On the stability of isolated iridium sites in N-rich frameworks against agglomeration under reducing conditions

Iemhoff, Andree, Vennewald, Maurice, Artz, Jens, Mebrahtu, Chalachew ORCID: https://orcid.org/0000-0001-6122-0937, Meledin, Alexander ORCID: https://orcid.org/0000-0002-3200-0553, Weirich, Thomas E. ORCID: https://orcid.org/0000-0001-5539-0534, Hartmann, Heinrich ORCID: https://orcid.org/0000-0002-7244-495X, Besmehn, Astrid ORCID: https://orcid.org/0000-0001-8045-9118, Aramini, Matteo, Venturini, Federica, Mosselmans, Fred W. ORCID: https://orcid.org/0000-0001-6473-2743, Held, Georg ORCID: https://orcid.org/0000-0003-0726-4183, Arrigo, Rosa ORCID: https://orcid.org/0000-0002-2877-8733 and Palkovits, Regina ORCID: https://orcid.org/0000-0002-4970-2957 2022, 'On the stability of isolated iridium sites in N-rich frameworks against agglomeration under reducing conditions' , ChemCatChem, 14 (9) .

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Abstract

Stabilization of single metal atoms is a persistent challenge in heterogeneous catalysis. Especially supported late transitions metals are prone to undergo agglomeration to nanoparticles under reducing conditions. In this study, nitrogen-rich covalent triazine frameworks (CTFs) are used to immobilize iridium complexes. Upon reduction at 400°C, immobilized Ir(acac)(COD) on CTF does not form nanoparticles but transforms into a highly active Ir single atom catalyst. The resulting catalyst systems outperforms both the immobilized complex and supported nanoparticles in the dehydrogenation of formic acid as probe reaction. This superior performance could be traced back to decisive changes of the coordination geometry positively influencing activity, selectivity and stability. Spectroscopic analysis reveals an increase of electron density on the cationic iridium site by donation from the CTF macroligand after removal of the organic ligand sphere from the Ir(acac)(COD) precursor complex upon reductive treatment. This work demonstrates the ability of nitrogen moieties to stabilize molecular metal species against agglomeration and opens avenues for catalysts design using isolated sites in high-temperature applications under reducing atmosphere.

Item Type:	Article
Schools:	Schools > School of Environment and Life Sciences
Journal or Publication Title:	ChemCatChem
Publisher:	Wiley
ISSN:	1867-3899
Related URLs:	Publisher
Funders:	Diamond Light Source, Studienstiftung des Deutschen Volkes
SWORD Depositor:	Publications Router
Depositing User:	Publications Router
Date Deposited:	09 May 2022 12:22
Last Modified:	17 Aug 2022 09:48
URI:	https://usir.salford.ac.uk/id/eprint/63767

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