Control of the single atom/nanoparticle ratio in Pd/C catalysts to optimize the cooperative hydrogenation of alkenes

• Type: Article in International Scientific Journal
• Date: 2021

Authors

C. Rivera Cárcamo (Author) Other; I. C. Gerber (Author) Other; I. del Rosal (Author) Other; B. Guicheret (Author) Other; R. Castro Contreras (Author) Other; L. Vanoye (Author) Other; A. Favre Réguillon (Author) Other; Bruno F. Machado (Author) FEUP; J. Audevard (Author) Other; C. de Bellefon (Author) Other; R. Philippe (Author) Other; P. Serp (Author) Other

Journal

Title: Catalysis Science and Technology

Vol. 11

Pages: 984-999

ISSN: 2044-4753

Publisher: Royal Society of Chemistry

Indexing

ISI Web of Knowledge - 0 Citations

Scopus - 3 Citations

Other information

Authenticus ID: P-00T-23V

DOI: 10.1039/d0cy01938k

Abstract (EN): We recently reported (R. Castro Contreras, B. Guicheret, B. F. Machado, C. Rivera-Carcamo, M. A. Curiel Alvarez, B. Valdez Salas, M. Ruttert, T. Placke, A. Favre Reguillon, L. Vanoye, C. de Bellefon, R. Philippe and P. Serp, J. Catal., 2019, 372, 226-244) that a structure/activity correlation exists in Pd/C catalysts for myrcene hydrogenation, which integrates the Pd dispersion, and the surface concentration of oxygen groups and defects of the support. Here, through a combined experimental-theoretical study, we provide an explanation of the influence of these three structural characteristics of Pd/C catalysts for alkene hydrogenation. Highly dispersed Pd nanoparticles (Pd-NP) are necessary to activate dihydrogen. A high concentration of surface defects on the support is necessary to stabilize Pd single atoms (Pd-SA), which coexist with Pd-NP on Pd/C catalysts. A high concentration of oxygenated surface groups is also necessary on the support to allow hydrogen spillover. We demonstrate that such a combination allows cooperative catalysis to operate between Pd-NP and Pd-SA that involves the formation of Pd-SA-H species, which are much more active than Pd-NP-H for alkene hydrogenation but also isomerization. Importantly, we also report an efficient method to control the ratio between Pd-SA and Pd-NP in Pd/C catalysts of similar loadings and show that the control of this ratio allows the development of a new generation of stable and highly active catalysts integrating the ultra-rational use of precious metals in short supply. Indeed, for myrcene hydrogenation, activity variations of several orders of magnitude were measured as a function of the value of this ratio.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 16