Regio- and Chemoselective Hydrogenation over NHC-Decorated Pd Nanoparticles on Carbon Support

Regio- and Chemoselective Hydrogenation over NHC-Decorated Pd Nanoparticles on Carbon Support Full article

Journal

ACS Catalysis
ISSN: 2155-5435

Output data

Year: 2026, Volume: 16, Number: 17, Pages: 16920-16934 Pages count : 15 DOI: 10.1021/acscatal.6c03688

Authors

Shaydullin Ruslan R. ¹ , Parshin Timur V. ^2,1 , Galushko Alexey S. ¹ , Burykina Julia V. ¹ , Kaichev Vasily V. ³ , Ananikov Valentine P. ¹

Affiliations

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
2	Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia
3	Boreskov Institute of Catalysis, Novosibirsk 630090, Russia

Selective hydrogenation of multifunctional unsaturated substrates remains a persistent challenge for heterogeneous palladium catalysts because high activity is commonly accompanied by poor control over chemo- and regioselectivity and extensive overreduction. Here, we show that surface modification of carbon-supported Pd nanoparticles with N-heterocyclic carbenes (NHCs) provides a practical strategy to regulate hydrogenation selectivity. Pd nanoparticles supported on multiwalled carbon nanotubes (MWCNT) were functionalized with a series of NHC ligands, and the resulting materials displayed strongly ligand-dependent behavior. Among the ligands examined, IMes (1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) produced the most pronounced change in catalytic performance, enabling efficient hydrogenation of terminal alkynes with high selectivity for the alkene at full conversion, while strongly suppressing the reactivity of internal alkynes. This selectivity pattern was observed in model alkyne hydrogenations and extended to more complex substrates, including limonene, linalool, and 1,4-decadiyne, where the NHC-modified catalyst outperformed unmodified Pd in control of product distribution. TEM, XPS, ESI-HRMS, kinetic analysis, and DFT calculations collectively indicate that NHC coordination alters the steric and electronic environment of the Pd surface, thereby influencing the competition between different substrates for active sites. These results demonstrate that molecular ligand design can be translated to supported metal nanoparticles to create heterogeneous hydrogenation catalysts with tunable and synthetically exploitable selectivity.

Shaydullin R.R. , Parshin T.V. , Galushko A.S. , Burykina J.V. , Kaichev V.V. , Ananikov V.P.
Regio- and Chemoselective Hydrogenation over NHC-Decorated Pd Nanoparticles on Carbon Support
ACS Catalysis. 2026. V.16. N17. P.16920-16934. DOI: 10.1021/acscatal.6c03688 WOS Scopus OpenAlex

Submitted:	May 12, 2026
Published online:	Sep 4, 2026

≡ Web of science:	WOS:001857079100001
≡ Scopus:	2-s2.0-105051048430
≡ OpenAlex:	W7204763014