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Cas Database

67-56-1

67-56-1

Identification

  • Product Name:Methanol

  • CAS Number: 67-56-1

  • EINECS:200-659-6

  • Molecular Weight:32.0422

  • Molecular Formula: CH4O

  • HS Code:2905 11 00

  • Mol File:67-56-1.mol

Synonyms:Alcohol, methyl;Carbinol;Methanol cluster;Bieleski's solution;Methyl alcohol;Wood alcohol;

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Safety information and MSDS view more

  • Pictogram(s):HarmfulXn, ToxicT, FlammableF

  • Hazard Codes:Xn,T,F

  • Signal Word:Danger

  • Hazard Statement:H225 Highly flammable liquid and vapourH301 Toxic if swallowed H311 Toxic in contact with skin H331 Toxic if inhaled

  • 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. Refer for medical attention . 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 Induce vomiting (ONLY IN CONSCIOUS PERSONS!). Refer for medical attention . Exposure to excessive vapor causes eye irritation, head- ache, fatigue and drowsiness. High concentrations can produce central nervous system depression and optic nerve damage. 50,000 ppm will probably cause death in 1 to 2 hrs. Can be absorbed through skin. Swallowing may cause death or eye damage. (USCG, 1999) Treatment thresholds for methanol poisoning are based on case reports and published opinion. Most guidelines recommend treatment for a methanol level > or = 20 mg/dL in a nonacidotic patient. No supportive data have been offered nor has the time of the exposure been addressed. For instance, no distinction has been drawn between a methanol level drawn 1 hr vs. 24 hr from ingestion. ...All published cases of methanol poisoning /were analyzed/ to determine the applicability of the 20 mg/dL threshold in a nonacidotic patient, specifically those arriving early for care (within 6 hr) with a peak or near-peak blood methanol concentration. ...Dating to 1879, 372 articles in 18 languages were abstracted using a standard format; 329 articles (2433 patients) involved methanol poisoning, and 70 articles (173 patients) met inclusion criteria. Only 22 of these patients presented for care within 6 hr of ingestion with an early methanol level. All but 1 patient was treated with an inhibitor of alcohol dehydrogenase (ADH). A clear acidosis developed only with a methanol level > or = 126 mg/dL. The patient that did not receive an ADH inhibitor was an infant with an elevated early methanol level (46 mg/dL) that was given folate alone and never became acidotic. Intra and inter-rater reliability were 0.95. Nearly all reports of methanol poisoning involve acidotic patients far removed from ingestion. The small amount of data regarding patients arriving early show that 126 mg/dL is the lowest early blood methanol level ever clearly associated with acidosis. Contrary to conventional teaching, there are case reports of acidosis after only a few hours of ingestion. The data are insufficient to apply 20 mg/dL as a treatment threshold in a nonacidotic patient arriving early for care.

  • Fire-fighting measures: Suitable extinguishing media If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all containers with flooding quantities or water. Apply water from as far a distance as possible. Use "alcohol" foam, dry chemical or carbon dioxide. Behavior in Fire: Containers may explode. (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. Personal protection: chemical protection suit including self-contained breathing apparatus. Evacuate danger area! Ventilation. Collect leaking and spilled liquid in sealable containers as far as possible. Wash away remainder with plenty of water. Remove vapour with fine water spray. General Spill Actions: Stop or reduce discharge of material if this can be done without risk. Eliminate all sources of ignition. Avoid skin contact and inhalation. A fluorocarbon water foam can be applied to the spill to diminish vapor and fire hazard. Hycar and carbopol, which are absorbent materials, have shown possible applicability for vapor suppression and/or containment of methanol in spill situations. Leaking containers should be removed to the outdoors or to an isolated, well-ventilated area and the contents transferred to other suitable containers. The following materials are recommended for plugging leaks of methanol: polyester (eg Glad bag), imid polyester (eg brown-in-bag), stafoam urethane foam, sea-going epoxy putty, and MSA urethane.

  • 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 and food and feedstuffs. Cool.When large amounts of methanol are stored in enclosed 14 Methanol spaces, monitoring by means of lower explosion limit monitors is desirable.

  • Exposure controls/personal protection:Occupational Exposure limit valuesRecommended Exposure Limit: 10 Hour Time-Weighted Average: 200 ppm (260 mg/cu m), skinRecommended Exposure Limit: 15 Minute Short-Term Exposure Limit: 250 ppm (325 mg/cu m), skin.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:Sigma-Aldrich
  • Product Description:Methanol anhydrous for analysis (max. 0.003% H?O)
  • Packaging:1 L
  • Price:$ 50.6
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:CombiMethanol Solvent for volumetric Karl Fischer titration with one component reagents max. 0.01% H?O Aquastar?
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  • Product Description:Methanol anhydrous for analysis (max. 0.003% H O)
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methanol anhydrous, 99.8%
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  • Product Description:Methanol analytical standard
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  • Product Description:Methanol
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  • Product Description:Methanol Pharmaceutical Secondary Standard; Certified Reference Material
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:Methanol histology grade
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Relevant articles and documentsAll total 1895 Articles be found

C-C Bond Cleavage of Acetonitrile by a Dinuclear Copper(II) Cryptate

Lu, Tongbu,Zhuang, Xiaomei,Li, Yanwu,Chen, Shi

, p. 4760 - 4761 (2004)

The dinuclear copper(II) cryptate [Cu2L](ClO4)4 (1) cleaves the C?C bond of acetonitrile at room temperature to produce a cyanide bridged complex of [Cu2L(CN)](ClO4)3·2CH3CN·4H2O (2). The cleavage mechanism is presented on the basis of the results of the crystal structure of 2, electronic absorption spectra, ESI-MS spectroscopy, and GC spectra of 1, respectively. Copyright

Photo-induced reduction of CO2 using a magnetically separable Ru-CoPc@TiO2@SiO2@Fe3O4 catalyst under visible light irradiation

Kumar, Pawan,Chauhan,Sain, Bir,Jain, Suman L.

, p. 4546 - 4553 (2015)

An efficient photo-induced reduction of CO2 using magnetically separable Ru-CoPc@TiO2@SiO2@Fe3O4 as a heterogeneous catalyst in which CoPc and Ru(bpy)2phene complexes were attached to a solid support via covalent attachment under visible light is described. The as-synthesized catalyst was characterized by a series of techniques including FTIR, UV-Vis, XRD, SEM, TEM, etc. and subsequently tested for the photocatalytic reduction of carbon dioxide using triethylamine as a sacrificial donor and water as a reaction medium. The developed photocatalyst exhibited a significantly higher catalytic activity to give a methanol yield of 2570.78 μmol per g cat after 48 h. This journal is

Kassel

, p. 493 (1936)

CO2 Reduction Promoted by Imidazole Supported on a Phosphonium-Type Ionic-Liquid-Modified Au Electrode at a Low Overpotential

Iijima, Go,Kitagawa, Tatsuya,Katayama, Akira,Inomata, Tomohiko,Yamaguchi, Hitoshi,Suzuki, Kazunori,Hirata, Kazuki,Hijikata, Yoshimasa,Ito, Miho,Masuda, Hideki

, p. 1990 - 2000 (2018)

The catalytic conversion of CO2 to useful compounds is of great importance from the viewpoint of global warming and development of alternatives to fossil fuels. Electrochemical reduction of CO2 using aromatic N-heterocylic molecules is a promising research area. We describe a high performance electrochemical system for reducing CO2 to formate, methanol, and CO using imidazole incorporated into a phosphonium-type ionic liquid-modified Au electrode, imidazole@IL/Au, at a low onset-potential of -0.32 V versus Ag/AgCl. This represents a significant improvement relative to the onset-potential obtained using a conventional Au electrode (-0.56 V). In the reduction carried out at -0.4 V, formate is mainly generated and methanol and CO are also generated with high efficiency at -0.6 ~ -0.8 V. The generation of methanol is confirmed by experiments using 13CO2 to generate 13CH3OH. To understand the reaction behavior of CO2 reduction, we characterized the reactions by conducting potential- and time-dependent in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (SEIRAS) measurements in D2O. During electrochemical CO2 reduction at -0.8 V, the C-O stretching band for CDOD (or COD) increases and the C=O stretching band for COOD increases at -0.4 V. These findings indicate that CO2 reduction intermediates, CDOD (or COD) and COOD, are formed, depending on the reduction potential, to convert CO2 to methanol and formate, respectively.

Photochemical and enzymatic synthesis of methanol from HCO3 - with dehydrogenases and zinc porphyrin

Amao, Yutaka,Watanabe, Tomoe

, p. 1544 - 1545 (2004)

Photochemical and enzymatic methanol synthesis from HCO3 - with formate dehydrogenase (FDH), aldehyde dehydrogenase (AldDH), and alcohol dehydrogenase (ADH) via the photoreduction of MV2+ using ZnTPPS photosensitization wa

Patart

, p. 1330 (1924)

Catalytic Activity of Nanosized CuO-ZnO Supported on Titanium Chips in Hydrogenation of Carbon Dioxide to Methyl Alcohol

Ahn, Ho-Geun,Lee, Hwan-Gyu,Chung, Min-Chul,Park, Kwon-Pil,Kim, Ki-Joong,Kang, Byeong-Mo,Jeong, Woon-Jo,Jung, Sang-Chul,Lee, Do-Jin

, p. 2024 - 2027 (2016)

In this study, titanium chips (TC) generated from industrial facilities was utilized as TiO2 support for hydrogenation of carbon dioxide (CO2) to methyl alcohol (CH3OH) over Cu-based catalysts. Nanosized CuO and ZnO catalysts were deposited on TiO2 support using a co-precipitation (CP) method (CuO-ZnO/TiO2), where the thermal treatment of TC and the particle size of TiO2 are optimized on CO2 conversion under different reaction temperature and contact time. Direct hydrogenation of CO2 to CH3OH over CuO-ZnO/TiO2 catalysts was achieved and the maximum selectivity (22%) and yield (18.2%) of CH3OH were obtained in the range of reaction temperature 210~240 °C under the 30 bar. The selectivity was readily increased by increasing the flow rate, which does not affect much to the CO2 conversion and CH3OH yield.

Photocatalytic conversion of carbon dioxide into methanol in reverse fuel cells with tungsten oxide and layered double hydroxide photocatalysts for solar fuel generation

Morikawa, Motoharu,Ogura, Yuta,Ahmed, Naveed,Kawamura, Shogo,Mikami, Gaku,Okamoto, Seiji,Izumi, Yasuo

, p. 1644 - 1651 (2014)

The phenomena of the photocatalytic oxidation of water and photocatalytic reduction of CO2 were combined using reverse photofuel cells, in which the two photocatalysts, WO3 and layered double hydroxide (LDH), were separated by a polymer electrolyte (PE) film. WO3 was used for the photooxidation of water, whereas LDH, comprising Zn, Cu, and Ga, was used for the photoreduction of CO2. For this process, photocatalysts pressed on both sides of the PE film were irradiated with UV-visible light through quartz windows and through the space in carbon electrode plates and water-repellent carbon paper for both gas flow and light transmission. 45% of the photocatalyst area was irradiated through the windows. The protons and electrons, which were formed on WO3 under the flow of helium and moisture, transferred to the LDH via the PE and external circuit, respectively. Methanol was the major product from the LDH under the flow of CO2 and helium. The observed photoreduction rates of CO2 to methanol accounted for 68%-100% of photocurrents. This supports the effectiveness of the combined photooxidation and photoreduction mechanism as a viable strategy to selectively produce methanol. In addition, we tested reverse photofuel cell-2, which consisted of a WO3 film pressed on C paper and LDH film pressed on Cu foil. The photoelectrodes were immersed in acidic solutions of pH 4, with the PE film distinguishing the two compartments. Both the photoelectrodes were completely irradiated by UV-visible light through the quartz windows. Consequently, the photocurrent from the LDH under CO2 flow to WO 3 under N2 flow was increased by 2.4-3.4 times in comparison to photofuel cell-1 tested under similar conditions. However, the major product from the LDH was H2 rather than methanol using photofuel cell-2. The photogenerated electrons in the irradiated area of the photocatalysts were obliged to diffuse laterally to the unirradiated area of photocatalysts in contact with the C papers in photofuel cell-1. This lateral diffusion reduced the photocatalytic conversion rates of CO2, despite the advantages of photofuel cell-1 in terms of selective formation and easy separation of gas-phase methanol. This journal is the Partner Organisations 2014.

Comparative Study of Diverse Copper Zeolites for the Conversion of Methane into Methanol

Park, Min Bum,Ahn, Sang Hyun,Mansouri, Ali,Ranocchiari, Marco,van Bokhoven, Jeroen A.

, p. 3705 - 3713 (2017)

The characterization and reactive properties of copper zeolites with twelve framework topologies (MOR, EON, MAZ, MEI, BPH, FAU, LTL, MFI, HEU, FER, SZR, and CHA) are compared in the stepwise partial oxidation of methane into methanol. Cu2+ ion-exchanged zeolite omega, a MAZ-type material, reveals the highest yield (86 μmol g(cat.)?1) among these materials after high-temperature activation and liquid methanol extraction. The high yield is ascribed to the relatively high density of copper–oxo active species, which form in its three-dimensional 8-membered (MB) ring channels. In situ UV/Vis studies show that diverse copper species form in different zeolites after high-temperature activation, suggesting that there are no universally active species. Nonetheless, there are some dominant factors required for achieving high methanol yields: 1) highly dispersed copper–oxo species; 2) large amount of exchanged copper in small-pore zeolites; 3) moderately high temperature of activation; and 4) use of proton form zeolite precursors. Cu-omega and Cu-mordenite, with the proton form of mordenite as the precursor, yield methanol after activation in oxygen and reaction with methane at only 200 °C, that is, under isothermal conditions.

Experimental measurements and kinetic modeling of CH4/O 2 and CH4/C2H6/02 conversion at high pressure

Rasmussen, Christian Lund,Geest Jakobsen,Glarborg, Peter

, p. 778 - 807 (2008)

A detailed chemical kinetic model for homogeneous combustion of the light hydrocarbon fuels CH4 and C2H6 in the intermediate temperature range roughly 500-1100 K, and pressures up to 100 bar has been developed and validated experimentally. Rate constants have been obtained from critical evaluation of data for individual elementary reactions reported in the literature with particular emphasis on the conditions relevant to the present work. The experiments, involving CH4/02 and CH4/C2H6/O2 mixtures diluted in N2 have been carried out in a high-pressure flow reactor at 600-900 K, 50-100 bar, and reaction stoichiometrics ranging from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Finally, the mechanism was extended with a number of reactions important at high temperature and tested against data from shock tubes, laminar flames, and flow reactors.

Spontaneous hydrolysis of ionized phosphate monoesters and diesters and the proficiencies of phosphatases and phosphodiesterases as catalysts

Wolfenden, Richard,Ridgway, Caroline,Young, Gregory

, p. 833 - 834 (1998)

-

Cobalt phthalocyanine immobilized on graphene oxide: An efficient visible-active catalyst for the photoreduction of carbon dioxide

Kumar, Pawan,Kumar, Arvind,Sreedhar, Bojja,Sain, Bir,Ray, Siddharth S.,Jain, Suman L.

, p. 6154 - 6161 (2014)

New graphene oxide (GO)-tethered-CoII phthalocyanine complex [CoPc-GO] was synthesized by a stepwise procedure and demonstrated to be an efficient, cost-effective and recyclable photocatalyst for the reduction of carbon dioxide to produce methanol as the main product. The developed GO-immobilized CoPc was characterized by X-ray diffraction (XRD), FTIR, XPS, Raman, diffusion reflection UV/Vis spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). FTIR, XPS, Raman, UV/Vis and ICP-AES along with elemental analysis data showed that CoII-Pc complex was successfully grafted on GO. The prepared catalyst was used for the photocatalytic reduction of carbon dioxide by using water as a solvent and triethylamine as the sacrificial donor. Methanol was obtained as the major reaction product along with the formation of minor amount of CO (0.82%). It was found that GO-grafted CoPc exhibited higher photocatalytic activity than homogeneous CoPc, as well as GO, and showed good recoverability without significant leaching during the reaction. Quantitative determination of methanol was done by GC flame-ionization detector (FID), and verification of product was done by NMR spectroscopy. The yield of methanol after 48 h of reaction by using GO-CoPc catalyst in the presence of sacrificial donor triethylamine was found to be 3781.8881 μmolg-1cat., and the conversion rate was found to be 78.7893 μmolg-1cat.h-1. After the photoreduction experiment, the catalyst was easily recovered by filtration and reused for the subsequent recycling experiment without significant change in the catalytic efficiency. Very photoactive! Cobalt phthalocyanine grafted to the chemically functionalized graphene oxide was found to be an efficient heterogeneous visible-light-induced photoredox catalyst for the photoreduction of carbon dioxide to methanol in a very good yield. The developed photocatalyst exhibited superior activity compared with the existing photocatalytic systems and gave methanol as the major reaction product (see scheme).

Facile synthesis of ZnO particles: Via benzene-assisted co-solvothermal method with different alcohols and its application

Maneechakr, Panya,Karnjanakom, Surachai,Samerjit, Jittima

, p. 73947 - 73952 (2016)

In this study, ZnO particles with different morphologies were synthesized by a novel co-solvothermal method using benzene. The prepared samples were characterized by Brunauer-Emmett-Teller (BET) measurements, X-ray diffractometry (XRD), scanning electron microscopy coupled with an energy dispersive X-ray detector (SEM-EDX), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometry (XPS), and H2-temperature programmed reduction (H2-TPR). The results showed that the molecular sizes and carbon numbers of the alcohols used in the reaction and the addition of benzene had a great effect on the morphologies, textural properties, and crystalline structures of the material products in our reaction system. Different ZnO morphologies, such as spherical coral-like, carnation-like, rose-like, and plate-like structures, were obtained using methanol, ethanol, propanol, and butanol, respectively. Moreover, Cu particles loaded on ZnO with different morphologies were also investigated for the hydrogenation of CO2 to CH3OH. High catalytic activity and selectivity (82.8%) for CH3OH formation were obtained using ZnO prepared from methanol with Cu doping (Cu/ZnO-Me).

Dynamics of Reaction of (meso-Tetrakis(2,6-dimethyl-3-sulfonatophenyl)porphinato)iron(III) Hydrate with tert-Butyl Hydroperoxide in Aqueous Solution. 2. Establishment of a Mechanism That Involves Homolytic O-O Bond Breaking and One-Electron Oxidation of the Iron(III) Porphyrin

Balasubramanian, P. N.,Lindsay Smith, John R.,Davies, Michael J.,Kaaret, Thomas W.,Bruice, Thomas C.

, p. 1477 - 1483 (1989)

The reaction of t-BuOOH with the water soluble and non-μ-oxo dimer forming (5,10,15,20-tetrakis(2,6-dimethyl-3-sulfonatophenyl)porphinato)iron(III) hydrate ((1)FeIII(X)(H2O) where X=H2O or HO(1-)) was studied in aqueous solution between pH 2 and 13 in the absence of an agent for the trapping of reaction intermediates.Products of t-BuOOH decomposition are (CH3)2CO (90percent), CH3OH (90percent), and t-BuOH (15percent), while neither CH4, C2H6, O2, nor (t-BuO)2 could be detected.That (CH3)2CO and CH3OH are formed through fragmentation of t-BuO. to (CH3)2CO and CH3. is shown by theobservation that the reaction of Ph(CH3)2COOH with (1)FeIII(X)(H2O) provides acetophenone but not phenol.This must be a consequence of homolytic O-O bond scission with the formation of Ph(CH3)2CO..The reaction of (1)FeIII(X)(H2O) with m-ClC6H4CO3H and the hydroperoxides t-BuOOH, Ph(CH3)2COOH, Ph2C(CO2CH3)OOH, and Ph2C(CN)OOH between pH 5 and 7 leads to the buildup of (1)FeIV(X)(H2O) species.The formation of an iron(IV)-oxo porphyrin species was established by titrimetric experiments as well as by carbon microelectrode voltommetry and 1e(1-) spectroelectrochemical generation of authentic (1)FeIV(X)(H2O) species.Formation of (1)FeIV(X)(H2O) species on oxidation of (1)FeIII(X)(H2O) with m-ClC6H4CO3H occurs in the absence of O2, while formation of (1)FeIV(X)(H2O) species on oxidation of (1)FeIII(X)(H2O) by the alkyl hydroperoxides, t-BuOOH and Ph(CH3)2COOH, requires the presence of O2.These observations require for the peracid a 2e(1-) oxidation with heterolytic O-O bond cleavage III(X)(H2O) --> m-ClC6H4CO2H + (+.1)FeIV(X)(H2O)> followed by a comproportionation reaction III(X)(H2O)+ (+.1)FeIV(X)(H2O) --> 2(1)FeIV(X)(H2O)>, while in the case of the reaction of the alkyl hydroperoxides a 1e(1-) oxidation occurs with homolytic O-O bond breaking.The fragmentation of the resultant t-BuO. provides (CH3)2CO and CH3., and reaction of the latter with (1)FeIII(X)(H2O) yields CH3OH and (1)FeII(X)(H2O).The resultant iron(II) porphyrin species reacts with O2 II(X)(H2O) + O2 --> 2(1)FeIV(X)(H2O)>.The putative (1)FeII(X)(H2O) intermediate was identified by its trapping with CO.Also, t-BuO. and CH3. intermediates were identified by their spin trapping with 5,5-dimethyl-1-pyrroline N-oxide.The rate constant for reaction of hydrogen peroxide with (1)FeIV(X)(H2O) exceeds that for other hydroperoxides investigated.Thus, (1)FeIV(X)(H2O) does not accumulate in the reaction of H2O2 with (1)FeIII(X)(H2O).The rapid reaction of H2O2 with (1)FeIV(X)(H2O) provides (1)FeIII(X)(H2O) and presumably O2.- + H(1+).This marks the first observation of the reaction of H2O2 with a compound II species.The pH dependence of the kinetics for the reaction of (1)FeIII(X)(H2O) with t-BuOOH has been determined and shown to be comparable to those of a previous study which...

Efficient ionic liquid-based platform for multi-enzymatic conversion of carbon dioxide to methanol

Zhang, Zhibo,Muschiol, Jan,Huang, Yuhong,Sigurdardóttir, Sigyn Bj?rk,Von Solms, Nicolas,Daugaard, Anders E.,Wei, Jiang,Luo, Jianquan,Xu, Bao-Hua,Zhang, Suojiang,Pinelo, Manuel

, p. 4339 - 4348 (2018)

Low yields commonly obtained during enzymatic conversion of CO2 to methanol are attributed to low CO2 solubility in water. In this study, four selected ionic liquids with high CO2 solubility were separately added to the multi-enzyme reaction mixture and the yields were compared to the pure aqueous system (control). In an aqueous 20% [CH][Glu] system, yield increased ca. 3.5-fold compared to the control (ca. 5-fold if NADH regeneration was incorporated). Molecular dynamics simulation revealed that CO2 remains for longer in a productive conformation in the enzyme in the presence of [CH][Glu], which explains the marked increase of yield that was also confirmed by isothermal titration calorimetry-lower energy (ΔG) binding of CO2 to FDH. The results suggest that the accessibility of CO2 to the enzyme active site depends on the absence/presence and nature of the ionic liquid, and that the enzyme conformation determines CO2 retention and hence final conversion.

Development of highly stable catalyst for methanol synthesis from carbon dioxide

Li, Congming,Yuan, Xingdong,Fujimoto, Kaoru

, p. 306 - 311 (2014)

Zr-doped Cu-Zn-Zr-Al (CZZA) catalyst showed excellent performances for the methanol synthesis from carbon dioxide and hydrogen such as activity, selectivity and especially stability under mild conditions (such as 230 C and 3.0 MPa). The catalyst showed excellent tolerance against water vapor. It was found that added alumina promoted the dispersion of Cu whereas it suppressed the reduction of copper oxide. On the other hand, added Zr promoted the catalytic activity of methanol synthesis from CO2 and suppressed the inhibitive effect of water for the reaction as well as the catalyst deactivation. It was concluded that the methanol formation from CO2 proceeds through two routes: one is the direct hydrogenation of CO2 to methanol and another is the one which pass through the CO formation. The Zr-promoted catalyst gave methanol and CO at the selectivity ratio of 0.4 to 0.6, whereas the un-promoted catalyst gave only CO at the initial stage of the reaction. It was claimed that the doped Zr promote the in-situ reduction of oxidized Cu (which should be caused by the reaction with the co-product H2O) by H 2 to increase the content of reduced Cu (active site) and thus the catalyst activity. The promoted reductivity of the Zr-containing catalyst prevents the crystal growth of CuOx which cause the irreversible deactivation of catalyst.

Comparative study of hydrotalcite-derived supported Pd2Ga and PdZn intermetallic nanoparticles as methanol synthesis and methanol steam reforming catalysts

Ota, Antje,Kunkes, Edward L.,Kasatkin, Igor,Groppo, Elena,Ferri, Davide,Poceiro, Beatriz,Navarro Yerga, Rufino M.,Behrens, Malte

, p. 27 - 38 (2012)

An effective and versatile synthetic approach to produce well-dispersed supported intermetallic nanoparticles is presented that allows a comparative study of the catalytic properties of different intermetallic phases while minimizing the influence of differences in preparation history. Supported PdZn, Pd2Ga, and Pd catalysts were synthesized by reductive decomposition of ternary Hydrotalcite-like compounds obtained by co-precipitation from aqueous solutions. The precursors and resulting catalysts were characterized by HRTEM, XRD, XAS, and CO-IR spectroscopy. The Pd2+ cations were found to be at least partially incorporated into the cationic slabs of the precursor. Full incorporation was confirmed for the PdZnAl-Hydrotalcite-like precursor. After reduction of Ga- and Zn-containing precursors, the intermetallic compounds Pd2Ga and PdZn were present in the form of nanoparticles with an average diameter of 6 nm or less. Tests of catalytic performance in methanol steam reforming and methanol synthesis from CO2 have shown that the presence of Zn and Ga improves the selectivity to CO2 and methanol, respectively. The catalysts containing intermetallic compounds were 100 and 200 times, respectively, more active for methanol synthesis than the monometallic Pd catalyst. The beneficial effect of Ga in the active phase was found to be more pronounced in methanol synthesis compared with steam reforming of methanol, which is likely related to insufficient stability of the reduced Ga species in the more oxidizing feed of the latter reaction. Although the intermetallic catalysts were in general less active than a Cu-/ZnO-based material prepared by a similar procedure, the marked changes in Pd reactivity upon formation of intermetallic compounds and to study the tunability of Pd-based catalysts for different reactions.

Cu-Erionite Zeolite Achieves High Yield in Direct Oxidation of Methane to Methanol by Isothermal Chemical Looping

Knorpp, Amy J.,Liu, Zhendong,Mizuno, Stefanie C. M.,Newton, Mark A.,Okubo, Tatsuya,Sushkevich, Vitaly L.,Van Bokhoven, Jeroen A.,Wakihara, Toru,Zhu, Jie

, p. 1448 - 1453 (2020)

We herein report that a copper-ion-exchanged erionite zeolite (Cu-ERI) exhibited a methanol yield as high as 147 μmol/g-zeolite, equaling 0.224 μmol/μmol-Cu, in the direct oxidation of methane to methanol. Moreover, this high methanol yield was achieved using an isothermal chemical looping with both oxygen activation and reaction with methane carried out at 300 °C, in contrast to the conventional stepwise protocol where activation is performed at a high temperature (450 °C and above) and the methane reaction at a lower temperature (typically 200 °C). Under isobaric conditions (1 bar), the Cu-ERI still gave a high yield of 80 μmol/g-zeolite after a single aqueous extraction of methanol. Such improvements indicate that high yields can be obtained over Cu-ERI in the direct conversion of methane to methanol by chemical looping without any temperature or pressure swing.

Self-sufficient and exclusive oxygenation of methane and its source materials with oxygen to methanol via metgas using oxidative bi-reforming

Olah, George A.,Prakash, G. K. Surya,Goeppert, Alain,Czaun, Miklos,Mathew, Thomas

, p. 10030 - 10031 (2013)

A combination of complete methane combustion with oxygen of the air coupled with bi-reforming leads to the production of metgas (H2/CO in 2:1 mole ratio) for exclusive methanol synthesis. The newly developed oxidative bi-reforming allows direct oxygenation of methane to methanol in an overall economic and energetically efficient process, leaving very little, if any, carbon footprint or byproducts.

-

Hofmann,K. A.,Schibsted

, p. 1398 (1918)

-

Spinel-Structured ZnCr2O4 with Excess Zn Is the Active ZnO/Cr2O3 Catalyst for High-Temperature Methanol Synthesis

Song, Huiqing,Laudenschleger, Daniel,Carey, John J.,Ruland, Holger,Nolan, Michael,Muhler, Martin

, p. 7610 - 7622 (2017)

A series of ZnO/Cr2O3 catalysts with different Zn:Cr ratios was prepared by coprecipitation at a constant pH of 7 and applied in methanol synthesis at 260-300 °C and 60 bar. The X-ray diffraction (XRD) results showed that the calcined catalysts with ratios from 65:35 to 55:45 consist of ZnCr2O4 spinel with a low degree of crystallinity. For catalysts with Zn:Cr ratios smaller than 1, the formation of chromates was observed in agreement with temperature-programmed reduction results. Raman and XRD results did not provide evidence for the presence of segregated ZnO, indicating the existence of Zn-rich nonstoichiometric Zn-Cr spinel in the calcined catalyst. The catalyst with Zn:Cr = 65:35 exhibits the best performance in methanol synthesis. The Zn:Cr ratio of this catalyst corresponds to that of the Zn4Cr2(OH)12CO3 precursor with hydrotalcite-like structure obtained by coprecipitation, which is converted during calcination into a nonstoichiometric Zn-Cr spinel with an optimum amount of oxygen vacancies resulting in high activity in methanol synthesis. Density functional theory calculations are used to examine the formation of oxygen vacancies and to measure the reducibility of the methanol synthesis catalysts. Doping Cr into bulk and the (10-10) surface of ZnO does not enhance the reducibility of ZnO, confirming that Cr:ZnO cannot be the active phase. The (100) surface of the ZnCr2O4 spinel has a favorable oxygen vacancy formation energy of 1.58 eV. Doping this surface with excess Zn charge-balanced by oxygen vacancies to give a 60% Zn content yields a catalyst composed of an amorphous ZnO layer supported on the spinel with high reducibility, confirming this as the active phase for the methanol synthesis catalyst.

Understanding and Optimizing the Performance of Cu-FER for The Direct CH4 to CH3OH Conversion

Pappas, Dimitrios K.,Borfecchia, Elisa,Dyballa, Michael,Lomachenko, Kirill A.,Martini, Andrea,Berlier, Gloria,Arstad, Bj?rnar,Lamberti, Carlo,Bordiga, Silvia,Olsbye, Unni,Svelle, Stian,Beato, Pablo

, p. 621 - 627 (2019)

Cu-exchanged zeolites with the Ferrierite topology were investigated in the direct CH4 to CH3OH conversion. Samples with a systematic compositional variation in terms of Na/Al and Cu/Al ratios where synthesized by liquid ion exchange. The presence of Na is observed to be beneficial for the Cu exchange and thereby higher Cu loadings were achieved. The overall performance of Cu-FER samples depends on Cu loading as well as the conditions of the reaction. Elevated O2 activation temperature as well as long CH4 loading times are proven to enhance the CH3OH yield of the Cu-FER sample with Cu/Al=0.2. In addition, the productivity depends on the Cu/Al ratio, at low values the sample is almost inactive indicating a Cu threshold that needs to be surpassed. We employed X-ray absorption and IR of adsorbed CO spectroscopies in order to rationalize the performance as well as the effect of Cu/Al ratio. From the in situ spectroscopies we ultimately establish structure-activity relationships between the reducibility of Cu species and the CH3OH yield.

Dodge

, p. 89 (1930)

Smith,Hirst

, p. 634,1039 (1930)

A novel low-temperature methanol synthesis method from CO/H2/CO2 based on the synergistic effect between solid catalyst and homogeneous catalyst

Zhao, Tian-Sheng,Zhang, Kun,Chen, Xuri,Ma, Qingxiang,Tsubaki, Noritatsu

, p. 98 - 104 (2010)

The activity of a binary catalyst in alcoholic solvents for methanol synthesis from CO/H2/CO2 at low temperature was investigated in a concurrent synthesis course. Experiment results showed that the combination of homogeneous potassium formate catalyst and solid copper-magnesia catalyst enhanced the conversion of CO2-containing syngas to methanol at temperature of 423-443 K and pressure of 3-5 MPa. Under a contact time of 100 g h/mol, the maximum conversion of total carbon approached the reaction equilibrium and the selectivity of methanol was 99%. A reaction pathway involving esterification and hydrogenolysis of esters was postulated based on the integrative and separate activity tests, along with the structural characterization of the catalysts. Both potassium formate for the esterification as well as Cu/MgO for the hydrogenolysis were found to be crucial to this homogeneous and heterogeneous synergistically catalytic system. CO and H2 were involved in the recycling of potassium formate.

Effects of alkaline-earth oxides on the performance of a CuO-ZrO2 catalyst for methanol synthesis via CO2 hydrogenation

Zhong, Chenglin,Guo, Xiaoming,Mao, Dongsen,Wang, Song,Wu, Guisheng,Lu, Guanzhong

, p. 52958 - 52965 (2015)

CuO-ZrO2 catalysts doped with alkaline-earth oxides were prepared by a urea-nitrate combustion method. The catalysts were characterized with N2 adsorption, N2O titration, XRD, H2-TPR, XPS and CO2-TPD techniques and tested for methanol synthesis from CO2 hydrogenation. With the incorporation of alkaline-earth oxides, the copper surface area increases remarkably, whereas the reducibility of CuO in the catalyst decreases. The doping of alkaline-earth oxides leads to an increase in the strength and contribution of the strong basic site on the catalyst surface. The results of catalytic tests indicate that the conversion of CO2 depends not only on the copper surface area but also on the reducibility of CuO in the catalyst, and the latter is a predominant factor for CaO-, SrO- and BaO-doped CuO-ZrO2 catalysts. The selectivity to methanol is related to the basicity of the catalyst. Moreover, the influence of the doping amount of MgO on the properties of CuO-ZrO2 was investigated, and the optimum catalytic activity is obtained as the amount of MgO doping is 5 mol%.

Continuous supercritical low-temperature methanol synthesis with n-butane as a supercritical fluid

Reubroycharoen, Prasert,Bao, Jun,Zhang, Yi,Tsubaki, Noritatsu

, p. 790 - 791 (2008)

A process of supercritical low-temperature methanol synthesis from syngas containing CO2 was carried out at 443 K and 60 bar. The 2-butanol and n-butane was used as catalytic solvent and supercritical medium, respectively. The results showed that the total carbon conversion, especially the CO 2 conversion of the methanol synthesis was increased significantly under the supercritical condition. Copyright

Reversible Switching of Catalytic Activity by Shuttling an Atom into and out of Gold Nanoclusters

Cai, Xiao,Saranya, Govindarajan,Shen, Kangqi,Chen, Mingyang,Si, Rui,Ding, Weiping,Zhu, Yan

, p. 9964 - 9968 (2019)

It is challenging to control the catalyst activation and deactivation by removal and addition of only one central atom, as it is almost impossible to precisely abstract an atom from a conventional catalyst and analyze its catalysis. Here we report that th

Molybdenum-Bismuth Bimetallic Chalcogenide Nanosheets for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Methanol

Sun, Xiaofu,Zhu, Qinggong,Kang, Xinchen,Liu, Huizhen,Qian, Qingli,Zhang, Zhaofu,Han, Buxing

, p. 6771 - 6775 (2016)

Methanol is a very useful platform molecule and liquid fuel. Electrocatalytic reduction of CO2 to methanol is a promising route, which currently suffers from low efficiency and poor selectivity. Herein we report the first work to use a Mo-Bi bimetallic chalcogenide (BMC) as an electrocatalyst for CO2 reduction. By using the Mo-Bi BMC on carbon paper as the electrode and 1-butyl-3-methylimidazolium tetrafluoroborate in MeCN as the electrolyte, the Faradaic efficiency of methanol could reach 71.2 % with a current density of 12.1 mA cm-2, which is much higher than the best result reported to date. The superior performance of the electrode resulted from the excellent synergistic effect of Mo and Bi for producing methanol. The reaction mechanism was proposed and the reason for the synergistic effect of Mo and Bi was discussed on the basis of some control experiments. This work opens a way to produce methanol efficiently by electrochemical reduction of CO2.

Formation of Methanol by Microwave-Plasma Reduction of CO2 with H2O

Ihara, Tatsuhiko,Ouro, Takashi,Ochiai, Tomoyuki,Kiboku, Mitsuo,Iriyama, Yu

, p. 241 - 244 (1996)

Reduction of CO2 with H2O was carried out by microwave plasma for the formation of methanol. The results of steam chromatography and mass spectrometry showed that the plasma products contained methanol. The methanol formation was also found in H2O-plasma-cleaning process, in which materials which had been deposited in the reaction between CO2 and H2O were removed. The most adequate plasma energy density for the formation of methanol was found to be 0.26 GJ kg-1 of W/FM. The methanol yield at the system pressure of 400 Pa was 3.5 times higher than at 240 Pa for both the CO2-H2O synthetic process and the H2O-cleaning process.

Characterization of modified Fischer-Tropsch catalysts promoted with alkaline metals for higher alcohol synthesis

Cosultchi, Ana,Perez-Luna, Miguel,Morales-Serna, Jose Antonio,Salmon, Manuel

, p. 368 - 377 (2012)

Two series of Cu/Co/Cr modified Fischer-Tropsch catalyst promoted with Zn or Mn and an alkaline metal (Me: Li, Na, K, Rb, Cs) were prepared by co-precipitation method and tested for high alcohol synthesis (HAS) at one hour on-stream and at two temperatures, 300 and 350 °C. The results indicate that the best selectivity toward high alcohols depends on temperature and catalysts composition and is obtained as follows: a) at 300 °C over catalysts without Zn and containing K, Na and Rb; b) at 350 °C over catalysts without Zn and containing K; c) at 350 °C over catalysts containing Zn as well as Li and Cs.

Conversion of CH4 to CH3OH: Reactions of CoO+ with CH4 and D2, Co+ with CH3OD and D2O, and Co+(CH3OD) with Xe

Chen, Yu-Min,Clemmer,Armentrout

, p. 7815 - 7826 (1994)

The mechanisms and energetics involved in the conversion of CH4 to CH3OH by CoO+ are examined by using guided ion beam mass spectrometry. The forward and reverse reactions, CoO+ + CH4 ? Co+ + CH3OH, the collisional activation of Co+(CH3OH), and the related reactions, CoO+ + D2 ? Co+ + D2O, are studied. It is found that the oxidations of methane and D2 by CoO+, both exothermic reactions, do not occur until overcoming activation barriers of 0.56 ± 0.08 and 0.75 ± 0.04 eV, respectively. The behavior of the forward and reverse reactions in both systems is consistent with reactions that proceed via the insertion intermediates R-Co+-OH, where R = CH3 or H. The barrier is probably attributable to a four-centered transition state associated with addition of RH across the CoO+ bond. In the Co+ + CH3OH system (where CH3OD labeled reactant is used), reactions explained by initial C-H and O-H activation are also observed. The reaction mechanisms and potential energy surfaces for these systems are derived and discussed. Phase space theory calculations are used to help verify these details for the CoO+ + D2 system. Thermochemistry for several species including CoOH+, CoD+, CoH, CoCH3+, Co+(CH3OD), CoOCH3+, and possibly OCoCH3+ is derived from measurements of reaction thresholds.

ACID-CATALYZED HYDROLYSIS OF 2-METHOXYPROPENAL

Fedoronko, Michal,Petrusova, Maria,Tvaroska, Igor

, p. 85 - 94 (1983)

2-Methoxypropenal in acid media undergoes general acid-catalyzed hydrolysis with formation of 2-oxopropanal.The kinetics of this reaction were studied, the rate constants established, and a reaction mechanism is suggested.Hydrolysis of 2-methoxypropenal is governed by a mechanism of the vinyl ether type, and the presence of the aldehyde group causes a decrease in the reaction rate.The analogy of the acid-catalyzed hydrolysis of 2-methoxypropenal to that of a vinyl ether was shown by the solvent isotope-effect, kD/kH=0.41, and the value of the Broensted exponent, α=0.60.The activation parameters found and quantum-chemical calculations of charge distribution in 2-methoxypropenal and other model compounds were also utilized to explain the mechanism of the acid-catalyzed hydrolysis of the title compound.

Selective electrocatalytic oxidation of a re-methyl complex to methanol by a surface-bound RuII polypyridyl catalyst

Coggins, Michael K.,Mndez, Manuel A.,Concepcion, Javier J.,Periana, Roy A.,Meyer, Thomas J.

, p. 15845 - 15848 (2014)

The complex [Ru(Mebimpy)(4,′-((HO)2OPCH2)2bpy)(OH2)]2+ surface bound to tin-doped indium oxide mesoporous nanoparticle film electrodes (nanoITO-RuII(OH2)2+) is an electrocatalyst for the selective oxidation of methylrhenium trioxide (MTO) to methanol in acidic aqueous solution. Oxidative activation of the catalyst to nanoITO-RuIV(OH)3+ induces oxidation of MTO. The reaction is first order in MTO with rate saturation observed at [MTO] > 12 mM with a limiting rate constant of k = 25 s-1. Methanol is formed selectively in 87% Faradaic yield in controlled potential electrolyses at 1.3 V vs NHE. At higher potentials, oxidation of MTO by nanoITO-RuV(O)3+ leads to multiple electrolysis products. The results of an electrochemical kinetics study point to a mechanism in which surface oxidation to nanoITO-RuIV(OH)3+ is followed by direct insertion into the rhenium-methyl bond of MTO with a detectable intermediate.

Carbon Dioxide Conversion to Methanol over Size-Selected Cu4 Clusters at Low Pressures

Liu, Cong,Yang, Bing,Tyo, Eric,Seifert, Soenke,Debartolo, Janae,Von Issendorff, Bernd,Zapol, Peter,Vajda, Stefan,Curtiss, Larry A.

, p. 8676 - 8679 (2015)

The activation of CO2 and its hydrogenation to methanol are of much interest as a way to utilize captured CO2. Here, we investigate the use of size-selected Cu4 clusters supported on Al2O3 thin films for CO2 reduction in the presence of hydrogen. The catalytic activity was measured under near-atmospheric reaction conditions with a low CO2 partial pressure, and the oxidation state of the clusters was investigated by in situ grazing incidence X-ray absorption spectroscopy. The results indicate that size-selected Cu4 clusters are the most active low-pressure catalyst for catalytic CO2 conversion to CH3OH. Density functional theory calculations reveal that Cu4 clusters have a low activation barrier for conversion of CO2 to CH3OH. This study suggests that small Cu clusters may be excellent and efficient catalysts for the recycling of released CO2.

New and revisited insights into the promotion of methanol synthesis catalysts by CO2

Martin, Oliver,Perez-Ramirez, Javier

, p. 3343 - 3352 (2013)

CO hydrogenation, CO2 hydrogenation, and water-gas shift (WGS) reactions have been simultaneously investigated over industry-like catalysts based on Cu-ZnO-Al2O3, under methanol synthesis conditions (513 K, 5.0 MPa). For this, a novel methodology has been applied: the concentration of carbon dioxide in the syngas feed was consecutively increased (R = CO2:(CO + CO2) = 0-100) resulting in a volcano-type plot of the rate of methanol formation and forming a hysteresis loop when decreasing the CO2 concentration again. H2O co-feeding experiments revealed that the enhancement of activity can be correlated with the WGS activity linking both hydrogenation paths of CO and CO2. On the other hand, excessive amounts of surface hydroxyls seem to inhibit methanol production, explaining the drop in activity at high CO2 concentrations. An investigation of the catalytic performance was accompanied by an extensive characterisation of the fresh and used catalytic materials by X-ray diffraction, temperature-programmed reduction by H2, N 2O pulse chemisorption, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. It was shown that the copper surface area affects the CO2 hydrogenation; however, this parameter is unambiguously not the key descriptor for CO2-promoted methanol synthesis, which is a consequence of the synergistic interaction of zinc oxide and copper. This structural feature is further promoted by Al2O3 through stabilisation of the surface. The position of the activity maximum is determined by the surface ratio Cu:Zn. The hysteresis behaviour is a result of the continuous decrease of Cu dispersion and the fixation of copper species in its monovalent oxidation state, both detrimental for CO2 hydrogenation. CO hydrogenation is strongly affected by the Cu:Zn bulk ratio and thus the reducibility of the catalyst. These facts could be substantiated by the use of impregnated model catalysts. The Royal Society of Chemistry.

Selective Photoreduction of Carbon Dioxide to Methanol on Titanium Dioxide Photocatalysts in Propylene Carbonate Solution

Kuwabata, Susumu,Uchida, Hiroyuki,Ogawa, Akihiro,Hirao, Shigeki,Yoneyama, Hiroshi

, p. 829 - 830 (1995)

Methanol is selectively photosynthesised from carbon dioxide using TiO2 photocatalysts in propylene carbonate containing propan-2-ol as a hole scavenger.

Fluorine-modified Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol

Gao, Peng,Li, Feng,Zhan, Haijuan,Zhao, Ning,Xiao, Fukui,Wei, Wei,Zhong, Liangshu,Sun, Yuhan

, p. 78 - 82 (2014)

Fluorine-modified Cu/Zn/Al/Zr catalysts were prepared by calcination of the fluorine-containing Cu/Zn/Al/Zr hydrotalcite-like compounds and tested for CO2 hydrogenation to methanol. The results revealed that the CH 3OH selectivity was greatly improved by the remarkable increase of the proportion of strongly basic sites, while the CO2 conversion decreased slightly. It is also found that the activity of catalysts is closely related to the synergy between the Cu and basic sites. The CH3OH yield for the fluorine-modified Cu/Zn/Al/Zr catalysts was higher than that for the fluorine-free catalysts; thus, the introduction of fluorine favored the methanol formation.

Effect of Γ-alumina nanorods on CO hydrogenation to higher alcohols over lithium-promoted CuZn-based catalysts

Choi, SuMin,Kang, YoungJong,Kim, SangWoo

, p. 188 - 196 (2018)

To achieve high catalytic activities and long-term stability to produce higher alcohols via CO hydrogenation, the catalytic activities were tuned by controlling the loading amounts of γ-alumina nanorods and Al3+ ions added to modify Cu-Zn catalysts promoted with Li. The selectivity of higher alcohols and the CO conversion to higher alcohols over a Li-modified Cu0.45Zn0.45Al0.1 catalyst supported on 10% nanorods were 1.8 and 2.7 times higher than those with a Cu-Zn catalyst without nanorods and Al3+ ions, respectively. The introduction of the thermally and chemically stable γ-Al2O3 nanorod support and of Al3+ to the modified catalysts improves the catalytic activities by decreasing the crystalline size of CuO and increasing the total basicity. Along with the nanorods, a refractory CuAl2O4 formed by the thermal reaction of CuO and Al3+ enhances the long-term stability by increasing the resistance to sintering of the catalyst.

Isolated single-atom Pt sites for highly selective electrocatalytic hydrogenation of formaldehyde to methanol

Hu, Guangzhi,Liu, Xijun,Liu, Yifan,Luo, Jun,Mi, Yuying,Peng, Xianyun,Tang, Xiaolong,Wen, Yanfeng,Zhao, Shunzheng,Zhuo, Longchao

, p. 8913 - 8919 (2020)

The direct electrochemical conversion of noxious formaldehyde into value-added chemicals is a quite promising technique for resolving the increasingly serious environmental issue arising from industrial formaldehyde-containing wastewater. However, thus far, it has not been examined, to the best of our knowledge. This study reports the electrocatalytic hydrogenation of formaldehyde to methanol in a neutral aqueous medium under ambient conditions over a Pt single-atom catalyst, and this catalyst exhibits a favorable methanol yield rate and a high faradaic efficiency of 30.7 mg h-1 mgcat.-1 and 95.8% at -0.8 V versus the reversible hydrogen electrode in 0.1 M Na2SO4. Also, it exhibits excellent durability. Atomic-scale structural characterization and theoretical calculations revealed that the above-mentioned efficient performance is related to atomically dispersed Pt-O sites, which could lower the free-energy change for the chemisorption of formaldehyde and activate the C-H bond.

CO2 Conversion into Methanol Using Granular Silicon Carbide (α6H-SiC): A Comparative Evaluation of 355 nm Laser and Xenon Mercury Broad Band Radiation Sources

Gondal, Mohammed Ashraf,Ali, Mohammed Ashraf,Dastageer, Mohamed Abdulkader,Chang, Xiaofeng

, p. 108 - 117 (2013)

Granular silicon carbide (α6H-SiC) was investigated as a photo-reduction catalyst for CO2 conversion into methanol using a 355 nm laser from the third harmonic of pulsed Nd:YAG laser and 500 W collimated xenon mercury (XeHg) broad band lamp. The reaction cell was filled with distilled water, α6H-SiC granules and pressurized with CO2 gas at 50 psi. Maximum molar concentration of methanol achieved was 1.25 and 0.375 mmol/l and the photonic efficiencies of CO2 conversion into methanol achieved were 1.95 and 1.16 % using the laser and the XeHg lamp respectively. The selectivity of methanol produced using the laser irradiation was 100 % as compared to about 50 % with the XeHg lamp irradiation. The band gap energy of silicon carbide was estimated to be 3.17 eV and XRD demonstrated that it is a highly crystalline material. This study demonstrated that commercially available granular silicon carbide is a promising photo-reduction catalyst for CO 2 into methanol. Graphical Abstract: Gas Chromatograms of reaction products collected at 30-120 min irradiation in the presence of 355 nm laser having 40 mJ/pulse energy. The inset shows the comparison of retention time of GC peaks with the methanol standard and it is at 2.46 min.[Figure not available: see fulltext.]

Development of molecular and solid catalysts for the direct low-temperature oxidation of methane to methanol

Palkovits, Regina,von Malotki, Christian,Baumgarten, Martin,Müllen, Klaus,Baltes, Christian,Antonietti, Markus,Kuhn, Pierre,Weber, Jens,Thomas, Arne,Schüth, Ferdi

, p. 277 - 282 (2010)

The direct low-temperature oxidation of methane to methanol is demonstrated on a highly active homogeneous molecular catalyst system and on heterogeneous molecular catalysts based on polymeric materials possessing ligand motifs within the material structure. The N-(2-methylpropyl)-4,5-diazacarbazolyl-dichloro-platinum(II) complex reaches significantly higher activity compared to the well-known Periana system and allows first conclusions on electronic and structural requirements for high catalytic activity in this reaction. Interestingly, comparable activities could be achieved utilizing a platinum modified poly(benzimidazole) material, which demonstrates for the first time a solid catalyst with superior activity compared to the Periana system. Although the material shows platinum leaching, improved activity and altered electronic properties, compared to the conventional Periana system, support the proposed conclusions on structure-activity relationships. In comparison, platinum modified triazine-based catalysts show lower catalytic activity, but rather stable platinum coordination even after several catalytic cycles. Based on these systems, further development of improved solid catalysts for the direct low-temperature oxidation of methane to methanol is feasible.

Continuous precipitation of Cu/ZnO/Al2O3 catalysts for methanol synthesis in microstructured reactors with alternative precipitating agents

Simson, Georg,Prasetyo, Eko,Reiner, Stefanie,Hinrichsen, Olaf

, p. 1 - 12 (2013)

Ternary Cu/ZnO/Al2O3 catalyst systems were systematically prepared by innovative synthesis routes in microstructured synthesis setups, allowing to study different types of micromixers. The coprecipitation in the slit plate and valve-assisted mixers was operated continuously under exact control of pH, temperature, concentration and ageing time. Due to the enhanced surface to volume ratio in microstructured reactors, a precise temperature control and efficient mixing of the reactants are enabled. The precipitation was performed with sodium, ammonium and potassium carbonate as well as sodium hydroxide. To evaluate the potential of the novel synthesis routes, reference samples in a conventional batch process were prepared. The catalysts were synthesized according to the constant pH method with a molar ratio of 60:30:10 for copper, zinc and aluminum. The synthesis routes applied have a significant influence on the structures of hydroxycarbonate precursors and on the catalytic activity in methanol synthesis. XRD patterns of hydroxycarbonate precursors from the synthesis in micromixers, especially using ammonium carbonate as precipitating agent, display high crystallinity and sharp reflections of malachite and rosasite. Cu/ZnO/Al2O3 catalysts prepared in continuously operated micromixers in general show higher specific copper surface areas than catalysts prepared in conventional batch processes. The highest methanol productivity of all prepared catalyst systems was observed with the catalyst precipitated in the slit plate mixer with ammonium carbonate.

A study on the precipitating and aging processes of CuO/ZnO/Al2O3 catalysts synthesized in micro-impinging stream reactors

Zhang, Qing-Cheng,Cheng, Kun-Peng,Wen, Li-Xiong,Guo, Kai,Chen, Jian-Feng

, p. 33611 - 33621 (2016)

CuO/ZnO/Al2O3 catalyst precursors were precipitated in a novel micro-impinging stream reactor (MISR) and a traditional stirred tank reactor (STR), respectively, followed by a period time of aging in the mother liquid. Being different from the simultaneous precipitating and aging of catalyst precursors within the same STR reactor, these two processes occurred in two separate containers in the MISR route, hence providing a more uniform and steady environment for both the precipitating and aging processes on top of the higher micromixing efficiency and better process control of the MISR. Therefore, substantial changes in the phase compositions and microstructures of the catalyst precursors were obtained with MISR, which resulted in smaller and more homogeneous catalyst particles with a larger BET surface area and specific copper surface area, better Cu/Zn dispersion as well as higher catalytic activity when compared to those prepared in the STR. The aging process also played an important role in catalyst preparation and it could be controlled more easily and precisely in the MISR route to form a more desirable phase structure, morphology and eventually more superior catalytic performance in methanol synthesis for the final catalysts.

Stable amorphous georgeite as a precursor to a high-activity catalyst

Kondrat, Simon A.,Smith, Paul J.,Wells, Peter P.,Chater, Philip A.,Carter, James H.,Morgan, David J.,Fiordaliso, Elisabetta M.,Wagner, Jakob B.,Davies, Thomas E.,Lu, Li,Bartley, Jonathan K.,Taylor, Stuart H.,Spencer, Michael S.,Kiely, Christopher J.,Kelly, Gordon J.,Park, Colin W.,Rosseinsky, Matthew J.,Hutchings, Graham J.

, p. 83 - 87 (2016)

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable - and hence little known and largely ignored - georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions - a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

Electrochemical reduction of carbon dioxide with an electrode mediator and homogeneous catalysts

Ogura,Migita,Nagaoka

, p. 276 - 283 (1989)

Carbon dioxide has been reduced catalytically to methanol with an electrode mediator and homogeneous catalysts, using a hydrogen fuel cell as an energy source to regenerate the active mediator. Thermodynamic assessment predicts that the reversible potential for the reaction H+ + e- = 1/2 H2 should be more negative than that for the reaction CO2 + 6H+ + 6e- = CH3OH + H2O whenever a fuel cell with hydrogen as the fuel and CO2 as the oxidant is feasible. As reaction proceeded, the pH of the catholyte rose but that of the anolyte dropped, until finally reduction of CO2 ceased. Hence, adjustment of the pH values in both temperatures was necessary to maintain CO2 reduction over long time periods.

The partial oxidation of methane to methanol with nitrite and nitrate melts

Lee, Bor-Jih,Kitsukawa, Shigeo,Nakagawa, Hidemoto,Asakura, Shukuji,Fukuda, Kenzo

, p. 679 - 682 (1998)

The effect of reduced oxygen species on the partial oxidation of methane to methanol was examined with nitrite melts. The experimental results support the suggestion that the formation of methanol or C2 compounds depends on different reduced oxygen species, as observed in our previous work using nitrate melts. It has been suggested that the partial oxidation of methane proceeds to CH3OH or C2 compounds via parallel pathways. This suggestion was verified by increasing the oxygen concentration to carry out the partial oxidation of methane in 25 mol% NaNO3 - 75 mol% KNO3 melts. A methanol selectivity of 8.2% and a methanol yield of 0.43% were observed with CH4/O2 = 15/1 at 575 °C, whereas with CH4/O2 = 7/1 methanol selectivity and yield increased to 23.7% and 1.1%, respectively. The results further confirm the contribution of the superoxide ion O2- on methanol formation.

Low pressure CO2 hydrogenation to methanol over gold nanoparticles activated on a CeOx/TiO2 Interface

Yang, Xiaofang,Kattel, Shyam,Senanayake, Sanjaya D.,Boscoboinik, J. Anibal,Nie, Xiaowa,Graciani, Jesús,Rodriguez, José A.,Liu, Ping,Stacchiola, Darío J.,Chen, Jingguang G.

, p. 10104 - 10107 (2015)

Capture and recycling of CO2 into valuable chemicals such as alcohols could help mitigate its emissions into the atmosphere. Due to its inert nature, the activation of CO2 is a critical step in improving the overall reaction kinetics during its chemical conversion. Although pure gold is an inert noble metal and cannot catalyze hydrogenation reactions, it can be activated when deposited as nanoparticles on the appropriate oxide support. In this combined experimental and theoretical study, it is shown that an electronic polarization at the metal-oxide interface of Au nanoparticles anchored and stabilized on a CeOx/TiO2 substrate generates active centers for CO2 adsorption and its low pressure hydrogenation, leading to a higher selectivity toward methanol. This study illustrates the importance of localized electronic properties and structure in catalysis for achieving higher alcohol selectivity from CO2 hydrogenation.

Carbon dioxide hydrogenation to methanol over Cu/ZrO2/CNTs: Effect of carbon surface chemistry

Wang, Guannan,Chen, Limin,Sun, Yuhai,Wu, Junliang,Fu, Mingli,Ye, Daiqi

, p. 45320 - 45330 (2015)

Methanol synthesis from CO2 hydrogenation in a fixed-bed plug flow reactor was investigated over Cu-ZrO2 catalysts supported on CNTs bearing various functional groups. The highest methanol activity (turnover frequency 1.61 × 10-2 s-1, space time yield 84.0 mg gcat-1 h-1) was obtained over the Cu/ZrO2/CNTs catalyst (CZ/CNT-3) with CNTs functionalized by nitrogen-containing groups and Cu loading only about 10.3 wt% under the reaction conditions of 260 °C, 3.0 MPa, V(H2):V(CO2):V(N2) = 69:23:8 and GHSV of 3600 h-1. The catalysts were fully characterized by N2 physisorption, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR) and temperature-programmed desorption of H2 (H2-TPD) techniques. The excellent performance of CZ/CNT-3 is attributed to the presence of nitrogen-containing groups on the CNTs surface, which increase the dispersion of copper oxides, promote their reduction, decreases the crystal size of Cu, and enhances H2 and CO2 adsorption capability, thus leading to good catalytic performance towards methanol synthesis. This journal is

New catalyst systems for the catalytic conversion of methane into methanol

Muehlhofer, Michael,Strassner, Thomas,Herrmann, Wolfgang A.

, p. 1745 - 1747 (2002)

Palladium complexes with N-heterocyclic carbenes, such as in the biscarbene chelate ligands shown (R = tBu, Me; X = Br, I), have proved to be stable in strongly acidic media and were tested in the catalytic conversion of methane into methanol. The prominent influence of the halogenide ligand is shown since, in contrast to the bromo complex, the iodo complex does not catalyze the reaction. The steric bulk of the substituents R also influences the catalytic activity.

Hydrogenation of Esters by Manganese Catalysts

Li, Fu,Li, Xiao-Gen,Xiao, Li-Jun,Xie, Jian-Hua,Xu, Yue,Zhou, Qi-Lin

, (2022/01/13)

The hydrogenation of esters catalyzed by a manganese complex of phosphine-aminopyridine ligand was developed. Using this protocol, a variety of (hetero)aromatic and aliphatic carboxylates including biomass-derived esters and lactones were hydrogenated to primary alcohols with 63–98% yields. The manganese catalyst was found to be active for the hydrogenation of methyl benzoate, providing benzyl alcohol with turnover numbers (TON) as high as 45,000. Investigation of catalyst intermediates indicated that the amido manganese complex was the active catalyst species for the reaction. (Figure presented.).

Binary Au–Cu Reaction Sites Decorated ZnO for Selective Methane Oxidation to C1 Oxygenates with Nearly 100% Selectivity at Room Temperature

Gong, Zhuyu,Liu, Huifen,Luo, Lei,Ma, Jiani,Tang, Junwang,Xing, Jialiang,Xu, Youxun

supporting information, p. 740 - 750 (2022/01/03)

Direct and efficient oxidation of methane to methanol and the related liquid oxygenates provides a promising pathway for sustainable chemical industry, while still remaining an ongoing challenge owing to the dilemma between methane activation and overoxidation. Here, ZnO with highly dispersed dual Au and Cu species as cocatalysts enables efficient and selective photocatalytic conversion of methane to methanol and one-carbon (C1) oxygenates using O2 as the oxidant operated at ambient temperature. The optimized AuCu–ZnO photocatalyst achieves up to 11225 μmol·g–1·h–1 of primary products (CH3OH and CH3OOH) and HCHO with a nearly 100% selectivity, resulting in a 14.1% apparent quantum yield at 365 nm, much higher than the previous best photocatalysts reported for methane conversion to oxygenates. In situ EPR and XPS disclose that Cu species serve as photoinduced electron mediators to promote O2 activation to ?OOH, and simultaneously that Au is an efficient hole acceptor to enhance H2O oxidation to ?OH, thus synergistically promoting charge separation and methane transformation. This work highlights the significances of co-modification with suitable dual cocatalysts on simultaneous regulation of activity and selectivity.

Synthesis of phenol from degraded lignin using synergistic effect of iron-oxide based catalysts: Oxidative cracking ability and acid-base properties

Fumoto, Eri,Ishimaru, Hiroya,Masuda, Takao,Nakasaka, Yuta,Sato, Shinya,Yoshikawa, Takuya

, (2022/02/05)

The effects of ZrO2 and TiO2 incorporated into Fe2O3 matrix on oxidative cracking of degraded lignin and on the acid-base properties were investigated. After lignin degradation, cracking into lower-molecular-weight products was greatest using ZrO2-FeOX. Reactivity of the lattice oxygen was evaluated using H2-TPR, which revealed that the reactivity was improved. Thus, ZrO2-FeOX promoted oxidative decomposition of lignin to oligomers. In the cracking of 2-methoxyphenol, TiO2-FeOX and ZrO2-FeOX resulted in a 5- to 6-fold greater yield of phenol than the yield over Fe2O3. According to Mulliken population analysis, the charge density difference between Fe-O increased by ca. 12% in TiO2-FeOX and ZrO2-FeOX as compared with Fe2O3. This result suggests that addition of TiO2 and ZrO2 improved the acid-base properties of the catalyst, which promoted demethoxylation of 2-methoxyphenol. Thus, ZrO2-FeOX enhanced oxidative decomposition using its lattice oxygen that converted degraded lignin into lower molecule oligomers, followed by demethoxylation to produce phenol.

Acid-assisted hydrogenation of CO2to methanol using Ru(ii) and Rh(iii) RAPTA-type catalysts under mild conditions

Kumar, Abhinav,Kumar, Sanjay,Pandey, Indresh Kumar,Rath, Nigam P.,Sharma, Pooja,Trivedi, Manoj

supporting information, p. 8941 - 8944 (2021/09/13)

A highly efficient homogeneous catalyst system for production of CH3OH from CO2using single molecular defined ruthenium and rhodium RAPTA-type catalysts [Ru(η6-p-cymene)X2(PTA)] (X = I(1), Cl(2); PTA = 1,3,5-triaza-7-phosphaadamantane) and rhodium catalysts [Rh(η5-C5Me5)X2(PTA/PTA-BH3)] (X = Cl(3), H(4) and PTA-BH3, H(5)) developed in acidic media under mild conditions. A TON of 4752 is achieved using a [Ru(η6-p-cymene)I2(PTA)] catalyst which represents the first example of CO2hydrogenation to CH3OH using single molecular defined Ru and Rh RAPTA-type catalysts.

Unprecedentedly high efficiency for photocatalytic conversion of methane to methanol over Au-Pd/TiO2-what is the role of each component in the system?

Cai, Xiaojiao,Fang, Siyuan,Hu, Yun Hang

supporting information, p. 10796 - 10802 (2021/05/14)

Direct and highly efficient conversion of methane to methanol under mild conditions still remains a great challenge. Here, we report that Au-Pd/TiO2 could directly catalyze the conversion of methane to methanol with an unprecedentedly high methanol yield of 12.6 mmol gcat-1 in a one-hour photocatalytic reaction in the presence of oxygen and water. Such an impressive efficiency is contributed by several factors, including the affinity between Au-Pd nanoparticles and intermediate species, the photothermal effect induced by visible light absorption of Au-Pd nanoparticles, the employment of O2 as a mild oxidant, and the effective dissolution of methanol in water. More importantly, for the first time, thermo-photo catalysis is demonstrated by the distinct roles of light. Namely, UV light is absorbed by TiO2 to excite charge carriers, while visible light is absorbed by Au-Pd nanoparticles to increase the temperature of the catalyst, which further enhances the driving force of corresponding redox reactions. These results not only provide a valuable guide for designing a photocatalytic system to realize highly efficient production of methanol, but also, highlight the great promise of thermo-photo catalysis. This journal is

Process route upstream and downstream products

Process route

ethanol
64-17-5

ethanol

Trimethylmethoxysilane
1825-61-2

Trimethylmethoxysilane

methanol
67-56-1

methanol

ethyl trimethylsilyl ether
1825-62-3

ethyl trimethylsilyl ether

Conditions
Conditions Yield
at 21.9 ℃; Equilibrium constant;
1-Methoxy-4-(1-methoxy-vinyl)-benzene
51440-56-3

1-Methoxy-4-(1-methoxy-vinyl)-benzene

methanol
67-56-1

methanol

1-(4-methoxyphenyl)ethanone
100-06-1

1-(4-methoxyphenyl)ethanone

Conditions
Conditions Yield
With water; at 25 ℃; calculated const. and ΔG for the isodesmic equilibra;
<i>N</i>-methyl-<i>N</i>-nitro-benzenesulfonamide
59263-03-5

N-methyl-N-nitro-benzenesulfonamide

methanol
67-56-1

methanol

methyl(phenylsulfonyl)amide
5183-78-8

methyl(phenylsulfonyl)amide

benzenesulfonic acid
98-11-3

benzenesulfonic acid

Conditions
Conditions Yield
With sulfuric acid; In water; at 25 ℃; Rate constant; Dependence of the decomposition rate on concentration of H2SO4;
C<sub>8</sub>H<sub>10</sub>N<sub>4</sub>O<sub>3</sub>
73779-17-6

C8H10N4O3

methanol
67-56-1

methanol

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
In methanol; water; at 60 ℃; for 24h; Mechanism; thermal decomposition;
In methanol; water; Mechanism; Irradiation;
para-methoxynitrobenzene
100-17-4

para-methoxynitrobenzene

methanol
67-56-1

methanol

Conditions
Conditions Yield
With borate buffer (20percent free base); In water; at 80 ℃; Rate constant; var. buffers and/or amount of free base;
1,1-dimethoxy-1-(4-methoxyphenyl)ethane
27150-99-8

1,1-dimethoxy-1-(4-methoxyphenyl)ethane

methanol
67-56-1

methanol

1-(4-methoxyphenyl)ethanone
100-06-1

1-(4-methoxyphenyl)ethanone

Conditions
Conditions Yield
With hydrogenchloride; In water; Rate constant; also for reaction catalysed with various bases;
4-methoxyacetophenone methyl hemiacetal

4-methoxyacetophenone methyl hemiacetal

methanol
67-56-1

methanol

1-(4-methoxyphenyl)ethanone
100-06-1

1-(4-methoxyphenyl)ethanone

Conditions
Conditions Yield
With hydrogenchloride; In water; Rate constant; also for reaction catalysed with various bases;
p-Methoxybenzoic acid methyl orthoester
4316-33-0

p-Methoxybenzoic acid methyl orthoester

methanol
67-56-1

methanol

4-methoxybenzoic acid
100-09-4

4-methoxybenzoic acid

Conditions
Conditions Yield
With hydrogenchloride; potassium chloride; In acetonitrile; at 30 ℃; Rate constant; also in biphosphate buffer solution; kinetic isotope effect;
methyl 4-nitrophenyl thionocarbonate
1014-94-4

methyl 4-nitrophenyl thionocarbonate

methanol
67-56-1

methanol

carbon oxide sulfide
463-58-1

carbon oxide sulfide

Conditions
Conditions Yield
With borate buffer; potassium chloride; In water; at 25 ℃; Rate constant; Mechanism;
(4-nitro-phenoxysulfonyl)-carbamic acid methyl ester
92385-24-5

(4-nitro-phenoxysulfonyl)-carbamic acid methyl ester

methanol
67-56-1

methanol

methyl carbamate
598-55-0

methyl carbamate

Conditions
Conditions Yield
With hydrogen chloride; In [D3]acetonitrile; at 50 ℃; Rate constant; Thermodynamic data; other solvent; var. temp. and pH's; ΔH(excit.); ΔS(excit.); deuterium isotope effect;

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