A density functional theory study of methane activation on MgO supported Ni9M1 cluster: role of M on C–H activation

Methane activation is a pivotal step in the application of natural gas converting into high-value added chemicals via methane steam/dry reforming reactions. Ni element was found to be the most widely used catalyst. In present work, methane activation on MgO supported Ni–M (M = Fe, Co, Cu, Pd, Pt) cluster was explored through detailed density functional theory calculations, compared to pure Ni cluster. CH₄ adsorption on Cu promoted Ni cluster requires overcoming an energy of 0.07 eV, indicating that it is slightly endothermic and unfavored to occur, while the adsorption energies of other promoters M (M = Fe, Co, Pd and Pt) are all higher than that of pure Ni cluster. The role of M on the first C–H bond cleavage of CH₄ was investigated. Doping elements of the same period in Ni cluster, such as Fe, Co and Cu, for C–H bond activation follows the trend of the decrease of metal atom radius. As a result, Ni–Fe shows the best ability for C–H bond cleavage. In addition, doping the elements of the same family, like Pd and Pt, for CH₄ activation is according to the increase of metal atom radius. Consequently, C–H bond activation demands a lower energy barrier on Ni–Pt cluster. To illustrate the adsorptive dissociation behaviors of CH₄ at different Ni–M clusters, the Mulliken atomic charge was analyzed. In general, the electron gain of CH₄ binding at different Ni–M clusters follows the sequence of Ni–Cu (–0.02 e) < Ni (–0.04 e) < Ni–Pd (–0.08 e) < Ni–Pt (–0.09 e) < Ni–Co (–0.10 e) < Ni–Fe (–0.12 e), and the binding strength between catalysts and CH ₄ raises with the CH₄ electron gain increasing. This work provides insights into understanding the role of promoter metal M on thermal-catalytic activation of CH₄ over Ni/MgO catalysts, and is useful to interpret the reaction at an atomic scale.     

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.     

甲醇合成催化剂的工艺参数优化及反应机理探讨

对自主研制的甲醇合成催化剂进行工艺参数优化,同时根据实验结果对合成气条件下甲醇合成的反应机理进行探讨。实验采用16通道反应器,考察反应温度和接触时间对合成甲醇反应速率的影响,确定适宜的催化剂工艺条件。结果表明,在较长接触时间下,随着温度的升高,CO转化率、H_2转化率和甲醇相对含量先升高后降低,CO_2转化率降低。在较低温度下,CO_2转化率随接触时间延长基本不变,表明甲醇中碳元素主要来自于CO,而CO_2浓度处于水汽变换反应与加氢形成甲醇反应之间的平衡状态。     

Synthesis and characterization of switchable ionic compound based on DBU,CH3OH,and CO2

Switchable ionic compounds have wide applications in chemical processes. A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), CH₃OH and CO₂ was synthesized and characterized. DBU/ CH₃OH/CO₂ ionic compound was prepared in the presence of excess methanol, and then the excess methanol was removed by reduced pressure distillation in CO₂ atmosphere. The product yield (100%) reached the theoretical maximumfor the first time. Its structurewas identified by NMR, FT-IR, and XRD. The crystal product shows 8 strong peaks in XRD at 2θ values of 16.0547°, 16.4308°, 16.7651°, 18.8714°, 19.2140°, 21.9471°, 22.0780°, and 25.5661°. Its decomposition onset temperature (53 ℃) was affirmed by TGA, which is lower than its melting point. And its ionic switch point was measured by conductivity.     

Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH_3O–NO bond will break with a bond energy of 1.91 eV, and the produced CH_3O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C–H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH_3O and NO takes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that(i) at low coverage, a successive dehydrogenation of the adsorbed CH_3O to CO and H is favored while(ii) at high coverage, hydrogenation of CH_3O to methanol and carbonylation of CH_3O to methyl formate are more preferred. On the basis of the proposed reaction mechanism,two meaningful ways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.     

Methanol partial oxidation on carbon-supported Pt and Pd catalysts

Different Pt and Pd catalysts supported on an activated carbon were prepared by using different metal precursors. Prepared catalysts were pretreated at 400 °C under different atmospheres to decompose the precursor compound and reduce the metal. After pretreatments, the supported catalysts were characterized by H₂ chemisorption, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy to know their metal dispersion, particle size, distribution and oxidation state. Afterwards, the catalysts were tested in methanol partial oxidation with two different O₂/CH₃OH molar ratios. Results obtained in this reaction were compared with those obtained for methanol decomposition in inert atmosphere. For Pt catalysts, there was an increase in methanol conversion and hydrogen production and a decrease in carbon monoxide production under oxidizing conditions. Both methanol conversion and partial oxidation reactions appear to be sensitive to Pt particle structure in the particle size range studied. Results obtained under oxidizing conditions differed between Pd and Pt catalysts. Finally, catalytic activity in methanol partial oxidation was more affected by Pt than Pd particle size in the size range studied.     

Low-temperature catalytic combustion of methanol and its decomposed derivatives over supported gold catalysts

Gold can be compared favorably with Pd and Pt in the catalytic combustion of CH₃OH, HCHO and HCOOH when it is deposited on some reducible metal oxides (-Fe₂O₃, TiO₂, etc.). While the supported gold catalysts are less active in H₂ oxidation, they exhibit much higher activities in CO oxidation. For Au/TiO₂, the effect of catalyst preparation was further investigated. Since the activity for CO oxidation of the gold catalysts is not depressed but enhanced by moisture, they are practically applicable to CO removal from air at room temperature. Gold supported on manganese oxide is especially effective in the selective CO removal from hydrogen, indicating its potential applicability to polymer electrolyte fuel cells using the reformed gas of methanol.     

低温甲醇合成研究进展

日本学者Tsubaki等开创了一种全新的低温甲醇合成反应路径。该路径以含有二氧化碳的合成气为反应原料,使用单一低碳醇(包括甲醇)同时作为催化剂和溶剂,实现了反应原料一氧化碳在低温(443 K)条件下,一步转化率达到70%～100%。原位红外和多种表征手段证明,该反应能够在低温条件下进行,是由于催化剂上吸附的甲酸盐物种可以和多种低碳醇溶剂在低温条件发生酯化反应,生成相对应的甲酸酯。而生成的甲酸酯很容易在低温条件下,铜基催化剂表面,发生加氢反应,生成甲醇和相应的溶剂醇。该种全新的甲醇合成路径克服了常规甲醇合成过程中,甲酸盐必须在高温条件下才能发生加氢反应的关键步骤。同时,还介绍了适用于低温甲醇合成反应的金属Cu/ZnO催化剂制备方法的研究进展。全新的溶胶-凝胶-燃烧法、固相研磨-燃烧法以及甲酸辅助燃烧法直接制备高活性、纳米尺度、高分散的金属Cu/ZnO催化剂,而不需要额外的还原流程。     

SCR of NOx with CH3OH on H-mordenite: mechanism and reaction intermediates

The selective reduction of NO_x over H-mordenite (H-m) was studied using CH₃OH as reducing agent. Results are compared with those obtained with other conventional reducing agents (ethylene and methane), with gas-phase reactions, and with other metal-exchanged mordenites (Cu-mordenite (Cu-m) and Co-mordenite (Co-m)). H-m was found to be an effective catalyst for the SCR of NO_x with CH₃OH. When different reducing agents were compared over H-m, CH₃OH > C₂H₄ > CH₄ was the order according to the maximum NO conversion obtained using 1% of oxygen in the feed. Instead, if selectivity is considered, the order results CH₄ > CH₃OH > C₂H₄. In reaction experiments, two distinct zones defined by two maxima with NO to N₂ conversion are obtained at two different temperatures. A correlation exists between the said zones and the CO : CO₂ ratio. At low temperatures, CO prevails whereas at high temperatures CO₂ prevails. These results indicate that there exist different reaction intermediates. Evidence from reaction experiments, FTIR results, and transient experiments suggest that the reaction mechanism involves formaldehyde and dimethyl ether (DME) as intermediates in the 200–500°C temperature range. The surface interaction between CH₃OH (or its decomposition products) and NO is negligible if compared with NO₂, indicating that the oxidation of NO to NO₂ on acid sites is a fundamental path in this system. Different from other non-oxygenated reductants (methane and ethylene), a gas-phase NO_x initiation effect on hydrocarbon combustion was not observed.     

Microwave-assisted catalyst-free hydrolysis of fibrous cellulose for deriving sugars and biochemicals

Microwave (MW) assisted catalyst-free hydrolysis of fibrous cellulose (FC, cellulolysis) at 200°C promoted a cellulose conversion of ca. 37.2% and quantitative production of valuable C5/C6 sugars (e.g., glucose) and the according platform biochemicals (e.g., 5-hydroxymethylfurfural), corresponding to an overall selectivity of 96.5%. Conversely, conventional hydrothermal cellulolysis under similar conditions was not effective, even after 24 h, carbonising the FC. Based on the systematic study of MW-assisted cellulolysis, the specific interaction between water molecules and macroscopic FC under the MW irradiation was proposed, accounting for the interpretation of the experimental observation. The kinetic energy of water molecules under the MW irradiation facilitated the C–C (in the non-hindered surface –CH₂OH groups) and C–O–C bond breaking (inside the cellulose cavities) in FC, producing primary cellulolysis products of xylose, glucose and cellobiose.     

PERMEATION THROUGH KAPTON® POLYIMIDE AT ELEVATED TEMPERATURES

The permeabilities of CH₄, CO₂, CH₃OH, H₂O, O₂, and CO through films of Kapton® polyimide were measured at temperatures of 50, 100, 150, 200, and 250°C and pressures below 1 atm. Apparent activation energies for the permeation of the pure components ranged from 31.6kJ mol^-1 for CH₄ to nearly 0 for H₂O under the conditions studied. The ideal permselectivity for methanol relative to methane decreased from over 100 to under 10 as the temperature was increased from 50 to 250°C.     

The Catalytic Hydrogenation of Carbon Monoxide. The Formation of C1 Hydrocarbons

Both the production of methane and methanol from CO and H₂ are important processes in chemical technology. They also have a distinguished history as the formation of methane was first reported by Sabatier and Senderens [1] in 1902. Methanol synthesis from CO and H₂ was first reported by Patart [2] in 1921, and in 1923 Badische Anilin and Soda Fabrik (BASF) announced the synthesis of CH₃OH to the exclusion of other products [3]. The catalytic reactions that produced these two molecules, however, have been subjected to molecular scale studies only recently. We shall review here what is known about the kinetics and mechanisms of these reactions, about the catalytically active surface, and the nature of the surface chemical bond of CO, H₂, and the reaction intermediates.     

Methanol electro-oxidation on carbon-supported and Pt-modified Au nanoparticles

Methanol electro-oxidation on Pt-modified Au nanoparticles was studied in aqueous 0.5 M H₂SO₄/1 M CH₃OH. The Pt-modified Au nanoparticles showed lower values than pure Pt nanoparticles in area-specific current densities. The activity also decreased with lower amounts of Pt on the Pt-modified Au nanoparticles. This result indicates that the intrinsic activities of the Pt-modified Au nanoparticles were lower than that of Pt/C. This phenomenon may be due to the strengthened Pt–CO bonding or the weakened ensemble effect in the methanol electro-oxidation. However, in the Pt-specific current densities, the Pt-modified Au nanoparticles showed higher values than pure Pt nanoparticles. This enhanced electrocatalytic activity could be attributed to more reaction-favorable surface structures of Pt-modified Au nanoparticles, which most likely lead a high level of Pt utilization for the electro-oxidation reaction.     

In situ FTIR study on reaction pathways in Ni(CO)4/CH3OK catalytic system for low-temperature methanol synthesis in a liquid medium

An in situ infrared spectroscopic study was conducted to elucidate the reaction pathways for low-temperature methanol synthesis in a catalytic system composed of Ni(CO)₄ and CH₃OK (denoted as Ni(CO)₄/CH₃OK). The reaction was conducted in a liquid medium at 313–333 K with an initial pressure of 3.0 MPa. When CH₃OK was added to Ni(CO)₄ solution at 293 K, different carbonylnickelates, [Ni₅(CO)₁₂]²⁻, [Ni₆(CO)₁₂]²⁻ and [Ni(CO)₃(COOCH₃)]⁻, were immediately formed from Ni(CO)₄. The species and the composition of the carbonylnickel complexes varied with temperature. The variations in concentrations of methanol (MeOH) and methyl formate (MF) during the run, which were determined from their IR absorptions, indicated a pattern characteristic of consecutive reactions with MF as an intermediate. Thus, it was shown that methanol was produced through the carbonylation of MeOH to MF and the subsequent hydrogenation of MF to MeOH. Stable hydridocarbonylnickel anions, [HNi(CO)₃]⁻ and/or [HNi₂(CO)₆]⁻, were observed together with a small amount of Ni(CO)₄ throughout the methanol synthesis. Since Ni(CO)₄ alone showed no activity for the hydrogenation of MF, the hydridocarbonylnickel anions generated in the presence of CH₃OK must be responsible for the reaction. The dual role of CH₃OK in the catalytic system was stated.     

KINETIC AND TRACER STUDIES ON METHANOL CONVERSION OVER SUPPORTED PLATINUM CATALYSTS

Hydrogen-deuterium exchange in methanol over Al₂,O₃, platinum black and alumina supported platinum catalysts have been investigated by means of mass spectrometry. The hydrogen-deuterium exchange proceeds faster over Pt/Al₂O₃ than either platinum black or alumina, and the rate (as well as the rate of dimethyl ether formation) increases with platinum dispersion. From the reactions CH₃OH + D₂, CD₃OH + H₂ and CD₃OH + D₂ the different exchange rates of the CH₃ and OH groups (R₁, and R₂, respectively) were determined. For all catalysts studied the exchange in the OH group was two or three orders of magnitude faster than CH₃ group. Exchange in the methyl group needs higher activation energy: R₁/R₂ ratio increases with temperature. Catalyst pretreatment has an important effect: higher activation temperature results in a higher R₁/R₂ ratio.

A methematical method is suggested for the evaluation of exchange rates of a molecule with two different types of hydrogen and a model is given for the interpretation of measured data: methanol is activated mainly on Al₂,O₃, forming surface methoxide groups on the Lewis acidic sites. This methoxide can react with deuterium atoms having been activated over platinum sites. With increasing dispersion the metal-support interface is enhanced which leads to higher rate of exchange.     

The Molecular Origins of Selectivity in Methanol Decomposition on Pd Nanoparticles

We have combined multi-molecular beam methods and in-situ time-resolved IR reflection absorption spectroscopy (IRAS) to explore the kinetics of methanol decomposition on a supported Pd model catalyst. The well-shaped Pd nanoparticles are prepared under ultra-high vacuum conditions on a well-ordered alumina film and have previously been characterized with respect to size, density, and morphology.Two competing decomposition pathways are observed: Whereas dehydrogenation to CO represents the dominating reaction channel, C-O bond scission proceeds at much lower rates and leads to the formation of carbon and hydrocarbon species. Using CO as a probe molecule, we show via IRAS spectroscopy that these carbon and hydrocarbon species preferentially block defect sites on the Pd particles such as steps or edges, whereas the (111) facet sites are affected to a lesser extent.Employing quantitative IR\Sigma AS and steady-state isotope exchange experiments, the reaction rates for both channels are measured as a function of carbon coverage. It is found that with increasing carbon coverage, the rate of carbon formation drops rapidly, whereas the kinetics of dehydrogenation is hardly affected. These results demonstrate that the rate of C-O bond scission is drastically enhanced at the particle steps and edges, whereas for the dehydrogenation pathway this is not the case.     

Partial oxidation of ethanol on Ru/Y2O3 and Pd/Y2O3 catalysts for hydrogen production

The partial oxidation of ethanol was investigated over Ru and Pd catalysts supported onto yttria over a wide range of temperatures (473–1073 K). The product distributions obtained over these catalytic systems were correlated with diffuse reflectance infrared spectroscopy analyses (DRIFTS). Results showed that reaction route depended strongly on the type of metal. The decomposition of ethoxy species to CH₄ and CO or oxidation to CO₂ was promoted by Pd, and the acetaldehyde desorption was predominant over Ru in the low temperature region. Furthermore, the acetate and carbonate formation prevailed over Pd, which explained the lower acetaldehyde selectivity. The presence of CH₄ and CO₂ at high temperature is assigned to the decomposition of acetate species via carbonates over Pd-based catalysts. Ru was more suitable system for H₂ production than Pd by achieving a selectivity of about 59%.     

Hydrogen production from methanol by oxidative steam reforming carried out in a membrane reactor

The aim of this work is to study from an experimental point of view the oxidative steam reforming of methanol by investigating the behaviour of a dense Pd/Ag membrane reactor (MR) in terms of methanol conversion as well as hydrogen production. The main parameters considered are the operating temperature and the O₂/CH₃OH feed ratio. This is a pioneer work in the application of MR to this kind of reaction, whose goal should be to produce a CO-free hydrogen stream suitable for hydrogen fuel cell applications. The experimental results show that the MR gives methanol conversions higher than traditional reactors (TRs) at each temperature investigated, confirming the good potential of the membrane reactor device for this interesting reaction system.     

基于FTIR分析的稻草热解机理

The pyrolysis mechanism of rice straw (RS) was investigated using a tube reactor with Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analyzer. The results show that the maximum pyrolysis rate increases with increasing heating rate and the corresponding temperature also increases. The three-pseudocomponent model could describe the pyrolysis behavior of rice straw accurately. The main pyrolysis gas products are H2O, CO2, CO, CH4, HCHO (formaldehyde), HCOOH (formic acid), CH3OH (methanol), C6H5OH (phenol), etc. The releasing of H2O, CO2, CO and CH4 mainly focuses at 220-400°C. The H2O formation process is separated into two stages corresponding to the evaporation of free water and the formation of primary volatiles. The release of CO2 first increases with increasing temperature and gets the maximum at 309°C. The releasing behavior of CO is similar to H2O and CO2 between 200 and 400°C. The production of CH4 happens, compared to CO2 and CO, at higher temperatures of 275-400°C with the maximum at 309°C. When the temperature exceeds 200°C, hydroxyl and aliphatic C H groups decrease significantly, while C O, olefinic C C bonds and ether structures increase first in the chars and then the aromatic structure develops with rising temperature. Above 500°C, the material becomes increasingly more aromatic and the ether groups decreases with an increase of temperature. The aromatization process starts at ≈350°C and continues to higher temperatures.     

焦炉煤气-甲醇产业链延伸技术方案的经济分析

与煤制甲醇和天然气制甲醇工艺相比,焦炉煤气制甲醇不仅可以有效利用焦炉煤气中的氢,而且具有低成本的优势。在焦炉煤气制甲醇工艺基础上,文中提出了3种具有发展潜力的焦炉煤气综合利用方案：①气化煤气-焦炉煤气制甲醇生产方案;② 焦炉煤气-乙炔-甲醇下游产品方案;③ 气化煤气-焦炉煤气-乙炔-甲醇下游产品方案。以200×10⁴ t焦炭的生产规模分析了3种方案经济性,其毛利润分别为24.21亿元,18.92亿元和28.74亿元;内部收益率分别为28.29%、24.34%和27.11%。气化煤气-焦炉煤气-乙炔-甲醇下游产品方案充分发挥了规模效应和产品高附加值的特点,具有明显的经济优势;系统灵活性高,抵御市场风险能力强。