Single-atom catalysis: a promising avenue for precisely controlling reaction pathways

doi:10.1007/s11705-024-2434-0

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (7) : 79 https://doi.org/10.1007/s11705-024-2434-0

Single-atom catalysis: a promising avenue for precisely controlling reaction pathways

Xiaobo Yang, Xuning Li(

), Yanqiang Huang(

)

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

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Abstract

Single-atom catalysts (SACs), characterized by exceptionally high atom efficiency, have garnered significant attention across various catalytic reactions. Recent studies have showcased SACs with robust capabilities for precise catalysis, specifically targeting reactions along designated pathways. This review focuses on the advances in the precise activation and reconstruction of chemical bonds on SACs, including precise activation of C–O and C–H bonds and selective couplings involving C–C and C–N bonds. Our discussion begins with a thorough exploration of the factors that render SACs skilled in precise catalytic processes, encompassing the narrow d-band electronic state of single atom site resulting in the adsorption tendency, isolate site resulting in unique adsorption structure, and synergy effect of a single atom site with its neighbors. Subsequently, we elaborate on the applications of SACs in electrocatalysis and thermocatalysis including four prominent reactions, namely, electrochemical CO₂ reduction, urea electrochemical synthesis, CO₂ hydrogenation, and CH₄ activation. Then the concept of rational design of SACs for precisely controlling reaction pathways is discussed from the aspects of pore structure design, support-metal strong interaction, and support hydrophilic/hydrophobic. Finally, we summarize the challenges encountered by SACs in the field of precise catalytic processes and outline prospects for their further development in this domain.

Keywords single atom catalysts selective oxidation CO₂RR bond coupling

Corresponding Author(s): Xuning Li,Yanqiang Huang

Just Accepted Date: 19 April 2024 Issue Date: 18 June 2024

Cite this article:

Xiaobo Yang,Xuning Li,Yanqiang Huang. Single-atom catalysis: a promising avenue for precisely controlling reaction pathways[J]. Front. Chem. Sci. Eng., 2024, 18(7): 79.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2434-0
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I7/79

Fig.1 The schematic of the importance of catalysis in current green synthesis.

Fig.2 The schematic of physicochemical property changes from nanocatalyst to single atom catalyst.

Fig.3 (a) The electronic structure change from bulk catalyst to SAC. Reprinted with permission from Ref. [59], copyright 2019, American Chemical Society. (b) The interaction model between broad s and narrow d band of metal toward orbital of adsorbate, and a simplified interaction model of narrow/wide metal band orbital and molecular orbital of the adsorbate. (c) The calculated d-band structure of Cu atom on AgCu₁ SAA (single-atom alloy, left) and bulk Cu (right). (d, e) The schematic diagram of adsorbed structures of schizolytic CH₃O* on (d) Cu (111) and (e) AgCu₁ SAA (111) surface. Reprinted with permission from Ref. [61], copyright 2018, Springer Nature.

Fig.4 (a) The schematic diagram of different structures (C=O species-left and C=C species-right) of crotonaldehyde adsorbed on SAA. (b) The adsorption tendency of crotonaldehyde on different SAAs and the differences in d-band interaction energy (z-axis) are affected by the d-band center value (y-axis) and width (HWHM, x-axis). (c) The density of state of crotonaldehyde adsorbed on AuFe₁ and AuPt₁ SAA with different adsorb models. Reprinted with permission from Ref. [63], copyright 2021, American Chemical Society.

Fig.5 (a) The schematic diagram of O₂ adsorbed on SAC and metal catalyst. (b) The schematic of H₂ oxidation on TiO₂ supported Pd single atom. Reprinted with permission from Ref. [65], copyright 2022, Springer Nature. (c, d) The HCOOH oxidation path and structure of intermediates on (c) Ir nanocluster, and (d) Ir-N₄-C catalyst. Reprinted with permission from Ref. [70], copyright 2020, Springer Nature.

Fig.6 (a) The scaling relation of reaction energy (x-axis) and activation energy (y-axis) on the nano metal catalyst and SAA (left), and the structure change of CH₄ dehydrogenation to CH₃* + H* on SAA (right). Reprinted with permission from Ref. [64], copyright 2018, American Chemical Society. (b) The structure schematic of intermediates and (c) free energy change of CH₃OH dehydrogenation on metal and SAA surface. Reprinted with permission from Ref. [72], copyright 2023, American Chemical Society.

Fig.7 (a) The adsorption energy of CO₂ on Ni-Co dual atom, Co single atom, and Ni SACs. (b) C–C bond coupling energy on Ni-Co dual atom, Co single atom, and Ni SACs. (c) The CO reduction free energy profile on Ni-Co dual atom catalyst. Reprinted with permission from Ref. [81], copyright 2024, John Wiley and Sons. (d) Hydrohalogenation energy barrier on different Pd sites. Reprinted with permission from Ref. [82], copyright 2021, Springer Nature. (e) The atom structure changes during HOR process on Ir-P atom pair. Reprinted with permission from Ref. [58], copyright 2023, Springer Nature. (f) Chemoselective hydrogenation of nitroarenes on Ni (111) and RuNi (111). Reprinted with permission from Ref. [85], copyright 2022, Springer Nature.

Fig.8 (a) The electronic structure of Ni(I)N₄ site and the corresponding CO₂ activation mechanism. (b) The CO₂RR product selectivity of four different Ni-based SACs. Reprinted with permission from Ref. [89], copyright 2018, Springer Nature. (c) The adsorption structure and energy of CO₂ on Sn(II)Pc and O-Sn(IV)Pc catalysts. (d) The CO₂RR process on O-Sn(IV)Pc catalyst. Reprinted with permission from Ref. [90], copyright 2023, American Chemical Society.

Fig.9 (a) The FE of urea on Fe single atom, Ni single atom, Fe/Ni dual single atom, as well as FeNi dual catalysts. (b) The summarize of CO₂RR and NO₃RR and co-reduction performance of Ni single, Fe single, and FeNi dual atom catalysts. Reprinted with permission from Ref. [96], copyright 2022, Springer Nature. (c) The performance of urea yield of CuM alloy with different M amounts (M = Bi, Sn, Sb). Reprinted with permission from Ref. [97], copyright 2023, John Wiley and Sons. (d) The schematic of N₂ and CO₂ co-reduction on M₂N₆ dual atom catalysts. Reprinted with permission from Ref. [99], copyright 2023, John Wiley and Sons. (e) The free energy profile and structure of N₂-CO coupling on ZnMn dual atom catalyst. (f) The FE of urea on the different potential of ZnMn dual atom catalyst. Reprinted with permission from Ref. [100], copyright 2023, John Wiley and Sons.

Fig.10 (a) The reaction process and free energy diagram of CO₂ hydrogenation to HCOOH on Ir single atom site. Reprinted with permission from Ref. [106], copyright 2019, Springer Nature. (b) The reaction path and free energy barrier of CO₂ hydrogen to CH₃OH/CO on Cu-N₄/N₃ catalysts. Reprinted with permission from Ref. [107], 2021, copyright Springer Nature. (c) The electron distribution of Ir-In₂O₃ and In₂O₃ catalysts as well as corresponding free energy diagram of CO₂ hydrogenation to CO. (d) The product selectivity of CO₂ hydrogenation to ethanol on different Ir-In₂O₃ catalysts. Reprinted with permission from Ref. [109], copyright 2019, Springer Nature.

Fig.11 (a) The product yield and (b) the TOF values of different Ru-UiO-66 catalysts with different Ru state during CH₄ conversion. (c) The model structure of Zr and Ru site during CH₄ activation and corresponding free energy barriers. (d) The free energy barriers of formation of ?OOH and O₂ on Zr oxo–?OH* and Ru₁=O* sites. Reprinted with permission from Ref. [115], copyright 2023, American Chemical Society.

Fig.12 (a) The schematic diagram of CO₂ reduction to CH₃OH on CoPc catalyst supported on single wall carbon nano tube with tensile strain and plane support with no strain. Reprinted with permission from Ref. [121], copyright 2023, Springer Nature. (b) The relation between energies of dissociative adsorption of H₂ on Sv of strained films and MoS₂ nanotubes. (c) The free energy diagram of CO₂ hydrogenation to CH₃OH on Cu₁-MoS₂ with tensile and compressive strain. (d) The free energy diagram of O hydrogenation on Cu₁-MoS₂ with tensile and compressive strain. Reprinted with permission from Ref. [122], copyright 2023, Springer Nature. (e) The schematic diagram of metal support interaction of Pt single atom and Pt nanoparticle toward TiO₂ support at different temperatures. Reprinted with permission from Ref. [125], copyright 2020, John Wiley and Sons.

Fig.13 Schematic perspective of synthesis, mechanism investigation, and applications amplification of SACs.

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