Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

Abstract

The abundance of cheap, natural gas has transformed the energy landscape, whereby revealing new possibilities for sustainable chemical technologies or impacting those that have relied on traditional fossil fuels. The primary component, methane, is underutilized and wastefully exhausted, leading to anthropogenic global warming. Historically, the manipulation of methane remained "clavis aurea," an insurmountable yet rewarding challenge and thus the focus of intense research. This is primarily due to an inability to dissociate C−H bonds in methane selectively, which requires a high energy penalty and is an essential prerequisite for the direct conversion of methane into a large set of value-added products. The discovery of such processes would promise an energy gainful use of natural gas benefiting several essential chemical processes associated with C1 chemistry. This first C−H bond dissociation step of the methane molecule appears in numerous catalytic mechanisms as the rate-determining step or most essential barrier sequence for all subsequent steps that follow in the production of C−C, C−O, or C x −H y −O z bonds found in value added products. A main goal is to catalytically reduce the energy barrier for the first C−H bond dissociation to be able to achieve the activation of methane at low or moderate temperatures. As such there is great value in understanding the fundamental nature of the active sites responsible for bond breaking or formation and thus be able to facilitate better control of this chemistry, leading to the development of new technologies for fuel production and chemical conversion. Surface science studies offer enhanced perspectives for a careful manipulation of bonds over the last layer atoms of catalyst surfaces, an essential factor for the design of atomically precise catalysts and unravelling of the reaction mechanism. With the advent of new surface imaging, spectroscopy, and in situ tools, it has been possible to decipher the surface chemistry of complex materials systems and further our understanding of atomic active sites on the surfaces of metals, oxides, and carbides or metal−oxide and metal−carbide interfaces. The once considered near impossible step of C−H bond activation is now observed at low temperatures with high propensity over a collection of oxide, metal−oxide, and metal−carbide systems in a conventional or inverse configuration (oxide or carbide on metal). The enabling of C− H activation at low temperature has opened interesting possibilities for the specific production of chemicals such as methanol directly from methane, a step toward facile synthesis of liquid fuels. We highlight the most recent of these results and present the key aspects of active site configurations engineered from surface science studies which enable such a simple reactive event through careful manipulation of the last surface layer of atoms found in the catalyst structure. New concepts which help in the activation and conversion of methane are discussed.

Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

“…[61][62][63][64] However,t he selective methane oxidation reaction (MOR) has been long considered as one of the grand challenges in catalysis due to the demanding CÀHbond activation (439 kJ mol À1 )a nd easy over-oxidation to undesired CO 2 . [61,65] In aqueous electrolytes,t he *O intermediate generated by electrocatalytic water splitting serves as the oxidizing agent for the conversion of CH 4 to adsorbed *CH 3 O intermediates. [66] Theoretical studies validated alinear scaling relation between the activation energy of the first CÀHbond and the binding strength of *O (DG O ).…”

Low‐Temperature H2 Reduction of Copper Oxide Subnanoparticles

“…The CuO particles with low atomicity easily release oxygen atoms because of their surface‐strained structure and the unprecedented elongation of their Cu−O bonds [20c] . This work provides a new strategy for preparing catalytically enhanced CuO SNPs for hydrocarbon oxidation reactions under ambient temperature [24] . A detailed investigation to explain the decrease in the reduction temperature is currently in progress.…”

Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

“…Direct electrocatalytic conversion of methane to methanol is a revolutionary alternative to gas flaring at remote oil fields, in which over 145 billion cubic meters of natural gas is burned annually, contributing 1 % of the global CO 2 emissions [61–64] . However, the selective methane oxidation reaction (MOR) has been long considered as one of the grand challenges in catalysis due to the demanding C−H bond activation (439 kJ mol −1 ) and easy over‐oxidation to undesired CO 2 [61, 65] . In aqueous electrolytes, the *O intermediate generated by electrocatalytic water splitting serves as the oxidizing agent for the conversion of CH 4 to adsorbed *CH 3 O intermediates [66] .…”