苯氧基亚胺钛化合物催化甲基丙烯酸丁酯聚合

3,5-二叔丁基水杨醛与苯胺缩合得到3,5-二叔丁基水杨醛缩苯胺配体1a;配体1a的钠盐与TiC l4.2THF反应得到相应的水杨醛亚胺钛配合物1;以色谱-质谱联用(GC/MS)、核磁共振氢谱(1H NMR)、元素分析等手段表征了中间化合物及配合物1;在三异丁基铝助催化下,钛配合物1高效催化甲基丙烯酸丁酯(BMA)本体聚合;在反应温度为60℃,BMA/三异丁基铝/钛配合物1(摩尔比为2 000∶20∶1)反应18 h,84.28%BMA转化为粘均分子量为12.80万聚甲基丙烯酸丁酯。     

3,5-二叔丁基-4-羟基苯甲酸的生产工艺研究

研究了利用柯尔伯-施密特（Kolbe—Schmitt）反应的合成原理,以2,6-二叔丁基苯酚（2,6-DTBP）为原料,在苯环上引入羧基,制得3,5-二叔丁基-4-羟基苯甲酸产品的生产工艺.讨论了物料配比,反应温度、压力及时间对反应转化率和收率的影响,确定了合理的生产工艺,即：2,6-DTBP与甲醇钠摩尔比为1.00：1.10;反应温度90～120℃;反应釜CO2通气压力,即叙述中的“反应压力”0.3～0.5MPa;反应时间16～20h.     

草酸催化DTBHQ合成研究

以对苯二酚和叔丁醇为原料、草酸为催化剂,合成2,5-二叔丁基对苯二酚(DTBHQ).通过实验,得到合成DTBHQ的适宜工艺条件:叔丁醇与对苯二酚摩尔比为3:1,催化剂与对苯二酚质量比为0.6:1,反应时间为6 h,反应温度为90℃.在此条件下,产物中的2,5-二叔丁基对苯二酚的最高收率为25.2%.     

5-硝基水杨醛硝化法的改进

探讨了以水杨醛为原料,混酸代替发烟硝酸为硝化剂制备5-硝基水杨醛的合成工艺,研究了混酸的用量、温度、溶剂和反应时间等条件对5-硝基水杨醛收率的影响.结果表明:在硝酸的用量是理论用量的1.25倍,浓硝酸与浓硫酸的物质的量比为1:2.5,在5～10℃反应3 h,然后升温到40℃充分反应2 h,5-硝基水杨醛的收率可达56.5%.     

光稳定剂3,5-二叔丁基-4-羟基-苯甲酸-2,4-二叔丁基苯基酯的合成

研究了以3,5-二叔丁基-4-羟基-苯甲酸和2,4-二叔丁基苯酚为原料,SOCl2为酰化试剂,一锅法合成光稳定剂3,5-二叔丁基-4-羟基-苯甲酸-2,4-二叔丁基苯基酯的工艺.通过实验考察了投料比、温度及酰化试剂用量对反应的影响,确定了较佳的工艺条件:3,5-二叔丁基-4-羟基-苯甲酸与2,4-二叔丁基苯酚的物质的量比为1∶1.1;酰化剂SOCl2与3,5-二叔丁基-4-羟基-苯甲酸的物质的量比为1.2∶1;反应温度为70℃;反应时间为11 h.还考察了结晶溶剂的种类、用量和温度对产品质量和收率的影响,得到了较佳的结晶工艺条件:V(正丁醇)/m(初产物)为1.4 m L/g;结晶温度为25℃.产品总收率可达83.0%.     

4-溴-2,6-二异丙基苯胺的合成工艺研究

以溴和2,6-二异丙基苯胺为原料合成4-溴-2,6-二异丙基苯胺,讨论了冰醋酸,投料顺序、温度、原料配比及其反应时间对反应的影响,获得了较佳的反应条件。合成4-溴-2,6-二异丙基苯胺的反应条件为:以溴和2,6-二异丙基苯胺的摩尔比1.014∶1,先投2,6-二异丙基苯胺及二氯甲烷,溴在0～10℃下滴加,保温2～3小时。得产品收率94.5%,含量95.2%。     

二氧化硒氧化3-甲基吡啶合成烟酸的研究

 采用二氧化硒为氧化剂,以3-甲基吡啶为原料经液相氧化法合成烟酸,适宜的反应条件为:3-甲基吡啶与二氧化硒摩尔比为1:1.6,3-甲基吡啶浓度2 mol/L,反应温度130℃,反应时间120 min,此条件下产品收率达到40.3%,所得产品达到国家GB14757—93标准.     

对叔丁基苯甲酸甲酯的硫酸钛催化反应研究

采用硫酸钛作催化剂,以对叔丁基苯甲酸和甲醇为原料直接酯化,对对叔丁基苯甲酸甲酯的合成工艺进行了研究,着重考察了催化剂用量、反应时间、醇酸摩尔比、带水剂用量等因素对反应收率的影响,并优化反应条件。当甲醇与对叔丁基苯甲酸的摩尔比为8∶1时,在催化剂硫酸钛(用量为对叔丁基苯甲酸的20%)作用下,加入带水剂苯12 mL,于回流温度下反应6h,产品收率可达86.6%。     

卤代水杨醛的简便合成

以水杨醛(1)为起始原料,乙醇为溶剂,液溴为溴化剂,在10℃的温度下经溴代反应以82.7%的收率得到了5-溴水杨醛(2);以PEG-400为溶剂,NBS(N-溴代丁二酰亚胺)为溴化剂、NCS(N-氯代丁二酰亚胺)为氯化剂,在室温下分别经溴代反应、氯代反应以74.1%、34.8%的收率得到了3,5-二溴水杨醛(3)和3,5-二氯水杨醛(4)。     

1-甲基-3-烷基咪唑/AlCl3催化合成反丁烯二酸二甲酯

研究了顺丁烯酸酐和甲醇在1-甲基-3-烷基咪唑/AlCl3催化作用下,经异构化和酯化反应合成反丁烯二酸二甲酯化合物。用统计序贯实验设计方法对合成过程进行了优化。开发了一条产品收率高,与盐酸、三氯化钕等催化工艺相比具有无腐蚀、无污染、价廉等优点的制备工艺。实验结果表明,1-甲基-3-烷基咪唑/AlCl3催化剂具有异构化和酯化两种催化作用,省去了以顺丁烯二酸酐为原料先制备富马酸中间产品的过程,反应条件温和,操作简便,一步法即可得到产品,其纯度为99.4%。最佳工艺条件为:催化剂用量与顺丁烯二酸酐摩尔比为0.17∶1、甲醇与顺丁烯二酸酐摩尔比为4.01∶1、反应温度为93.0℃、反应时间为5.0小时。在实验条件下,反丁烯二酸二甲酯的收率达到90%。     

Layered La-Ba-Cu mixed oxides with perovskite structure as catalyst for NO reduction by CO

The mixed oxides, including LaBa₂Cu₃O₇, LaBaCu₂O₅, La₄BaCu₅O₁₂ with perovskite structure, were prepared. The catalysts were characterized by means of chemical analysis, XRD, H₂-TPR. It was found that their structures were layered ABO₃ perovskite structure and they were the active catalysts for the NO reduction by CO. The existance of Cu³⁺ is an important factor to give the catalysts a high activity for the NO reduction by CO.     

CuO/CeO2催化剂在温度变动过程中的CO-PROX催化性能

采用浸渍方法制备不同Cu/Ce原子比的CuO/CeO₂催化剂,用于富氢气体中CO优先氧化反应(CO-PROX),考察其在温度变动情况下的催化性能. 利用X射线衍射(XRD)、程序升温还原(TPR)方法对反应前后催化剂样品进行了表征. XRD测试表明,催化反应后的催化剂中有金属Cu0生成. 这与文献结果一致. 与不含CO₂的情况比较,当模拟富氢气体中含有CO₂时,低温段催化活性明显下降. Cu/Ce原子比为10%的催化剂在温度变动过程中具有较稳定的催化性能.      

La掺杂对SrTiO_3纳米颗粒光催化性能的影响

采用高温固相反应法,向SrTiO_3中掺杂不同含量La制备光催化剂,通过XRD、SEM、UV-Vis等手段对其结构和形貌进行表征,并以罗丹明B(RhB)为模拟污染物,研究掺杂不同含量La所制催化剂对RhB的光催化降解能力的影响,从而评价所制催化剂的光催化性能。结果表明,随着掺La含量的增加,所制催化剂的晶体结构从SrTiO_3的立方晶系逐步向La_2Ti_2O_3的单斜晶系转变;La掺杂使得所制催化剂的禁带宽度减小、对紫外光的吸收阈值增大,使其光催化性能得到显著提升;掺La含量越高,所制催化剂的光催化性能越好。     

Hydrotalcite-supported Pd-Cu catalyst for nitrate adsorption and reduction from water

With the rapid development of industry and agricul- ture, the nitrate contamination in groundwater becomes increasingly serious in many countries [1]. Therefore, the remediation of nitrate-contaminated groundwater is one of the targets urgently confronted…     

Surface interactions of MoO3/ α-Fe2O3 system

α-Fe₂O₃ -supported molybdena catalysts have been prepared by heating a mixture of MoO₃ and α-Fe₂O₃. XRD, XPS, LRS, TG-DTA and Mössbauer spectroscopy were used to characterize the interactions between MoO₃ and α-Fe₂O₃. The dispersion capacity of MoO₃ on the surface of α-Fe₂O₃ determined by XRD and XPS was 0.8 mmol/100m² α-Fe₂O₃ in the samples calcined at 420 . For the sample with low MoO₃ loading, LRS and FT-IR results showed that Mo⁶⁺ ions were located in the tetrahedral vacant sites on the surface of α-Fe₂O₃, signed as Mo- . The amount of Mo-II species, formed by Mo6+ ions incorporated into the octahedral vacant sites, increased with the MoO₃ loading. Based on the assumption that the (001) plane of α-Fe₂O₃ is preferentially exposed, almost all the Mo⁶⁺ ions of the dispersed molybdena species existed at the surface octahedral sites for the sample with MoO₃ loading close or beyond the dispersion capacity, and formed the Mo-II species. In this case, the capping O^2- ions linking with the incorporated Mo⁶⁺ ions formed a surface epitaxial structure, which was in good agreement with the results predicted by the incorporation model proposed previously. XRD and Mössbauer spectroscopy of the MoO₃ α-Fe₂O₃ samples calcined at different temperatures showed that the calcination temperature could strongly influence the interaction extent: ( i) at 420 , MoO₃ dispersed on the surface of α-Fe₂O₃ and formed surface Mo species; (ii ) at 500 , MoO₃ reacted with the bulk of α-Fe₂O₃ and formed Fe₂(MoO₄)₃ compound.     

The preparation and performance of high activity Ni-Cr binary catalysts for direct borohydride fuel cells

Ni-Cr binary anode catalysts used in direct borohydride fuel cells (DBFCs) were prepared using a constant potential electrodepo- sition method. Compared with pure metal Ni catalysts, the electro-oxidation currents of borohydride ions (BH-4) more than doubled when using Ni-Cr binary catalysts under the same conditions. The enhanced activity of the Ni-Cr binary catalysts could be attributed to the change in distribution of BH-4ions on the surface of the Ni electrode. This is due to Cr electrodeposits, which allows a greater number of hydrogen atoms to catalyze from each tetrahedron BH-4 ion. The performance of Ni-Cr binary catalysts could also be improved by optimizing the electrodeposition conditions. The results show that Ni-Cr binary catalysts are optimally prepared using an electrodeposition method of 1s with a Cr3+ concentration of 0.2 mol L-1 and a potential of -0.100 V.     

纳米Pt/Graphene复合电极的制备及对甲醇电催化性能的影响

采用一步还原法制备直接甲醇燃料电池纳米Pt/graphene (Pt/G)阳极. XRD和SEM表征表明Pt纳米均匀分散于石墨烯表面.循环伏安和计时电流的电化学测定结果表明:复合纳米Pt/G的催化活性和稳定性优于纯铂;采用计时电量法测定298 K时甲醇在硫酸溶液中扩散系数为1.37×10-9 cm2·s-1,以及在不同阶跃电位下甲醇催化氧化反应速率常数k_f.      

Surface modification of γ-Al2O3 by sodium ions

¹H/²³Na double resonance NMR techniques were employed to study the modification of surface hydroxyls on γ-Al₂O₃ by sodium ions. ¹H→²³Na cross polarization (CP) experiment can resolve three kinds of sodium cations that are closely associated with surface hydroxyl groups, while the signal of deposited salt-Na₂CO₃, which is not connected to surface hydroxyl groups, is completely suppressed. ¹H{²³Na} spin echo double resonance experiments reveal the surface modification in more detail. At low Na⁺ coverage (5%, 10%), the acidic hydroxyl groups are preferentially coordinated with sodium ions, while both the acidic and the basic hydroxyl groups are accessible for sodium ions at high coordination that causes proton of the OH groups to be easily dissolved, which is evidenced by the fact that with calcination temperature of the catalysts increasing, the acidic hydroxyl groups are preferentially removed and only the basic hydroxyl groups remain when the calcination temperature is raised to 600℃.     

SiO_2修饰TiO_2负载钴基费-托合成催化剂及性能研究

采用Stber法和浸渍法制备了SiO2修饰的TiO2载体,并用浸渍法制备了钴基费-托合成催化剂,考察了其费-托合成催化性能.分别采用透射电子显微镜(TEM)、X-射线衍射(XRD)、低温氮气物理吸附-脱附、氢气程序升温还原(H2-TPR)等技术对载体和催化剂进行了表征,在固定床反应器上对催化剂的催化性能进行了评价.结果表明:SiO2的引入能减弱钴物种与TiO2之间的相互作用力,提高钴物种的还原性,使催化剂的催化性能显著提高.     

三种多元复合结构的核壳催化剂研究进展

以核壳结构复合而成的催化剂,在催化反应中常表现出较高的整体活性、大的比表面积、优异的择形催化效果和良好的热稳定性.部分催化载体因具有优异的择形效果和结构稳定性,在多元复合核壳催化剂的设计中也占据了一定的地位.本文主要介绍了几种常用催化剂载体(Al_2O_3、SiO_2、ZSM-5)参与复合的核壳催化剂制备与应用的概况.