A theoretical study of alcohol oxidation by ferrate

The conversion of methanol to formaldehyde mediated by ferrate (FeO(4)2-), monoprotonated ferrate (HFeO4-), and diprotonated ferrate (H2FeO4) is discussed with the hybrid B3LYP density functional theory (DFT) method. Diprotonated ferrate is the best mediator for the activation of the O-H and C-H bonds of methanol via two entrance reaction channels: (1) an addition-elimination mechanism that involves coordination of methanol to diprotonated ferrate; (2) a direct abstraction mechanism that involves H atom abstraction from the O-H or C-H bond of methanol. Within the framework of the polarizable continuum model (PCM), the energetic profiles of these reaction mechanisms in aqueous solution are calculated and investigated. In the addition-elimination mechanism, the O-H and C-H bonds of ligating methanol are cleaved by an oxo or hydroxo ligand, and therefore the way to the formation of formaldehyde is branched into four reaction pathways. The most favorable reaction pathway in the addition-elimination mechanism is initiated by an O-H cleavage via a four-centered transition state that leads to intermediate containing an Fe-O bond, followed by a C-H cleavage via a five-centered transition state to lead to formaldehyde complex. In the direct abstraction mechanism, the oxidation reaction can be initiated by a direct H atom abstraction from either the O-H or C-H bond, and it is branched into three pathways for the formation of formaldehyde. The most favorable reaction pathway in the direct abstraction mechanism is initiated by C-H activation that leads to organometallic intermediate containing an Fe-C bond, followed by a concerted H atom transfer from the OH group of methanol to an oxo ligand of ferrate. The first steps in both mechanisms are all competitive in energy, but due to the significant energetical stability of the organometallic intermediate, the most likely initial reaction in methanol oxidation by ferrate is the direct C-H bond cleavage.     

A first-principles study of methanol decomposition on Pt(111)

A periodic, self-consistent, Density Functional Theory study of methanol decomposition on Pt(111) is presented. The thermochemistry and activation energy barriers for all the elementary steps, starting with O[bond]H scission and proceeding via sequential hydrogen abstraction from the resulting methoxy intermediate, are presented here. The minimum energy path is represented by a one-dimensional potential energy surface connecting methanol with its final decomposition products, CO and hydrogen gas. It is found that the rate-limiting step for this decomposition pathway is the abstraction of hydroxyl hydrogen from methanol. CO is clearly identified as a strong thermodynamic sink in the reaction pathway while the methoxy, formaldehyde, and formyl intermediates are found to have low barriers to decomposition, leading to very short lifetimes for these intermediates. Stable intermediates and transition states are found to obey gas-phase coordination and bond order rules on the Pt(111) surface.     

Binding maps for the study and prediction of bimetallic catalyst surface reactions: The case of methanol oxidation

Focusing on the competing pathways of methanol oxidation on platinum and platinum/gold bimetallic catalysts, we explore a novel density functional theory (DFT)‐based approach to the study of reactions on catalyst surfaces. Traditionally, DFT has been used to compute binding energies of products and intermediates as proxies for catalytic activity, and to compute full reaction pathways and their activation energy barriers. Merging the computational simplicity and intuitive clarity of binding energy calculations with the site sensitivity of transition state calculations, we construct maps of the binding energies of relevant atoms and molecules at all sites on a surface. We show that knowledge of the arrangement of strong and weak binding sites on a surface is powerful in rationalizing the ease with which a reaction step proceeds on a given local motif of surface atoms. We highlight the prospects and challenges of this approach toward catalyst screening and prediction.     

Metal/zirconia catalysts for the synthesis of methanol: characterization by vibrational spectroscopy

The activation of carbon dioxide by catalytic hydrogenation has been studied as a route for methanol synthesis. Metal/zirconia catalysts suitable for this reaction have been prepared by (i) activation of amorphous metal alloys [1] or (ii) coprecipitation of amorphous zirconia and metal oxides [2]. Vibrational spectroscopy has been used to obtain information on the catalytic reaction mechanism, by the in situ identification of adsorbed species and intermediates under reaction conditions.The reverse water-gas shift reaction, producing CO from CO₂ and hydrogen, plays a crucial role in the reaction mechanism. This reduction is shown to proceed via surface formate, adsorbed close to the metal/zirconia interface. Over Pd/ZrO₂ and Ni/ZrO₂, formate is reduced to methane without further observable intermediates. Pivotal intermediates on the route to methanol, as observed on Cu/ZrO₂ catalysts, are -bound formaldehyde and surface methylate. Addition of silver as a promoter can result in enhanced selectivities and productivities for methanol formation. The synergy between the two metals becomes evident from the spectroscopic measurements; the most prominent feature of the silver-promoted catalysts is a high concentration of surface formaldehyde, which is either preferentially formed or stabilized by the silver component.     

Total oxidation of methanol on Cu(110): a density functional theory study

The partial and total oxidation of methanol on clean and oxygen-precovered Cu(110) has been studied by periodic density functional theory calculations within the generalized gradient approximation. Reaction paths including the geometry and the energetics of several reaction intermediates and the activation barriers between them have been determined, thus creating a complete scheme for methanol oxidation on copper. The calculations demonstrate that the specific structure of oxygen on copper plays an important role in both the partial and the total oxidation of methanol. For lower oxygen concentrations on the surface, the partial oxidation of methanol to formaldehyde is promoted by the presence of oxygen on the surface through the removal of hydrogen in the form of water, which prevents the recombinative desorption of methanol. At larger oxygen concentrations, the presence of isolated oxygen atoms reduces the C-H bond breaking barrier of adsorbed methoxy considerably, thus accelerating the formation of formaldehyde. Furthermore, oxygen also promotes the formation of dioxymethylene from formaldehyde, which then easily decays to formate. Formate is the most stable reaction intermediate in the total oxidation. Thus the formate decomposition represents the rate-limiting step in the total oxidation of methanol on copper.     

Kinetics of methanol steam reforming over COPZr-2 catalyst

The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact time W/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming （DR） and methanol decomposition （DE） were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test.     

甲醇水蒸气重整制氢反应条件的优化

对共沉淀法制备的CuO/ZnO/CeO₂-ZrO₂催化剂在甲醇水蒸气重整制氢反应体系中的性能进行了考察,并利用统计学实验设计方法对该反应的反应条件进行了优化。选择反应温度、水醇比和甲醇气体空速为独立要因,利用全因子实验设计方法,得到反应温度对两个响应值(甲醇转化率和重整气中CO物质的量分数)的影响最为显著,甲醇气体空速对重整气中CO物质的量分数的影响最小。固定甲醇气体空速为300 h^-1,利用中心旋转组合设计实验方法对反应温度和水醇比进行优化,得出当反应温度在249~258℃、水醇比在1.76~2.00时,甲醇能全部转化,重整气中CO物质的量分数小于0.5%。此模型的计算值与实验结果较为接近,表明采用统计学实验设计方法得出的结论对甲醇水蒸气重整制氢反应条件的优化具有指导意义。     

A novel Pt/Au/C cathode catalyst for direct methanol fuel cells with simultaneous methanol tolerance and oxygen promotion

A novel Pt/Au/C catalyst was prepared by depositing the Pt and Au nanoparticles on the carbon support. The synthesized catalysts were characterized by energy-dispersive X-ray (EDX) and transmission electron microscopy (TEM), and electrochemically analyzed for activity towards oxygen-reduction reaction and methanol oxidation reaction. EDX and TEM results reveal that Pt nanoparticles supported on carbon supports were separated by Au nanoparticles. The electrochemical analysis indicate that the novel catalyst showed the enhanced methanol tolerance while maintaining a high catalytic activity for the oxygen-reduction reaction, which could be attributed to the less methanol adsorption on Pt/Au/C catalyst.     

Kinetic mechanism of methanol decomposition on Ni(111) surface: a theoretical study

The decomposition of methanol on the Ni(111) surface has been studied with the pseudopotential method of density functional theory-generalized gradient approximation (DFT-GGA) and with the repeated slab models. The adsorption energies of possible species and the activation energy barriers of the possible elementary reactions involved are obtained in the present work. The major reaction path on Ni surfaces involves the O-H bond breaking in CH(3)OH and the further decomposition of the resulting methoxy species to CO and H via stepwise hydrogen abstractions from CH(3)O. The abstraction of hydrogen from methoxy itself is the rate-limiting step. We also confirm that the C-O and C-H bond-breaking paths, which lead to the formation of surface methyl and hydroxyl and hydroxymethyl and atom hydrogen, respectively, have higher energy barriers. Therefore, the final products are the adsorbed CO and H atom.     

Theoretical modeling study for the phosphonylation mechanisms of the catalytic triad of acetylcholinesterase by sarin

Potential energy surfaces for the process of phosphonylation of the catalytic triad of acetylcholinesterase by sarin have been explored at the B3LYP/6-311G(d,p) level of theory through a computational study. It is concluded that the phosphonylation process involves a critical addition-elimination mechanism. The first nucleophilic addition process is the rate-determining step. The following elimination process of the fluoride ion comprises a composite reaction that includes several steps, and it occurs rapidly by comparison with the rate-determining step. The mobility characteristics of histidine play an important role in the reaction. A double proton-transfer mechanism is proposed for the catalytic triad during the phosphonylation process of sarin on AChE. The effect of aqueous solvation has been considered via the polarizable continuum model (PCM). One concludes that the energy barriers are generally lowered in solvent, compared to the gas-phase reactions.     

Reaction mechanism of methanol decomposition on Pt‐based model catalysts: A theoretical study

The decomposition mechanisms of methanol on five different Pt surfaces, the flat surface of Pt(111), Pt‐defect, Pt‐step, Pt(110)(1 × 1), and Pt(110)(2 × 1), have been studied with the DFT‐GGA method using the repeated slab model. The adsorption energies under the most stable configuration of the possible species and the activation energy barriers of the possible elementary reactions involved are obtained in this work. Through systematic calculations for the reaction mechanism of methanol decomposition on these surfaces, we found that such a reaction shows the same reaction mechanism on these Pt‐based model catalysts, that is, the final products are all H (H_ads) and CO (CO_ads) via O? H bond breaking in methanol and C? H bond scission in methoxy. These results are in general agreement with the previous experimental observations. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010.     

ZSM-5酸改性对甲醇芳构化性能的影响

利用硝酸、草酸和酒石酸溶液对ZSM-5分子筛进行改性,并采用XRD、SEM、NH₃-TPD、XRF、²⁷Al MAS NMR、吡啶吸附红外光谱和N₂吸附-脱附对ZSM-5分子筛结构、酸量、比表面积及孔体积等物化性质进行表征分析。在反应温度为422℃,甲醇质量空速为4.74 h^-1的条件下,考察了ZSM-5分子筛的催化活性。结果表明,采用不同酸改性ZSM-5分子筛,影响了分子筛的比表面积、酸性及孔体积,从而改变了催化剂的催化性能。在甲醇芳构化（MTA）反应中,酸改性后的分子筛表现出良好的催化活性,且草酸改性后的催化剂表现出较高的催化活性及选择性,反应8 h时,芳烃及BTX收率分别达到57.40%和39.40%。     

Simultaneous determination of formaldehyde and methanol by flow-injection catalytic spectrophotometry

A flow-injection method is proposed for the simultaneous catalytic determination of formaldehyde and methanol on the basis of the catalytic action of formaldehyde upon the redox reaction between crystal violet and potassium bromate in a phosphoric acid medium and on-line oxidization of methanol into formaldehyde using a lead dioxide solid-phase reactor. The indicator reaction is monitored spectrophotometrically by measuring the decrease in the absorbance of crystal violet at the maximum absorption wavelength of 610 nm. A technique based on three sampling loops with a single injection valve is developed. The flow-injection system produces a signal of main peak with two shoulders of the same height. The height of the shoulders corresponds to the formaldehyde concentration, and the height difference between the shoulders and the main peak corresponds to the methanol concentration. The detection limit is 0.1 μg/mL for formaldehyde and 1.0 μg/mL for methanol with the sampling rate of 10 samples per hour. The relative standard deviations for 11 replicate determinations of formaldehyde (1.0 μg/mL) and methanol (10 μg/mL) are 1.1 and 2.1%, respectively. The method has been successfully applied to the simultaneous determination of formaldehyde and methanol in some gas samples. The text was submitted by the authors in English.     

Catalytic conversion of methane to methanol over Cu-mordenite

Methane can be converted to methanol over copper-exchanged mordenite at 200 °C. Methanol could be recovered at the end of the reactor. This multi-step reaction opens the possibility for methane to methanol conversion in a closed catalytic cyclic reaction system.     

Synthesis of dimethyl carbonate by vapor phase oxidative carbonylation of methanol over Cu-based catalysts

Dimethyl carbonate (DMC) synthesis reaction by oxidative carbonylation of methanol has been studied using vapor phase flow reaction system in the presence of Cu-based catalysts. A series of Cu-based catalysts were prepared by the conventional impregnation method using activated carbon (AC) as support. The effect of various promoters and reaction conditions on the catalytic reactivities were intensively evaluated in terms of methanol conversion and DMC selectivity. The morphological analysis by X-ray diffraction and SEM was also conducted in order to characterize the emloyed catalysts. Regardless of catalyst compositions, the optimal reaction temperature for oxidative carbonylation of methanol was found to be around 120–130°C. The reaction rate was too slow below 100°C, while too much by-products was produced above 150°C. Among the various catalysts employed, CuCl₂/NaOH/AC catalyst with the molar ratio of OH/Cu=0.5–1.0, has shown the best catalytic performance, which appears to have a strong relationship with the formation of intermediate species, Cu₂(OH)₃Cl.     

On the nature of radicals formed in methanol catalytic oxidation

The quantum-chemical calculations of the hydroxymethyl radical •CH₂OH were performed for the first time and a theoretical EPR spectrum of this radical was constructed. The formation of the hydroxymethyl radical in the reaction of methanol oxidation is thermodynamically favorable. The shape and parameters of the constructed spectrum differed from those for radicals experimentally detected in the catalytic oxidation of methanol using the matrix isolation method. However, they are consistent with the spectrum ascribed to the EPR spectrum of •CH₂OH observed in the direct photolysis of methanol. This result allows one to refine the identification of the nature of radicals formed in the catalytic reaction of methanol oxidation.     

Cobalt-modified nickel–zinc catalyst for electrooxidation of methanol in alkaline medium

Cobalt-modified nickel-zinc catalyst CuNi(Zn)Co is prepared on a copper substrate by using electrodeposition. Its catalytic efficiency for methanol oxidation is studied with cyclic voltammetry, chronoamperometry, and chronopotentiometry techniques. The surface morphology and chemical composition of catalyst are characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The oxidation kinetic parameters activation energy (Ea), active species on the surface (Γ), and rate constant (k) are determined from cyclic voltammograms which are performed at different methanol concentrations and temperatures. The results show that Ni(Zn)Co catalyst has higher catalytic activity than Ni, Co, and NiZn coatings as a composite catalyst for a promising choice of methanol electrooxidation in the alkaline medium.     

造纸白泥催化花生油与甲醇酯交换的特性研究

从催化剂用量、酯交换温度及时间、醇油物质的量比等影响因素出发,并借助热重、X射线荧光光谱、X射线衍射、氮气吸附与哈米特指示剂等催化剂表征手段,研究造纸白泥催化花生油与甲醇的酯交换特性.造纸白泥通过800 ℃煅烧-常温水合-600 ℃活化处理后,成分以CaO为主、比表面积为7.28 m²/g、碱性强度为9.8相似文献   

Bifunctionality of Cu/ZnO catalysts for alcohol-assisted low-temperature methanol synthesis from syngas:Effect of copper content

Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO_X catalysts while varying the copper content(X). Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction intermediate in this reaction, creating a different reaction pathway. The formation of crystalline phases and characteristic morphology of the co-precipitated precursors during the co-precipitation step were important factors in obtaining an efficient Cu/ZnO catalyst with a high dispersion of metallic copper,which is one of the main active sites for methanol synthesis. The acidic properties of the Cu/ZnO catalyst were also revealed as important factors, since alcohol esterification is considered the rate-limiting step in alcohol-assisted low-temperature methanol synthesis. As a consequence, bifunctionality of the Cu/ZnO catalyst such as metallic copper and acidic properties was required for this reaction. In this respect, the copper content(X) strongly affected the catalytic activity of the Cu/ZnO_X catalysts, and accordingly, the Cu/ZnO_0.5 catalyst with a high copper dispersion and sufficient acid sites exhibited the best catalytic performance in this reaction.     

First catalytic and green synthesis of aryl-(Z)-vinyl chlorides and its plausible addition-elimination mechanism

Via a catalytic cycle in the presence of scandium triflate (2 mol %)/DMF (1 mol %)/benzoyl chloride (5 mol %), aromatic ketones were treated with bis(trichloromethyl) carbonate (BTC) to afford aryl-(Z)-vinyl chlorides. All metal triflates tested in the reaction showed highly catalytic activity. A plausible addition-elimination mechanism was proposed. The present work describes the first catalytic and green route to the synthesis of aryl-(Z)-vinyl chlorides. [reaction: see text]