109-87-5Relevant articles and documents
An easily accessible Re-based catalyst for the selective conversion of methanol: Evidence for an unprecedented active site structure through combined operando techniques
Yoboue, Anthony,Susset, Audrey,Tougerti, Asma,Gallego, Daniel,Ramani, Sudarsan Venkat,Kalyanikar, Malathi,Dolzhnikov, Dmitriy S.,Wubshet, Sileshi G.,Wang, Yilun,Cristol, Sylvain,Briois, Valerie,La Fontaine, Camille,Gauvin, Regis. M.,Paul, Jean-Franois,Berrier, Elise
, p. 4285 - 4287 (2011)
Heterogeneous Re/SiO2 catalysts prepared using a one pot sol-gel synthesis were found to display high activity in the direct, selective methanol conversion to methylal, which is correlated to an unprecedented rhenium oxide structure.
Carbon molecular sieves as catalysts and catalyst supports
Grunewald, Gerald C.,Drago, Russell S.
, p. 1636 - 1639 (1991)
Ultrahigh surface area (>2500 m2/g) carbon molecular sieves (CMS's) are shown to be very effective catalysts and catalyst supports for the oxidative dehydrogenation and dehydration of a variety of substrates. Studies of methanol, ethanol, 1- and 2-propanol, and propanal provide mechanistic insight concerning the reactivity of these materials. The activities are superior to many inorganic oxide based systems. As catalysts, CMS systems are shown to have the ability to function via hydride or hydrogen atom abstraction mechanisms, depending on the nature of the substrate. As catalyst supports, a synergism is demonstrated between the CMS support and metal dopants, which enables the system to have greater activity than that of either of the constituents alone. The highly reactive surface, the ability to disperse and stabilize metal clusters, and the extraordinary adsorption capabilities of the CMS materials are the key contributors to their high activity. One of the catalysts studied (a 15% MoO3/CMS system) has pronounced activity toward methanol oxidation: 70% of the substrate is converted to methyl formate in a single pass with over 95% selectivity. A further significant finding involves the metal-catalyzed conversion of the carbonaceous support itself to small molecular weight products via reactions with methanol fragments. This finding has fundamental implications in heterogeneous catalyzed CO reductions and in the conversion of methanol to gasoline in zeolites.
Niobium-substituted octahedral molecular sieve (OMS-2) materials in selective oxidation of methanol to dimethoxymethane
Wasalathanthri, Niluka D.,Guild, Curtis,Nizami, Quddus A.,Dissanayake, Shanka L.,He, Junkai,Kerns, Peter,Fee, Jared,Achola, Laura,Rathnayake, Dinithi,Weerakkody, Chandima,Suib, Steven L.,Nandi, Partha
, p. 32665 - 32673 (2019)
Octahedral molecular sieve (OMS-2) refers to a one-dimensional 2 × 2 framework of octahedral manganese oxo units based on the cryptomelane-type framework. Herein, we describe a niobium (Nb) substituted mixed metal oxide of Nb and Mn where the cryptomelane-type framework is retained. These materials are hydrothermally synthesized from the reaction of potassium permanganate, manganese sulfate, and homogeneous niobium(v) precursors. Niobium incorporation up to 31 mol% can be achieved without destroying the one dimensional 2 × 2 framework. The yields of the materials vary between 70 and 90%. These materials are analyzed by powder XRD, BET isotherm, TEM, SEM, XRF, and XPS studies. The synthesized materials show promising activity in selective oxidation of methanol to dimethoxymethane (DMM) at 200 °C. Normalized activity correlations followed the trend 21% Nb-OMS-2 > 15% Nb-OMS-2 > 31% Nb-OMS-2 > 68% Nb-OMS-2 > K-OMS-2. A fluctuation in methanol conversion was observed around 125-150 °C in most samples, suggesting this to be a catalytically important temperature regime when forming active sites for DMM production.
Kinetic relationships in synthesis of dimethoxymethane
Danov,Kolesnikov,Logutov
, p. 1994 - 1996 (2004)
The kinetics of formation of dimethoxymethane by acetalization of formaldehyde with methanol, catalyzed by silicotungstic heteropoly acid, were studied.
Synthesis of propylene from renewable allyl alcohol by photocatalytic transfer hydrogenolysis
Caner, Joaquim,Liu, Zijun,Takada, Yuki,Kudo, Akihiko,Naka, Hiroshi,Saito, Susumu
, p. 4093 - 4098 (2014)
Photochemical transformation of biomass-derived or renewable substances with promising scalability is an important challenge for promoting green and sustainable chemistry. We report here that photocatalytic transfer hydrogenolysis of allyl alcohol (obtained from glycerol) gives potentially sustainable propylene with high chemo- and redox selectivity, promoted by powdered Pd/TiO2 in CH3OH (obtained from CO2) under near-ultraviolet-visible light irradiation (λ > 365 nm) at ambient temperature.
Direct Synthesis of Hydrogen and Dimethoxylmethane from Methanol on Copper/Silica Catalysts with Optimal Cu+/Cu0 Sites
Wu, Liubi,Li, Bolong,Zhao, Chen
, p. 1140 - 1147 (2018)
Hydrogen is an important sustainable resource, and here we report a catalytic route for the direct production of hydrogen (with a purity of 95 %) and dimethoxylmethane (DMM) from supercritical methanol over a Cu/SiO2 catalyst prepared by deposition–precipitation with ammonia (DPA) at 240°C in a one-pot process. The procedure starts with methanol dehydrogenation to hydrogen and formaldehyde at the interface of the Cu2O?SiO2–Cu0 particle mixture, and subsequently, the formaldehyde intermediate condenses with substantial methanol to form DMM in the liquid phase. The Cu0, CuO, and chrysocolla species are inactive for hydrogen generation from methanol, and the intrinsic active species for methanol decomposition is the Cu2O?SiO2–Cu0 nanoparticle interface, which is produced from the hydrogen reduction of Cu2Si2O5(OH)2 or from the methanol reduction of Cu?O?Si moieties. A correlation between the structure and activity on reduced Cu/SiO2 (DPA) suggested that only Cu0 was not active, but the combined Cu0 and Cu+ sites with interfaces on SiO2 with an optimal Cu+/Cu0 ratio of 1.56 were highly active for methanol dehydrogenation and subsequent condensation steps. The developed new catalytic system offers a facile and atom-economical way to generate pure hydrogen (almost CO free) from liquid methanol that can be used in fuel cell and hydrogen-involved biomass reactions.
A Composite Fe–V/g-C3N4 for Liquid-Phase Selective Oxidation of Methanol with O2 Oxidant
Zhang, Jing,Wang, Hongxia,Lu, Bin,Zhao, Jingxiang,Cai, Qinghai
, p. 909 - 919 (2021)
Abstract: A composite material Fe–V/g-C3N4 prepared by impregnation achieved an efficient performance for heterogeneously catalytic oxidation of methanol to dimethoxymethane (DMM) and poly(oxymethylene) dimethyl ethers (POM) by O2 oxidant in batch reactor, exhibiting 34.3% conversion and > 99.0% selectivity to DMM and POM. However, a pioneered strategy for tuneable synthesis of DMM and POM was realized by controlling the reaction time. The experimental results revealed that FeVO4 and V2O5 nanoparticle crystallizes served as the active sites and higher specific areas 29.3–51.9 m3/g for the catalysts were jointly responsible for the high activity. Besides, the catalyst could be easily recovered and effectively reused. Graphic Abstract: A composite material Fe–V/g-C3N4 with higher specific area exhibited efficient performance for heterogeneously catalytic oxidation of methanol to dimethoxymethane (DMM) and polyoxymethylene dimethyl ether (POM) in batch reactor using O2 oxidant. Moreover, a pioneered strategy for tunable synthesis of DMM and POM was realized by controlling the reaction time. The catalyst was easily recovered and had excellent recycle lifetime and stability. [Figure not available: see fulltext.]
Highly selective oxidation of methanol to dimethoxymethane over SO42-/V2O5-ZrO2
Tao, Meng,Wang, Hongxia,Lu, Bin,Zhao, Jingxiang,Cai, Qinghai
, p. 8370 - 8376 (2017)
The sulfated vanadia-zirconia SO42-/V2O5-ZrO2 catalyst, prepared by an impregnation method and calcined at various temperatures, was found to have a high catalytic activity for methanol oxidation to dimethoxymethane in a fixed bed reactor and a batch autoclave using O2 as the oxidant due to the crystalline V2O5 dispersed on the surface as redox active sites, as well as stronger acidic sites.
Amorphous oxide as a novel efficient catalyst for direct selective oxidation of methanol to dimethoxymethane
Royer, Sebastien,Secordel, Xavier,Brandhorst, Markus,Dumeignil, Franck,Cristol, Sylvain,Dujardin, Christophe,Capron, Mickael,Payen, Edmond,Dubois, Jean-Luc
, p. 865 - 867 (2008)
We report for the first time the use of an amorphous oxide catalyst for the selective oxidation of methanol in the gas phase, leading at 553 K to the production of dimethoxymethane with a selectivity as high as 90% at high methanol conversion (68%). The Royal Society of Chemistry.
Initial Carbon–Carbon Bond Formation during the Early Stages of the Methanol-to-Olefin Process Proven by Zeolite-Trapped Acetate and Methyl Acetate
Chowdhury, Abhishek Dutta,Houben, Klaartje,Whiting, Gareth T.,Mokhtar, Mohamed,Asiri, Abdullah M.,Al-Thabaiti, Shaeel A.,Basahel, Suliman N.,Baldus, Marc,Weckhuysen, Bert M.
, p. 15840 - 15845 (2016)
Methanol-to-olefin (MTO) catalysis is a very active field of research because there is a wide variety of sometimes conflicting mechanistic proposals. An example is the ongoing discussion on the initial C?C bond formation from methanol during the induction period of the MTO process. By employing a combination of solid-state NMR spectroscopy with UV/Vis diffuse reflectance spectroscopy and mass spectrometry on an active H-SAPO-34 catalyst, we provide spectroscopic evidence for the formation of surface acetate and methyl acetate, as well as dimethoxymethane during the MTO process. As a consequence, new insights in the formation of the first C?C bond are provided, suggesting a direct mechanism may be operative, at least in the early stages of the MTO reaction.
