Challenges for the utilization of methane as a chemical feedstock

Franz, Robert; Uslamin, Evgeny A.; Pidko, Evgeny A.

doi:10.1016/j.mencom.2021.09.002

Cited by 28 publications

(23 citation statements)

References 102 publications

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“…Methane is an essential chemical feedstock for many chemicals, such as methanol, olefins, aromatic hydrocarbons, acetic acid, dimethyl ether, and so on. 10 Therefore, the utilization of methane with high reaction efficiency has great potential for relieving energy crises and atmospheric pollution. The direct conversion of methane to value-added chemicals is incredibly challenging, as CH 4 is the most stable and inert hydrocarbon (ΔH C−H = 104 kcal mol −1 : C−H bond dissociation enthalpy of 4.55 eV at 298 K).…”

Section: Introductionmentioning

confidence: 99%

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Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Kumar

Al‐Attas

et al. 2022

ACS Nano

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Direct conversion of methane (CH 4 ) to C 1−2 liquid oxygenates is a captivating approach to lock carbons in transportable value-added chemicals, while reducing global warming. Existing approaches utilizing the transformation of CH 4 to liquid fuel via tandemized steam methane reforming and the Fischer−Tropsch synthesis are energy and capital intensive. Chemocatalytic partial oxidation of methane remains challenging due to the negligible electron affinity, poor C−H bond polarizability, and high activation energy barrier. Transition-metal and stoichiometric catalysts utilizing harsh oxidants and reaction conditions perform poorly with randomized product distribution. Paradoxically, the catalysts which are active enough to break C−H also promote overoxidation, resulting in CO 2 generation and reduced carbon balance. Developing catalysts which can break C−H bonds of methane to selectively make useful chemicals at mild conditions is vital to commercialization. Single atom catalysts (SACs) with specifically coordinated metal centers on active support have displayed intrigued reactivity and selectivity for methane oxidation. SACs can significantly reduce the activation energy due to induced electrostatic polarization of the C−H bond to facilitate the accelerated reaction rate at the low reaction temperature. The distinct metal−support interaction can stabilize the intermediate and prevent the overoxidation of the reaction products. The present review accounts for recent progress in the field of SACs for the selective oxidation of CH 4 to C 1−2 oxygenates. The chemical nature of catalytic sites, effects of metal−support interaction, and stabilization of intermediate species on catalysts to minimize overoxidation are thoroughly discussed with a forward-looking perspective to improve the catalytic performance.

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Section: Introductionmentioning

confidence: 99%

“…Methane is an essential chemical feedstock for many chemicals, such as methanol, olefins, aromatic hydrocarbons, acetic acid, dimethyl ether, and so on . Therefore, the utilization of methane with high reaction efficiency has great potential for relieving energy crises and atmospheric pollution.…”

Section: Introductionmentioning

confidence: 99%

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Kumar

Al‐Attas

et al. 2022

ACS Nano

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“…Hence, the catalytic version of the POM is still under investigation, focusing the attention on developing a suitable catalytic formulation that requires being not only suitable to activate methane to produce CO selectively but also able to exhibit an adequate thermal stability to tolerate the aggressive reaction conditions (near 1000 °C). 13 CH 0.5O CO 2H…”

Section: Methanementioning

confidence: 98%

“…Despite being slightly more endothermic than SRM, DRM has attracted the attention of the scientific and industrial community from the environmental perspective as CO 2 is one of the reagents and produces a syngas stream with a larger carbon (CO) content. 13 Though several catalyst formulations have been proposed to catalyze DRM, the compositions containing noble metals such as Pt have reported promising results due to their lower tendency to form coke, 14 which is a deactivating agent. Hence, improvements in the catalyst design are needed on the way to scale up for industrial application.…”

Section: Methanementioning

confidence: 99%

“…DRM is also an endothermic reaction (Δ H R,25°C ° = 260 kJ mol –1 ) which, as can be observed in eq , yields 2 mol of hydrogen and 2 mol of CO per mole of converted methane. Despite being slightly more endothermic than SRM, DRM has attracted the attention of the scientific and industrial community from the environmental perspective as CO 2 is one of the reagents and produces a syngas stream with a larger carbon (CO) content . Though several catalyst formulations have been proposed to catalyze DRM, the compositions containing noble metals such as Pt have reported promising results due to their lower tendency to form coke, which is a deactivating agent.…”

Section: Methanementioning

confidence: 99%

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Decarbonizing Petrochemical Processes: Contribution and Perspectives of the Selective Oxidation of C₁–C₃ Paraffins

et al. 2023

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In this perspective, we present an overview of the most relevant advances in the selective oxidation of light paraffins to contribute to the petrochemical decarbonization processes. An analysis of the catalysts reported for methane to chemicals focusing the attention on the oxidative coupling, the dehydroaromatization, the oxidation to formaldehyde, and, more particularly, the direct oxidation to methanol is done. For ethane, the examination is centered on the catalysts investigated for the oxidative dehydrogenation to ethylene, the ammoxidation to acetonitrile, and the partial oxidation to acetic acid. Finally, in the case of propane, the scrutiny is focused on the oxidative dehydrogenation to propylene, the selective oxidation to acrolein and acrylic acid, and the ammoxidation to acrylonitrile. The main challenges to face on the catalyst design and process development are pointed out.

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Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Hao,

Chen,

Peng

et al. 2023

Adv Funct Materials

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Partial oxidation of methane (CH4) to value‐added products is significantly challenging due to the highly inert chemical property of CH4 at ambient conditions and easy over‐oxidation into carbon dioxide (CO2) or carbon monoxide (CO) at elevated temperatures and pressures. Targeting this challenge, the efficient photocatalytic coupling of CO2 and CH4 into ethanol is demonstrated, using a cerium (Ce)‐doped zinc oxide (ZnO) photocatalyst with abundant Ce─O─Zn units. Under light illumination, CO2 is adsorbed on the Ce atoms and photo‐reduced to CO, and CH4 is captured by the Zn atoms and photo‐oxidized to hydroperoxymethane (CH3OOH). The close proximity of Ce and Zn atoms on the Ce─O─Zn units allowed to further efficiently couple the as‐formed CO and CH3OOH into ethanol. Without additional Oxygen (O2) oxidant or sacrificial regent, the ethanol production rate reached 580 µmol g−1 h−1, substantially exceeding previously reports on photocatalytic CH4 oxidation. This work features to convert two greenhouse gases into value‐added chemicals with adjacent and asymmetric reaction sites, suggesting attractive potentials for CH4 and CO2 utilization.

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Challenges for the utilization of methane as a chemical feedstock

Cited by 28 publications

References 102 publications

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Decarbonizing Petrochemical Processes: Contribution and Perspectives of the Selective Oxidation of C₁–C₃ Paraffins

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

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Challenges for the utilization of methane as a chemical feedstock

Cited by 28 publications

References 102 publications

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

Decarbonizing Petrochemical Processes: Contribution and Perspectives of the Selective Oxidation of C1–C3 Paraffins

Photocatalytic Coupling of CH4 and CO2 to Ethanol on Asymmetric Ce−O−Zn Sites

Contact Info

Product

Resources

About

Decarbonizing Petrochemical Processes: Contribution and Perspectives of the Selective Oxidation of C₁–C₃ Paraffins

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites