PtRu nanoparticles supported on 1-aminopyrene-functionalized multiwalled carbon nanotubes and their electrocatalytic activity for methanol oxidation

A new synthesis method for the preparation of high-performance PtRu electrocatalysts on multiwalled carbon nanotubes (MWCNTs) is reported. In this method, bimetallic PtRu electrocatalysts are deposited onto 1-aminopyrene (1-AP)-functionalized MWCNTs by a microwave-assisted polyol process. The noncovalent functionalization of MWCNTs by 1-AP is simple and can be carried out at room temperature without the use of expensive chemicals or corrosive acids, thus preserving the integrity and the electronic structure of MWCNTs. PtRu electrocatalysts on 1-AP-functionalized MWCNTs show much better distribution with no formation of aggregates, higher electrochemically active surface area, and higher electrocatalytic activity for the electrooxidation of methanol in direct methanol fuel cells as compared to that on conventional acid-treated MWCNTs and carbon black supported PtRu electrocatalysts. PtRu electrocatalysts on 1-AP-functionalized MWCNTs also show significantly enhanced stability.     

APPI-MS: Effects of mobile phases and VUV lamps on the detection of PAH compounds

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of nonpolar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e., 相似文献   

Platinized mesoporous tungsten carbide for electrochemical methanol oxidation

Mesoporous WC with hexagonal crystal structure was synthesized by a surfactant-assisted polymer method. A new electrocatalyst composed of a small amount of Pt supported on the mesoporous WC exhibited higher activity for electrooxidation of methanol than microporous Pt/WC or Pt/W₂C as well as commercial Pt–Ru(1:1)/C catalysts. The mesoporosity and the phase of WC appear important for the high activity. Compared to the commercial Pt–Ru/C catalyst, the Pt/WC (mesoporous) showed the higher activity per mass of Pt by a factor of six even without Ru. Since the catalyst is also stable in electrochemical environment, it could become an alternative electrocatalyst for direct methanol fuel cells.     

Multiwalled carbon nanotube supported PtRu for the anode of direct methanol fuel cells

The activity of the methanol oxidation reaction of a multiwalled carbon nanotube (MWCNT)-supported PtRu catalyst was investigated and compared with the Vulcan XC-72 carbon-supported catalyst. The PtRu nanoparticles with 1:1 and 7:3 atomic ratios (with similar PtRu loadings and morphological structures) were deposited both on the MWCNTs and on the carbon. Cyclicvoltammetry results demonstrated that the MWCNT-supported PtRu catalyst exhibited a higher mass activity (mA mg(-1) of PtRu) for the methanol oxidation reaction than the carbon-supported PtRu under the condition that both catalysts possess more or less the same PtRu loadings, particle sizes, dispersions, and electrochemical surface area. The direct methanol fuel cell performance test data showed that MWCNT-supported PtRu catalysts yielded about 35-39% higher power densities than the carbon-supported PtRu.     

Surface modified multi‐walled carbon nanotubes and Nafion nanocomposite membranes for use in fuel cell applications

The preparation and characterization of the nanocomposite polyelectrolyte membranes, based on Nafion, sulfonated multi‐walled carbon nanotubes (MWCNT‐SO₃H) and imidazole modified multi‐walled carbon nanotubes (MWCNT‐Im), for direct methanol fuel cell applications is described. The results showed that the modification of multi‐walled carbon nanotubes (MWCNT) with proton‐conducting groups (sulfonic acid groups or imidazole groups) could enhance the proton conductivity of the nanocomposite membranes in comparison to Nafion 117. Regarding the interactions between the protonated imidazole groups, grafted on the surface of MWCNT, and the negatively charged sulfonic acid groups of Nafion, new electrostatic interactions can be formed in the interface of the Nafion and MWCNT‐Im, which result in both lower methanol permeability and higher proton conductivity. The physical characteristics of these manufactured nanocomposite membranes were investigated by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, water uptake, methanol permeability, and ion exchange capacity, as well as proton conductivity. The Nafion/MWCNT‐Im membranes showed the higher proton conductivity, lower methanol permeability, and, as a consequence, a higher selectivity parameter in comparison to the neat Nafion or Nafion membrane containing MWCNT‐SO₃H or ─OH functionalized multi‐walled carbon nanotubes (MWCNT‐OH) membranes. The obtained results indicated that the Nafion/MWCNT‐Im membranes could be used as efficient polyelectrolyte membranes for direct methanol fuel cell applications.     

生物质气催化合成甲醇的研究

在高压微型反应装置上进行了生物质气合成甲醇的研究。利用组成为H2/CO/CO2 /N2(体积比)=52.5/21.5/22.8/3.2 的富CO2原料气考察了不同温度、压力和空速条件时甲醇的时空产率和质量分数。结果表明,在所考察的范围内,甲醇的产率和质量分数在260 ℃达到最大。产率和质量分数随反应压力升高而增大,空速增加使产率增大,甲醇的质量分数降低。当p=4 MPa,t=260 ℃,WHSV=5 280 h-1时, 甲醇的时空产率为0.79 g·（mL·h）－１,质量分数为96.2%,与工业合成气相比,分别下降25.8％和1.64％。     

GC-MS identification of amine-solvent condensation products formed during analysis of drugs of abuse.

The use of methanol or ethanol as the injection solvent for the gas chromatographic-mass spectral (GC-MS) analysis of low molecular weight amine drugs of abuse results in the formation of additional components in the sample. Primary amines, such as amphetamine, 3,4-methylenedioxyamphetamine, and phenethylamine, yield imines upon injection as methanol or ethanol solutions. In methanol, the imine formed has a mass that is 12 mass units higher than the parent compound. In ethanol, the products formed have 26 additional mass units. Secondary amines appear to undergo methylation under similar conditions with methanol as the injection solvent. These products are absent from the analysis of equivalent amine samples dissolved in chloroform.     

电喷雾萃取电离质谱法检测1-羟基芘

采用电喷雾萃取电离质谱(EESI-MS)分析致癌性环境有机污染物多环芳烃(PAHs)生物标志物1-羟基芘(1-OHP),探究1-OHP在EESI源中电离的可行性,考察ESI溶剂和样品溶液组成对方法灵敏度的影响,初步建立I-OHP的EESI MS半定量分析方法.结果表明,溶液中1-OHP能够在EES1源中有效电离,生成准分子离子[M-H]- (m/z 217),并得到其二级质谱特征碎片离子[M- H- CO]- (m/z 189);水、甲醇、乙醇、正丙醇和正丁醇5种ESI溶剂中,使用甲醇时,离子峰m/z 217信噪比最大.样品溶液中甲醇含量越高,离子峰m/z 217强度越强.离子峰m/z 217强度与1-OHP浓度在10～200 μg/L内的线性相关性相对最好;相关系数(R)0.982;相对标准偏差(RSD)为3.4％～14.0％(n=5);定量下限约为10 μg/L(S/N=10);单次检测时间小于0.5 min.     

THE PHOTOSENSITIZERS BENZOPHENOXAZINE and THIAZINES: COMPREHENSIVE INVESTIGATION OF PHOTOPHYSICAL and PHOTOCHEMICAL PROPERTIES

Eight differently substituted title dye compounds have been investigated regarding intersystem crossing, triplet state, fluorescence and singlet excited state pKa properties. In general, non-halogenated oxazines and thiazines as well as a mono bromooxazine show very low triplet quantum yields, phi tau (less than 0.03) and relatively long triplet lifetimes (approximately 40 microseconds) in acidic methanol. The phi tau data correlate well with known singlet oxygen yields. In basic methanol no triplet transient is observed but a significant yield of a ground state transient protonated (base dye) form is produced with a short lifetime, approximately 400 ns. Fluorescence can be seen simultaneously from both the excited base and the protonated base dye forms in basic methanol. For iodinated oxazine or thiazines, the triplet yield increases and can be as high as 0.5 (diiodo case) in acidic methanol. The triplet lifetimes are further shortened to approximately 10 microseconds compared to the non-iodinated derivatives above. The triplet yields of the iodo compounds are higher or equal to known singlet oxygen yields. In basic methanol triplet yields up to 0.2 can be seen, the triplet lifetime are shortened still further to 1 microsecond but no observable protonated form is produced (in distinction to the non-iodinated cases). Consideration is given to the correlation of triplet and singlet oxygen yields, ground and excited pKa properties, spin-orbit coupling and internal conversion properties, solvent effects, and phototherapeutic activity of these dyes.     

Highly selective adsorption of methanol in carbon nanotubes immersed in methanol-water solution

The systems of open-ended carbon nanotubes (CNTs) immersed in methanol-water solution are studied by molecular dynamics simulations. For the (6,6) CNT, nearly pure methanol is found to preferentially occupy interior space of the CNT. Even when the mass fraction (MF) of methanol in bulk solution is as low as 1%, the methanol MF within the CNT is still more than 90%. For CNTs with larger diameters, the methanol concentrations within CNTs are also much higher than those outside CNTs. The methanol selectivity decreases with increasing CNT diameter, but not monotonically. From microscopic structural analyses, we find that the primary reason for the high selectivity of methanol by CNTs lies on high preference of methanol in the first solvation shell near the inner wall of CNT, which stems from a synergy effect of the van der Waals interaction between CNT and the methyl groups of methanol, together with the hydrogen bonding interaction among the liquid molecules. This synergy effect may be of general significance and extended to other systems, such as ethanol aqueous solution and methanol/ethanol mixture. The selective adsorption of methanol over water in CNTs may find applications in separation of water and methanol, detection of methanol, and preservation of methanol purity in fuel cells.     

Methanol dehydrogenation and oxidation on Pt(111) in alkaline solutions

Adsorption, dehydrogenation, and oxidation of methanol on Pt(111) in alkaline solutions has been examined from a fundamental mechanistic perspective, focusing on the role of adsorbate-adsorbate interactions and the effect of defects on reactivity. CO has been confirmed as the main poisoning species, affecting the rate of methanol dehydrogenation primarily through repulsive interactions with methanol dehydrogenation intermediates. At direct methanol fuel cell (DMFC)-relevant potentials, methanol oxidation occurs almost entirely through a CO intermediate, and the rate of CO oxidation is the main limiting factor in methanol oxidation. Small Pt island defects greatly enhance CO oxidation, though they are effective only when the CO coverage is 0.20 ML or higher. Large Pt islands enhance CO oxidation as well, but unlike small Pt islands, they also promote methanol dehydrogenation. Perturbations in electronic structure are responsible for the CO oxidation effect of defects, but the role of large Pt islands in promoting methanol dehydrogenation is primarily explained by surface geometric structure.     

Carbon Aerogels Supported Pt Nanoparticles as Electrocatalysts for Methanol Oxidation in Alkaline Media

Carbon aerogels (CAs) were prepared by sol‐gel polycondensation of resorcinol and formaldehyde with BET surface area of 616 m² g^?1 and the average pore size of 9.8 nm. The prepared CAs were used as supports for Pt nanoparticles for methanol oxidation in alkaline media. In comparison with Pt supported on commercial Vulcan XC‐72R carbon (Pt/C) electrocatalysts, Pt supported on CAs (Pt/CAs) electrocatalysts exhibited higher peak current density and more negative onset potential toward methanol oxidation. The effects of different parameters such as NaOH concentration, methanol concentration, and scan rate on the methanol oxidation reaction were investigated in detail. The results showed that the Pt/CAs electrocatalysts had promising application for methanol oxidation in alkaline media.     

Density functional theory calculations of structure, FT-IR and Raman spectra of S-phenyl thioacetate

A catalyst composed of a Pd(5)Cu mixed oxide supported over Al(2)O(3)-CeO(2) with general formula Pd(5)CuO(x)/Al(2)O(3)-CeO(2) (Al/Ce atomic ratio=1/1) has been prepared by a wet impregnation method and tested in the methanol conversion. The structural and morphological characterization of the catalyst evidences that it is a mesoporous material thermally stable up to 873 K. At that temperature the specific surface area value is 170 m(2)/g, and a CeO(2) cubic phase is identified together with ill-defined diffraction peaks tentatively assigned to Cu-Pd clusters, suggesting that the active phase is well dispersed over the support. Infrared studies prove that methanol conversion takes place over the catalyst to a high extent yielding syngas as main product in the range 473-723 K and methane at higher temperatures. Oxygenated intermediates containing methoxy, carbonile or formiate species are not detected, which evidences that methanol conversion to methane very probably takes place according to a via-carbide mechanism.     

反相高效液相色谱法对八种吡嗪类化合物保留性能的研究

在Ｓｐｈｅｒｉｓｏｒｂ－Ｃ（１８）反相柱上,以甲醇－水为流动相,对八种吡嗪类化合物的保留性能进行了考察。同时用不同浓度下的冲洗剂所得保留值和关系式ｌｎｋ＇＝ａ＋ｃＣｂ中的参数ａ、ｃ作线性关系,得到很好的相关性。流动相中不同的无机盐及微量有机胺类改性剂的加入,可有效地改进分离。当甲醇：０．２ｍｌ／ＬＨＡｃ－ＮａＡｃ缓冲液（ｐＨ４．５）：三乙胺为４０：５９：１（Ｖ／Ｖ）时,除两种同分异构体不能分离外,所有组分在２５ｍｉｎ内可实现较理想的分离。     

Kinetic studies on light-induced cationic ring-opening reactions on 2,3-epoxypropyl phenyl ether

Light-induced cationic ring-opening reactions of 2,3-epoxypropyl phenyl ether (phenyl glycidyl ether, PGE) in acetone, methanol and bulk were studied. Cations are produced by electron transfer from excited sensitizers (anthracene, An; 9,10-phenanthrenequinone, PQ; benzophenone, BP) or from photolytically cleaved sensitizer (benzoin isoproyl ether, BIPE) to diphenyliodonium hexafluorophosphate. With excess of acetone and methanol, addition reactions take place resulting in 2,2-dimethyl-4-phenoxymethyl-1,3-dioxolane and 1-methoxy-3-phenoxy propan-2-ol as main products. The efficiency of the sensitizers taken from the quantum yields of PGE conversion, follows the order An ? BIPE > PQ > BP in acetone and An ～ BP > BIPE ? PQ in methanol. Unlike bulk polymerization, in these addition reactions no steady-state concentration of cations exists and the reaction accelerates with time. When alcohol is added in only small proportions, the initial addition reactions goes over into a linear oligomerization. The relatively higher basicity of methanol over PGE influences the nature of the active center, and the course of reaction depends on methanol concentration. Kinetic expressions, which account for all possible types of active centers, have been derived to express the rate of PGE reactions in methanol.     

High efficiency direct methanol fuel cell based on poly(styrenesulfonic) acid (PSSA)-poly(vinylidene fluoride) (PVDF) composite membranes

semi-Interpenetrating polymer network (sIPN) composite membranes consisting of poly(styrenesuflonic) acid (PSSA) and poly(vinylidene fluoride) (PVDF) have been prepared and evaluated as proton exchange membrane electrolytes in direct methanol fuel cells (DMFCs). The membranes fabricated were evaluated in terms of their proton conductivity, methanol permeability, and their performance characteristics in direct methanol fuel cells (DMFCs). PSSA-PVDF membranes demonstrated decreased methanol crossover during operation of direct methanol fuel cells compared to state-of-art Nafion^®-H membranes, yielding improved efficiency. PSSA-PVDF membranes have been demonstrated to operate efficiently in 1 in. × 1 in. and 2 in. × 2 in. direct methanol fuel cells. Fuel cells operating with PSSA-PVDF membranes were observed to have dramatically lower crossover rates compared to Nafion^® 117 systems. Greater than 95% reduction in crossover was observed in some cases. These properties of PSSA-PVDF membranes resulted in improved fuel performance and fuel cell efficiencies for direct methanol fuel cells. It was also observed that the PSSA-PVDF membranes behave quite differently compared with Nafion^®-based systems in terms water management characteristics at the cathode. The best performance with the new membranes was observed with very low oxygen or air flow rates at the cathode which is in contrast to Nafion^®-based systems, which generally require higher flow rates due to excessive water accumulation at the cathode, resulting in flooding.     

Association of methanol and water in ionic liquids elucidated by infrared spectroscopy using two-dimensional correlation and multivariate curve resolution

Water and methanol associations in ionic liquids (ILs) have been studied by means of FTIR spectroscopy. Spectra at different concentrations of water or methanol in ILs were obtained by means of on-line dilution using a flow injection analysis system. Spectral features in the OH stretching region revealed that most of the water and methanol molecules tended to be isolated from each other and to interact with the anion of the IL via H bonding. By means of two-dimensional correlation spectroscopy, the formation of methanol and water dimers was also detected. Multivariate curve resolution was used to recover pure spectra and concentration profiles of the different species. Methanol dimers form at concentrations higher than 0.8% (w/w) in the three studied ILs, 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF4), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). Self-association of water molecules takes place in emimBF4 and bmimBF4 at a molar ratio similar to that of methanol molecules; however, water dimers cannot be detected in bmimPF6, the most hydrophobic IL studied. No evidence was found that bigger water clusters are formed in these ILs at the studied cosolvent concentrations.     

高稳定性的氮掺杂氧化钽光催化甲醇C−H活化和直接C−C偶联制乙二醇

乙二醇是非常重要的基础化学品,不仅可以作为合成聚合物(如聚对苯二甲酸乙二醇酯)的重要单体,也可以用作防冻剂和燃料添加剂等,具有广泛的用途.乙二醇的年产量超过2500万吨,目前主要的工业合成路线是由石油衍生的乙烯通过环氧化制环氧乙烷,环氧乙烷再水解制乙二醇.甲醇是一种清洁的平台化合物,不仅可以由天然气和煤炭通过传统的合成气过程生产,也可以由生物质和CO2直接合成.直接以甲醇为原料是合成乙二醇的理想过程,但目前热催化还未实现该过程.通过太阳能驱动的C?H活化和C?C偶联过程,可以实现甲醇直接偶联制乙二醇的理想反应过程.光催化甲醇制乙二醇可以在十分温和的条件下进行,目前已报道的甲醇制乙二醇光催化剂均为硫化物半导体材料,如CdS,ZnS和Zn2In2S5,但硫化物存在的光腐蚀和毒性等问题迫使我们去发展一种更加稳定和环境友好的光催化剂.氧化物基半导体材料,如Ta2O5,TiO2,ZnO和WO3等,是一类相对硫化物半导体材料更加稳定的光催化材料,然而目前还没有氧化物基半导体光催化剂用于光催化甲醇制乙二醇的报道.本文率先将金属氧化物光催化剂Ta2O5,用于甲醇制乙二醇的光催化反应,实现了乙二醇的选择性合成.在单纯的Ta2O5催化剂上,乙二醇选择性可达73％.Ta2O5十分独特,可以实现甲醇的光催化C?C偶联制乙二醇,而其他金属氧化物光催化剂(如TiO2,ZnO,WO3和Nb2O5)光催化转化甲醇只生成甲醛和甲酸等C1产物.进一步通过简单、方便的氨气焙烧法,制备了一系列不同氮掺杂量的氧化钽(N-Ta2O5)催化剂.在未经助催化剂修饰的氮含量为2.3％的2％N-Ta2O5光催化剂上,乙二醇选择性为71％,生成速率可达4.0 mmol gcat?1 h?1,约为Ta2O5的9倍,同时显著高于已报道的未经助催化剂修饰的CdS催化剂性能.通过光电流、表面光电压谱和理论计算等方法系统地研究了氮掺杂氧化钽具有高的光催化甲醇制乙二醇性能的重要原因,发现氮掺杂氧化钽高的电荷分离能力是决定其具有高活性的关键因素.另一方面,氮掺杂氧化钽表现出了非常高的反应稳定性,在超过160 h的循环测试过程中,乙二醇的生成速率基本保持不变,这是目前已报道的金属硫化物光催化剂所未能实现的.在长达60 h的反应过程中,未经助催化剂修饰的2％N-Ta2O5催化剂上乙二醇生成量基本随时间线性增长,收率可达3.6％.进一步研究发现,钽基半导体材料(Ta2O5和N-Ta2O5)可以在保持甲醇羟基不变的情况下优先活化甲醇C?H键,生成羟甲基自由基(?CH2OH),随后羟甲基自由基经C?C偶联生成乙二醇.钽基半导体光催化剂是一种环境友好且十分稳定的甲醇光催化偶联制乙二醇的优异催化剂,未来基于该类催化剂不仅有希望发展出更加高效、稳定的甲醇制乙二醇光催化剂,还有希望为更广的羟基存在下的C?H键选择性活化反应过程设计高效稳定的催化剂提供借鉴和指导.     

Chemical modification of an antitumor alkaloid camptothecin: synthesis and antitumor activity of 7-C-substituted camptothecins.

A radical substitution reaction of 20(S)-camptothecin (1) with methanol furnished 7-hydroxymethylcamptothecin (2). Reaction of 1 with primary alcohols higher than methanol gave 7-alkylcamptothecins (4), of which alkyl groups were one carbon less than the alcohols used and also 7-hydroxyalkylcamptothecins (5). For the preparation of 7-alkylcamptothecin (4), aldehydes were used as a radical source and several alkylated derivatives were synthesized. 7-Acyloxymethyl derivatives (6), 7-carbaldehyde (7), iminomethyl derivatives (10), acid (11), esters (12) and amides (13) were synthesized starting from 2. 7-Ethyl- (4b) and 7-propylcamptothecin (4c), acyloxymethyl compounds 6a, 6c and ethyl ester (12b) exhibited higher antitumor activity than 1 against L1210 in mice.     

Relative importance of basicity in the gas phase and in solution for determining selectivity in electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry is a critically important technique for the determination of small molecules, but its application for this purpose is complicated by its selectivity. For positive ion ESI-MS analysis of basic analytes, several investigators have pointed to the importance of analyte basicity as a source of selectivity. Currently, however, it is not known whether basicity in the gas phase or in solution is ultimately most important in determining responsiveness. The objective of these studies was to investigate the relative importance of basicity in solution and in the gas phase as factors that predict selectivity in positive ion ESI-MS analysis. ESI-MS response was compared for a diverse series of protonatable analytes in two different solvents, neat methanol and methanol with 0.5% acetic acid. A correlation was observed between analyte pK(b) and electrospray response. However, the response for the analytes with very high pK(b) values was significantly higher than would be expected based on concentration of the protonated form or the analyte in solution, and this higher response did not appear to result from gas-phase proton transfer reactions. Although all of the analytes investigated had higher gas-phase basicities than the solvent, their relative responses were not dictated by gas-phase basicity. Higher response was observed for all of the analytes studied in acidified methanol compared with neat methanol, and this higher response was most pronounced for weakly basic analytes. These findings support the use of analyte pK(b) for rational method development in ESI-MS analysis of small molecules.