Enhanced Catalytic Activity of N-heterocyclic Carbene Stabilized Surface Adatoms for CO Reduction Reaction

Overview

Journal Commun Chem

Publisher Springer Nature

Specialty Chemistry

Date 2023 Dec 11

PMID 38082090

Authors

Yuxiang Gao

Lei Tao

Yu-Yang Zhang

Shixuan Du

Affiliations

Soon will be listed here.

Abstract

Adatom engineering represents a highly promising opportunity for enhancing electrochemical CO reduction reaction (CORR). However, the aggregation of adatoms under typical reaction conditions often leads to a decline in catalyst activity. Recent studies have revealed that N-heterocyclic carbene (NHC) can stabilize surface adatoms. Herein, based on density functional theory calculations, we reveal a significant enhancement in the catalytic activity of Cu adatoms decorated with NHC molecules for CORR. The NHC decoration strengthens the interaction between the d orbital of the Cu adatom and the p orbital of the C atom, reducing the energy barriers in both CO hydrogenation and C-C coupling steps. Moreover, the CORR catalytic activity of the NHC decorated adatom can be further improved by tuning the side groups of NHC molecules. These results provide insights for the design of efficient CORR catalysts and offer a theoretical framework that can be extended to other hydrogenation reactions.

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PMID: 39653746 PMC: 11628612. DOI: 10.1038/s42004-024-01359-0.

References

Jain M, Gerstmann U, Schmidt W, Aldahhak H . Adatom mediated adsorption of N-heterocyclic carbenes on Cu(111) and Au(111). J Comput Chem. 2021; 43(6):413-420. DOI: 10.1002/jcc.26801. View

Wang S, Wang X . Imidazolium Ionic Liquids, Imidazolylidene Heterocyclic Carbenes, and Zeolitic Imidazolate Frameworks for CO2 Capture and Photochemical Reduction. Angew Chem Int Ed Engl. 2015; 55(7):2308-20. DOI: 10.1002/anie.201507145. View

Yang H, Wu Y, Li G, Lin Q, Hu Q, Zhang Q . Scalable Production of Efficient Single-Atom Copper Decorated Carbon Membranes for CO Electroreduction to Methanol. J Am Chem Soc. 2019; 141(32):12717-12723. DOI: 10.1021/jacs.9b04907. View

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

Bakker A, Timmer A, Kolodzeiski E, Freitag M, Gao H, Monig H . Elucidating the Binding Modes of N-Heterocyclic Carbenes on a Gold Surface. J Am Chem Soc. 2018; 140(38):11889-11892. DOI: 10.1021/jacs.8b06180. View

Kaeffer N, Mance D, Coperet C . N-Heterocyclic Carbene Coordination to Surface Copper Sites in Selective Semihydrogenation Catalysts from Solid-State NMR Spectroscopy. Angew Chem Int Ed Engl. 2020; 59(45):19999-20007. DOI: 10.1002/anie.202006209. View

Blochl . Projector augmented-wave method. Phys Rev B Condens Matter. 1994; 50(24):17953-17979. DOI: 10.1103/physrevb.50.17953. View

Calle-Vallejo F, Koper M . Theoretical considerations on the electroreduction of CO to C2 species on Cu(100) electrodes. Angew Chem Int Ed Engl. 2013; 52(28):7282-5. DOI: 10.1002/anie.201301470. View

Vos R, Kolmeijer K, Jacobs T, van der Stam W, Weckhuysen B, Koper M . How Temperature Affects the Selectivity of the Electrochemical CO Reduction on Copper. ACS Catal. 2023; 13(12):8080-8091. PMC: 10278069. DOI: 10.1021/acscatal.3c00706. View

10.

Bagger A, Arnarson L, Hansen M, Spohr E, Rossmeisl J . Electrochemical CO Reduction: A Property of the Electrochemical Interface. J Am Chem Soc. 2019; 141(4):1506-1514. DOI: 10.1021/jacs.8b08839. View

11.

Wang L, Wang L, Meng X, Xiao F . New Strategies for the Preparation of Sinter-Resistant Metal-Nanoparticle-Based Catalysts. Adv Mater. 2019; 31(50):e1901905. DOI: 10.1002/adma.201901905. View

12.

Vidal-Iglesias F, Solla-Gullon J, Herrero E, Aldaz A, Feliu J . Pd adatom decorated (100) preferentially oriented Pt nanoparticles for formic acid electrooxidation. Angew Chem Int Ed Engl. 2010; 49(39):6998-7001. DOI: 10.1002/anie.201002501. View

13.

Yang P, Zhang X, Gao F, Zheng Y, Niu Z, Yu X . Protecting Copper Oxidation State via Intermediate Confinement for Selective CO Electroreduction to C Fuels. J Am Chem Soc. 2020; 142(13):6400-6408. DOI: 10.1021/jacs.0c01699. View

14.

Kaeffer N, Liu H, Lo H, Fedorov A, Coperet C . An N-heterocyclic carbene ligand promotes highly selective alkyne semihydrogenation with copper nanoparticles supported on passivated silica. Chem Sci. 2018; 9(24):5366-5371. PMC: 6009536. DOI: 10.1039/c8sc01924j. View

15.

Li H, Wang L, Dai Y, Pu Z, Lao Z, Chen Y . Synergetic interaction between neighbouring platinum monomers in CO hydrogenation. Nat Nanotechnol. 2018; 13(5):411-417. DOI: 10.1038/s41565-018-0089-z. View

16.

Danopoulos A, Simler T, Braunstein P . N-Heterocyclic Carbene Complexes of Copper, Nickel, and Cobalt. Chem Rev. 2019; 119(6):3730-3961. DOI: 10.1021/acs.chemrev.8b00505. View

17.

Li M, Wang H, Luo W, Sherrell P, Chen J, Yang J . Heterogeneous Single-Atom Catalysts for Electrochemical CO Reduction Reaction. Adv Mater. 2020; 32(34):e2001848. DOI: 10.1002/adma.202001848. View

18.

Appel A, Bercaw J, Bocarsly A, Dobbek H, DuBois D, Dupuis M . Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation. Chem Rev. 2013; 113(8):6621-58. PMC: 3895110. DOI: 10.1021/cr300463y. View

19.

Lu J, Fu B, Kung M, Xiao G, Elam J, Kung H . Coking- and sintering-resistant palladium catalysts achieved through atomic layer deposition. Science. 2012; 335(6073):1205-8. DOI: 10.1126/science.1212906. View

20.

Li J, Abbas S, Wang H, Zhang Z, Hu W . Recent Advances in Interface Engineering for Electrocatalytic CO Reduction Reaction. Nanomicro Lett. 2021; 13(1):216. PMC: 8545969. DOI: 10.1007/s40820-021-00738-9. View