参数13.7%。     

山西芮城永乐宫元代天花、藻井研究*

采用不同方法制备了一系列Ni/Al_2O_3催化剂,在无NH_3、无碱条件下对其己二腈催化加氢制1,6-己二胺的反应性能进行研究.通过XRD、 BET、 TEM、 XPS及程序升温实验等结果表明,采用沉淀剂有利于细小Ni纳米颗粒在催化剂介孔内的分散。然而较强的Ni与载体间相互作用不利于氢气的吸附活化,还原处理后催化剂中仍存在较高含量的氧化态Ni物种.采用浸渍法制备的Ni/Al_2O_3-I催化剂中颗粒的平均尺寸为18.5 nm, Ni颗粒暴露在载体表面,生成较高含量的还原态Ni0物种及有利于反应物吸附的中等强度酸性位点.该Ni/Al_2O_3-I催化剂表现出优良的低温活性,在60℃时,己二腈转化频率(TOF)可达39.7 h~(-1);80℃时转化率为100%, 1,6-己二胺收率可达73.0%.然而,由于Ni/Al_2O_3-I催化剂中Ni与Al_2O_3间相互作用较弱,经过3次循环性能测试,催化剂活性明显下降.进一步以少量Cu元素修饰低含量Ni/Al_2O_3-I催化剂, Cu助剂的引入有效改善了Ni纳米颗粒的分散性,并与部分Ni组分形成双金属纳米颗粒.Ni_(15)Cu_3/Al_2O_3催化剂经5次循环反应后无明显失活现象,催化剂的形貌及化学结构亦无明显变化, Cu的引入在保持Ni基催化剂低温活性的同时有效提升了催化剂的循环稳定性,催化剂的TOF为52.1 h~(-1).     

Ni-M/SiO2催化1,4-丁炔二醇加氢的金属助剂效应

以SiO₂气凝胶为载体,采用等体积浸渍法制备了Ni/SiO₂及不同金属助剂改性的Ni-M/SiO₂（M=Fe、Co、Cu）催化剂,利用ICP、BET、XRD、H₂-TPR、H₂-TPD等手段对催化剂进行了表征,考察了不同第二金属对催化剂结构与1,4-丁炔二醇加氢性能的影响.结果表明,第二金属与Ni物种具有不同程度的双金属协同效应,其中Cu的加入不仅能够提高Ni活性物种的分散度,而且Ni-Cu双金属间的相互作用改善了NiO物种的还原性能及氢活化能力,有利于氢和1,4-丁炔二醇在活性位点的快速转化.在反应温度50℃,氢压1 MPa,反应时间3 h的加氢评价条件下,15Ni5Cu/SiO₂催化剂不仅可以实现1,4-丁炔二醇的完全转化,而且能够有效降低难分离副产物2-羟基四氢呋喃的含量,具有最优的加氢活性和对1,4-丁烯二醇的选择性.     

Mn-Fe/Al2O3催化剂的低温脱硝性能研究

以Al_2O_3为载体,Fe、Mn为活性组分,采用浸渍法制备了Mn-Fe/Al_2O_3催化剂,研究了Mn-Fe/Al_2O_3催化剂的低温脱硝性能.实验结果表明,Fe负载量为7%时,7Fe/Al_2O_3催化剂显示出较佳的低温脱硝性能;添加Mn能明显改变7Fe/Al_2O_3催化剂低温脱硝性能,其中当Mn/Fe质量比为11∶7时,11Mn7Fe/Al_2O_3催化剂获得最佳低温脱硝效率.对催化剂的表征结果表明,比表面积和孔径的大小不是决定催化剂性能高低的主要因素;Mn O2和Fe2O3在x Mn7Fe/Al_2O_3催化剂中具有较强的相互作用,影响活性组分微观晶体结构,改善活性组分分散程度,从而提高了催化剂的低温脱硝性能;Fe的添加使催化剂表面酸性位点数目增加,从而提高7Fe/Al_2O_3催化剂的低温脱硝效率.添加Mn不仅增多了11Mn7Fe/Al_2O_3催化剂表面酸性位点数目增加,而且使催化剂表面出现新的中强性酸位点,使其低温脱硝效率进一步提高;经过详细分析,结果表明表面吸附氧Oβ、Mn4+和Fe3+的含量较高是11Mn7Fe/Al_2O_3催化剂脱硝活性较高的主要原因.     

助剂SiO_2对CoMo/Al2O3-SiO_2催化剂结构的影响研究

采用原位红外光谱、拉曼光谱、紫外光谱和H2-TPR表征技术对CoMo/Al_2O_3-SiO_2催化剂进行了表征。结果表明,增加CoMo/Al_2O_3-SiO_2催化剂中的SiO_2含量会促进八面体配位钼物种向四面体配位钼物种转变,SiO_2含量越高这种结构转变趋势越显著。在CoMo/Al_2O_3催化剂载体中加入适量的SiO_2能够改变载体与活性金属的相互作用,提高了催化剂加氢脱硫活性。     

SiO_2和Al_2O_3负载的Ni基催化剂在甲烷干重整中的催化性能差异（英文）

CH4与CO_2干重整反应对于环境保护和天然气资源的合理利用具有重要意义。SiO_2和Al_2O_3是适用于甲烷干重整反应的两种典型的催化剂载体。为了阐明这两种载体对催化剂性能的影响,本研究采用等体积浸渍法制备了Ni/Al_2O_3和Ni/SiO_2催化剂,并利用BET、TEM、H2-TPR、XRD、TG和Raman等技术对还原和反应后的催化剂进行了表征。结果表明,由于载体的性质不同,Ni基催化剂在甲烷干重整中的催化性能也不同。Ni/SiO_2催化剂的初始活性较高,但由于其金属-载体相互作用较弱,催化稳定性较差,在800℃下反应15 h其催化活性急剧下降;较弱的金属-载体相互作用使得Ni/SiO_2催化剂上的Ni颗粒较大,有利于积炭前驱物种的生成,导致催化剂快速失活。而对于Ni/Al_2O_3催化剂,金属-载体相互作用较强,Ni颗粒较小,但由于Ni与Al_2O_3生成了NiAlxOy物种,有效活性位减少,其催化活性相对较低,但催化稳定性较好,干重整反应进行50 h其活性保持稳定; Ni与Al_2O_3之间较强的相互作用有利于形成小且稳定的Ni粒子,能减少积炭,因而具有优异的催化稳定性。     

MoO3/TiO2-Al2O3催化剂表面结构的LRS研究

负载型Mo和Co-Mo催化剂由于工业上的广泛应用,多年来一直是催化工作者的重要研究课题.工业上应用的Mo和Co-Mo催化剂多以活性Al_2O_3和SiO_2-Al_2O_3为载体,近年来也有用TiO_2,ZrO_2和活性碳作为催化剂载体的研究报导.有关催化剂活性组分与载体之间相互作用对催化剂表面相结构和催化性能的影响方面研究已引起人们的重视。我们多年来在金属-载体相互作用研究基础上,以石油加氢精制催化剂为应用背景,开     

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。     

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。     

Enhanced photocatalytic activity of thin TiO2 films dotted with ZnS nanoparticles

The effect of Ni loading on the catalytic activity of Ni/ZrO₂ catalyst for methane steam reforming was investigated. The sample containing 15 wt.% Ni exhibited the highest activity as well as stability at 600°C. An erratum to this article is available at .     

Methane steam reforming over rhodium promoted Ni/Al2O3 catalysts

The effect of Rh addition upon catalyst characteristics and performance in methane steam reforming was investigated using Rh-promoted Ni/Al₂O₃ catalysts. The number of reduced metal atoms exposed on the surface increased for the Rh-promoted catalysts. Rh-promoted catalysts showed an increase in CH₄ reforming activity; however, constant turnover frequencies for promoted and unpromoted catalysts suggest that the increase in the number of metal surface atoms caused the activity enhancement. Rh also facilitated reduction of Ni/Al₂O₃.     

Total synthesis of (±)-camphorataimides and (±)-himanimides by NaBH4/Ni(OAc)2 or Zn/AcOH stereoselective reduction

Maleic anhydride 1 of Antrodia camphorate, which can be isolated from Chinese herbal medicine, is achieved in which the longest linear sequence is only five steps, in 40% overall yield from commercially available succinic anhydride. The crucial antrodimides 3 and 2 can be readily transformed by the chemoselective reduction with Zn/AcOH and NaBH₄/Ni(OAc)₂·4H₂O to afford the naturally occurring camphorataimides, 4 and 5, in high yields as well, respectively. This synthetic strategy can also be modified to give access to a variety of different maleic acid derivatives, himanimides 6-8.     

CO2 reforming of methane over zirconia-supported nickel catalysts, I. Catalytic specificity

CO₂ reforming of methane is performed over zirconia-supported nickel catalysts. The catalysts show high activity toward CH₄ and CO₂ conversions. Over the high Ni loading catalyst, long-term performances without significant deactivations have been achieved at 1023 K for 30 h and 1123 K for 20 h, respectively. The effects of reduction and calcination temperatures on the catalytic activities are also examined.     

Preparation of Cu/SiO2 Catalyst by Solution Exchange of Wet Silica Gel

Structural formation process of Ni/SiO₂ and Cu/SiO₂ catalysts prepared by solution exchange of wet silica gel was investigated. Microstructures of Cu/SiO₂ and Ni/SiO₂ were quite different from each other. In the case of Cu/SiO₂, Cu particles with diameter of ca. 3–5 nm dispersed homogeneously at less Cu content, and the particle size of Cu as well as pore size of silica gel support increased with increasing Cu content. In the Ni/SiO₂, the Ni particles with diameter of ca. 6–10 nm gathered densely to form aggregates in silica matrix resulting in sea-island structure, whereas the size of Ni particle slightly increased with increasing Ni content. The difference in the structure of the metal-silica composites is probably caused by the difference in interaction between silica gel network and metal ions during drying and heating processes.     

Synthesis and assembly of ultrathin film of Ni(OH)2 nanoparticles at gas/liquid interface, its high electrocatalytical oxidation toward bio-thiols and selective determination of cysteine

A facile strategy was reported to synthesize and assemble a stable ultrathin film of Ni(OH)₂ nanoparticles at gas/liquid interface where the aqueous phase contained Ni²⁺ and the organic phase was composed of triethylamine toluene solution. The ultrathin film of Ni(OH)₂ nanoparticles that precipitated at the interface was transferred onto the electrode surface for the electrocatalysis of bio-thiols and selective electroanalysis of cysteine. The preparation of Ni(OH)₂ ultrathin film and its transfer to an electrode substrate is very simple. The obtained Ni(OH)₂ ultrathin film modified electrodes are stable, showing high electrochemical oxidation toward bio-thiols and good selectivity toward cysteine in phosphate buffered solution of pH 7.5.     

Synthesis and characterization of flower-like β-Ni(OH)2 nanoarchitectures

Flower-like Ni(OH)₂ nanoarchitectures have been synthesized through a one-step mild hydrothermal reaction with the aid of ethylenediamine in NiCl₂ aqueous solution. The flower with the size of several micrometers in diameter is composed of the ultra-thin nanosheets of several nanometers in thickness. It was found the ethylenediamine is vital to the formation of the flower-like nanoarchitectures. The influence of the concentration of the ethylenediamine and the reaction temperature on the formation of the flowers was analyzed and the formation mechanism of the flowers was proposed. Such flower-like β-Ni(OH)₂ nanoarchitectures will find potential applications in the fields, such as electrode, or will be used as a starting material to produce NiO, which is widely used in the magnetic, catalysts, sensor and electrochromic devices.     

Facile Preparation of Indolyl-2/3-methylsulfoxides Using HF/H2O2

A variety of indolyl-2/3-methylsulfides tethered with sensitive functionalities were oxidized to the corresponding sulfoxides using a hitherto unexplored HF/H₂O₂ system.