Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

对二甲苯直接电解氧化反应的研究

研究了在有机溶剂、支持电解质和碳棒存在下，对二甲苯的直接电解氧化反应，使用GC－MS方法分析鉴定了主要电解氧化产物，讨论了电解氧化产物成分随电解时间的变化规律，提出了对二甲苯的直接电解氧化反应过程。     

近红外吸收功能染料的合成

以缩合剂1，5-二苯胺-戊-1，3-二烯盐酸化物与1，3，3，5-四甲基-2-亚甲基吲哚啉为主要原料合成了1，3，3．5，1’，3’，3’，5'-八甲基吲哚三碳菁近红外吸收染料，收率达61．5％，采用熔点测定、元素分析、IR验证了产品的结构。通过电子吸收光谱测得其最大吸收波长为760nm。     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

新型螺旋式浓硝酸漂白塔及其应用

针对传统的帽罩式浓硝酸漂白塔存在的缺点和不足，找出原因并予以改进，开发研制出螺旋式浓硝酸漂白塔，改进了工艺状况，减少了维修工作量，达到了节能降耗的目的，确保了直接法浓硝酸装置的长周期运行。     

聚乳酸的直接合成研究(Ⅱ)

研究了以乳酸单体为原料的直接熔融缩聚的工艺条件,包括工艺路线、原料含水率、催化剂种类、温度及余压对合成的影响。结果表明:采用适当的工艺能通过熔融缩聚法制备出高分子质量的聚乳酸,且具有良好的生物降解性能。     

硼矿制硼酸母液中硼含量的测定方法探讨

报道了笔者用水相直接显色型比色法测定硼酸母液中硼含量的实验和结果。     

异种双活性基染料湿摩擦牢度再探讨

影响异种双活性基染料湿摩擦牢度主要有四个基本因素:染色基质的可染性、活性染料的化学结构、洗涤效率和助剂因素。提出了棉坏布预处理、使用助剂、提高染料的固色率和吸尽率、提升力等9项改进此类染料湿处理牢度的措施。有3篇参考文献。     

直接甲醇燃料电池用碳气凝胶载铂催化剂的研究

利用溶胶—疑胶方法制备了高比表面积的碳气凝胶,利用浸渍还原法制备了Pt/碳气凝胶和Pt/C催化剂。采用BJH和TEM考察碳气凝胶的孔径分布和金属粒子的大小与分布,循环伏安曲线测试考察Pt/碳气凝胶对甲醇催化氧化性能的影响。结果表明,碳气凝胶的比表面积达到480 m2/g,孔径分布良好,催化剂金属颗粒较小,分散较好,循环伏安曲线图显示出Pt/碳气凝胶比传统的Pt/C对甲醇催化氧化性能高。     

Enzymatic esterification of glycerol II. Lipase-catalyzed synthesis of regioisomerically pure 1(3)-rac-monoacylglycerols

Regioisomerically pure 1(3)-rac-monoacylglycerols are conveniently prepared in high yields (>75%) and in multigram quantities by enzymatic esterification of glycerol in the presence of various lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) with a variety of different acyl donors, such as free fatty acids, fatty acid alkyl esters, vinyl esters and triacylglycerols, as well as natural fats and oils. All reactions are carried out in aprotic organic solvents with low water content, namelyn-hexane, diethyl ether, tBuOMe or mixtures of these solvents. Essential for the success of these transformations were the following two factors. First, the creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction medium by its adsorption onto a solid support. Second, a facile system for the separation of the desired monoacylglycerol from the reaction mixture, coupled with the continuous recycling of acyl donor and undesirable by-products.