A universal principle for a rational design of single-atom electrocatalysts

Xu, Haoxiang; Cheng, Daojian; Cao, Dapeng; Zeng, Xiao Cheng

doi:10.1038/s41929-018-0063-z

Cited by 1,275 publications

(1,185 citation statements)

References 59 publications

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“…Using the data cited in the literatures [19,45] and our new descriptor, a volcano relationship was established, which not only predict the best catalysts but also distinguish the catalytic mechanism ( Figure S15, Supporting Information). Using the data cited in the literatures [19,45] and our new descriptor, a volcano relationship was established, which not only predict the best catalysts but also distinguish the catalytic mechanism ( Figure S15, Supporting Information).…”

Section: Intrinsic Descriptors For Tm-sac Systemsmentioning

confidence: 99%

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Gong

Zhang

Lin

et al. 2019

Advanced Energy Materials

175

121

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energy such as wind and solar energy has attracted enormous interest for its significant roles in mitigating CO 2 emissions and reducing dependence on petrochemicals. [1,2] At the heart of the CO 2 conversion technology, electrocatalysts are needed to promote a critical reaction, CO 2 reduction reaction (CO 2 RR) that determines the efficiency and selectivity. To date, the electrocatalysts have confronted severe bottlenecks issue: poor selectivity about various accessory products in CO 2 conversion process, and loss of efficiency toward competing hydrogen evolution. [3] The former involves associated multielectron transfer process and is difficult to accurately control the reaction process by external conditions, [4] while the latter is mainly due to the fact that the equilibrium potentials for most of the CO 2 RR are very close to hydrogen evolution reaction (HER) toward undesirable side-products in aqueous electrolytes, which degrades the electrocatalytic performance during the CO 2 RR process. [5,6] Therefore, CO 2 RR is much more complex than other energy-related electrochemical reactions such as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and it is still a great challenge to design and synthesize electrocatalytic materials with higher product selectivity and catalytic activity for CO 2 RR.Among the electrocatalysts including metals oxides and metal-doped carbon materials, single-atom catalysts (SACs) represent an exciting class of catalysts with monodispersed metal catalytic centers and have emerged as the frontier science in both homogeneous and heterogeneous catalysis, including CO 2 conversion. [7][8][9][10] This type of catalysts contains M-N-C moiety with single atoms and is common in building metalorganic frameworks (MOFs), [11] covalent organic frameworks (COFs) [12] with transition metal macrocyclic clusters, such as porphyrin, phthalocyanine, and tetraazannulene, as well as metal-doped carbon materials [13] (e.g., graphene, carbon nanotubes, fullerene). In nature, the biomolecules, like chlorophyll (Mg-porphyrin) in leaves, and iron porphyrins in cytochrome c oxidase in blood cells, have similar structures as SACs, with special ability in photosynthesis and transforming CO 2 from cells with high efficiency and selectivity. [14] Through the selection of appropriate motifs, the construction principles of Direct conversion of CO 2 into carbon-neutral fuels or industrial chemicals holds a great promise for renewable energy storage and mitigation of greenhouse gas emission. However, experimentally finding an electrocatalyst for specific final products with high efficiency and high selectivity poses serious challenges due to multiple electron transfer, complicated intermediates, and numerous reaction pathways in electrocatalytic CO 2 reduction. Here, an intrinsic descriptor that correlates the catalytic activity with the topological, bonding, and electronic structures of catalytic centers on M-N-C based single-atom catalysts is discovered. The "volcano"-shaped relationships betwee...

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Section: Intrinsic Descriptors For Tm-sac Systemsmentioning

confidence: 99%

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Gong

Zhang

Lin

et al. 2019

Advanced Energy Materials

175

121

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“…(a) Linear relation between adsorption energies of various species on metal and sulfur sites of various transition metal (Mo, W, Nb, Ta) sulfide edges and the d‐band center of the transition metal site at zero coverage, reproduced with permission from Reference (copyright 2014 American Chemical Society); (b) Illustration of energy of lowest unoccupied states and its linear relation with H adsorption energies on basal planes of transition‐metal dichalcogenides, reprinted by permission from Macmillan Publishers Ltd: Nature Energy (Reference ), copyright 2017; (c) Example of p band peak and its linear relation with H adsorption energy on doped graphene, reprinted by permission from Macmillan Publishers Ltd: Nature Energy (Reference ), copyright 2016; (d) Relation between the proposed

φ = θ_{d} ((), E_{M} + α \times ((), n_{N} \times E_{N} + n_{C} \times E_{C})) / E_{sans-serifO / sans-serifH} false)

Section: Hydrogen Evolution Reactionmentioning

confidence: 99%

“…Note that in (g–h), two metal atoms are supported on graphene quadrovacancy and two adjacent graphene single vacancies. (a) and (b) reproduced with permission from References (copyright 2015 American Chemical Society), (c) reproduced with permission from Reference (copyright 2017 American Chemical Society), (d–g) reproduced with permission from Reference (copyright 2018 Macmillan Publishers Ltd: Nature Catalysis), (h‐j) reproduced with permission from Reference (copyright 2015 American Chemical Society), respectively…”

Section: Co2r Reactionmentioning

confidence: 99%

“…In this review, we present the advances in understanding the electronic structure of 2D materials for HER, CO2R, ORR/OER and NRR. A number of descriptors will be discussed, such as: d‐band center, valence band peak position, position of lowest unoccupied state, and those based on the atomic properties and coordination number of the active site and its neighboring atoms . Furthermore, we discuss the challenges and the future research directions towards rational design of 2D electrocatalysts: the effects of varying charge and fixed potential of the catalyst, the passivation of active sites, and the solvation effects need to be assessed.…”

Section: Introductionmentioning

confidence: 99%

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The electronic structure underlying electrocatalysis of two‐dimensional materials

Zhao

Shi

et al. 2019

WIREs Comput Mol Sci

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The understanding and development of advanced electrochemical catalysts have attracted intensive studies and achieved tremendous progress in the past decades. Two‐dimensional (2D) materials, such as doped graphene and atomically‐thin transition metal compounds, have shown great promise as electrocatalysts for various renewable energy conversion and storage reactions. Their further developments require improved understanding of the catalytic mechanisms at atomic level. Currently, most of the understandings are based on the formation free energies of the intermediates, which are determined by their binding strengths with the catalyst, usually calculated from density functional theory (DFT). These energies/binding strengths have been used as descriptor to describe the activity of many catalysts. However, it remains less explored why different catalysts have different binding strengths and what are the underlying factors controlling them, requiring studies going beyond atomic level to electronic level. This review aims to provide such links, focusing on 2D electrocatalysts for hydrogen evolution reaction (HER), oxygen reduction reaction/oxygen evolution reaction (ORR/OER), CO2 reduction reaction (CO2R) and nitrogen reduction reaction (NRR). We also discuss some of the significant issues that need to be addressed in DFT calculations, including the effects of varying charge and fixed potential of the catalyst, the passivation of active sites, and the solvation effects. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Structure and Mechanism > Computational Materials Science

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“…Recent reports have developed an effective way to increase the catalytic activity and selectivity by downsizing the metal particles with the catalytic active centers to the atomic scale . The first single‐atom catalysts (SACs) were reported by Zhang et al in 2011 .…”

Section: Introductionmentioning

confidence: 99%

Densely Populated Single Atom Catalysts

et al. 2019

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Developing highly efficient electrocatalysts with low cost is critical for the wide‐spread application of sustainable and renewable energy conversion technologies. Single‐atom catalysts (SACs) have attracted considerable attention owing to their high catalytic activity, selectivity, and stability. However, the high surface energy of the single atoms often results in an extremely low loading of metal atom catalysts with limited mass activity. In this context, densely populated SACs are more promising for practical applications due to their high active surface area and mass activity. Herein, the recent research progress of high loading (≥5 wt%) SACs for different electrocatalytic applications is summarized. An overview of various synthesis and characterization strategies of SACs is presented in this review. The influence of appropriate substrates on the preparation of high metal loading SACs is also discussed. In addition, this review provides valuable insights into the current challenges and future opportunities in the field of single‐atom catalysts.

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A universal principle for a rational design of single-atom electrocatalysts

Cited by 1,275 publications

References 59 publications

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

The electronic structure underlying electrocatalysis of two‐dimensional materials

Densely Populated Single Atom Catalysts

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A universal principle for a rational design of single-atom electrocatalysts

Cited by 1,275 publications

References 59 publications

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO2 Conversion

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO2 Conversion

The electronic structure underlying electrocatalysis of two‐dimensional materials

Densely Populated Single Atom Catalysts

Contact Info

Product

Resources

About

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion