Zinc Speciation and Propane Dehydrogenation in Zn/H-ZSM-5 Catalysts

Yuan, Yong; Lobo, Raul F.

doi:10.1021/acscatal.2c05898

Zinc Speciation and Propane Dehydrogenation in Zn/H-ZSM-5 Catalysts

Journal Article · Tue Mar 28 00:00:00 EDT 2023 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c05898· OSTI ID:2007299

^[1]; ^[2]

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

Zn/H-ZSM-5 catalysts have been frequently investigated for propane dehydrogenation (PDH); however, the active site remains unresolved due to the complexity of the system. We employed in situ FTIR spectroscopy and a kinetics method to correlate the Zn speciation and PDH activity in Zn/H-ZSM-5 with two Si/Al ratios (15 and 39) and a range of Zn/Al ratios (0–1.7). Incremental additions of zinc show that Zn²⁺ sites are preferentially formed on H-ZSM-5 over a fraction of paired Al sites followed by [Zn-O-Zn]²⁺ and [ZnOH]⁺ sites and then ZnO_x clusters. The [Zn-OH]⁺ and [Zn-O-Zn]²⁺ sites in H-ZSM-5 are more active and selective than isolated Zn²⁺ for PDH. [Zn-OH]⁺ species sublimate over time on stream, leading to catalyst deactivation, while [Zn-O-Zn]²⁺ species are stable even after high-temperature reduction (750 °C for 60 min). Three distinct Zn sites ([Zn-O-Zn]²⁺, Zn²⁺, and [ZnOH]⁺) show a similar propane reaction order (close to 1) and H₂ reaction order (close to 0). Combined with the lack of Zn hydride when propane flows over the catalyst at 550 °C, it is concluded that propane adsorption and dissociation is a rate-determining step and H₂ desorption is fast. This work indicates that the preparation of H-ZSM-5 with abundant Al pairs may be a strategy to form stable and selective Zn/H-ZSM-5 catalysts for propane dehydrogenation. Furthermore, it is also highlighted that examining the effect of both metal/Al ratios and Al distribution of the zeolite is crucial in identifying the metal cations in metal–zeolite systems.

View Accepted Manuscript (DOE)

Research Organization:: RAPID Manufacturing Institute, 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:: 2007299

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 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
Fourier transform infrared spectroscopy
Zn hydride
Zn/H-ZSM-5
Zn2+
[Zn-O-Zn]2+
[Zn-OH]+
anions
catalysts
in situ FTIR spectroscopy
oxides
paired framework Al atoms
propane dehydrogenation
pyridines

Zinc Speciation and Propane Dehydrogenation in Zn/H-ZSM-5 Catalysts

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