Dataset Information

Controllable Deposition of Bi onto Pd for Selective Hydrogenation of Acetylene.

ABSTRACT: The rational regulation of catalyst active sites at atomic scale is a key approach to unveil the relationship between structure and catalytic performance. Herein, we reported a strategy for the controllable deposition of Bi on Pd nanocubes (Pd NCs) in the priority order from corners to edges and then to facets (Pd NCs@Bi). The spherical aberration-corrected scanning transmission electron microscopy (ac-STEM) results indicated that Bi₂O₃ with an amorphous structure covers the specific sites of Pd NCs. When only the corners and edges of the Pd NCs were covered, the supported Pd NCs@Bi catalyst exhibited an optimal trade-off between high conversion and selectivity in the hydrogenation of acetylene to ethylene under ethylene-rich conditions (99.7% C₂H₂ conversion and 94.3% C₂H₄ selectivity at 170 °C) with remarkable long-term stability. According to the H₂-TPR and C₂H₄-TPD measurements, the moderate hydrogen dissociation and the weak ethylene adsorption are responsible for this excellent catalytic performance. Following these results, the selectively Bi-deposited Pd nanoparticle catalysts showed incredible acetylene hydrogenation performance, which provides a feasible perspective to design and develop highly selective hydrogenation catalysts for industrial applications.

SUBMITTER: Kang H

PROVIDER: S-EPMC10005703 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Controllable Deposition of Bi onto Pd for Selective Hydrogenation of Acetylene.

Kang Hongquan H Wu Jianzhou J Lou Baohui B Wang Yue Y Zhao Yilin Y Liu Juanjuan J Zou Shihui S Fan Jie J

Molecules (Basel, Switzerland) 20230303 5

The rational regulation of catalyst active sites at atomic scale is a key approach to unveil the relationship between structure and catalytic performance. Herein, we reported a strategy for the controllable deposition of Bi on Pd nanocubes (Pd NCs) in the priority order from corners to edges and then to facets (Pd NCs@Bi). The spherical aberration-corrected scanning transmission electron microscopy (ac-STEM) results indicated that Bi<sub>2</sub>O<sub>3</sub> with an amorphous structure covers th ...[more]

PMID: 36903580

Similar Datasets

Project description:Zeolites, with their ordered crystalline porous structure, provide a unique opportunity to confine metal catalysts, whether single atoms (e.g., transition metal ions (TMIs)) or metal clusters, when used as a catalyst support. The confined environment has been shown to provide rate and selectivity enhancement across a variety of reactions via both steric and electronic effects, such as size exclusion and transition state stabilization. In this review, we provide a survey of various zeolite confined catalysts used for the semihydrogenation of acetylene highlighting their performance, defined by ethylene selectivity at full acetylene conversion, in relationship to the synthesis technique employed. Synthesis methods that ensure confinement with the catalyst transition metal location in the extra-framework positions are reported to have the highest selectivity to ethylene. However, the underlying molecular factors responsible for selective catalysis within confinement remain elusive due to the difficulty in deconvoluting individual effects. Through the careful use of a combination of characterization and spectroscopic methods, insights into the relationship between the properties of zeolite confined catalysts and their performance have been explored in other works for a variety of reactions. More specifically, operando spectroscopy studies have revealed the dynamic behavior of zeolite confined catalysts under various conditions implying that the structure and properties observed ex situ do not always match those of the active catalyst under reaction conditions. Applying this type of analysis to acetylene semihydrogenation, a simple gas phase reaction, can help elucidate the structure-function relationship of zeolite confined catalysts allowing for more informed design choices and consequently their application to a wider variety of more complex reactions such as the liquid phase hydrogenation of alkynols where solvent effects must also be considered in addition to those of confinement.

Project description:Metal nanoparticles, often supported on metal oxide promoters, are a cornerstone of heterogeneous catalysis. Experimentally, size effects are well-established and are manifested through changes to catalyst selectivity, activity and durability. Density Functional Theory (DFT) calculations have provided an attractive way to study these effects and rationalise the change in nanoparticle properties. However such computational studies are typically limited to smaller nanoparticles (approximately up to 50 atoms) due to the large computational cost of DFT. How well can such simulations describe the electronic properties of the much larger nanoparticles that are often used in practice? In this study, we use the ONETEP code, which is able to achieve more favourable computational scaling for metallic nanoparticles, to bridge this size gap. We present DFT calculations on entire Pd and Pd carbide nanoparticles of more than 300 atoms (approximately 2.5 nm diameter), and find major differences in the electronic structure of such large nanoparticles, in comparison to the commonly investigated smaller clusters. These differences are also manifested in the calculated chemical properties such as adsorption energies for C2H2, C2H4 and C2H6 on the pristine Pd and PdC x nanoparticles which are significantly larger (up to twice in value) for the ∼300 atoms structures. Furthermore, the adsorption of C2H2 and C2H4 on PdC x nanoparticles becomes weaker as more C is introduced in the Pd lattice whilst the impact of C concentration is also observed in the calculated reaction energies towards the hydrogenation of C2H2, where the formation of C2H6 is hindered. Our simulations show that PdC x nanoparticles of about 5% C per atom fraction and diameter of 2.5 nm could be potential candidate catalysts of high activity in hydrogenation reactions. The paradigm presented in this study will enable DFT to be applied on similar sized metal catalyst nanoparticles as in experimental investigations, strengthening the synergy between simulation and experiment in catalysis.

Dataset Information

Controllable Deposition of Bi onto Pd for Selective Hydrogenation of Acetylene.

Publications

Controllable Deposition of Bi onto Pd for Selective Hydrogenation of Acetylene.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets