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      Conversion of Methane into Liquid Fuels—Bridging Thermal Catalysis with Electrocatalysis

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          Abstract

          The direct partial oxidation of methane to methanol promises an energy‐efficient and environmental‐friendly utilization of natural gas. Unfortunately, current technologies confront a grand challenge in catalysis, particularly in the context of distributed sources. Research has been focused on the design of homogenous and heterogenous catalysts to improve the activation of methane under thermal and electrochemical conditions. However, the intrinsic relationship between thermal and electrochemical systems has not been exploited yet. This review intends to bridge the studies of thermal and electrochemical catalysts, in both homogenous and heterogenous systems, for methane activation from a mechanistic point of view. It is expected to provide a framework to rationalize the design of electrocatalysts beyond the state of art. First, methane activation systems reported previously are reviewed and classified into two basic mechanisms: dehydrogenation and deprotonation. Based on the mechanism types, activity and selectivity descriptors are defined to understand the performance of current catalysts and guide the design of future catalysts. Moreover, methods to enhance the activity and selectivity are discussed to emphasize the unique advantage of electrocatalysis in overcoming the limitations of traditional thermal catalysis. Finally, immense opportunities and challenges for catalyst design are discussed by unifying thermal and electrochemical catalysis.

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          Most cited references127

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          Combining theory and experiment in electrocatalysis: Insights into materials design

          Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. This review discusses design strategies for state-of-the-art heterogeneous electrocatalysts and associated materials for several different electrochemical transformations involving water, hydrogen, and oxygen, using theory as a means to rationalize catalyst performance. By examining the common principles that govern catalysis for different electrochemical reactions, we describe a systematic framework that clarifies trends in catalyzing these reactions, serving as a guide to new catalyst development while highlighting key gaps that need to be addressed. We conclude by extending this framework to emerging clean energy reactions such as hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, where the development of improved catalysts could allow for the sustainable production of a broad range of fuels and chemicals.
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            Computational high-throughput screening of electrocatalytic materials for hydrogen evolution.

            The pace of materials discovery for heterogeneous catalysts and electrocatalysts could, in principle, be accelerated by the development of efficient computational screening methods. This would require an integrated approach, where the catalytic activity and stability of new materials are evaluated and where predictions are benchmarked by careful synthesis and experimental tests. In this contribution, we present a density functional theory-based, high-throughput screening scheme that successfully uses these strategies to identify a new electrocatalyst for the hydrogen evolution reaction (HER). The activity of over 700 binary surface alloys is evaluated theoretically; the stability of each alloy in electrochemical environments is also estimated. BiPt is found to have a predicted activity comparable to, or even better than, pure Pt, the archetypical HER catalyst. This alloy is synthesized and tested experimentally and shows improved HER performance compared with pure Pt, in agreement with the computational screening results.
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              Over the past decade the theoretical description of surface reactions has undergone a radical development. Advances in density functional theory mean it is now possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare favourably with experiments. Theoretical methods can be used to describe surface chemical reactions in detail and to understand variations in catalytic activity from one catalyst to another. Here, we review the first steps towards using computational methods to design new catalysts. Examples include screening for catalysts with increased activity and catalysts with improved selectivity. We discuss how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure.
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                Author and article information

                Contributors
                Journal
                Advanced Energy Materials
                Advanced Energy Materials
                Wiley
                1614-6832
                1614-6840
                October 2020
                September 27 2020
                October 2020
                : 10
                : 40
                Affiliations
                [1 ] Research Laboratory of Electronics Massachusetts Institute of Technology Cambridge MA 02139 USA
                [2 ] Department of Chemical Engineering Massachusetts Institute of Technology Cambridge MA 02139 USA
                [3 ] Department of Materials Science and Engineering Massachusetts Institute of Technology Cambridge MA 02139 USA
                [4 ] Department of Mechanical Engineering Massachusetts Institute of Technology Cambridge MA 02139 USA
                Article
                10.1002/aenm.202002154
                451f234b-5b2a-45db-a185-d3acf495bee2
                © 2020

                http://onlinelibrary.wiley.com/termsAndConditions#vor

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