Single-Atom Alloys as a Reductionist Approach to the Rational Design of Heterogeneous Catalysts

While single-atom catalysts (SACs) have achieved great success in the past decade, their application is potentially limited by the simplistic single-atom active centers, which makes single-cluster catalysts (SCCs) a natural extension. SCCs with precise numbers of atoms and structural configurations possess SAC’s merits, yet have greater potentials for catalyzing complex reactions and/or bulky reactants. Through systematic quantum-chemical studies and computational screening, we report here the rational design of transition metal trimer clusters anchored on graphdiyne as a novel kind of stable SCCs with great potentials for efficient and precise heterogenous catalysis. By investigating their structures and catalytic performance for oxygen reduction reaction, hydrogen evolution reaction, and CO2 reduction reactions, we provide theoretical guidelines for their potential applications as heterogeneous catalysts. These graphdiyne supported SCCs provide an ideal benchmark scaffold for rational design of precise catalysts for industrially important chemical reactions.

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Single-atom catalyst: a rising star for green synthesis of fine chemicals

National Science Review ◽

10.1093/nsr/nwy077 ◽

2018 ◽

Vol 5 (5) ◽

pp. 653-672 ◽

Cited By ~ 55

Author(s):

Leilei Zhang ◽

Yujing Ren ◽

Wengang Liu ◽

Aiqin Wang ◽

Tao Zhang

Keyword(s):

Green Synthesis ◽

Active Sites ◽

Rational Design ◽

Heterogeneous Catalysts ◽

Catalytic Performance ◽

Research Area ◽

Single Atom ◽

Metal Species ◽

Future Research ◽

Fine Chemicals

Abstract The green synthesis of fine chemicals calls for a new generation of efficient and robust catalysts. Single-atom catalysts (SACs), in which all metal species are atomically dispersed on a solid support, and which often consist of well-defined mononuclear active sites, are expected to bridge homogeneous and heterogeneous catalysts for liquid-phase organic transformations. This review summarizes major advances in the SAC-catalysed green synthesis of fine chemicals in the past several years, with a focus on the catalytic activity, selectivity and reusability of SACs in various organic reactions. The relationship between catalytic performance and the active site structure is discussed in terms of the valence state, coordination environment and anchoring chemistry of single atoms to the support, in an effort to guide the rational design of SACs in this special area, which has traditionally been dominated by homogeneous catalysis. Finally, the challenges remaining in this research area are discussed and possible future research directions are proposed.

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Statistical learning goes beyond the d-band model providing the thermochemistry of adsorbates on transition metals

Nature Communications ◽

10.1038/s41467-019-12709-1 ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 16

Author(s):

Rodrigo García-Muelas ◽

Núria López

Keyword(s):

Density Functional ◽

Rational Design ◽

Heterogeneous Catalysts ◽

Principal Component ◽

Single Atom ◽

Reaction Networks ◽

Band Model ◽

Functional Theory ◽

Near Surface ◽

Formation Energies

Abstract The rational design of heterogeneous catalysts relies on the efficient survey of mechanisms by density functional theory (DFT). However, massive reaction networks cannot be sampled effectively as they grow exponentially with the size of reactants. Here we present a statistical principal component analysis and regression applied to the DFT thermochemical data of 71 C$${}_{1}$$ 1 –C$${}_{2}$$ 2 species on 12 close-packed metal surfaces. Adsorption is controlled by covalent ($$d$$ d -band center) and ionic terms (reduction potential), modulated by conjugation and conformational contributions. All formation energies can be reproduced from only three key intermediates (predictors) calculated with DFT. The results agree with accurate experimental measurements having error bars comparable to those of DFT. The procedure can be extended to single-atom and near-surface alloys reducing the number of explicit DFT calculation needed by a factor of 20, thus paving the way for a rapid and accurate survey of whole reaction networks on multimetallic surfaces.

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A Novel Series of Single-Cluster Catalysts: Transition Metal Trimer Clusters Supported on Graphdiyne

10.26434/chemrxiv.13160282.v1 ◽

2020 ◽

Author(s):

Jin-Cheng Liu ◽

Hai Xiao ◽

Xiao-Kun Zhao ◽

Nan-Nan Zhang ◽

Yuan Liu ◽

...

Keyword(s):

Transition Metal ◽

Rational Design ◽

Heterogeneous Catalysts ◽

Natural Extension ◽

Single Atom ◽

Great Success ◽

Active Centers ◽

Heterogenous Catalysis ◽

Computational Screening ◽

Single Cluster

While single-atom catalysts (SACs) have achieved great success in the past decade, their application is potentially limited by the simplistic single-atom active centers, which makes single-cluster catalysts (SCCs) a natural extension. SCCs with precise numbers of atoms and structural configurations possess SAC’s merits, yet have greater potentials for catalyzing complex reactions and/or bulky reactants. Through systematic quantum-chemical studies and computational screening, we report here the rational design of transition metal trimer clusters anchored on graphdiyne as a novel kind of stable SCCs with great potentials for efficient and precise heterogenous catalysis. By investigating their structures and catalytic performance for oxygen reduction reaction, hydrogen evolution reaction, and CO2 reduction reactions, we provide theoretical guidelines for their potential applications as heterogeneous catalysts. These graphdiyne supported SCCs provide an ideal benchmark scaffold for rational design of precise catalysts for industrially important chemical reactions.

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Rational Design of Single-Atom Catalysts for Enhanced Electrocatalytic Nitrogen Reduction Reaction

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.1c00742 ◽

2021 ◽

Author(s):

Sakshi Agarwal ◽

Ritesh Kumar ◽

Rakesh Arya ◽

Abhishek K. Singh

Keyword(s):

Rational Design ◽

Reduction Reaction ◽

Single Atom ◽

Nitrogen Reduction

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Engineering Ruthenium-Based Electrocatalysts for Effective Hydrogen Evolution Reaction

Nano-Micro Letters ◽

10.1007/s40820-021-00679-3 ◽

2021 ◽

Vol 13 (1) ◽

Author(s):

Yingjie Yang ◽

Yanhui Yu ◽

Jing Li ◽

Qingrong Chen ◽

Yanlian Du ◽

...

Keyword(s):

Hydrogen Evolution ◽

Hydrogen Evolution Reaction ◽

Rational Design ◽

Energy System ◽

Structure Design ◽

Single Atom ◽

Research Progress ◽

Pure Hydrogen ◽

Hydrogen Energy ◽

Practical Applications

AbstractThe investigation of highly effective, durable, and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) is a prerequisite for the upcoming hydrogen energy society. To establish a new hydrogen energy system and gradually replace the traditional fossil-based energy, electrochemical water-splitting is considered the most promising, environmentally friendly, and efficient way to produce pure hydrogen. Compared with the commonly used platinum (Pt)-based catalysts, ruthenium (Ru) is expected to be a good alternative because of its similar hydrogen bonding energy, lower water decomposition barrier, and considerably lower price. Analyzing and revealing the HER mechanisms, as well as identifying a rational design of Ru-based HER catalysts with desirable activity and stability is indispensable. In this review, the research progress on HER electrocatalysts and the relevant describing parameters for HER performance are briefly introduced. Moreover, four major strategies to improve the performance of Ru-based electrocatalysts, including electronic effect modulation, support engineering, structure design, and maximum utilization (single atom) are discussed. Finally, the challenges, solutions and prospects are highlighted to prompt the practical applications of Ru-based electrocatalysts for HER.

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Catalytic activity of palladium-doped silver dilute nanoalloys for formate oxidation from a theoretical perspective

Physical Chemistry Chemical Physics ◽

10.1039/c9cp04530a ◽

2019 ◽

Vol 21 (40) ◽

pp. 22598-22610 ◽

Cited By ~ 20

Author(s):

Nan Zhang ◽

Fuyi Chen ◽

Longfei Guo

Keyword(s):

Catalytic Activity ◽

Oxidation Reaction ◽

Theoretical Perspective ◽

Single Atom ◽

High Catalytic Activity ◽

Formate Oxidation ◽

First Time ◽

Single Atom Alloys

We demonstrate for the first time that the Pd1Ag single-atom alloys exhibit a high catalytic activity for formate oxidation reaction.

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Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting

Nature Communications ◽

10.1038/s41467-021-24828-9 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Panlong Zhai ◽

Mingyue Xia ◽

Yunzhen Wu ◽

Guanghui Zhang ◽

Junfeng Gao ◽

...

Keyword(s):

Hydrogen Evolution ◽

Water Splitting ◽

Layered Double Hydroxide ◽

Hydrogen Evolution Reaction ◽

Active Sites ◽

Density Functional ◽

Rational Design ◽

Single Atom ◽

Nickel Iron ◽

Double Hydroxide

AbstractRational design of single atom catalyst is critical for efficient sustainable energy conversion. However, the atomic-level control of active sites is essential for electrocatalytic materials in alkaline electrolyte. Moreover, well-defined surface structures lead to in-depth understanding of catalytic mechanisms. Herein, we report a single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets (Ru1/D-NiFe LDH). Under precise regulation of local coordination environments of catalytically active sites and the existence of the defects, Ru1/D-NiFe LDH delivers an ultralow overpotential of 18 mV at 10 mA cm−2 for hydrogen evolution reaction, surpassing the commercial Pt/C catalyst. Density functional theory calculations reveal that Ru1/D-NiFe LDH optimizes the adsorption energies of intermediates for hydrogen evolution reaction and promotes the O–O coupling at a Ru–O active site for oxygen evolution reaction. The Ru1/D-NiFe LDH as an ideal model reveals superior water splitting performance with potential for the development of promising water-alkali electrocatalysts.

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