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      Metal-metal interactions in correlated single-atom catalysts

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          Abstract

          Single-atom catalysts (SACs) include a promising family of electrocatalysts with unique geometric structures. Beyond conventional ones with fully isolated metal sites, an emerging class of catalysts with the adjacent metal single atoms exhibiting intersite metal-metal interactions appear in recent years and can be denoted as correlated SACs (C-SACs). This type of catalysts provides more opportunities to achieve substantial structural modification and performance enhancement toward a wider range of electrocatalytic applications. On the basis of a clear identification of metal-metal interactions, this review critically examines the recent research progress in C-SACs. It shows that the control of metal-metal interactions enables regulation of atomic structure, local coordination, and electronic properties of metal single atoms, which facilitate the modulation of electrocatalytic behavior of C-SACs. Last, we outline directions for future work in the design and development of C-SACs, which is indispensable for creating high-performing new SAC architectures.

          Abstract

          Abstract

          Correlated single-atom catalysts with intersite metal-metal interactions is a highly flexible and efficient catalyst family.

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          Most cited references99

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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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            Single-atom catalysis of CO oxidation using Pt1/FeOx.

            Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.
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              Heterogeneous single-atom catalysis

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                Author and article information

                Contributors
                Role: ConceptualizationRole: InvestigationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing
                Role: ConceptualizationRole: MethodologyRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing
                Role: Writing - original draftRole: Writing - review & editing
                Role: SupervisionRole: ValidationRole: Writing - review & editing
                Role: ConceptualizationRole: Funding acquisitionRole: Project administration
                Role: ConceptualizationRole: Funding acquisitionRole: InvestigationRole: Project administrationRole: Supervision
                Journal
                Sci Adv
                Sci Adv
                sciadv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                April 2022
                29 April 2022
                : 8
                : 17
                : eabo0762
                Affiliations
                [1 ]School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA 5005, Australia.
                [2 ]Department of Chemistry and Biochemistry and Advanced Materials and Liquid Crystal Institute, Kent State University, Kent, OH 44242, USA.
                Author notes
                [* ]Corresponding author. Email: yao.zheng01@ 123456adelaide.edu.au (Y.Z.); s.qiao@ 123456adelaide.edu.au (S.-Z.Q.)
                Author information
                https://orcid.org/0000-0003-4308-5027
                https://orcid.org/0000-0002-8249-4897
                https://orcid.org/0000-0002-1178-5611
                https://orcid.org/0000-0002-2411-8041
                https://orcid.org/0000-0002-4568-8422
                Article
                abo0762
                10.1126/sciadv.abo0762
                9054016
                35486734
                e0f20942-d6d4-4361-a630-f8e4b6481c59
                Copyright © 2022 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

                This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

                History
                : 12 January 2022
                : 16 March 2022
                Funding
                Funded by: FundRef http://dx.doi.org/10.13039/501100000923, Australian Research Council;
                Award ID: FL170100154
                Funded by: FundRef http://dx.doi.org/10.13039/501100000923, Australian Research Council;
                Award ID: FT200100062
                Funded by: FundRef http://dx.doi.org/10.13039/501100000923, Australian Research Council;
                Award ID: DP190103472
                Categories
                Review
                Physical and Materials Sciences
                SciAdv reviews
                Materials Science
                Materials Science
                Custom metadata
                Penchie Limbo

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