Bioinspired Oxidation of Methane: From Academic Models of Methane Monooxygenases to Direct Conversion of Methane to Methanol

Shteinman, A. A.

doi:10.1134/s0023158420030180

Cited by 12 publications

(4 citation statements)

References 105 publications

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“…Cavitins are of interest in the development of tandem methylation reactions utilizing CO 2 as a one-carbon building block that would enable a more sustainable chemical industry (Rooney et al, 2021). The development of the direct low-temperature selective oxidation of methane to methanol has remained an active area of research over the last 50 years (Shteinman, 2020). Compared to WS and CO 2 conversion, the effective and selective chemical routes to valorize methane with participation of cavitins are relatively less elaborated.…”

Section: Co 2 and Methanementioning

confidence: 99%

“…Direct methane conversion has been carried out in the gas phase over Cu-and Fecontaining zeolites in the stepwise cyclic process that involves activating the transition metal with O 2 or N 2 O at 400-500 o C, then methane reaction with active intermediates at 200 o C, and finally product extraction with water steam. However, the rate and productivity of these processes are still very low (Shteinman, 2020). Catalytic processes for the hydroxylation of methane on zeolite Fe-Cu-ZSM-5 with a selectivity of 20-80% under aqueous conditions at 50 °C using H 2 O 2 were proposed (Hammond et al, 2012;Yu T. et al, 2021).…”

Section: Co 2 and Methanementioning

confidence: 99%

“…The mechanism based on catalytic, spectroscopic, and theoretical results was suggested (Yu T. et al, 2021): the acid sites adjacent to iron Bronsted contribute to the formation of an active Fe (V) O intermediate via the dehydration of formed Fe−OOH in the aqueous H 2 O 2 solution, enabling the homolytic cleavage of the primary C−H by radical-rebound mechanism to generate •CH 3 radicals that are quickly captured by •OH radicals to form CH 3 OH. Contrary to Cu-and Fe-containing zeolites, the study of MOF-based MMO mimics is still at the early stage and suffers from the same problems which are low productivity and rate and low methanol selectivity due to overoxidation (Shteinman, 2020).…”

Section: Co 2 and Methanementioning

confidence: 99%

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Metallocavitins as Promising Industrial Catalysts: Recent Advances

Shteinman

2022

Front. Chem.

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The energy, material, and environmental problems of society require clean materials and impose an urgent need to develop effective chemical processes for obtaining and converting energy to ensure further sustainable development. To solve these challenges, it is necessary, first of all, to learn solar energy harvesting through the development of artificial photosynthesis. In our planet, water, carbon dioxide, and methane are such affordable and inexhaustible clean materials. Electro/photocatalytic water splitting, and also CO2 and CH4 transforming into valuable products, requires the search for relevant efficient and selective processes and catalysts. Of great interest is the emerging new generation of bioinspired catalysts—metallocavitins (MCs). MCs are attracting increasing attention of researchers as advanced models of metalloenzymes, whose efficiency and selectivity are well known. The primary field of MC application is fine organic synthesis and enantioselective catalysis. On the other hand, MCs demonstrate high activity for energy challenging reactions involving small gas molecules and high selectivity for converting them into valuable products. This mini-review will highlight some recent advances in the synthesis of organic substances using MCs, but its main focus will be on the rapid development of advanced catalysts for the activation of small molecules, such as H2O, CO2, and CH4, and the prospects for creating related technological processes in the future.

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Section: Co 2 and Methanementioning

confidence: 99%

Section: Co 2 and Methanementioning

confidence: 99%

Section: Co 2 and Methanementioning

confidence: 99%

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Metallocavitins as Promising Industrial Catalysts: Recent Advances

Shteinman

2022

Front. Chem.

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“…Corrolazines, formed by replacing the meso-position carbon atoms of corroles with N atoms, are very similar in structure to porphyrins, but have more π electrons than porphyrins, and can better stabilize high-valent metals ( Ramdhanie et al, 2001 ; Goldberg et al, 2003 ; Fox et al, 2004 ; Lansky et al, 2005 ; Lansky and Goldberg, 2006 ; Goldberg 2007 ; McGown et al, 2009 ; Prokop et al, 2011 ; Pierloot et al, 2012 ; Baglia et al, 2015 ; Joslin et al, 2016 ; Jung et al, 2016 ; Zaragoza et al, 2016 ; Ghosh 2017 ; Zhu et al, 2018 ; Dedić et al, 2021 ; Wang et al, 2021 ; Zhu et al, 2021 ). As Fe is the active center metal of methane monooxygenase ( Shteinman 2020 ; Freakley et al, 2021 ), which can selectively convert methane to methanol under natural environmental conditions. Fe-corrolazine is very likely to catalyze the oxidation of methane to methanol under very mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Oriented External Electric Fields Regurating the Reaction Mechanism of CH4 Oxidation Catalyzed by Fe(IV)-Oxo-Corrolazine: Insight from Density Functional Calculations

Long

Wang

et al. 2022

Front. Chem.

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Methane is the simplest alkane and can be used as an alternative energy source for oil and coal, but the greenhouse effect caused by its leakage into the air is not negligible, and its conversion into liquid methanol not only facilitates transportation, but also contributes to carbon neutrality. In order to find an efficient method for converting methane to methanol, CH4 oxidation catalyzed by Fe(IV)-Oxo-corrolazine (Fe(IV)-Oxo-Cz) and its reaction mechanism regulation by oriented external electric fields (OEEFs) are systematically studied by density functional calculations. The calculations show that Fe(IV)-Oxo-Cz can abstract one H atom from CH4 to form the intermediate with OH group connecting on the corrolazine ring, with the energy barrier of 25.44 kcal mol−1. And then the product methanol is formed through the following rebound reaction. Moreover, the energy barrier can be reduced to 20.72 kcal mol−1 through a two-state reaction pathway. Furthermore, the effect of OEEFs on the reaction is investigated. We found that OEEFs can effectively regulate the reaction by adjusting the stability of the reactant and the transition state through the interaction of electric field-molecular dipole moment. When the electric field is negative, the energy barrier of the reaction decreases with the increase of electric intensity. Moreover, the OEEF aligned along the intrinsic Fe‒O reaction axis can effectively regulate the ability of forming the OH on the corrolazine ring by adjusting the charges of O and H atoms. When the electric field intensity is −0.010 a.u., the OH can be directly rebounded to the CH3· before it is connecting on the corrolazine ring, thus forming the product directly from the transition state without passing through the intermediate with only an energy barrier of 17.34 kcal mol−1, which greatly improves the selectivity of the reaction.

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Methane Activation Over Zeolites

Shah¹,

Taylor²

2022

Heterogeneous Catalysis for Sustainable Energy

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Bioinspired Oxidation of Methane: From Academic Models of Methane Monooxygenases to Direct Conversion of Methane to Methanol

Cited by 12 publications

References 105 publications

Metallocavitins as Promising Industrial Catalysts: Recent Advances

Metallocavitins as Promising Industrial Catalysts: Recent Advances

Oriented External Electric Fields Regurating the Reaction Mechanism of CH4 Oxidation Catalyzed by Fe(IV)-Oxo-Corrolazine: Insight from Density Functional Calculations

Methane Activation Over Zeolites

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