Effect of Co/SiO2 Single-Site Heterogeneity on Small Alkane Dehydrogenation Kinetics

Srinivas, Sanjana; Srivastava, Kaveri; Yu, Kewei; Vlachos, Dionisios G.; Caratzoulas, Stavros

doi:10.1021/acscatal.3c03273

Title: Effect of Co/SiO₂ Single-Site Heterogeneity on Small Alkane Dehydrogenation Kinetics

Journal Article · 19 November 2023 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.3c03273 · OSTI ID:2217324

^[1]; Srivastava, Kaveri ^[2];

^[2];

^[2]

Univ. of Delaware, Newark, DE (United States); University of Delaware
Univ. of Delaware, Newark, DE (United States)

Atomically dispersed, high-spin Co(II) atoms in distorted tetrahedral coordination to an amorphous silica (am-SiO₂) support, and more recently in zeolite frameworks, are active and selective for light alkane dehydrogenation. This paper investigates how variations in the geometry of the active sites affect the ethane dehydrogenation activity of atomically dispersed Co(II) on an am-SiO₂ support. We generate a distribution of sites and determine the geometric parameters that exhibit the strongest correlation with the coordination geometry and activity of the metal atom by means of linear dimensionality reduction techniques. We perform electronic structure calculations and microkinetic modeling and deduce the mechanism and kinetics for a representative sample of sites. Irrespective of the active site geometry, the rate of ethane dehydrogenation is governed by the β-hydride elimination, which involves quartet-doublet spin-crossing and proceeds adiabatically due to strong spin-orbit coupling. Informed by the complete microkinetic analysis of the sites, we derive the reduced rate expression as a function of three site-dependent quantities. We show that these site-dependent quantities correlate with the energy of formation of the ethyl intermediate that forms via C-H bond activation. This correlation allows us to derive the site-averaged rate for the entire distribution of sites. Among various sites, the tri-coordinate and planar tetra-coordinate Co sites exhibit higher Lewis acidity than the tetrahedral sites, and consequently, higher initial rates. Finally, we discuss the implications for more active catalysts.

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Research Organization:: American Institute of Chemical Engineers (AIChE), New York, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)

Grant/Contract Number:: EE0007888

OSTI ID:: 2217324

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 23 Vol. 13; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ethane dehydrogenation
amorphous silica
single atoms
spin-crossing
density-functional theory
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site-averaged kinetics

Title: Effect of Co/SiO2 Single-Site Heterogeneity on Small Alkane Dehydrogenation Kinetics

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References (36)

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Title: Effect of Co/SiO₂ Single-Site Heterogeneity on Small Alkane Dehydrogenation Kinetics