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Oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are three critical reactions for energy-related applications, such as water electrolyzers and metal-air batteries. Graphene-supported single-atom catalysts (SACs) have been widely explored; however, either experiments or density functional theory (DFT) computations cannot screen catalysts at high speed. Herein, based on DFT computations of 104 graphene-supported SACs (M@C3, M@C4, M@pyridine-N4, and M@pyrrole-N4), we built up machine learning (ML) models to describe the underlying pattern of easily obtainable physical properties and limiting potentials (errors = 0.013/0.005/0.020 V for ORR/OER/HER, respectively), and employed these models to predict the catalysis performance of 260 other graphene-supported SACs containing metal-NxCy active sites (M@NxCy). We recomputed the top catalysts recommended by ML towards ORR/OER/HER by DFT, which confirmed the reliability of our ML model, and identified two OER catalysts (Ir@pyridine-N3C1 and Ir@pyridine-N2C2) outperforming noble metal oxides, RuO2 and IrO2. The ML models quantitatively unveiled the significance of various descriptors and fast narrowed down the potential list of graphene-supported single-atom catalysts. This approach can be easily used to screen and design other SACs, and significantly accelerate the catalyst design for many other important reactions.
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Single atom electrocatalysts supported on graphene or graphene-like carbons
Electrocatalysis plays an essential role in diverse electrochemical energy conversion processes that are vital for improving energy utilization efficiency and mitigating the aggravating global warming challenge. The noble metals such as platinum are generally the most frequently used electrocatalysts to drive these reactions and facilitate the relevant energy conversion processes. The high cost and scarcity of these materials pose a serious challenge for the wide-spread adoption and the sustainability of these technologies in the long run, which have motivated considerable efforts in searching for alternative electrocatalysts with reduced loading of precious metals or based entirely on earth-abundant metals. Of particular interest are graphene-supported single atom catalysts (G-SACs) that integrate the merits of heterogeneous catalysts and homogeneous catalysts, such as high activity, selectivity, stability, maximized atom utilization efficiency and easy separation from reactants/products. The graphene support features a large surface area, high conductivity and excellent (electro)-chemical stability, making it a highly attractive substrate for supporting single atom electrocatalysts for various electrochemical energy conversion processes. In this review, we highlight the recent advancements in G-SACs for electrochemical energy conversion, from the synthetic strategies and identification of the atomistic structure to electrocatalytic applications in a variety of reactions, and finally conclude with a brief prospect on future challenges and opportunities.
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- Award ID(s):
- 1800580
- PAR ID:
- 10204908
- Date Published:
- Journal Name:
- Chemical Society Reviews
- Volume:
- 48
- Issue:
- 20
- ISSN:
- 0306-0012
- Page Range / eLocation ID:
- 5207 to 5241
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Single atoms of select transition metals supported on carbon substrates have emerged as a unique system for electrocatalysis because of maximal atom utilization (≈100%) and high efficiency for a range of reactions involved in electrochemical energy conversion and storage, such as the oxygen reduction, oxygen evolution, hydrogen evolution, and CO2reduction reactions. Herein, the leading strategies for the preparation of single atom catalysts are summarized, and the electrocatalytic performance of the resulting samples for the various reactions is discussed. In general, the carbon substrate not only provides a stabilizing matrix for the metal atoms, but also impacts the electronic density of the metal atoms due to strong interfacial interactions, which may lead to the formation of additional active sites by the adjacent carbon atoms and hence enhanced electrocatalytic activity. This necessitates a detailed understanding of the material structures at the atomic level, a critical step in the construction of a relevant structural model for theoretical simulations and calculations. Finally, a perspective is included highlighting the promises and challenges for the future development of carbon‐supported single atom catalysts in electrocatalysis.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9CS00422J
