Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.     

TiO2/MIL-53(Al)和TiO2/Al2O3催化剂的制备及其光催化性能研究

采用溶剂热法合成了MIL-53(Al),以此为载体负载TiO_2制备得到TiO_2/MIL-53(Al)光催化剂用于污水中次甲基蓝的催化降解研究,并与传统载体材料Al_2O_3负载的TiO_2催化剂的光催化效果进行比较。样品通过热重-差热扫描量热(TG-DSC)、红外光谱(FTIR)、扫描电镜(SEM)、X射线衍射(XRD)、N_2物理吸附-脱附等方法进行表征。采用光度吸收法分析污水中次甲基蓝的降解率,结果显示,TiO_2/MIL-53(Al)光催化剂对次甲基蓝的光催化降解率达到98.6%,而TiO_2/Al_2O_3光催化剂对次甲基蓝的降解率只有70.3%,TiO_2/MIL-53(Al)光催化剂对污水中次甲基蓝的降解去除能力明显优于TiO_2/Al_2O_3光催化剂对次甲基蓝的降解去除能力。     

Catalytic hydration of terminal alkenes to primary alcohols

Direct catalytic hydration of terminal alkenes to primary alcohols would be an inexpensive route to industrially useful alcohols and a convenient synthetic route for the synthesis of terminal alcohols in general. The reaction between trans- PtHCl(PMe(3))(2) (where Me = CH(3)) and sodium hydroxide in a one-to-one mixture of water and 1-hexene yields a species that, at 60 degrees C and in the presence of the phasetransfer catalyst benzyltriethylammonium chloride, catalyzes selective hydration of 1-hexene to n-hexanol at a rate of 6.9 +/- 0.2 turnovers per hour. Hydration of 1-dodecene to n-dodecanol occurs at a rate of 8.3 +/- 0.4 turnovers per hour at 100 degrees C. Deuterium labeling experiments with trans-PtDCl(PMe(3))(2) show that hydration involves reductive elimination of a C-H bond. At low hydroxide concentrations (<8 equivalents), hydration of the water-soluble olefin 3-butene-1-ol to 1,4-butanediol exhibited a first-order dependence on hydroxide concentration for loss of catalytic activity. This suggests that hydroxide attacks the coordinated alkene slowly. At high hydroxide concentrations, the rate of catalysis was hydroxide-independent and first order in alkene. Substitution of coordinated water (k(1) = 9.3 +/- 0.5 x 10(-3) liters per mol per second) appears to be limitng under these conditions.     

纳米TiO_2/PbWO_4可见光催化降解糖蜜酒精废水研究

采用表面活性剂辅助分散沉淀法制备了不同TiO2含量的纳米TiO2/PbWO4复合氧化物可见光催化剂系列,在400 W汞灯模拟光源条件下,对糖蜜酒精废水的光催化降解性能进行了研究,并考察了TiO2质量分数、催化剂用量、空气流量及废水pH值对废水光降解脱色率的影响.结果显示,当TiO2含量为质量分数8%时,担载二氧化钛的钨酸铅(TiO2/PbWO4)催化剂光催化降解活性达到最佳,在TiO2/PbWO4用量为2 g/L、鼓泡空气流量为120 mL/min及废水pH值为1.7的条件下,光催化降解120 min时,     

Green, catalytic oxidation of alcohols in water

Alcohol oxidations are typically performed with stoichiometric reagents that generate heavy-metal waste and are usually run in chlorinated solvents. A water-soluble palladium(II) bathophenanthroline complex is a stable recyclable catalyst for the selective aerobic oxidation of a wide range of alcohols to aldehydes, ketones, and carboxylic acids in a biphasic water-alcohol system. The use of water as a solvent and air as the oxidant makes the reaction interesting from both an economic and environmental point of view.     

醇、醛类有机物对中华绒螯蟹N-乙酰-β-D-氨基葡萄糖苷酶的影响

以甲醇、乙醇、异丙醇、甲醛和戊二醛为效应物,研究它们对中华绒螯蟹N-乙酰-β-D-氨基葡萄糖苷酶(NAGase)活力的影响.结果表明:戊二醛对NAGase活力影响不大;低浓度的甲醇和乙醇对NAGase有激活作用;高浓度的甲醇、乙醇、异丙醇和甲醛对NAGase的作用为可逆抑制.甲醇、乙醇、异丙醇对NAGase表现出竞争性抑制,抑制常数(KI)分别为3.663、0.360和0.480 mol.L-1;甲醛表现为非竞争性抑制类型,其KI为0.288 mol.L-1.     

Platinum catalysts for the high-yield oxidation of methane to a methanol derivative

Platinum catalysts are reported for the direct, low-temperature, oxidative conversion of methane to a methanol derivative at greater than 70 percent one-pass yield based on methane. The catalysts are platinum complexes derived from the bidiazine ligand family that are stable, active, and selective for the oxidation of a carbon-hydrogen bond of methane to produce methyl esters. Mechanistic studies show that platinum(II) is the most active oxidation state of platinum for reaction with methane, and are consistent with reaction proceeding through carbon-hydrogen bond activation of methane to generate a platinum-methyl intermediate that is oxidized to generate the methyl ester product.     

Integrated electromicrobial conversion of CO2 to higher alcohols

One of the major challenges in using electrical energy is the efficiency in its storage. Current methods, such as chemical batteries, hydraulic pumping, and water splitting, suffer from low energy density or incompatibility with current transportation infrastructure. Here, we report a method to store electrical energy as chemical energy in higher alcohols, which can be used as liquid transportation fuels. We genetically engineered a lithoautotrophic microorganism, Ralstonia eutropha H16, to produce isobutanol and 3-methyl-1-butanol in an electro-bioreactor using CO(2) as the sole carbon source and electricity as the sole energy input. The process integrates electrochemical formate production and biological CO(2) fixation and higher alcohol synthesis, opening the possibility of electricity-driven bioconversion of CO(2) to commercial chemicals.     

聚合物/纳米TiO2复合材料研究进展

简述聚合物/纳米TiO2复合材料的作用机理,综述国内外对环氧树脂、聚酰亚胺、聚氯乙烯等聚合物/纳米TiO2复合材料的研究进展。     

Enantioselective C-H crotylation of primary alcohols via hydrohydroxyalkylation of butadiene

The direct, by-product-free conversion of basic feedstocks to products of medicinal and agricultural relevance is a broad goal of chemical research. Butadiene is a product of petroleum cracking and is produced on an enormous scale (about 12 × 10(6) metric tons annually). Here, with the use of a ruthenium catalyst modified by a chiral phosphate counterion, we report the direct redox-triggered carbon-carbon coupling of alcohols and butadiene to form products of carbonyl crotylation with high levels of anti-diastereoselectivity and enantioselectivity in the absence of stoichiometric by-products.     

TiO2/C制备及光催化降解性能

以钛酸四丁酯为钛源负载活性炭制备了TiO2/C复合催化剂,从催化剂的用量、循环使用次数以及与P25比较等几个方面分别考察了该复合催化剂的催化降解甲基橙的活性.实验结果表明,TiO2/C复合催化剂提高了催化活性.     

Fe3 O4／TiO2复合物的制备

[目的]以钛铁矿为原料,制备包覆性Fe_3O_4/TiO_2磁性光催化剂。[方法]研究不同温度、反应时间、钛铁矿颗粒大小、是否冷凝回流等条件下钛铁矿的溶解情况以及TiO_2、Fe_3O_4/TiO_2的产率和催化效果,并采用X射线粉末衍射仪(XRD)、红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)等对催化剂产物进行表征,且验证催化剂的磁性能。[结果]该方法可以制备出磁性良好、包覆效果好、较纯净的Fe_3O_4/TiO_2包覆性光催化材料。[结论]制备出的Fe_3O_4/TiO_2复合物保持了Fe_3O_4的磁性,是一种性能优良的包覆性光催化材料。     

CeO2/TiO2/海泡石复合体的制备和光催化降解甲基橙的研究

以TiCl4和Ce(SO4)2为原料,以天然海泡石为载体,采用过氧化氢络合物热水解法制备CeO2/TiO2/海泡石复合体光催化剂,然后以甲基橙为目标降解物进行正交试验,研究得到制备的最佳条件。通过对甲基橙溶液降解率的影响因素进行分析,结果表明,在优化条件下,用海泡石为载体所制取的CeO2/TiO2对甲基橙具有较好的光催化活性。     

纳米二氧化钛改性竹炭光催化降解2,4-二氯苯酚的研究

研究发展了一种以钛酸四丁酯和竹炭为原料,采用溶胶-凝胶-浸渍法制备的纳米改性竹炭新材料,用X射线粉末衍射仪表征了改性竹炭的粒径,分析了该材料在不同质量浓度、不同pH值下对2,4-二氯苯酚溶液降解性能,对比分析了纳米二氧化钛改性竹炭、竹炭和二氧化钛粉末3种不同体系下2,4-二氯苯酚的降解率,还测试了改性竹炭再生性能。结果表明,改性竹炭材料具有良好光催化降解性能,在溶液中2,4-二氯苯酚初始质量浓度为120 mg.L-1,pH 10,反应75 min时降解率达到了96.4%,pH 6时,降解率仅为61.7%,再生改性竹炭降解率为96.3%,表现出良好的再生性能。图3表1参14     

木材的苯酚及多羟基醇液化

为拓展新的木材加工领域 ,使木材液化这一先进的木材化学加工技术尽早地应用于我国的木材行业 ,提高木材的综合利用率 .该文系统归纳了高温高压法、溶剂分解法、催化剂法及无催化剂法等木材液化方法 ,高温高压法是最早的木材液化方法 ,而采用硫酸、盐酸、磷酸和草酸等作为酸性催化剂的催化剂法是目前研究最多、最具实用价值的木材液化方法 .该方法进一步系统深入地讨论了木材的苯酚液化和多羟基醇液化 ,以及木材主成分 (纤维素与木素 )的液化反应路径 ,并对木材液化生成物的用途进行了探讨。作者认为有必要深入研究木材的液化机理 ,开发新的环保型液化剂和“绿色化”液化方法 ,开展液化产物与其他材料复合的研究 ,研制具有优异性能的新型复合材料 ,如酚化木材 蒙脱土纳米插层复合材料等     

甘油/TiO2聚偏氟乙烯微孔膜的制备及在膜蒸馏中的应用

[目的]研究甘油/TiO2聚偏氟乙烯(PVDF)微孔膜的制备及其在膜蒸馏中的应用.[方法]采用浸没沉淀相转化法制备PVDF微孔膜,研究了不同TiO2质量分数下加入甘油形成不同比例的混合添加剂对微孔膜结构及性能的影响.[结果]所制备的微孔膜具有较高的牛血清蛋白截留率,基本上都在90％以上;纯水通量集中在3～22 L/(m2·h)之间.[结论]当TiO2为3％、甘油添加量为0.4g时,膜的性能相对较好.随后把该条件下制备的微孔膜应用到膜蒸馏过程中进行NaCl溶液分离的试验研究,脱盐率最高可达30％;并且得到了膜装置运行的最优条件:料液温度为50℃、流量为5L/h、料液浓度为15 g/L.     

Hydrodefluorination of perfluoroalkyl groups using silylium-carborane catalysts

Carbon-fluorine bonds are among the most unreactive functionalities in chemistry. Interest in their activation arises in part from the high global warming potentials of anthropogenic polyfluoroorganic compounds. Conversion to carbon-hydrogen bonds (hydrodefluorination) is the simplest modification of carbon-fluorine bonds, but efficient catalytic hydrodefluorination of perfluoroalkyl groups has been an unmet challenge. We report a class of carborane-supported, highly electrophilic silylium compounds that act as long-lived catalysts for hydrodefluorination of trifluoromethyl and nonafluorobutyl groups by widely accessible silanes under mild conditions. The reactions are completely selective for aliphatic carbon-fluorine bonds in preference to aromatic carbon-fluorine bonds.     

UV/Fenton/TiO_2光催化氧化降解微囊藻毒素的研究

[目的]研究UV/Fenton/TiO2光催化氧化降解供水水源深水湖库水体中微囊藻毒素MC-RR和MC-LR的效果。[方法]以Fen-ton-TiO2作为光催化剂,考察不同反应时间、初始pH值、H2O2浓度、Fe2＋浓度、TiO2投加量、光照强度、藻毒素起始浓度对UV/TiO2/Fen-ton多相光催化氧化降解微囊藻毒素的影响,并对多相光催化氧化与UV光分解对藻毒素的去除效果进行比较。[结果]在H2O2起始浓度为0.1mmol/L、[H2O2]/[FeSO4]为15∶1、pH值为4.0、反应液距UV灯管1cm、TiO2投加量为0.05g/L和反应温度为（16±2）℃的条件下,反应3min后,浓度为0.35mg/L的MC-RR和浓度为0.29mg/L的MC-LR去除率可分别达到91.5%和90.2%。[结论]UV/Fen-ton/TiO2光催化氧化法能高效降解微囊藻毒素。     

TiO2/Ta2O5复合薄膜对医用NiTi合金的表面改性

采用 AFM,XRD和 XPS等对 Ni Ti表面离子束合成 Ti O2 /Ta2 O5复合薄膜的表面微观形貌、微结构和表面化学组成进行了表征。同时研究了膜层的力学性能、抗模拟体液腐蚀性和抗凝血性。结果表明 ,适当组成的 Ti O2 /Ta2 O5复合薄膜能显著提高 Ni Ti合金的抗腐蚀性和抗凝血性     

Wet electrons at the H2O/TiO2(110) surface

At interfaces of metal oxide and water, partially hydrated or "wet-electron" states represent the lowest energy pathway for electron transfer. We studied the photoinduced electron transfer at the H2O/TiO2(110) interface by means of time-resolved two-photon photoemission spectroscopy and electronic structure theory. At approximately 1-monolayer coverage of water on partially hydroxylated TiO2 surfaces, we found an unoccupied electronic state 2.4 electron volts above the Fermi level. Density functional theory shows this to be a wet-electron state analogous to that reported in water clusters and which is distinct from hydrated electrons observed on water-covered metal surfaces. The decay of electrons from the wet-electron state to the conduction band of TiO2 occurs in 相似文献