Selective Oxidation of Methane to Methanol via In Situ H<sub>2</sub>O<sub>2</sub> Synthesis

Ni, Fenglou; Richards, Thomas; Smith, Louise; Morgan, David; Davies, Thomas E.; Lewis, Richard J.; Hutchings, Graham J.

doi:10.1021/acsorginorgau.3c00001

Cited by 12 publications

(7 citation statements)

References 38 publications

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“…These include poor selective H 2 utilization, rapid catalyst deactivation, and the formation of complex product mixtures, necessitating extensive purification and the inclusion of promoters. Indeed, in many cases, it is the presence of H 2 , required to generate H 2 O 2 in situ, that largely promotes the formation of such byproducts. , Such concerns are not limited to alkene epoxidation, with product distributions for a range of transformations influenced by competitive unselective hydrogenation pathways. , It is the overcoming of these challenges that has motivated extensive research from our laboratory, with particular focus placed on the application of Pd-based catalysts for (i) alkane upgrading, − (ii) alcohol oxidation, ,− and recently (iii) the ammoximation of cyclohexanone (and other cyclic ketones) to the corresponding oxime. ,, Regarding alkane oxidation, we direct the reader to our recent Account on methane valorization for an extensive discussion of our contribution to this field …”

Section: Challenging Current Industrial Processesmentioning

confidence: 99%

Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Lewis,

Hutchings

2023

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Hydrogen peroxide (H 2 O 2 ) for industrial applications is manufactured through an indirect process that relies on the sequential reduction and reoxidation of quinone carriers. While highly effective, production is typically centralized and entails numerous energyintensive concentration steps. Furthermore, the overhydrogenation of the quinone necessitates periodic replacement, leading to incomplete atom efficiency. These factors, in addition to the presence of propriety stabilizing agents and concerns associated with their separation from product streams, have driven interest in alternative technologies for chemical upgrading. The decoupling of oxidative transformations from commercially synthesized H 2 O 2 may offer significant economic savings and a reduction in greenhouse gas emissions for several industrially relevant processes. Indeed, the production and utilization of the oxidant in situ, from the elements, would represent a positive step toward a more sustainable chemical synthesis sector, offering the potential for total atom efficiency, while avoiding the drawbacks associated with current industrial routes, which are inherently linked to commercial H 2 O 2 production. Such interest is perhaps now more pertinent than ever given the rapidly improving viability of green hydrogen production.The application of in situ-generated H 2 O 2 has been a long-standing goal in feedstock valorization, with perhaps the most significant interest placed on propylene epoxidation. Until very recently a viable in situ alternative to current industrial oxidative processes has been lacking, with prior approaches typically hindered by low rates of conversion or poor selectivity toward desired products, often resulting from competitive hydrogenation reactions. Based on over 20 years of research, which has led to the development of catalysts for the direct synthesis of H 2 O 2 that offer high synthesis rates and >99% H 2 utilization, we have recently turned our attention to a range of oxidative transformations where H 2 O 2 is generated and utilized in situ. Indeed, we have recently demonstrated that it is possible to rival state-of-the-art industrial processes through in situ H 2 O 2 synthesis, establishing the potential for significant process intensification and considerable decarbonization of the chemical synthesis sector.We have further established the potential of an in situ route to both bulk and fine chemical synthesis through a chemo-catalytic/ enzymatic one-pot approach, where H 2 O 2 is synthesized over heterogeneous surfaces and subsequently utilized by a class of unspecific peroxygenase enzymes for C−H bond functionalization. Strikingly, through careful control of the chemo-catalyst, it is possible to ensure that competitive, nonenzymatic pathways are inhibited while also avoiding the regiospecific and selectivity concerns associated with current energy-intensive industrial processes, with further cost savings associated with the operation of the chemo-enzymatic appr...

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Section: Challenging Current Industrial Processesmentioning

confidence: 99%

Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Lewis,

Hutchings

2023

Acc. Chem. Res.

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“…The development of active materials for this conversion in a high-pressure batch process has been explored on various supported metal sites and metal alloys. − Wang and co-workers reported the conversion of methane over oxo dicopper anchored on carbon nitride with a methanol production of 129.7 mmol/g Cu ·h . Hutchings and co-workers reported the production of 7.02 μmol of oxygenates in 30 min of using AuPdCu supported on titania .…”

Section: Introductionmentioning

confidence: 99%

Atmospheric-Pressure Continuous-Flow Methane Oxidation to Methanol and Acetic Acid Using H₂O₂ over the Au–Fe Catalyst

Jagtap,

Kumar,

Gupta

et al. 2024

ACS Sustainable Chem. Eng.

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An enormous value proposition exists when molecules such as acetic acid and methanol are derived from natural gas. With abundant worldwide resources, the conversion of methane to methanol (M2M) by partial oxidation or to acetic acid through C-insertion is considered one of the most enterprising chemical transformations in catalysis. Methane partial oxidation using H 2 O 2 as the oxidant is reported at high-pressure conditions with an excess of oxidant. In this work, significant catalytic challenges successfully tackled are the continuous partial oxidation of methane to methanol and acetic acid at atmospheric pressure. Under continuous flow and at atmospheric pressure, a modified silica-supported bimetallic (AuFeHS) catalyst catalyzed the conversion of methane to methanol using H 2 O 2 with an impressive yield of 224 mmol/g Fe+Au . Cofeeding of CO in the stream produces acetic acid, demonstrating a selectivity switch from methanol with an overall yield of 92 mmol/g Fe+Au .

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“…Converting methane to methanol is another considerable way to reduce methane gas emission because of its significant cost advantages in transportation and storage. , Converting methane to methanol through partial oxidation at room temperature has remained a challenging issue in catalysis for decades. − The CH 4 molecule has a tetrahedral shape, which confers stability and a nonpolar nature. The difficulty arises not only from the strong bonding energy of the C(sp 3 )–H bond (439 kJ mol –1 ) but also the overoxidation tendency, leading to the formation of CO 2 . − Mounting research has suggested H 2 O 2 as an excellent oxidant for converting methane to methanol because of its green oxidation byproduct (water). − …”

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confidence: 99%

Water Microdroplets-Initiated Methane Oxidation

Song,

Basheer,

Zare

2023

J. Am. Chem. Soc.

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Selective Oxidation of Methane to Methanol via In Situ H₂O₂ Synthesis

Cited by 12 publications

References 38 publications

Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Atmospheric-Pressure Continuous-Flow Methane Oxidation to Methanol and Acetic Acid Using H₂O₂ over the Au–Fe Catalyst

Water Microdroplets-Initiated Methane Oxidation

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Selective Oxidation of Methane to Methanol via In Situ H2O2 Synthesis

Cited by 12 publications

References 38 publications

Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Atmospheric-Pressure Continuous-Flow Methane Oxidation to Methanol and Acetic Acid Using H2O2 over the Au–Fe Catalyst

Water Microdroplets-Initiated Methane Oxidation

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Product

Resources

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Selective Oxidation of Methane to Methanol via In Situ H₂O₂ Synthesis

Atmospheric-Pressure Continuous-Flow Methane Oxidation to Methanol and Acetic Acid Using H₂O₂ over the Au–Fe Catalyst