Doped Metal Clusters As Bimetallic AuCo Nanocatalysts: Insights into Structural Dynamics and Correlation with Catalytic Activity by Spectroscopy

Overview

Journal Faraday Discuss

Specialty Chemistry

Date 2022 Nov 4

PMID 36330869

Authors

Noelia Barrabes

Jon Ostolaza

Sarah Reindl

Martin Mahr

Florian Schrenk

Hedda Drexler

Christoph Rameshan

Wojciech Olszewski

Gunther Rupprechter

Affiliations

Soon will be listed here.

Abstract

Co-doped Au nanoclusters with different numbers of doping atoms were synthesized and supported on CeO. The catalytic properties were studied in the CO oxidation reaction. In all cases, an enhancement in catalytic activity was observed compared to the pure Au nanocluster catalyst. Interestingly, a different catalytic performance was obtained depending on the number of Co atoms within the cluster. This was related to the mobility of atoms within the cluster's structure under pretreatment and reaction conditions, resulting in active CoAu nanoalloy sites. The evolution of the doped Au clusters into nanoalloys with well-distributed Co atoms within the Au cluster structure was revealed by combined XAFS, DRIFTS, and XPS studies. Overall, these studies contribute to a better understanding of the dynamics of doped nanoclusters on supports upon pretreatment and reaction, which is key information for the future development and application of bimetallic nanocluster (nanoalloy) catalysts.

Citing Articles

Computational insights into the physico-chemical properties of pure and single-atom copper-indium sub-nanometre clusters: a DFT-genetic algorithm approach.

Alotaibi N, Abdulhussein H, Alamri S, Hamza N, Abo Nasria A RSC Adv. 2025; 15(8):5856-5875.

PMID: 39980995 PMC: 11841672. DOI: 10.1039/d4ra07404a.

Dynamic behaviour of platinum and copper dopants in gold nanoclusters supported on ceria catalysts.

Muller N, Banu R, Loxha A, Schrenk F, Lindenthal L, Rameshan C Commun Chem. 2023; 6(1):277.

PMID: 38110481 PMC: 10728199. DOI: 10.1038/s42004-023-01068-0.

References

Khodakov A, Chu W, Fongarland P . Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. Chem Rev. 2007; 107(5):1692-744. DOI: 10.1021/cr050972v. View

Kurashige W, Yamazoe S, Yamaguchi M, Nishido K, Nobusada K, Tsukuda T . Au25 Clusters Containing Unoxidized Tellurolates in the Ligand Shell. J Phys Chem Lett. 2015; 5(12):2072-6. DOI: 10.1021/jz500901f. View

Yan J, Zhang X, Akita T, Haruta M, Xu Q . One-step seeding growth of magnetically recyclable Au@Co core-shell nanoparticles: highly efficient catalyst for hydrolytic dehydrogenation of ammonia borane. J Am Chem Soc. 2010; 132(15):5326-7. DOI: 10.1021/ja910513h. View

Zhang B, Kaziz S, Li H, Wodka D, Malola S, Safonova O . Pd2Au36(SR)24 cluster: structure studies. Nanoscale. 2015; 7(40):17012-9. DOI: 10.1039/c5nr04324g. View

Kazan R, Muller U, Burgi T . Doping of thiolate protected gold clusters through reaction with metal surfaces. Nanoscale. 2019; 11(6):2938-2945. DOI: 10.1039/c8nr09214a. View

Hossain S, Niihori Y, Nair L, Kumar B, Kurashige W, Negishi Y . Alloy Clusters: Precise Synthesis and Mixing Effects. Acc Chem Res. 2018; 51(12):3114-3124. DOI: 10.1021/acs.accounts.8b00453. View

Martinez-Banderas A, Aires A, Plaza-Garcia S, Colas L, Moreno J, Ravasi T . Magnetic core-shell nanowires as MRI contrast agents for cell tracking. J Nanobiotechnology. 2020; 18(1):42. PMC: 7069006. DOI: 10.1186/s12951-020-00597-3. View

Zhang B, Sels A, Salassa G, Pollitt S, Truttmann V, Rameshan C . Ligand Migration from Cluster to Support: A Crucial Factor for Catalysis by Thiolate-protected Gold Clusters. ChemCatChem. 2019; 10(23):5372-5376. PMC: 6348379. DOI: 10.1002/cctc.201801474. View

Luo G, Deng Y, Zhu L, Liu J, Zhang B, Zhang Y . Au-Co nanoparticles-embedded N-doped carbon nanotube hollow polyhedron modified electrode for electrochemical determination of quercetin. Mikrochim Acta. 2020; 187(10):546. DOI: 10.1007/s00604-020-04531-0. View

10.

Ravel B, Newville M . ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Radiat. 2005; 12(Pt 4):537-41. DOI: 10.1107/S0909049505012719. View

11.

Garcia C, Truttmann V, Lopez I, Haunold T, Marini C, Rameshan C . Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation. J Phys Chem C Nanomater Interfaces. 2020; 124(43):23626-23636. PMC: 7604939. DOI: 10.1021/acs.jpcc.0c05735. View

12.

Hossain S, Ono T, Yoshioka M, Hu G, Hosoi M, Chen Z . Thiolate-Protected Trimetallic AuAgPd and AuAgPt Alloy Clusters with Controlled Chemical Composition and Metal Positions. J Phys Chem Lett. 2018; 9(10):2590-2594. DOI: 10.1021/acs.jpclett.8b00910. View

13.

Pollitt S, Truttmann V, Haunold T, Garcia C, Olszewski W, Llorca J . The Dynamic Structure of Au(SR) Nanoclusters Supported on CeO upon Pretreatment and CO Oxidation. ACS Catal. 2020; 10(11):6144-6148. PMC: 7295362. DOI: 10.1021/acscatal.0c01621. View

14.

Negishi Y, Munakata K, Ohgake W, Nobusada K . Effect of Copper Doping on Electronic Structure, Geometric Structure, and Stability of Thiolate-Protected Au25 Nanoclusters. J Phys Chem Lett. 2015; 3(16):2209-14. DOI: 10.1021/jz300892w. View

15.

Negishi Y, Takasugi Y, Sato S, Yao H, Kimura K, Tsukuda T . Magic-numbered Au(n) clusters protected by glutathione monolayers (n = 18, 21, 25, 28, 32, 39): isolation and spectroscopic characterization. J Am Chem Soc. 2004; 126(21):6518-9. DOI: 10.1021/ja0483589. View

16.

Hakkinen H, Walter M, Gronbeck H . Divide and protect: capping gold nanoclusters with molecular gold-thiolate rings. J Phys Chem B. 2006; 110(20):9927-31. DOI: 10.1021/jp0619787. View

17.

Truttmann V, Drexler H, Stoger-Pollach M, Kawawaki T, Negishi Y, Barrabes N . CeO Supported Gold Nanocluster Catalysts for CO Oxidation: Surface Evolution Influenced by the Ligand Shell. ChemCatChem. 2022; 14(14):e202200322. PMC: 9400996. DOI: 10.1002/cctc.202200322. View

18.

Jin R, Li G, Sharma S, Li Y, Du X . Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures. Chem Rev. 2020; 121(2):567-648. DOI: 10.1021/acs.chemrev.0c00495. View

19.

Lukashuk L, Yigit N, Rameshan R, Kolar E, Teschner D, Havecker M . Operando Insights into CO Oxidation on Cobalt Oxide Catalysts by NAP-XPS, FTIR, and XRD. ACS Catal. 2018; 8(9):8630-8641. PMC: 6135594. DOI: 10.1021/acscatal.8b01237. View

20.

Lu A, Peng D, Chang F, Skeete Z, Shan S, Sharma A . Composition- and Structure-Tunable Gold-Cobalt Nanoparticles and Electrocatalytic Synergy for Oxygen Evolution Reaction. ACS Appl Mater Interfaces. 2016; 8(31):20082-91. DOI: 10.1021/acsami.6b06087. View