14742-26-8Relevant academic research and scientific papers
Utilizing terminal oxidants to achieve P450-catalyzed oxidation of methane
Chen, Mike M.,Coelho, Pedro S.,Arnold, Frances H.
, p. 964 - 968 (2012)
Terminal oxidant-supported P450 reactions alleviate the need for substrate binding to initiate catalysis by chemically generating "compound I." This allows investigation of the innate substrate range of the enzyme active site. Using iodosylbenzene as the oxidant, CYP153A6, a medium-chain terminal alkane hydroxylase, exhibits methanol formation in the presence of methane demonstrating that P450-mediated methane hydroxylation is possible. Copyright
Methane to acetic acid over Cu-exchanged zeolites: Mechanistic insights from a site-specific carbonylation reaction
Narsimhan, Karthik,Michaelis, Vladimir K.,Mathies, Guinevere,Gunther, William R.,Griffin, Robert G.,Romn-Leshkov, Yuriy
, p. 1825 - 1832 (2015)
The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 μmol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the CuII-O-CuII sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu2+ site is formed at Cu/Al 0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Bronsted acid site in the 8MR to undergo carbonylation.
Catalytic Hydrogenation of CO2to Methanol Using Multinuclear Iridium Complexes in a Gas-Solid Phase Reaction
Kanega, Ryoichi,Onishi, Naoya,Tanaka, Shinji,Kishimoto, Haruo,Himeda, Yuichiro
, p. 1570 - 1576 (2021)
We report a novel approach toward the catalytic hydrogenation of CO2 to methanol performed in the gas-solid phase using multinuclear iridium complexes at low temperature (30-80 °C). Although homogeneous CO2 hydrogenation in water catalyzed by amide-based iridium catalysts provided only a negligible amount of methanol, the combination of a multinuclear catalyst and gas-solid phase reaction conditions led to the effective production of methanol from CO2. The catalytic activities of the multinuclear catalyst were dependent on the relative configuration of each active species. Conveniently, methanol obtained from the gas phase could be easily isolated from the catalyst without contamination with CO, CH4, or formic acid (FA). The catalyst can be recycled in a batchwise manner via gas release and filling. A final turnover number of 113 was obtained upon reusing the catalyst at 60 °C and 4 MPa of H2/CO2 (3:1). The high reactivity of this system has been attributed to hydride complex formation upon exposure to H2 gas, suppression of the liberation of FA under gas-solid phase reaction conditions, and intramolecular multiple hydride transfer to CO2 by the multinuclear catalyst.
Selective hydroxylation of methane by dioxiranes under mild conditions
Annese, Cosimo,D'Accolti, Lucia,Fusco, Caterina,Curci, Ruggero
, p. 2142 - 2144 (2011)
The direct conversion of methane to methanol at low temperatures was achieved selectively using dioxiranes 1a,b either in the isolated form or generated in situ from aqueous potassium caroate and the parent ketone at a pH close to neutrality. Results suggest that the more powerful dioxirane TFDO (1b) should be the oxidant of choice.
A mild synthesis of13C-methanol
Fr?hlich, J?rg,Berger, Stefan
, p. 2522 - 2524 (2005)
The formation of oxazolidinon-2-ones from amino alcohols and carbon dioxide is well known. Until now it was not possible to reduce the fixed carbon dioxide to any basic chemical like formaldehyde or methanol, only the less interesting N-methyl compounds w
Aqueous Electrochemical Reduction of Carbon Dioxide and Carbon Monoxide into Methanol with Cobalt Phthalocyanine
Boutin, Etienne,Wang, Min,Lin, John C.,Mesnage, Matthieu,Mendoza, Daniela,Lassalle-Kaiser, Benedikt,Hahn, Christopher,Jaramillo, Thomas F.,Robert, Marc
, p. 16172 - 16176 (2019)
Conversion of CO2 into valuable molecules is a field of intensive investigation with the aim of developing scalable technologies for making fuels using renewable energy sources. While electrochemical reduction into CO and formate are approaching industrial maturity, a current challenge is obtaining more reduced products like methanol. However, literature on the matter is scarce, and even more for the use of molecular catalysts. Here, we demonstrate that cobalt phthalocyanine, a well-known catalyst for the electrochemical conversion of CO2 to CO, can also catalyze the reaction from CO2 or CO to methanol in aqueous electrolytes at ambient conditions of temperature and pressure. The studies identify formaldehyde as a key intermediate and an unexpected pH effect on selectivity. This paves the way for establishing a sequential process where CO2 is first converted to CO which is subsequently used as a reactant to produce methanol. Under ideal conditions, the reaction shows a global Faradaic efficiency of 19.5 % and chemical selectivity of 7.5 %.
Hydrogenation of CO2 to Methanol by Pt Nanoparticles Encapsulated in UiO-67: Deciphering the Role of the Metal-Organic Framework
Gutter?d, Emil S.,Lazzarini, Andrea,Fjermestad, Torstein,Kaur, Gurpreet,Manzoli, Maela,Bordiga, Silvia,Svelle, Stian,Lillerud, Karl P.,Skúlason, Egill,?ien-?Degaard, Sigurd,Nova, Ainara,Olsbye, Unni
, p. 999 - 1009 (2020)
Metal-organic frameworks (MOFs) show great prospect as catalysts and catalyst support materials. Yet, studies that address their dynamic, kinetic, and mechanistic role in target reactions are scarce. In this study, an exceptionally stable MOF catalyst consisting of Pt nanoparticles (NPs) embedded in a Zr-based UiO-67 MOF was subject to steady-state and transient kinetic studies involving H/D and 13C/12C exchange, coupled with operando infrared spectroscopy and density functional theory (DFT) modeling, targeting methanol formation from CO2/H2 feeds at 170 °C and 1-8 bar pressure. The study revealed that methanol is formed at the interface between the Pt NPs and defect Zr nodes via formate species attached to the Zr nodes. Methanol formation is mechanistically separated from the formation of coproducts CO and methane, except for hydrogen activation on the Pt NPs. Careful analysis of transient data revealed that the number of intermediates was higher than the number of open Zr sites in the MOF lattice around each Pt NP. Hence, additional Zr sites must be available for formate formation. DFT modeling revealed that Pt NP growth is sufficiently energetically favored to enable displacement of linkers and creation of open Zr sites during pretreatment. However, linker displacement during formate formation is energetically disfavored, in line with the excellent catalyst stability observed experimentally. Overall, the study provides firm evidence that methanol is formed at the interface of Pt NPs and linker-deficient Zr6O8 nodes resting on the Pt NP surface.
Efficient Hole Trapping in Carbon Dot/Oxygen-Modified Carbon Nitride Heterojunction Photocatalysts for Enhanced Methanol Production from CO2 under Neutral Conditions
Wang, Yiou,Godin, Robert,Durrant, James R.,Tang, Junwang
, p. 20811 - 20816 (2021)
Artificial photosynthesis of alcohols from CO2 is still unsatisfactory owing to the rapid charge relaxation compared to the sluggish photoreactions and the oxidation of alcohol products. Here, we demonstrate that CO2 is reduced to me
Tandem amine and ruthenium-catalyzed hydrogenation of CO2to methanol
Rezayee, Nomaan M.,Huff, Chelsea A.,Sanford, Melanie S.
, p. 1028 - 1031 (2015)
This Communication describes the hydrogenation of carbon dioxide to methanol via tandem catalysis with dimethylamine and a homogeneous ruthenium complex. Unlike previous examples with homogeneous catalysts, this CO2-to-CH3OH process proceeds under basic reaction conditions. The dimethylamine is proposed to play a dual role in this system. It reacts directly with CO2 to produce dimethylammonium dimethylcarbamate, and it also intercepts the intermediate formic acid to generate dimethylformamide. With the appropriate selection of catalyst and reaction conditions, >95% conversion of CO2 was achieved to form a mixture of CH3OH and dimethylformamide.
Highly Efficient CO2 Electroreduction to Methanol through Atomically Dispersed Sn Coupled with Defective CuO Catalysts
Guo, Weiwei,Liu, Shoujie,Tan, Xingxing,Wu, Ruizhi,Yan, Xupeng,Chen, Chunjun,Zhu, Qinggong,Zheng, Lirong,Ma, Jingyuan,Zhang, Jing,Huang, Yuying,Sun, Xiaofu,Han, Buxing
, p. 21979 - 21987 (2021)
Using renewable electricity to drive CO2 electroreduction is an attractive way to achieve carbon-neutral energy cycle and produce value-added chemicals and fuels. As an important platform molecule and clean fuel, methanol requires 6-electron transfer in the process of CO2 reduction. Currently, CO2 electroreduction to methanol suffers from poor efficiency and low selectivity. Herein, we report the first work to design atomically dispersed Sn site anchored on defective CuO catalysts for CO2 electroreduction to methanol. It exhibits high methanol Faradaic efficiency (FE) of 88.6 % with a current density of 67.0 mA cm?2 and remarkable stability in a H-cell, which is the highest FE(methanol) with such high current density compared with the results reported to date. The atomic Sn site, adjacent oxygen vacancy and CuO support cooperate very well, leading to higher double-layer capacitance, larger CO2 adsorption capacity and lower interfacial charge transfer resistance. Operando experiments and density functional theory calculations demonstrate that the catalyst is beneficial for CO2 activation via decreasing the energy barrier of *COOH dissociation to form *CO. The obtained key intermediate *CO is then bound to the Cu species for further reduction, leading to high selectivity toward methanol.
