Bio‐Inspired In Situ Tuning of the Hydrophobic Environment Around Catalytically Active Organic Ligand‐Stabilized Ruthenium Nanoparticles

Sufyan, Sayed Abu; Oblad, Paul F.; van Devener, Brian; Perez, Jesus Paulo L.; Dousti, Ahmad; Shiri, Samira; Nigra, Michael M.

doi:10.1002/cctc.202500275

Title: Bio‐Inspired In Situ Tuning of the Hydrophobic Environment Around Catalytically Active Organic Ligand‐Stabilized Ruthenium Nanoparticles

Journal Article · 15 March 2025 · ChemCatChem

DOI: https://doi.org/10.1002/cctc.202500275 · OSTI ID:2531021

^[1];

^[2]; van Devener, Brian ^[3]; Perez, Jesus Paulo L. ^[3]; Dousti, Ahmad ^[4];

^[4];

^[1]

Department of Chemical Engineering University of Utah Salt Lake City Utah 84112 USA
Department of Chemistry University of Utah Salt Lake City Utah 84112 USA
Electron Microscopy and Surface Analysis Laboratory University of Utah Salt Lake City Utah 84112 USA
Department of Mechanical Engineering University of Utah Salt Lake City Utah 84112 USA

Abstract The organic ligand environment surrounding enzymatic and homogeneous catalytic active sites often determines catalytic activity. Ruthenium nanoparticles, ≤1 nm in diameter, are synthesized using monodentate thiol, monodentate phosphine, and bidentate bisphosphine ligands. Even though some of the ruthenium surface is blocked by the ligands, catalytic activity is still observed for CO oxidation and H ₂ O ₂ decomposition. All three ligand‐stabilized ruthenium nanoparticles have similar CO oxidation rates; however, the bisphosphine‐stabilized Ru nanoparticles are approximately 2.5 times less active than the monothiol‐stabilized and monophosphine‐stabilized ruthenium nanoparticles for H ₂ O ₂ decomposition. It is observed that the organic ligand environment is modulated in situ during nanoparticle synthesis via partial oxidation of the bisphosphine as confirmed by ³¹ P NMR measurements. We hypothesize that bisphosphine‐bound Ru nanoparticles consist of a Ru core with some of the ligands bound in a monodentate manner where the other P atom is oxidized and not bound to the Ru surface leading to a thicker hydrophobic layer around the Ru nanoparticles. The increase in hydrophobicity is confirmed via contact angle and zeta potential measurements. H ₂ O ₂ decomposition rates are known to decrease with increasing hydrophobicity, and this work illustrates a pathway for increasing hydrophobicity in situ using ligand‐bound metallic nanoparticles.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: FE0032174

OSTI ID:: 2531021

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 8 Vol. 17; ISSN 1867-3880

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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