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

<p>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 CO<sub>2</sub> 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. </p>

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Computational Screening of Metal–Organic Framework-Supported Single-Atom Transition-Metal Catalysts for the Gas-Phase Hydrolysis of Nerve Agents

ACS Catalysis ◽

10.1021/acscatal.9b03594 ◽

2019 ◽

Vol 10 (2) ◽

pp. 1310-1323 ◽

Cited By ~ 8

Author(s):

Matthew L. Mendonca ◽

Randall Q. Snurr

Keyword(s):

Transition Metal ◽

Gas Phase ◽

Metal Organic Framework ◽

Nerve Agents ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Single Atom ◽

Computational Screening ◽

Metal Organic ◽

Hydrolysis Of

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Computational screening of efficient graphene-supported transition metal single atom catalysts toward the oxygen reduction reaction

Journal of Materials Chemistry A ◽

10.1039/d0ta06892f ◽

2020 ◽

Vol 8 (37) ◽

pp. 19319-19327 ◽

Cited By ~ 1

Author(s):

Lei Li ◽

Rao Huang ◽

Xinrui Cao ◽

Yuhua Wen

Keyword(s):

Transition Metal ◽

Oxygen Reduction Reaction ◽

Oxygen Reduction ◽

Reduction Reaction ◽

Single Atom ◽

Nitrogen Doped ◽

Single Atoms ◽

Computational Screening ◽

Nitrogen Doped Graphene ◽

Doped Graphene

Transition metal single atoms anchored on nitrogen-doped graphene toward the oxygen reduction reaction have been screened.

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Highly-efficient RuNi single-atom alloy catalysts toward chemoselective hydrogenation of nitroarenes

10.21203/rs.3.rs-878026/v1 ◽

2021 ◽

Author(s):

Wei Liu ◽

Yusen Yang ◽

Haisong Feng ◽

Yiming Niu ◽

Lei Wang ◽

...

Keyword(s):

Selective Hydrogenation ◽

High Performance ◽

Heterogeneous Catalysts ◽

Theoretical Calculations ◽

Single Atom ◽

Structure Property ◽

Active Centers ◽

Preferential Cleavage ◽

Rate Determining Step ◽

Single Atom Alloy

Abstract The design and exploitation of high-performance catalysts as well as understanding the structure-property correlation have gained considerable attention in selective hydrogenation reactions, but remain a huge challenge. Herein, we report a RuNi single atom alloy (SAA) in which Ru single atoms are anchored onto Ni nanoparticle surface via Ru–Ni coordination accompanied with electron transfer from sub-surface Ni to Ru. The optimal catalyst 0.4% RuNi SAA exhibits simultaneously improved activity (TOF value: 4293 h− 1) and chemoselectivity toward selective hydrogenation of 4-nitrostyrene to 4-aminostyrene (yield: >99%), which is, to the best of our knowledge, the highest level compared with reported heterogeneous catalysts. In situ experimental researches based on XAFS, FT-IR measurements and theoretical calculations reveal that the Ru–Ni interfacial sites as intrinsic active centers facilitate the preferential cleavage of N–O bond in nitro group with a decreased energy barrier by 0.35 eV. In addition, the Ru–Ni synergistic catalysis promotes the formation of intermediates (C8H7NO* and C8H7NOH*) and accelerates the rate-determining step (hydrogenation of C8H7NOH*), resulting in the extraordinary activity and chemoselectivity toward nitroarenes hydrogenation.

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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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Enabling Direct H2O2 Production in Acidic Media through Rational Design of Transition Metal Single Atom Catalyst

Chem ◽

10.1016/j.chempr.2019.12.008 ◽

2020 ◽

Vol 6 (3) ◽

pp. 658-674 ◽

Cited By ~ 50

Author(s):

Jiajian Gao ◽

Hong bin Yang ◽

Xiang Huang ◽

Sung-Fu Hung ◽

Weizheng Cai ◽

...

Keyword(s):

Transition Metal ◽

Rational Design ◽

Single Atom ◽

H2o2 Production ◽

Acidic Media

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Rational design of transition metal single-atom electrocatalysts: a simulation-based, machine learning-accelerated study

Journal of Materials Chemistry A ◽

10.1039/d0ta06207c ◽

2020 ◽

Vol 8 (37) ◽

pp. 19290-19299

Author(s):

Lianping Wu ◽

Tian Guo ◽

Teng Li

Keyword(s):

Machine Learning ◽

Transition Metal ◽

Rational Design ◽

Utilization Efficiency ◽

Single Atom ◽

Simulation Based ◽

New Research

With maximum atom-utilization efficiency, single atom catalysts (SACs) are surging as a new research frontier in catalysis science.

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

Accounts of Chemical Research ◽

10.1021/acs.accounts.8b00490 ◽

2018 ◽

Vol 52 (1) ◽

pp. 237-247 ◽

Cited By ~ 80

Author(s):

Georgios Giannakakis ◽

Maria Flytzani-Stephanopoulos ◽

E. Charles H. Sykes

Keyword(s):

Rational Design ◽

Heterogeneous Catalysts ◽

Single Atom ◽

Reductionist Approach ◽

Single Atom Alloys

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Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Nature Communications ◽

10.1038/s41467-021-25811-0 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Wenchao Wan ◽

Yonggui Zhao ◽

Shiqian Wei ◽

Carlos A. Triana ◽

Jingguo Li ◽

...

Keyword(s):

Water Oxidation ◽

Rational Design ◽

Reduction Reaction ◽

Utilization Efficiency ◽

Single Atom ◽

Active Centers ◽

Half Wave ◽

Fe Sites ◽

Dual Atom ◽

Dual Site

AbstractSingle-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm−2. We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O2 atop the Ni-O-Fe sites.

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Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials

Chemical Society Reviews ◽

10.1039/d0cs00835d ◽

2020 ◽

Vol 49 (19) ◽

pp. 6884-6946 ◽

Cited By ~ 3

Author(s):

Federico Franco ◽

Clara Rettenmaier ◽

Hyo Sang Jeon ◽

Beatriz Roldan Cuenya

Keyword(s):

Transition Metal ◽

Nanostructured Materials ◽

Rational Design ◽

Co2 Reduction ◽

Nanostructured Catalysts ◽

Single Atom ◽

Molecular Systems ◽

Atoms And Molecules ◽

Electrochemical Conversion ◽

Electrochemical Co2 Reduction

An overview of the main strategies for the rational design of transition metal-based catalysts for the electrochemical conversion of CO2, ranging from molecular systems to single-atom and nanostructured catalysts.

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