Catalytic hydrogenation of 1,3-butadiene on Pd particles evaporated on carbonaceous supports: Particle size effect

doi:10.1016/0021-9517(91)90002-L

Journal of Catalysis

Volume 129, Issue 1, May 1991, Pages 1-11

https://doi.org/10.1016/0021-9517(91)90002-L Get rights and content

Abstract

The catalytic activity of Pd aggregates obtained by atomic-beam vacuum deposition on carbonaceous substrates (amorphous carbon and graphite) has been measured in the 1,3-butadiene hydrogenation reaction. The particle sizes have been determined by TEM. Whatever the support, this reaction appears to be very size sensitive. Metal particles larger than 2.8 nm behave similarly to bulk palladium. The size effect is marked in the 2.8 to 1.4 nm specific diameter range. No activity remains for sizes below 1.4 nm. Highly marked deactivation processes are responsible for the main variations in the catalytic behavior.

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Citation Excerpt :
By precisely controlling the thickness of Al2O3 layers through atomic layer deposition, Lu et al. [10] showed that the activity and selectivity can be systematically manipulated and a total butene selectivity of 95% can be afforded at the full BD conversion over the optimal catalyst. The hydrogenation of 1,3-butadiene has been identified as a structure-sensitive reaction over different metals-based systems (Pd [33,34] Pt [14,35,36], Au [37]). Thus, dramatically different catalytic behaviors might occur when the metal particles are downsized to the single-atom regime.
A systematic study on the structure sensitivity, host effect, and the deactivation mechanism of Ir-catalyzed selective hydrogenation of 1,3-butadiene, a key process in the purification of alkadiene for the upgrading of C4 cut, is presented by coupling steady-state catalytic testing, in-depth characterization, kinetic evaluation, and density functional theory calculations. We reveal that: (i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm, and the H₂ dissociation energy is a reliable activity descriptor; (ii) The nature of the NC hosts exerts a critical impact on the catalytic performance, and balanced nitrogen content and speciation seem key for the optimized performance; and (iii) Different deactivation mechanisms occur: fouling by coke deposition on the catalysts with a high N:C ratio (>1), and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene. These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.
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Citation Excerpt :
This behavior of the highly unsaturated molecules was explained by their strong adsorption at very small Pd nanoparticles (likely at a threshold of ca. 4.2 nm). The particle size effect was later investigated by Tardy and co-workers [21]. Small Pd nanoparticles (ca. 0.9–2.8 nm) with a very narrow size distribution were deposited on both amorphous carbon and graphite by using an atomic-beam vacuum deposition method.
Selective hydrogenation of 1,3-butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector. Catalyst design is crucial to achieve a virtually alkadiene-free product while avoiding over-hydrogenating valuable olefins. In addition to the great industrial relevance, this demanding selectivity pattern renders 1,3-butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia. Nonetheless, critical reviews on the catalyst development are extremely lacking in literature. In this review, we aim to provide the reader an in-depth overview of different catalyst families, particularly the precious metal-based monometallic catalysts (Pd, Pt, and Au), developed in the last half century. The emphasis is placed on the development of new strategies to design high-performance architectures, the establishment of structure-performance relationships, and the reaction and deactivation mechanisms. Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.
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In recent years, high value utilization of waste biomass has been a hot topic in scientific research. Herein, waste eggshell (ES) rich in sulfonic groups was utilized as a natural modified support to load Pd and Ag nanoparticles (NPs), leading to efficient Pd-Ag/ES catalysts for the catalytic hydrogenation of 1,3-butadiene. Through series of characterizations such as SEM, TEM, BET, XPS, and FTIR, it was found that the porous ES not only has hierarchical structures to facilitate the metal dispersion, but also interacts strongly with Pd and Ag NPs via the inherent surface sulfonic groups, which are responsible for the enhanced catalytic performance. The optimized Pd-Ag/ES catalyst exhibited butenes selectivity of 95.8% and 1,3-butadiene conversion of 95% at 45 °C with excellent stability for at least 30 h on-stream. Furthermore, the first-principles density functional theory (DFT) calculation and in situ DRIFTS were performed to explore the plausible mechanism underlying the enhanced catalytic performance due to sulfonic groups. It is suggested that the sulfonic groups can effectively reduce the adsorption energy of butenes and 1,3-butadiene on the surface of Pd NPs which are beneficial to the selectivity of butenes. This work exemplifies that the waste ES with inherent sulfonic groups can be used as excellent support materials for loading active metal nanoparticles for selective hydrogenation reactions. Collectively, we verified that biological waste like eggshell has a great potential in serving as catalyst carrier due to its unique advantages.

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Catalytic hydrogenation of 1,3-butadiene on Pd particles evaporated on carbonaceous supports: Particle size effect

Abstract

Surf. Sci.

Surf. Sci.

J. Catal.

Surf. Sci.

Appl. Surf. Sci.

Appl. Catal.

thesis UCB-LYON

Z. Phys. D. Atoms Mol. Clusters

Appl. Surf. Sci.

Phys. Rev. Lett.

J. Vac. Sci. Technol.

J. Catal.

Ph.D. thesis