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Cas Database

107-31-3

107-31-3

Identification

  • Product Name:Methyl formate

  • CAS Number: 107-31-3

  • EINECS:203-481-7

  • Molecular Weight:60.0526

  • Molecular Formula: C2H4O2

  • HS Code:2915 13 00

  • Mol File:107-31-3.mol

Synonyms:Methanoicacid methyl ester;Methyl methanoate;Formiate de methyle;Methylformiaat;Methylformiat;

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Safety information and MSDS view more

  • Pictogram(s):HighlyF+,HarmfulXn

  • Hazard Codes:F+,Xn

  • Signal Word:Danger

  • Hazard Statement:H224 Extremely flammable liquid and vapourH302 Harmful if swallowed H319 Causes serious eye irritation H332 Harmful if inhaled H335 May cause respiratory irritation

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Refer for medical attention. In case of skin contact Remove contaminated clothes. Rinse skin with plenty of water or shower. In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Rinse mouth. Do NOT induce vomiting. Rest. Refer for medical attention . Inhalation causes irritation of mucous membranes. Prolonged inhalation can produce narcosis and central nervous symptoms, including some temporary visual disturbance. Contact with liquid irritates eyes and may irritate skin if allowed to remain. Ingestion causes irritation of mouth and stomach and central nervous system depression, including visual disturbances. (USCG, 1999) Removal to fresh air, immediate removal of contact lenses and contaminated clothing and washing of the skin followed by adequate rest is recommended. Respiratory irritation may be ameliorated by inhalation of a mist of a 5% sodium bicarbonate solution. If pulmonary edema develops, medical advice should be sought. Oxygen should be administered if the patient exhibits signs of respiratory failure.

  • Fire-fighting measures: Suitable extinguishing media If material on fire or involved in fire: Do not extinguish unless flow can be stopped. Use "alcohol" foam, dry chemical or carbon dioxide. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Do not use water on material itself. Behavior in Fire: Vapor is heavier than air and may travel considerable distance to a source of ignition and flash back. (USCG, 1999) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Remove all ignition sources. Evacuate danger area! Consult an expert! Personal protection: complete protective clothing including self-contained breathing apparatus. Ventilation. Collect leaking liquid in sealable containers. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. 1. Remove all ignition sources. 2. Ventilate area of spill or leak. 3. For small quantities, absorb on paper towels. Evaporate in a safe place (such as a fume hood). Allow sufficient time for evaporating vapors to completely clear the hood ductwork. Burn the paper in a suitable location away from combustible materials. Large quantities can be reclaimed or collected and atomized in a suitable combustion chamber.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Fireproof. Separated from strong oxidants. Cool.Store in cool, dry, well-ventilated location. Seperate from alkalis, oxidizing materials, and moisture. Outside or detached storage is prefered.

  • Exposure controls/personal protection:Occupational Exposure limit valuesRecommended Exposure Limit: 10 Hr Time-Weighted Avg: 100 ppm (250 mg/cu m).Recommended Exposure Limit: 15 Min Short-Term Exposure Limit: 150 ppm (375 mg/cu m).Biological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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  • Manufacture/Brand:TRC
  • Product Description:Methyl Formate
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  • Manufacture/Brand:TCI Chemical
  • Product Description:Methyl Formate [Standard Material for GC] >99.5%(GC)
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  • Manufacture/Brand:TCI Chemical
  • Product Description:Methyl Formate [for Spectrophotometry] >98.0%(GC)
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  • Manufacture/Brand:TCI Chemical
  • Product Description:Methyl Formate >95.0%(GC)
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methyl formate for synthesis. CAS 107-31-3, pH 4 - 5 (200 g/l, H O, 20 °C)., for synthesis
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methyl formate for synthesis
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methyl formate for synthesis. CAS 107-31-3, pH 4 - 5 (200 g/l, H O, 20 °C)., for synthesis
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methyl formate for synthesis
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methyl formate for synthesis. CAS 107-31-3, pH 4 - 5 (200 g/l, H O, 20 °C)., for synthesis
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Relevant articles and documentsAll total 452 Articles be found

Effects of the MoO3 structure of Mo-Sn catalysts on dimethyl ether oxidation to methyl formate under mild conditions

Liu, Guangbo,Zhang, Qingde,Han, Yizhuo,Tsubaki, Noritatsu,Tan, Yisheng

, p. 1057 - 1064 (2015)

The selective oxidation of dimethyl ether (DME) to methyl formate (MF) was conducted in a fixed-bed reactor over the MoO3-SnO2 catalysts with different Mo/Sn ratios. The MF selectivity reached 94.1% and the DME conversion was 33.9% without the formation of COx over the MoSn catalyst at 433 K. The catalysts were deeply characterized by NH3-TPD, CO2-TPD, BET, XPS and H2-TPR. The characterization results showed that different compositions of catalysts obviously affected the surface properties of the catalysts, but the valence of the metal hardly changed with the Mo/Sn ratios. Raman spectroscopy, XRD and XAFS were further used to characterize the structure of the catalysts. The results indicated that the catalyst composition exerted a significant influence on the structure of MoO3. The formation of oligomeric MoO3 and the appropriate coordination numbers of Mo-O at 1.94 ? are the main reasons for the distinct high catalytic activity of the MoSn catalyst. This journal is

Surface and catalytic properties of Ce-, Zr-, Au-, Cu-modified SBA-15

Kaminski, Piotr,Ziolek, Maria

, p. 249 - 262 (2014)

Au- and CeO2-containing catalysts, supported on SBA-15 mesoporous molecular sieves and loaded with additives such as Cu and Zr species, were obtained and characterised. Cerium oxides are preferentially located in the bulk of SBA-15, whereas Zr species on its surface. Gold and copper loaded on supports strongly interact resulting in the electron transfer from Cu + to metallic gold, thus enhancing redox properties. Moreover, cerium species interact with gold, increasing redox properties of the system. The presence of copper increases the gold dispersion. Ce- and Zr-containing supports contain Lewis acid sites (LAS). The number of LAS is increased by the modification with copper species, whereas gold loading diminishes the LAS content. The presence of Zr species is responsible for Bronsted acidity and directs the oxidation of methanol to dimethyl ether. Copper enhances the selectivity to methyl formate. Gold and cerium are responsible for total oxidation of methanol, which is enhanced by modification with copper. The most attractive catalyst for low temperature total oxidation of methanol is bimetallic AuCu/CeSBA-15.

Cu Sub-Nanoparticles on Cu/CeO2 as an Effective Catalyst for Methanol Synthesis from Organic Carbonate by Hydrogenation

Tamura, Masazumi,Kitanaka, Takahisa,Nakagawa, Yoshinao,Tomishige, Keiichi

, p. 376 - 380 (2016)

Cu/CeO2 works as an effective heterogeneous catalyst for hydrogenation of dimethyl carbonate to methanol at 433 K and even at low H2 pressure of 2.5 MPa, and it provided 94% and 98% methanol yield based on the carbonyl and total produced methanol, respectively. This is the first report of high yield synthesis of methanol from DMC by hydrogenation with H2 over heterogeneous catalysts. Characterization of the Cu/CeO2 catalyst demonstrated that reduction of Cu/CeO2 produced Cu metal with 2 surface, which is responsible for the high catalytic performance.

VAPOR PHASE CARBONYLATION OF METHYL ACETATE, METHANOL, AND DIMETHYL ETHER WITH MOLYBDENUM-ACTIVE CARBON CATALYST

Shikada, Tsutomu,Yagita, Hiroshi,Fujimoto, Kaoru,Tominaga, Hiro-o

, p. 547 - 550 (1985)

A molybdenum-active carbon catalyst was found to catalyze the vapor phase carbonylation of methyl acetate and related compounds under pressurized conditions in the presence of methyl iodide promoter.Acetic anhydride was formed from methyl acetate with an yield of 15percent and a selectivity of 83percent at 250 deg C and 45 atm.The molybdenum-active carbon catalyst was active also for the carbonylation of methanol and dimethyl ether to form methyl acetate.

Synergetic Behavior of TiO2-Supported Pd(z)Pt(1-z) Catalysts in the Green Synthesis of Methyl Formate

Baldovino-Medrano, Víctor G.,Pollefeyt, Glenn,Bliznuk, Vitaliy,Van Driessche, Isabel,Gaigneaux, Eric M.,Ruiz, Patricio,Wojcieszak, Robert

, p. 1157 - 1166 (2016)

Methyl formate (MF) is a valuable platform molecule, the industrial production of which is far from being green. In this contribution, TiO2-supported Pd(z)Pt(1-z) catalysts were found to be effective in the green synthesis of methyl formate (MF) - at T=323 K and ambient pressure - through methanol (MeOH) oxidation. Two series of catalysts with similar bulk Pd/(Pd+Pt) molar ratios, z, were prepared; one by a water-in-oil microemulsion (MicE) method and the other by an incipient wetness impregnation (IWI). The MicE method led to more efficient catalysts owing to a weak influence of z on particle size distributions and nanoparticles composition. Pd(z)Pt(1-z)-MicE catalysts exhibited strong synergistic effects for MF production but weak synergistic effects for MeOH conversion. The catalytic performance of Pd(z)Pt(1-z)-MicE was superior to that of Pd(z)Pt(1-z)-IWI catalysts despite the latter displaying synergetic effects during the reaction. The catalytic behavior of TiO2-supported Pd(z)Pt(1-z) catalysts was explained from correlations between XRD, TEM, and X-ray photoelectron spectroscopy characterizations.

Chemical species active for selective oxygenation of methane with hydrogen peroxide catalyzed by vanadium-containing compounds

Seki, Yasuhiro,Mizuno, Noritaka,Misono, Makoto

, p. 1195 - 1196 (1998)

UV-vis data revealed that monoperoxomonovanadate is an active species for liquid-phase oxygenation of methane with hydrogen peroxide catalyzed vanadium-containing catalysts in trifluoroacetic anhydride.

The mechanism of dimethyl carbonate synthesis on Cu-exchanged zeolite Y

Zhang, Yihua,Bell, Alexis T.

, p. 153 - 161 (2008)

The mechanism of dimethyl carbonate (DMC) synthesis from oxidative carbonylation of methanol over Cu-exchanged Y zeolite has been investigated using in situ infrared spectroscopy and mass spectrometry under transient-response conditions. The formation of DMC is initiated by reaction of molecularly adsorbed methanol with oxygen to form either mono- or di-methoxide species bound to Cu+ cations. Reaction of the mono-methoxide species with CO produces monomethyl carbonate (MMC) species. DMC is formed via two distinct reaction pathways-CO addition to di-methoxide species or by reaction of methanol with MMC. The rate-limiting step in DMC synthesis is found to be the reaction of CO with mono-methoxide or di-methoxide species. The first of these reactions produces MMC, which then reacts rapidly with methanol to produce DMC, whereas the second of these reactions produces DMC directly. Formaldehyde was identified as an intermediate in the formation of dimethoxy methane (DMM) and methyl formate (MF). Both byproducts are thought to form via a hemiacetal intermediate produced by the reaction of methanol with adsorbed formaldehyde at a Cu+ site.

Ester synthesis by NAD(+)-dependent dehydrogenation of hemiacetal: production of methyl formate by cells of methylotrophic yeasts.

Murdanoto,Sakai,Sembiring,Tani,Kato

, p. 1391 - 1393 (1997)

A water-soluble ester, methyl formate, was detected as a metabolite in the culture medium of methylotrophic yeasts. Methyl formate synthase, which catalyses NAD(+)-dependent dehydrogenation of the hemiacetal adduct of methanol and formaldehyde, catalyses the ester synthesis. The enzyme activity was induced on a methanol medium and was increased further by the addition of formaldehyde. In the reaction system using intact cells of Pichia methanolica AKU 4262, 135 mM (8.1 g/liter) methyl formate was produced from 2 M methanol. This is a new biological process for ester synthesis that couples spontaneous formation of hemiacetal and alcohol dehydrogenase.

Study of thermolysis of peroxyacetals and peroxycetals

Helgorsky,Saux,Degueil-Castaing,Maillard

, p. 8263 - 8274 (1996)

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Redox chemistry of gaseous reactants inside photoexcited FeAlPO4 molecular sieve

Ulagappan,Frei

, p. 490 - 496 (2000)

Photochemical studies were conducted to probe the reactivity of the excited Fe-O ligand-to-metal charge-transfer state of the Fe-substituted aluminophosphate sieve with AFI structure (FeAlPO4-5 or FAPO-5), at the gas-micropore interface. Laser light at 350-430 nm was used to excite the metal centers, and low alcohols (methanol, 2-propanol) and O2 were used as donors and electron acceptor, respectively. Subsequent proton transfer and H atom abstraction yielded formaldehyde (acetone) and H2O2, resulting in an overall two-electron transfer process. In these products, acetone was stable in the sieve, while formaldehyde underwent fast Cannizzaro reaction and H2O2 disproportionated to H2O and O2. O2 was efficiently reduced by transient framework Fe+II, indicating that its reduction potential lies at least 0.50 of a volt more than that of a conduction band of dense-phase Fe2O3 particles, which may make available demanding photoreductions not accessible by photochemistry at iron oxide semiconductors materials.

Structural and reactive relevance of V + Nb coverage on alumina of V{single bond}Nb{single bond}O/Al2O3 catalytic systems

Lewandowska, Anna E.,Banares, Miguel A.,Ziolek, Maria,Khabibulin, Dzhalil F.,Lapina, Olga B.

, p. 94 - 103 (2008)

Vanadium and niobium species (together and separately) were loaded on gamma alumina, and the resulting catalysts were run in the methanol conversion. This reaction was studied by both GC analysis and FTIR study in the flow system. The catalytic properties are discussed based on the combined FTIR and 27Al, 51V and 1H MAS NMR studies. The NMR studies revealed a different mechanism of interaction between Nb and Al2O3 than that between V and Al2O3. This predetermines the structure of vanadium sites in bimetallic VNb/Al samples. The effect of coverage was considered for various metal loadings ranging from below to above monolayer. One of our most interesting findings is that the surface Nb oxide species exhibited a redox character below monolayer but were acidic above monolayer. 27Al MAS NMR revealed a strong alumina-Nb interaction that may account for its redox performance. Moreover, the role of sulfate from vanadium precursor is evidenced.

Highly active ruthenium complexes with bidentate phosphine ligands for the solvent-free catalytic synthesis of N,N-dimethylformamide and methyl formate

Kroecher, Oliver,Koeppel, Rene A.,Baiker, Alfons

, p. 453 - 454 (1997)

Complexes of the type [RuCl2L2] [L = Ph2P(CH2)nPPh2 (n = 1-3), Me2P(CH2)2PMe2] are shown to be highly active and selective catalysts for the synthesis of formic acid derivatives from carbon dioxide, hydrogen and dimethylamine or methanol-triethylamine, respectively, without any additional solvent, affording at 373 K with [RuCl2(dppe)2] an extremely high turnover frequency (TOF) of 360 000 h-1 in N,N-dimethylformamide synthesis and a TOF of 830 h-1 in methyl formate synthesis.

The new catalytic property of supported rhenium oxides for selective oxidation of methanol to methylal

Yuan, Youzhu,Shido, Takafumi,Iwasawa, Yasuhiro

, p. 1421 - 1422 (2000)

A new catalytic property of supported rhenium oxides has been found for selective methanol oxidation to methylal; high performances for the selective catalytic oxidation are observed with V2O5-, ZrO2-, Fe2O3- and TiO2-supported Reoxide catalysts, which are characterized by pulse experiments, XRD and XPS.

Ruthenium trichloride as a new catalyst for selective production of dimethoxymethane from liquid methanol with molecular oxygen as sole oxidant

Li, Meilan,Long, Yan,Deng, Zhiyong,Zhang, Hua,Yang, Xiangui,Wang, Gongying

, p. 46 - 48 (2015)

Dimethoxymethane was first synthesized from methanol with a liquid phase intermittent process which only used molecular oxygen as the sole oxidant. RuCl3 was proved to be an efficient catalyst as it posses the ability of oxidizing methanol and Lewis acidic which promotes the oxidation of methanol to formaldehyde and then methanol condensed with formaldehyde to form dimethoxymethane at Lewis acid site.

Novel anion exchange resin-based catalyst for liquid-phase methanol synthesis at 373-393 K

Aika, Ken-Ichi,Kobayashi, Hidenobu,Harada, Kenji,Inazu, Koji

, p. 1252 - 1253 (2004)

A thermo-stable anion exchange resin-Raney Cu system was found as the most effective solid catalyst for low-temperature liquid-phase methanol synthesis at 373 to 393 K under 5.0 MPa of syngas (2H2/CO). With the catalyst (20 mL of the resin and 2.0 g of Cu) suspended in methanol solution 72% of CO was converted to methanol (70%) and methyl formate (HCOOCH3) (30%) in 4 h.

Selective oxidation of dimethylether to formaldehyde on small molybdenum oxide domains

Iglesia,Liu

, p. 1 - 5 (2002)

A study on the catalytic chemistry involved in the conversion of dimethyl ether (DME) to formaldehyde on active metal oxides was carried out. MoOx species dispersed as small domains on Al2O3, ZrO2, and SnO2 catalyzed the oxidative conversion of DME to formaldehyde with high primary selectivity (80-98% HCHO, CH3OH-free basis) at 500-550 K. The reaction proceeded via redox cycles utilizing lattice oxygen and turnover rates increased with the reducibility and size of MoOx domains. DME conversion rates and formaldehyde selectivities at 513 K were considerably higher than those previously observed on different catalysts at 620-880 K.

Vapor-phase dehydrogenation of methanol to methyl formate in catalytic membrane reactor with Pd/SiO2/ceramic composite membrane

Guo, Yanglong,Lu, Guanzhong,Mo, Xunhua,Wang, Yunsong

, p. 1628 - 1629 (2004)

Vapor-phase dehydrogenation of methanol to methyl formate was investigated in the catalytic membrane reactor (CMR) with the Pd/SiO2/ceramic composite membrane prepared by an impregnation method. The studies show that the CMR has much better performance than the fixed-bed reactor, in which no methyl formate is detected under the similar reaction conditions. Copyright

Investigation of the interaction between Cu(acac)2 and NH4Y in the preparation of chlorine-free CuY catalysts for the oxidative carbonylation of methanol to a fuel additive

Wang, Yuchun,Zheng, Huayan,Li, Zhong,Xie, Kechang

, p. 102323 - 102331 (2015)

The high temperature anhydrous interaction between copper(ii) acetylacetonate Cu(acac)2 and NH4Y was investigated to prepare a chlorine-free CuY catalyst for the oxidative carbonylation of methanol to dimethyl carbonate. When a physical mixture of Cu(acac)2 and NH4Y is heated from ambient temperature to 230 °C, Cu(acac)2 firstly sublimates and then is adsorbed immediately onto the surface of the Y zeolite. Simultaneously the ion exchange between Cu(acac)2 and NH4Y occurs at about 174 °C. During the activation process from 230 to 500 °C, the exchanged Cu2+ is reduced to a Cu+ active center, and the adsorbed and unreacted Cu(acac)2 on the NH4Y surface decomposes to nano-CuO. For NaY zeolite, no solid state ion-exchange occurs between Cu(acac)2 and NaY during the heat treatment and only CuO exists on the Cu/NaY catalyst surface. While for HY zeolite, there is less ion-exchanged Cu+ in the supercages. The Cu/NaY catalyst has no catalytic activity and the Cu/HY catalyst exhibits lower activity than the Cu/NH4Y catalyst. Strong evidence is provided that during heat treatment, a solid state ion-exchange between Cu(acac)2 and NH4Y occurs and makes more of the Cu+ located in the supercages accessible to reactants.

Zirconia-supported MoOx catalysts for the selective oxidation of dimethyl ether to formaldehyde: Structure, redox properties, and reaction pathways

Liu, Haichao,Cheung, Patricia,Iglesia, Enrique

, p. 4118 - 4127 (2003)

Dimethyl ether (DME) reacts to form formaldehyde with high selectivity at 500-600 K on MoOx-ZrO2 catalysts with a wide range of MoOx surface density (0.5-50.1 Mo/nm2) and local structure (monomers, oligomers, MoO3 crystallites, and ZrMo2O8). Reaction rates (per Mo-atom) increased markedly as MoOx surface density increased from 2.2 to 6.4 Mo/nm2 and two-dimensional polymolybdates and MoO3 clusters became the prevalent active species. The rate of incipient stoichiometric reduction of MoOx-ZrO2 samples in H2 also increased with increasing MoOx surface density, suggesting that catalytic turnovers involve redox cycles that become faster as the size and dimensionality of MoOx domains increase. DME reaction rates (per Mo-atom) decreased as MoOx surface densities increased above 6.4 Mo/nm2, as MoO3 and ZrMo2O8 clusters with increasingly inaccessible MoOx species form. On MoOx and ZrMo2O8, areal reaction rates reach a constant value at MoOx surface densities above 10 Mo/nm2, as the exposed surfaces become covered with the respective active species. ZrMo2O8 surfaces were more reducible in H2 than MoOx surfaces and showed higher areal reaction rates. Reaction rates were nearly independent of O2 pressure, but the reaction order in DME decreased from one at low pressures (60 kPa). DME reacts via primary pathways leading to HCHO, methyl formate, and COx, with rate constants k1, k2, and k3, respectively, and via secondary HCHO conversion to methylformate (k4) and COx (k5). Primary HCHO selectivities (and k1/(k2 + k3) ratios) increased with increasing MoOx surface density on MoOx-containing samples and reached values of 80-90% above 10 Mo/nm2. Kinetic ratios relevant to secondary HCHO reactions (k1/[(k4 + k5)CAO]; CAO inlet DME concentration) also increased with increasing MoOx surface density to values of a??0.1 and 0.8 on MoOx and ZrMo2O8 structures (at the constant inlet DME concentration CAO), respectively. Thus, increasing the coverage of ZrO2 surfaces with MoOx or ZrMo2O8 leads to more selective structures for HCHO synthesis from DME.

On the methylation of 3-cyano-6-hydroxypyridine-2(1H)-ones

Janin, Yves Louis,Chiki, Jaouad,Legraverend, Michel,Huel, Christiane,Bisagni, Emile

, p. 12797 - 12804 (1999)

In order to prepare new heterocyclic derivatives as building block for compounds with potential biological activities, we were led to study the O- methylation of 3-cyano-6-hydroxypyridine-2(1H)-ones such as 1. This enabled us to develop a new two steps method to prepare the corresponding 2,6- dimethoxy derivative 5 in 80 % yield. It consisted first in heating 1 in trimethylorthoformate, with or without an acidic catalyst, which gave a mixture of the two mono-methoxy isomers, then a classical methylation of the second hydroxy moiety led almost exclusively to 5. In this paper we present this 'methylation' method and various unexpected results recorded when we attempted to extend it to related derivatives or to other heterocycle containing lactim-lactam functions. An intramolecular transetherification mechanism requiring the simultaneous transfer of a hydrogen and a methyl is suggested.

Ozone-activated nanoporous gold: A stable and storable material for catalytic oxidation

Personick, Michelle L.,Zugic, Branko,Biener, Monika M.,Biener, Juergen,Madix, Robert J.,Friend, Cynthia M.

, p. 4237 - 4241 (2015)

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils, and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. This ozone-treated npAu is a functionally new catalytic material.

Preparation and evaluation of Cu-Mn/Ca-Zr catalyst for methyl formate synthesis from syngas

Zhao, Haijun,Lin, Minggui,Fang, Kegong,Zhou, Juan,Sun, Yuhan

, p. 276 - 283 (2016)

Cu-Mn/Ca-Zr catalysts were prepared by mechanical mixing, sol-gel and impregnation methods. The phase structure, surface morphology and the chemical states of catalysts were characterized by XRD, TEM, SEM and XPS. The basic property and reducibility of catalysts were investigated by CO2-TPD and H2-TPR techniques. Several types of basic sites with different basicity could be observed on the surface of catalysts. The sample prepared by impregnation method has the lowest reducibility, and the sample prepared by sol-gel method shows the highest reducibility. The catalytic performance was evaluated for the direct synthesis of methyl formate from syngas in a slurry phase. The catalyst prepared by mechanical mixing method shows the highest CO conversion of 14.2% and methyl formate selectivity of 83.4% among these catalysts, which could be attributed to the large amounts of strong basic sites and low reducibility of the catalyst.

Levulinic esters from the acid-catalysed reactions of sugars and alcohols as part of a bio-refinery

Hu, Xun,Li, Chun-Zhu

, p. 1676 - 1679 (2011)

Polymeric humin formation greatly diminishes levulinic acid yields in acid treatment of C6 sugars in aqueous medium. Protecting reactive functional groups of sugars and reaction intermediates via acetalisation and etherification in methanol medium effectively suppresses humin formation and remarkably enhances the production of levulinic esters.

CATALYTIC ACTIVITIES OF COPPERS IN THE VARIOUS OXIDATION STATES FOR THE DEHYDROGENATION OF METHANOL

Takagi, Katsuhiko,Morikawa, Yutaka,Ikawa, Tsuneo

, p. 527 - 530 (1985)

The catalytic activities of coppers for the conversion of methanol are individually different by their oxidation states.Cu(II) ion and Cu(O) catalyze the dehydrogenation to form methyl formate and formaldehyde, respectively, while Cu(I) ion is inactive.

ANIONIC GROUP 6B METAL CARBONYLS AS HOMOGENEOUS CATALYSTS FOR CARBON DIOXIDE/HYDROGEN ACTIVATION. THE PRODUCTION OF ALKYL FORMATES.

Darensbourg,Ovalles

, p. 3750 - 3754 (1984)

The production of alkyl formates from the hydrocondensation of carbon dioxide in alcohols utilizing anionic group 6B carbonyl hydrides as catalysts is reported. HM(CO)//5** minus (M equals Cr, W; derived from mu -H left bracket M//2(CO)//1//0 right bracket ** minus ) and their products of carbon dioxide insertion, HCO//2M(CO)//5** minus , have been found to be effective catalysts for the hydrogenation of CO//2 in alcohols under rather mild conditions (loading pressures of CO//2 and H//2, 250 psi each, and 125 degree C) to provide alkyl formates. The only metal carbonyl species detected in solution via infrared spectroscopy, both at the end of a catalytic period and during catalysis, were M(CO)//6 and HCO//2M(CO)//5** minus .

A Promoting Effect of Phosphorus-Addition to Cu/SiO2 on Selective Synthesis of Formaldehyde by Dehydrogenation of Methanol

Yamamoto, Takeshi,Shimoda, Akihide,Okuhara, Toshio,Misono, Makoto

, p. 273 - 276 (1988)

Copper supported on SiO2, which was prepared from Cu(OCOCH3)3 and to which P was added, was a selective catalyst (80-85 percent at about 50 percent conversion) for the formation of HCHO by the dehydrogenation of CH3OH at 500 deg C.Among various additives such as P, B, K, Li, Mo, and Zn, the addition of P to the Cu/SiO2 significantly enhanced the rate for the formation of HCHO with an increase in the selectivity.

Photocatalytic cross-coupling of methanol and formaldehyde on a rutile TiO2(110) surface

Yuan, Qing,Wu, Zongfang,Jin, Yuekang,Xu, Lingshun,Xiong, Feng,Ma, Yunsheng,Huang, Weixin

, p. 5212 - 5219 (2013)

The photocatalytic oxidation of methanol on a rutile TiO2(110) surface was studied by means of thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). The combined TDS and XPS results unambiguously identify methyl formate as the product in addition to formaldehyde. By monitoring the evolution of various surface species during the photocatalytic oxidation of methanol on TiO2(110), XPS results give direct spectroscopic evidence for the formation of methyl formate as the product of photocatalytic cross-coupling of chemisorbed formaldehyde with chemisorbed methoxy species and clearly demonstrate that the photocatalytic dissociation of chemisorbed methanol to methoxy species occurs and contributes to the photocatalytic oxidation of methanol. These results not only greatly broaden and deepen the fundamental understanding of photochemistry of methanol on the TiO2 surface but also demonstrate a novel green and benign photocatalytic route for the synthesis of esters directly from alcohols or from alcohols and aldehydes.

Low temperature oxidation of methanol to methyl formate over Pd nanoparticles supported on γ-Fe2O3

Wojcieszak,Ghazzal,Gaigneaux,Ruiz

, p. 738 - 745 (2014)

Pd nanoparticles supported on γ-Fe2O3 (2 wt.%) were synthesized using the water-in-oil microemulsion method (using hydrazine as a reductant agent). Materials were characterized by N2-BET at low temperature, XRD, XPS, Raman, and FTIR and tested in the gas phase reaction of oxidation of methanol. The direct formation of methyl formate (MF) from methanol was observed. Supported palladium catalysts produced methyl formate at low temperature (+2/Fe+3 ratio (2:1, 1:1, 1:2) used for the preparation of the supports. Methyl formate is already formed at 50 °C with the maximum at about 80 °C. At higher temperature, methyl formate is no longer formed and the oxidation to CO2 and CO occurs. Raman studies indicated the changes in the structure of the Fe2O3 support in the case of the 1:2 sample after chemical reduction with hydrazine.

A comparative study on the effect of Zn addition to Cu/Ce and Cu/Ce-Al catalysts in the steam reforming of methanol

Mrad, Mary,Hammoud, Dima,Gennequin, Cédric,Abouka?s, Antoine,Abi-Aad, Edmond

, p. 84 - 90 (2014)

The performances of different catalysts xCu10Ce and xCu10Ce10Al (with x = 1, 3 and 5) in the steam reforming of methanol reaction were studied with and without the presence of zinc. The reaction was investigated at 350°C with a Gas Hourly Space Velocity o

Photocatalytically reducing CO2 to methyl formate in methanol over ag loaded SrTiO3 nanocrystal catalysts

Sui, Dandan,Yin, Xiaohong,Dong, Hongzhi,Jiang, Wanlin,Qin, Shiyue,Chen, Jingshuai

, p. 1202 - 1210,9 (2012)

Ag-SrTiO3 nanocrystal photocatalysts were prepared by hydrothermal synthesis method for reducing CO2 to methyl formate (MF) in methanol via ultraviolet irradiation. CO2 was reduced to MF by electrons on conduction band of the photocatalyst. In order to obtain a high rate of MF evolution, we researched and optimized the preparation procedure of Ag-SrTiO3 by changing the Ag dosage, hydrothermal temperature and time. The as synthesized photocatalystswere characterized with X-ray diffraction, UV-Vis absorption spectra, transmission electron microscope, N 2 sorption analysis at 77 K and activity evaluation. A catalyst of 7 wt% Ag on SrTiO3 with hydrothermal synthesis at 150 °C and 22 h was found to exhibit the highest photocatalytic activity inMF formation rate of 3,006 μmol/(h g cat), which was more remarkable than that of pristine SrTiO3.

The direct synthesis of dimethyl carbonate by the oxicarbonylation of methanol over Cu supported on carbon nanotube

Merza,László,Oszkó,Pótári,Baán,Erdohelyi

, p. 117 - 124 (2014)

The activity of Cu/MWCNT and Cu-Ni/MWCNT catalysts was investigated in the synthesis of dimethyl carbonate (DMC) by oxidative carbonylation of methanol. The catalysts were prepared via conventional incipient wetness impregnation technique. The samples were characterized by X-ray photoelectron spectroscopy (XPS), and DRIFT. The reaction was carried out in a continuous flow system at atmospheric pressure at 393 K. The main products were methyl formate (MF), DMC and CO2. The methanol conversion on Cu/MWCNT achieved a steady state value after 2 h, but on Cu-Ni/MWCNT the conversion decreased continuously. The DMC selectivity was more than 30% and the yield was 1.2% on Cu/MWCNT. Based on the XPS data we can establish that copper reduced to its metallic form during reduction but oxidized in the reaction mixture, and is mostly in the Cu + state, with some Cu2+ also present on the surface at the beginning of the reaction though its ratio decreased in time. We assume that the DMC formation rate depends on the surface concentration of oxidized Cu. Based upon the FTIR data adsorbed DMC is present on the surface of the Cu/MWCNT catalyst during the catalytic reaction but on Cu-Ni/MWCNT sample only methyl formate was detected in the gas phase.

Electrochemical activation of Au nanoparticles for the selective partial oxidation of methanol

Gonzalez-Cobos,Horwat,Ghanbaja,Valverde,De Lucas-Consuegra

, p. 293 - 302 (2014)

An electrochemical catalyst based on Au nanoparticles dispersed in an yttria-stabilized zirconia (YSZ) matrix was prepared by reactive cosputtering of zirconium-yttrium and Au targets on a K-βAl2O3 solid electrolyte. The Au/YSZ catalyst film deposited on K-βAl2O 3 was found to be active in the partial oxidation of methanol with a high selectivity toward methyl formate. This configuration allowed to electrochemically promote a highly dispersed Au catalyst by K+ ions and allowed to decrease the amount of metal used in the solid electrolyte cell. The back-spillover of K+ ions sharply increased the H2 and HCOOCH3 production rates up to more than 9 and 5 times, respectively. A number of experiments confirmed that the observed electro-promotional effect did not depend on the rate of K+ supply nor on the operation mode (galvanostatic or potentiostatic) and only depended on the promoter coverage (total applied charge). The stability of the Au-YSZ catalyst film under the explored conditions was also verified.

Low-temperature CO2 hydrogenation to liquid products via a heterogeneous cascade catalytic system

Chen, Yuan,Choi, Saemin,Thompson, Levi T.

, p. 1717 - 1725 (2015)

Research described in this paper targeted a cascade system for the hydrogenation of CO2 to methanol via formic acid and/or formate intermediates, a reaction sequence that has been accomplished previously using homogeneous catalysts. On the basis of results for the hydrogenation of CO2, formic acid, and ethyl formate over a series of Cu- and Mo2C-based catalysts, we selected a Cu chromite catalyst for CO2 hydrogenation to the formate and a Cu/Mo2C catalyst to convert the formate to methanol. These catalysts worked cooperatively in the presence of ethanol, yielding a methanol turnover frequency of 4.7 × 10-4 s-1 at 135 °C, 10 bar of CO2, and 30 bar of H2 in 1,4-dioxane. The performance for this Cu chromite:Cu/Mo2C cascade system surpassed the additive production of the individual catalysts by 60%. The results also allowed an investigation of the reaction pathways. The hydrogenation of CO2 to formic acid appeared to be the rate-limiting step for most of the catalysts. This is not surprising given the thermodynamics for this reaction. Finally, the hydrogenation of CO2 to dimethyl ether was also demonstrated using a system consisting of the Cu/Mo2C catalyst to produce methanol from CO2 and HZSM-5 to produce dimethyl ether from methanol. The systems described in this paper are, to our knowledge, the first demonstrating cascade CO2 hydrogenation via heterogeneous catalysts.

Photocatalytic partial oxidation of methanol to methyl formate under visible light irradiation on Bi-doped TiO2: Via tuning band structure and surface hydroxyls

Gao, Guanjun,Lei, Yanqiu,Ma, Yue,Su, Haiquan,Yan, Zhe,Yang, Xuzhuang,Zhang, Bingbing,Zhang, Yanbing

, p. 31442 - 31452 (2020)

Preparing visible light responsive catalysts for partial oxidation of methanol to methyl formate is a challenging issue. This work addresses the synthesis, characterization and theoretical calculation of Bi doped TiO2 catalysts as well as their photocatalytic performance and reaction mechanism for MF synthesis from methanol. The catalysts were prepared by a simple wet chemical method. The results of the characterization and theoretical calculation evidenced that bismuth was intercalated in the lattice of anatase by the substitution of titanium. Impurity levels were formed in the valence band, conduction band and between the two bands. The Bi 6s and 5p orbitals contributed to the formation of the impurity levels. The photo-excited electrons transited from the valence band via impurity levels, formed by Bi 6s orbitals, to the conduction band. The doping of Bi enhanced surface hydroxyls, reduced the band gaps and raised the valence band edges (VBE) of the Bi doped catalyst. The Bi doped catalysts were visible light responsive due to the reduced band gap. The surface hydroxyls were beneficial to the methanol conversion, and the rise of the VBE enhanced the redox potential of the photogenerated holes. Only moderate redox potentials and sufficient surface hydroxyls could lead to high methanol conversion and MF selectivity. This study is of great significance to the development of the photocatalytic synthesis theory and provides a green route for MF synthesis from methanol. This journal is

Hydrogenation of carbon dioxide in the presence of rhodium catalysts

Kolesnichenko,Ezhova,Kremleva,Slivinskii

, p. 2542 - 2545 (2004)

The results of CO2 hydrogenation in the presence of the Wilkinson complexes, viz., RhCl3 and acacRh(CO)2, at room temperature and excess PPh3 are presented. The influence of different ions on the catalytic properties of the Rh complexes was studied. Methanol and methyl formate are formed along with formic acid in the presence of an inorganic salt. Ions that are the most active in the formation of formic acid are the least active in methanol formation.

Methanol oxidation on VSiBEA zeolites: Influence of v content on the catalytic properties

Trejda, MacIej,Ziolek, Maria,Millot, Yannick,Chalupka, Karolina,Che, Michel,Dzwigaj, Stanislaw

, p. 169 - 176 (2011)

This study deals with the influence of V content on the catalytic properties of VxSiBEA zeolites in the oxidation of methanol. The samples are prepared following a postsynthesis method reported earlier (S. Dzwigaj, M.J. Peltre, P. Massiani, A. Davidson, M. Che, T. Sen, S. Sivasanker, Chem. Commun. (1998) 87). The incorporation of isolated mononuclear V(V) into the framework of SiBEA is evidenced by XRD, FTIR, diffuse reflectance UV-vis and NMR. It is found that, for low V content, V(V) ions are in pseudo-tetrahedral coordination only, either in nonhydroxylated (SiO)3VO or hydroxylated (SiO)2(OH)VO species in framework position. For higher V content, additional species appear in extraframework position with vanadium in octahedral coordination. FTIR investigations of pyridine adsorption show that strong Bronsted and Lewis acidic centres are present in SiBEA leading to dimethyl ether only, in methanol oxidation. Upon incorporation of vanadium into the BEA framework, Lewis acidic (V5+) and basic (O2-) centres are generated with simultaneous appearance of partial oxidation products mainly, whose total concentration increases with vanadium content. These results suggest that those centres are responsible for the oxidation activity of VxSiBEA zeolites. The selectivity toward formaldehyde increases with the amount of vanadium present as pseudo-tetrahedral hydroxylated (SiO) 2(HO)VO species. This selectivity is suggested to be related to the moderate nucleophilicity of the basic vanadyl oxygen (VO) of (SiO) 2(HO)VO species.

Promotional effect of potassium salt in low-temperature formate and methanol synthesis from CO/CO2/H2 on copper catalyst

Zhao, Tian-Sheng,Yoneyama, Yoshiharu,Fujimoto, Kaoru,Yamane, Nodyuki,Fujimoto, Kenichiro,Tsubaki, Noritatsu

, p. 734 - 735 (2007)

Alkyl formates can be formed from CO2-containing syngas with C1-C4 alkyl alcohol solvents in the presence of potassium carbonate, which changed to potassium formate as catalyst. The formates can be in situ hydrogenolysized further to produce methanol effectively over manganese oxide or magnesia-supported copper catalysts. These homogeneous and heterogeneous catalysts constitute a novel system for methanol synthesis from CO/CO2/H2 even at 443 K. Copyright

Highly active CuZn/SBA-15 catalyst for methanol dehydrogenation to methyl formate: Influence of ZnO promoter

Wang, Na,Quan, Yanhong,Zhao, Jinxian,Li, Haixia,Ren, Jun

, (2021)

Stable and efficient Cu/SBA-15 and xCuZn/SBA-15 (x = 5, 10 and 15) in methanol dehydrogenation to methyl formate (MF) are prepared through a double-solvent impregnation (DI) method. Among all catalysts, 10CuZn/SBA-15 shows the highest catalytic performance with selectivity to MF about 88.1 % and methanol conversion of 31.1 %, which is attributed to the well-dispersed Cu particles and high ratio of Cu°/(Cu° + Cu+). The proper amount of ZnO could improve dispersion of Cu because of its geometrical spacer, inhibiting growth of Cu particle, and the best dispersion is achieved in 10CuZn/SBA-15. Furthermore, the Cu°/(Cu° + Cu+) ratio is greatly promoted with the assistance of ZnO, attributed to Cu-ZnO interaction, which reaches maxima of 53.3 % at a Cu/Zn mole ratio of 10. Specially, the optimized catalyst shows evident suitability at high temperature for methanol dehydrogenation reactions along with high level of conversion and selectivity for 100 h. Overall, our findings reveal that modification by the appropriate amount of ZnO in Cu-based catalyst has a positive impact on obtaining MF for the methanol dehydrogenation.

Catalytic oxidation of alcohol via nickel phosphine complexes with pendant amines

Weiss, Charles J.,Das, Parthapratim,Miller, Deanna L.,Helm, Monte L.,Appel, Aaron M.

, p. 2951 - 2958 (2014)

Nickel complexes were prepared with diphosphine ligands that contain pendant amines, and these complexes catalytically oxidize primary and secondary alcohols to their respective aldehydes and ketones. Kinetic and mechanistic studies of these prospective electrocatalysts were performed to understand what influences the catalytic activity. For the oxidation of diphenylmethanol, the catalytic rates were determined to be dependent on the concentration of both the catalyst and the alcohol and independent of the concentration of base and oxidant. The incorporation of pendant amines to the phosphine ligand results in substantial increases in the rate of alcohol oxidation with more electron-donating substituents on the pendant amine exhibiting the fastest rates. (Chemical Equation Presented).

Broensted Basicity of Atomic Oxygen on the Au(110) Surface: Reactions with Methanol, Acetylene, Water, and Ethylene

Outka, Duane A.,Madix, R. J.

, p. 1708 - 1714 (1987)

The adsorption and reactions of methanol, acetylene, water, and ethylene were investigated on clean and oxidized Au(110) surfaces by temperature-programmed reaction spectroscopy.All of these molecules are only weakly and molecularly adsorbed on the clean Au(110) surface.Methanol, acetylene, and water, however, react with the oxidized surface.Methanol, activated by 0.25 monolayer of oxygen adatoms, reacts to form water, methyl formate, hydrogen, and carbon dioxide.A stable methoxy intermediate is identified in these reactions.Acetylene reacts to form water and carbon dioxide, and water is more strongly bonded to the Au(110) surface in the presence of oxygen adatoms.Ethylene is the only one of these molecules which does not react with oxygen adatoms on Au(110).This pattern of reactivity parallels that associated with the acidity of these molecules as measured in the gas phase which has been observed on Cu(110) and Ag(110) surfaces.These results complete the studies necessary to demonstrate the Broensted base character of oxygen adatoms on all of the group 1B metals.

Oxidation of methanol to methyl formate over supported Pd nanoparticles: Insights into the reaction mechanism at low temperature

Wojcieszak,Karelovic,Gaigneaux,Ruiz

, p. 3298 - 3305 (2014)

Pd nanoparticles supported on TiO2 and SiO2 (2 wt.%) were synthesized by the water-in-oil microemulsion method. The materials were characterized by standard physico-chemical methods (XRD, ICP, TEM, BET, XPS) and DRIFT in operando mode and tested in the gas-phase reaction of methanol oxidation. The direct formation of methyl formate (MF) from methanol was observed. Supported palladium catalysts produced methyl formate at low temperature (2 occurred. The DRIFT-operando study confirmed that methanol is adsorbed mainly in two forms, the undissociated gaseous methanol (via H bond) and dissociatively adsorbed methoxy species (CH3O-) on the surface. Methyl formate is formed already at RT with the maximum at about 80 °C. The mechanism of the formation of methyl formate from methanol at low temperature is discussed. the Partner Organisations 2014.

Comparative study on the photocatalytic decomposition of methanol on TiO2 modified by N and promoted by metals

Halasi, Gyula,Schubert, Gabor,Solymosi, Frigyes

, p. 199 - 206,8 (2012)

The photo-induced vapor-phase reaction of methanol was investigated on Pt metals deposited on pure and N-doped TiO2. Infrared spectroscopic measurements revealed that illumination of the CH3OH-TiO2 and CH3OH-M/TiO2 systems led to the conversion of adsorbed methoxy species into adsorbed formate. In the case of metal-promoted TiO 2 catalysts CO bonded to the metals was also detected. Pure titania exhibited very little photoactivity, its efficiency, however, increased with the narrowing of its bandgap by N-doping, a feature attributed to the prevention of electron-hole recombination. Deposition of Pt metals on pure and N-doped TiO2 dramatically enhanced the extent of photoreaction of methanol even in visible light: hydrogen and methyl formate with selectivities of 83-90% were the major products. The most active metal was Pt followed by Pd, Ir, Rh, and Ru. The effect of metal was explained by a better separation of charge carriers induced by illumination and by enhanced electronic interaction between metal nanoparticles and TiO2.

Simplified DEMS set up for electrocatalytic studies of porous PtRu alloys

Ianniello,Schmidt

, p. 83 - 86 (1995)

A simplified experimental apparatus for Differential Electrochemical Mass Spectrometry (DEMS) was constructed having only one turbomolecular pump and a modified gas inlet system. The setup allows the determination of the activity of porous PtRu electrodes for the electro-oxidation of small organic molecules. Various PtRu alloys with defined composition can be electrodeposited onto porous gold substrates. First results on the electrooxidation of methanol in acid solution were presented.

Alcohol-Activated Vanadium-Containing Polyoxometalate Complexes in Homogeneous Glucose Oxidation Identified with 51V-NMR and EPR Spectroscopy

Wesinger, Stefanie,Mendt, Matthias,Albert, Jakob

, p. 3662 - 3670 (2021)

Alcoholic solvents, especially methanol, show an activating affect for heteropolyacids in homogenously catalysed glucose transformation reactions. In detail, they manipulate the polyoxometalate-based catalyst in a way that thermodynamically favoured total oxidation to CO2 can be completely supressed. This allows a nearly 100 % carbon efficiency in the transformation reaction of glucose to methyl formate in methanolic solution at mild reaction conditions of 90 °C and 20 bar oxygen pressure. By using powerful spectroscopic tools like 51V-NMR and continuous wave EPR we could unambiguously prove that the vanadate-methanol-complex[VO(OMe)3]n is responsible for the selectivity shift in methanolic solution compared to the aqueous reference system.

CuO - Activated carbon catalysts for methanol decomposition to hydrogen and carbon monoxide

Tsoncheva, Tanya,Nickolov, Radostin,Vankova, Svetoslava,Mehandjiev, Dimitar

, p. 1096 - 1100 (2003)

A comparison of the abilities of CuO - activated carbon catalysts, prepared by different copper precursors and preparation techniques, in the methanol decomposition reaction to carbon monoxide and hydrogen, was undertaken. Higher catalytic activity and stability are found for the catalysts obtained from an ammonia solution of copper carbonate. The nature of the catalytic active complex in the samples is also discussed.

Effective Dawson type polyoxometallate catalysts for methanol oxidation

Dermeche, Leila,Salhi, Nassima,Hocine, Smain,Thouvenot, René,Rabia, Chérifa

, p. 29 - 35 (2012)

Dawson type polyoxometallates K6P2Mo xW18-xO62 (x = 0, 5, 6) and α1 and α2-K7P2Mo5VW12O62 were prepared and characterized by BET, IR, UV-vis and 31P NMR spectroscopies and thermal analysis (TG and DTA) and tested in methanol oxidation at 260°C in the presence of molecular oxygen. The Dawson compounds were found to be active in this reaction and the product distribution (formaldehyde, methyl formate, dimethylether, dimethoxymethane) depends on the polyanion composition and on the framework symmetry. α-K6P 2W18O62 exhibits an excellent catalytic performance with ca. 27% of methanol conversion and 98% of dimethylether selectivity. α1-K7P2Mo5VW 12O62 and α2-K7P2Mo 5VW12O62 show a similar activity (17-19% of conversion) with 49% of methyl formate selectivity and 41% of formaldehyde selectivity respectively. α-K6P2Mo6W 12O62 is the most oxidizing catalyst and the most selective toward the methyl formate (ca. 53%).

Selective oxidation of methanol to methyl formate on catalysts of Au-Ag alloy nanoparticles supported on titania under UV irradiation

Han, Chenhui,Yang, Xuzhuang,Gao, Guanjun,Wang, Jie,Lu, Huailiang,Liu, Jie,Tong, Min,Liang, Xiaoyuan

, p. 3603 - 3615 (2014)

We find that the Au-Ag alloy nanoparticles supported on titania exhibit superior methanol conversion and methyl formate selectivity for selective oxidation of methanol by low partial pressure oxygen in air under UV irradiation in the 15°C-45°C temperature range, with the highest methanol conversion above 90% and the highest selectivity towards methyl formate above 85%. The only by-product definitely detected is CO2. The superior photocatalytic performance of the catalyst is closely related to the special structure of the catalyst and the electronic properties of the alloy, which reduce the recombination of the photo-excited electron-hole pairs by transferring the photo-excited electrons in time from the conduction band of titania to the alloy on the one hand, and elevate the negative charge level of the alloy surface by the spd hybridization, the formation of Schottky barriers, the electron transfer from the conduction band of titania to the metal as well as the interband and intraband electron transitions under UV irradiation on the other hand. The photo-generated holes are responsible for the oxidation from methanol to coordinated methoxy, from coordinated methoxy to coordinated formaldehyde and finally to carbon dioxide. The methyl formate selectivity is dependent on the density of the surface methoxy. To enhance the efficiency of electron-hole separation is beneficial to the formation of the coordinated methoxy and coordinated formaldehyde and thus the selectivity to methyl formate. The negative charges on the surface of the metal are responsible for the dissociation of oxygen, which is the rate-determining step in the reaction. The dissociative oxygen repels the water molecules formed from the surface hydroxyls and refills the oxygen vacancies on the surface of titania. The surface oxygen is the acceptor of the hydrogen dissociated from methanol and/or methoxy and thus is beneficial for the formation of the coordinated methoxy and coordinated formaldehyde. The oxygen partial pressure remarkably influences the methanol conversion and the methyl formate selectivity. The light intensity has a remarkable impact on the methanol conversion but not on the methyl formate selectivity. These findings provide useful insight into the design of catalysts for selective oxidation of methanol to methyl formate in a more green way. This journal is the Partner Organisations 2014.

Capon et al.

, p. 1034 (1976)

RuO2 clusters within LTA zeolite cages: Consequences of encapsulation on catalytic reactivity and selectivity

Zhan, Bi-Zeng,Iglesia, Enrique

, p. 3697 - 3700 (2007)

(Figure Presented) Trapped! The title system (ca. 1 nm diameter; left) catalyzes methanol oxidation with higher turnover rates than clusters on SiO2 supports. Spatial constraints lead to the preferential oxidation of methanol over larger alcohols. Restricted access to active sites also protects encapsulated Ru clusters (right) against inhibition of ethene hydrogenation by organosulfur compounds.

Vapour-Phase Carbonylation of Methanol over Tin Catalyst Supported on Active Carbon

Omata, Kohji,Yagita, Hiroshi,Shikada, Tsutomu,Fujimoto, Kaoru,Tominaga, Hiro-o

, p. 2397 - 2398 (1987)

A Tin-active carbon showed a catalytic activity for the vapour phase carbonylation of methanol under pressurized conditions in the presence of methyl iodide promoter.

Preparation of MIL-88B(Fex,Co1?x) catalysts and their application in one-step liquid-phase methanol oxidation to methyl formate using H2O2

Cao, Qiyan,Ji, Shengfu,Liu, Jianfang,Ran, Zhenzhen

, p. 2254 - 2264 (2021/09/20)

The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products. The development of highly efficient and stable catalysts is critical for this transformation. In this study, a series of MIL-88B(Fex,Co1–x) bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method. X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, N2 adsorption-desorption, and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts. The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H2O2 in a liquid-phase batch reactor. The results show that the MIL-88B(Fex,Co1–x) catalysts exhibit uniform needle-like morphologies with an average length and width of 400–600 nm and 100–150 nm, respectively. Co2+ is incorporated into the framework by partially replacing Fe3+ in MIL-88B. Moreover, the catalyst efficiently promoted the conversion of methanol to methyl formate. When MIL-88B(Fe0.7,Co0.3) catalyst was used with a molar ratio of H2O2 to methanol of 0.5 at 80 °C for 60 min, 34.8% methanol conversion was achieved, and the selectivity toward methyl formate was 67.6%. The catalysts also showed great stability with a steady conversion and selectivity even after four cycles. The preliminary oxidation mechanism was also studied. It was determined that H2O2 is first adsorbed on the Fe3+ sites and subsequently activates these sites. Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid. Subsequently, formic acid reacts with the residual methanol at the Fe3+ and Co2+ Lewis acid sites to form methyl formate.

Methanol Dehydrogenation to Methyl Formate Catalyzed by Cu/SiO2 Catalysts: Impact of Precipitation Procedure and Calcination Temperature

Jia, X. Y.,Wang, A. L.,Ye, C. L.,Yin, H. B.

, p. 1302 - 1312 (2021/12/29)

Considering three options for the synthesis of a catalyst by the precipitation method, the Cu/SiO2 catalysts prepared by changing the precipitation procedure and calcination temperature for the dehydrogenation of methanol was studied. When the CuO/SiO2 catalyst precursors were prepared through the addition of a copper nitrate aqueous solution into an ammonia aqueous solution (reverse precipitation) and co-current flow addition of both aqueous solutions, after reduction with gaseous hydrogen, small-sized metallic copper nanocrystallites were formed in the reduced Cu/SiO2 catalysts as compared to those prepared by the addition of an ammonia aqueous solution into a copper nitrate aqueous solution (direct precipitation). The reduced Cu/SiO2 catalysts prepared by the reverse precipitation method with relatively lower acidity and basicity emonstrated higher catalytic activity for the synthesis of methyl formate in methanol dehydrogenation. The reduced Cu/SiO2 catalysts prepared by the calcination at a lower temperature showed higher catalytic activity for the formation of methyl formate. The surface metallic Cu0 and Cu+ species catalyzed the methanol dehydrogenation to methyl formate while the surface Cu+ cations enhanced the decomposition of the resultant methyl formate to CO and H2.

Method for preparing formate by using nitromethane process byproduct formic acid

-

Paragraph 0039-0046, (2021/07/08)

The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing formate by using a nitromethane process byproduct formic acid. The method comprises the following steps: adding alcohol into a nitromethane hydrolysis reaction solution to carry out esterification reaction, distilling and rectifying to obtain the formate, wherein the nitromethane hydrolysis reaction liquid contains formic acid and hydrochloric acid. The method solves the problems that in the prior art, formic acid is not easy to remove, and the added value of the byproduct calcium formate is low, and the byproduct formic acid can be fully recycled by adopting the esterification reaction of the low-carbon alcohol and the byproduct formic acid; the used low-carbon alcohol is ethanol or methanol, and the esterification product is low in boiling point and easy to separate; and the produced methyl formate and ethyl formate are high in added value and wide in application.

CATALYSTS FOR SELECTIVE OXIDATION OF METHANOL TO DIMETHOXYMETHANE AND RELATED METHODS

-

Paragraph 0074-0078, (2021/10/02)

Embodiments include catalyst compositions and methods of synthesizing catalyst compositions for the selective oxidation of methanol to dimethoxymethane, as well as methods of selective oxidation of methanol to dimethoxymethane using catalyst compositions. The catalyst composition can comprise vanadium oxide and a mixed metal oxide, wherein the vanadium oxide is supported on the mixed metal oxide and wherein the mixed metal oxide includes a redox component and an acid component. The method of selective oxidation of methanol to dimethoxymethane can comprise at least the following step: contacting methanol with a catalyst composition in the presence of an oxidizing agent to produce dimethoxymethane.

Process route upstream and downstream products

Process route

butyl-[1,2,4]trioxolane
767-09-9

butyl-[1,2,4]trioxolane

methanol
67-56-1

methanol

pentanal
110-62-3

pentanal

Dimethoxymethane
109-87-5

Dimethoxymethane

Methyl formate
107-31-3

Methyl formate

methyl valerate
624-24-8

methyl valerate

1,1-dimethoxy-pentane
26450-58-8

1,1-dimethoxy-pentane

valeric acid
109-52-4

valeric acid

Conditions
Conditions Yield
at 90 ℃; for 6h; Product distribution; Thermodynamic data; Rate constant; other temperature, ΔS (excit.), ΔG (excit.), ΔH (excit.);
20.4%
18.4%
18.3%
15.9%
3.7%
2.8%
butyl-[1,2,4]trioxolane
767-09-9

butyl-[1,2,4]trioxolane

pentanal
110-62-3

pentanal

Dimethoxymethane
109-87-5

Dimethoxymethane

Methyl formate
107-31-3

Methyl formate

1,1-dimethoxy-pentane
26450-58-8

1,1-dimethoxy-pentane

valeric acid
109-52-4

valeric acid

Conditions
Conditions Yield
In methanol; at 90 ℃; for 6h; Mechanism; Product distribution;
2.1%
18.3%
2.8%
18.4%
20.4%
15.9%
1-hexadecene ozonide
81618-17-9

1-hexadecene ozonide

Dimethoxymethane
109-87-5

Dimethoxymethane

n-pentadecanal
2765-11-9

n-pentadecanal

Methyl formate
107-31-3

Methyl formate

palmitic acid
1002-84-2

palmitic acid

pentadecanoic acid methyl ester
7132-64-1

pentadecanoic acid methyl ester

1,1-dimethoxy-pentadecane
52517-73-4

1,1-dimethoxy-pentadecane

Conditions
Conditions Yield
In methanol; at 90 ℃; for 6h; Mechanism; Product distribution; Kinetics; other solvents; other objects of study: energy data, velocity constant;
19.6%
8.8%
14.1%
21.3%
20.3%
2.2%
benzoyl(dichloro)acetaldehyde
160663-32-1

benzoyl(dichloro)acetaldehyde

Methyl formate
107-31-3

Methyl formate

2,2-dichloroacetophenone
2648-61-5

2,2-dichloroacetophenone

Conditions
Conditions Yield
With sodium methylate; In diethyl ether; for 1h; Ambient temperature;
para-xylene
106-42-3

para-xylene

methanol
67-56-1

methanol

methyl bromide
74-83-9

methyl bromide

Methyl formate
107-31-3

Methyl formate

acetic acid methyl ester
79-20-9

acetic acid methyl ester

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

carbon monoxide
201230-82-2

carbon monoxide

terephthalic acid
100-21-0

terephthalic acid

4-Carboxybenzaldehyde
619-66-9

4-Carboxybenzaldehyde

Conditions
Conditions Yield
With oxygen; sodium acetate; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 213 ℃; under 14251.4 Torr; Product distribution / selectivity;
0.35%
para-xylene
106-42-3

para-xylene

methyl bromide
74-83-9

methyl bromide

Methyl formate
107-31-3

Methyl formate

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

carbon monoxide
201230-82-2

carbon monoxide

terephthalic acid
100-21-0

terephthalic acid

4-Carboxybenzaldehyde
619-66-9

4-Carboxybenzaldehyde

Conditions
Conditions Yield
With methanol; oxygen; sodium acetate; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 185 - 213 ℃; under 14251.4 Torr; Product distribution / selectivity;
para-xylene
106-42-3

para-xylene

methanol
67-56-1

methanol

methyl bromide
74-83-9

methyl bromide

Methyl formate
107-31-3

Methyl formate

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

carbon monoxide
201230-82-2

carbon monoxide

terephthalic acid
100-21-0

terephthalic acid

4-Carboxybenzaldehyde
619-66-9

4-Carboxybenzaldehyde

Conditions
Conditions Yield
With acetic acid methyl ester; oxygen; sodium acetate; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 180 - 213 ℃; under 14251.4 Torr; Product distribution / selectivity;
0.28%
With oxygen; sodium acetate; hydrogen bromide; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 180 - 213 ℃; under 14251.4 Torr; Product distribution / selectivity;
0.28%
para-xylene
106-42-3

para-xylene

methyl bromide
74-83-9

methyl bromide

Methyl formate
107-31-3

Methyl formate

acetic acid methyl ester
79-20-9

acetic acid methyl ester

terephthalic acid
100-21-0

terephthalic acid

4-Carboxybenzaldehyde
619-66-9

4-Carboxybenzaldehyde

Conditions
Conditions Yield
With methanol; hydrogen bromide; oxygen; sodium acetate; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 185 ℃; for 6h; Product distribution / selectivity;
para-xylene
106-42-3

para-xylene

methanol
67-56-1

methanol

methyl bromide
74-83-9

methyl bromide

Methyl formate
107-31-3

Methyl formate

terephthalic acid
100-21-0

terephthalic acid

4-Carboxybenzaldehyde
619-66-9

4-Carboxybenzaldehyde

Conditions
Conditions Yield
With acetic acid methyl ester; hydrogen bromide; oxygen; sodium acetate; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 180 - 213 ℃; for 6h; Product distribution / selectivity;
With hydrogen bromide; oxygen; sodium acetate; cobalt(II) acetate; manganese(II) acetate; In water; acetic acid; at 213 ℃; for 6h; Product distribution / selectivity;
iron(II) formate

iron(II) formate

methanol
67-56-1

methanol

iron(II) oxide
1345-25-1

iron(II) oxide

Methyl formate
107-31-3

Methyl formate

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

carbon monoxide
201230-82-2

carbon monoxide

Conditions
Conditions Yield
In solid; byproducts: CH4; thermal decomposition of Fe(HCO2)2 under N2 at 200-250°C; detd. by XRD and IR;

Global suppliers and manufacturers

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  • Simagchem Corporation
  • Business Type:Manufacturers
  • Contact Tel:+86-592-2680277
  • Emails:sale@simagchem.com
  • Main Products:110
  • Country:China (Mainland)
  • Amadis Chemical Co., Ltd.
  • Business Type:Lab/Research institutions
  • Contact Tel:86-571-89925085
  • Emails:sales@amadischem.com
  • Main Products:29
  • Country:China (Mainland)
  • Antimex Chemical Limied
  • Business Type:Lab/Research institutions
  • Contact Tel:0086-21-50563169
  • Emails:anthony@antimex.com
  • Main Products:163
  • Country:China (Mainland)
  • Chemwill Asia Co., Ltd.
  • Business Type:Manufacturers
  • Contact Tel:021-51086038
  • Emails:sales@chemwill.com
  • Main Products:56
  • Country:China (Mainland)
  • Kono Chem Co.,Ltd
  • Business Type:Other
  • Contact Tel:86-29-86107037-8015
  • Emails:info@konochemical.com
  • Main Products:82
  • Country:China (Mainland)
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