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Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation

Olumide Bolarinwa Ayodele, Rongsheng Cai, Jianguang Wang, Yasmine Ziouani, Zhifu Liang, Maria Chiara Spadaro, Kirill Kovnir, Jordi Arbiol, Jaakko Akola, Richard Palmer Orcid Logo, Yury V. Kolen’ko

ACS Catalysis, Volume: 10, Issue: 1, Pages: 451 - 457

Swansea University Author: Richard Palmer Orcid Logo

Abstract

Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic app...

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Published in: ACS Catalysis
ISSN: 2155-5435 2155-5435
Published: American Chemical Society (ACS) 2020
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa53132
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Abstract: Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic approach using density functional theory (DFT) to identify the best catalyst in a Cu–Pt system. The DFT results showed that with a 55 atom system at ∼1.1 Pt/Cu ratio for Pt28Cu27/Al2O3, the d-band center shifted −2.2 eV relative to the Fermi level leading to electron-saturated Pt, which allows only adsorption of ethylene via a π-bond, resulting in theoretical 99.7% SC2H4 at nearly complete XC2H2. Based on the DFT results, Pt–Cu/Al2O3 (PtCu) and Pt/Al2O3 (Pt) nanocatalysts were synthesized via cluster beam deposition (CBD), and their properties and activities were correlated with the computational predictions. For bimetallic PtCu, the electron microscopy results show the formation of alloys. The bimetallic PtCu catalyst closely mimics the DFT predictions in terms of both electronic structure, as confirmed by X-ray photoelectron spectroscopy, and catalytic activity. The alloying of Pt with Cu was responsible for the high C2H4 specific yield resulting from electron transfer between Cu and Pt, thus making PtCu a promising catalyst for SHA.
Keywords: microkinetic model, hydrogenation, nanoclusters, alloys, cluster beam deposition
Issue: 1
Start Page: 451
End Page: 457