Propane Dehydrogenation on Pt x Zn y Active Sites in Silicalite‐1

Liu, Yilang; Bhowmick, Antara; Liu, Dongxia; Caratzoulas, Stavros; Vlachos, Dionisios G.

doi:10.1002/anie.202414578

Propane Dehydrogenation on Pt _x Zn _y Active Sites in Silicalite‐1

Journal Article · Wed Oct 30 00:00:00 EDT 2024 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202414578· OSTI ID:2475432

Liu, Yilang ^[1]; Bhowmick, Antara ^[2]; Liu, Dongxia ^[2]; Caratzoulas, Stavros ^[1]; ^[3]

RAPID Manufacturing Institute Catalysis Center for Energy Innovation Delaware Energy Institute Center for Plastics Innovation University of Delaware 221 Academy St. Newark DE 19716 USA
Department of Chemical and Biomolecular Engineering University of Delaware 150 Academy St. Newark DE 19716 USA
RAPID Manufacturing Institute Catalysis Center for Energy Innovation Delaware Energy Institute Center for Plastics Innovation University of Delaware 221 Academy St. Newark DE 19716 USA, Department of Chemical and Biomolecular Engineering University of Delaware 150 Academy St. Newark DE 19716 USA

Abstract

The improvement of Pt‐based catalysts for propane dehydrogenation (PDH) has progressed by recent investigations that have identified Zn as a promising promoter for Pt subnanometer catalysts. It is desirable to gain insights into the structure, stability, and activity of such active sites and the factors that influence them, such as Zn : Pt ratio, Pt coordination and nuclearity. Here, we employ density functional theory and microkinetic simulations to investigate the stability of Pt _x Zn _y ( x =1–3, y=0–3) active sites grafted on silanols of Silicalite‐1 and the PDH activity of Pt. We find that the coordination of a Pt atom to a nest of grafted Zn(II) atoms increases the stability of the Pt ₁ Zn _y sites, whose activity is similar for y=0–2 and drops dramatically for y>2. We further demonstrate, via linear scaling relations and microkinetic simulations, that the turnover frequency obeys a volcano law as a function of propylene binding strength. The Pt ₂ Zn ₁ and Pt ₃ Zn ₁ sites are stable and exhibit activity similar to Pt ₁ Zn ₂ , but only Pt ₁ Zn ₂ manifests reaction kinetics consistent with experimental data, strongly suggesting the active site composition in the synthesized catalyst samples. The methodology presented here suggests a general strategy for deducing active site information such as composition through simple kinetic experiments.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: EE0010313

OSTI ID:: 2475432

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 2 Vol. 64; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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