Identifying Active Sites for Stabilizing Fe-ZSM-5 for did not affect the zeolite crystalline structure of the
zeolite crystalline structure of the GSM catalyst. Initial investigation of the Fe
CO Hydrogenation
Jane N. Agwara1 and Marc Porosoff1*
1 absence of bulk Fe oxides in the Fe-Na-GSM catalyst, with 74% of the Fe present as Fe3+ (Oh/Th),
Department of Chemical Engineering, University of Rochester, Rochester, NY, USA
*marc.porosoff@rochester.edu
Introduction
Iron (Fe) is an extensively studied catalyst for CO hydrogenation to hydrocarbons
due to its abundance, low cost, and inherent activity. Supporting Fe on ZSM-5 zeolites can
improve the performance of Fe catalysts. The ZSM-5 zeolites improve the surface area of the
active Fe sites and can enhance the hydrocarbon selectivity via secondary reactions on the acid
sites of the zeolites.[1] Incipient wetness impregnation (IWI) is the traditional post-synthetic
method for Fe supported ZSM-5 catalysts, which typically results in the random deposition of
bulk Fe oxide particles, especially Fe2O3, on the external surfaces and pores of ZSM-5. During
CO hydrogenation, these Fe2O3 species are subsequently reduced and carburized to Fe carbides,
such as Fe5C2, the common active sites for CO hydrogenation to hydrocarbons. However, bulk
Fe oxide particles suffer from deactivation due to sintering, coke deposition, or Fe phase
changes.[2] The use of Na-form ZSM-5 has been found to enhance the formation of Fe carbides
and increase the stability of Fe-ZSM-5 under reaction conditions. However, the presence of Na
has also been shown to decrease the CO hydrogenation activity of the catalyst due to excess
carbides blocking the Fe active sites.[3]
Herein, we are using a one-pot grinding synthesis method (GSM),[4] where the anionic Fe
precursor is added to the synthesis medium of ZSM-5, promoting the incorporation of Fe inside
the zeolite pores during crystallization, and limiting the formation of bulk Fe oxide particles on
the zeolite external surfaces. We hypothesize that the synthesis method will result in highly
dispersed Fe species within the zeolite pores, minimizing particle agglomeration and improving
the stability of the catalyst. Structural characterizations indicates that Fe is not present as bulk
Fe oxides on the external surface of the zeolites, suggesting isolated and dinuclear Fe3+ sites are
active for CO hydrogenation.
Materials and Methods
Fe-Na-GSM was synthesized via a one-pot grinding synthesis method, with the Fe-
H-GSM synthesized via ion-exchange. Fe-Na-IWI and Fe-H-IWI controls were synthesized via
incipient wetness impregnation. All the catalysts have Si/Al equal to 15 with 4 wt% Fe loading.
The catalysts were characterized by XRD, Mössbauer, and TEM to identify the character of the
Fe within the catalysts. For reactor studies, 20 - 200 mg of catalysts was loaded into the reactor
and catalysts were reduced under hydrogen before flowing the reactant gases of H2:CO = 2 at
300 ºC and 300 psi, with GHSV 13,500 - 135,000 mL/g/h. The concentration of the products
was analyzed by an in-line Agilent gas chromatograph equipped with FID and TCD detectors.
Results and Discussion
The XRD profiles of the GSM catalysts and the IWI controls show the typical MFI
zeolites structure, indicating that incorporation of Fe precursor into the ZSM-5 synthesis medium
species using XRD shows high intensity peaks corresponding to Fe2O3 in the IWI catalyst, but
these peaks were absent in the GSM catalyst, suggesting high Fe dispersion and/or absence of
Fe2O3 bulk species. Investigating the Fe species using Mössbauer spectroscopy indicates the
22% as Fe3+ oligomers (Oh), and the rest as dinuclear Fe3+ (Oh). These Fe configurations suggest
Fe is predominantly framework Fe3+ or isolated extra-framework Fe3+ in cationic positions, in
contrast to the Fe-Na-IWI control catalyst where the Fe is predominantly Fe2O3 (data not shown).
Fe-Na-GSM has a total BET pore volume of 0.24 cm3/g, which is lower than that of Fe-Na-IWI
catalyst (0.40 cm3/g), suggesting that the Fe particles in the GSM catalysts are mostly within the
pores of the zeolite and more dispersed when compared to IWI, supporting the XRD.
Figure. Mössbauer spectra of as-synthesized Fe-Na-GSM (left), post-reaction Mössbauer
spectra of Fe-Na-GSM (center), and CO conversion vs time on stream of the catalysts (right).
For CO hydrogenation, the GSM catalysts in the Na- and H-ZSM-5 are stable throughout the
reaction. The activity of Fe-H-GSM and Fe-Na-GSM catalysts remains the same, suggesting that
the Na in Na-ZSM-5 does not affect the CO hydrogenation activity or play a role in stabilizing
the GSM catalysts. In contrast, both the IWI catalysts deactivate, with 11% and 30% deactivation
observed for the Fe-Na-IWI and Fe-H-IWI respectively. Interestingly, post-reaction Mössbauer
spectra of the Fe-Na-GSM catalyst shows that the Fe remains mostly as Fe3+ species (89%),
demonstrating carburization of the Fe within the GSM catalyst is unfavorable under reaction
conditions. Therefore, our data suggests that the enhanced stability observed over the GSM
catalysts may be caused by the resistance of the Fe3+ species to agglomeration and deactivation
perhaps due to the confinement and stabilization of Fe within cationic positions.
Significance
Fe is an abundant and cost-effective catalyst for CO conversion to valuable
hydrocarbons. However, catalyst deactivation remains a challenge for Fe supported on ZSM-5.
Identifying mechanisms for stabilizing Fe in ZSM-5 during reaction will aid the design of a low-
cost, active, selective, and stable Fe-based catalysts.
References
1. Agwara, J. N., Bakas, N. J., Neidig, M. L., et al. ChemCatChem, e202200289 (2022).
2. Lyu, S., Wang, L., Li, Z., et al. Nature communications, 11(1), 1-8 (2020).
3. Bukur, D. B., Mukesh, D., and Patel, S. A. Industrial & engineering chemistry
research, 29(2), 194-204 (1990).
4. Gu, Y., Chen, P., Wang, et al. ACS Catalysis, 11(12), 6771-6786 (2021).