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DOE OSTI2021

Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

Oxidative dehydrogenation of propane to propylene can be achieved using conventional, oxygen-assisted dehydrogenation of propane (O 2 –ODHP) or via the use of soft oxidants, such as CO 2 , N 2 O, S-containing compounds, and halogens/halides. The major roles of soft oxidants include inhibiting overoxidation and improving propylene selectivity, which are considered to be current challenges in O 2 -assisted dehydrogenation. For both CO 2 – and N 2 O–ODHP reactions, significant efforts have been devoted to developing redox-active (e.g., chromium, vanadate, iron, etc.), nonredox-type main group metal oxide (e.g., group IIIA, gallium), and other transition metal/metal oxide catalysts (e.g., molybdenum, palladium platinum, rhodium, ruthenium, etc.), as well as zeolite-based catalysts with adjustable acid–base properties, unique pore structures, and topologies. Metal sulfides have shown promising performance in DHP, whereas the development of suitable catalysts has lagged for SO 2 - or S-assisted ODHP. Recently, significant efforts have been focused on homogeneous and heterogeneous ODHP using halogens (e.g., Br 2 , I 2 , Cl 2 , etc.) and hydrogen halides (e.g., HCl and HBr) for the development of facile processes for C 3 H 6 synthesis. This work aims to provide a critical, comprehensive review of recent advances in oxidative dehydrogenation of propane with these soft oxidants, especially highlighting the current state of understanding of the following factors: (i) relationships between composition, structure, and catalytic performance, (ii) effects of the support, acidity, and promoters, (iii) reaction pathway and mechanistic insights, and (iv) the various roles of soft oxidants. Theoretical and computational insights toward understanding reaction mechanisms and catalyst design principles are also covered. Future research opportunities are discussed in terms of catalyst design and synthesis, deactivation and regeneration, reaction mechanisms, and alternative approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Understanding the Correlation between Ga Speciation and Propane Dehydrogenation Activity on Ga/H-ZSM-5 Catalysts

H-ZSM-5 zeolite-supported Ga (Ga/H-ZSM-5) has been considered as a selective catalyst for nonoxidative propane dehydrogenation (PDH) for decades; however, the reaction mechanism remains a topic of considerable discussion. In particular, the correlation between various Ga species present on the catalyst at the reaction conditions and the PDH activity has yet to be established. In this work, intrinsic PDH rates and activation energies were determined on Ga + –H + pair sites and isolated Ga + sites on Ga/H-ZSM-5 samples with a wide range of Si/Al and Ga/Al ratios. Here, the turnover frequency on Ga + –H + pair sites in the PDH is higher than that of isolated Ga + sites by a factor of ~15. Experimental measurements combined with a dual-site model show the activation energy in the PDH on the Ga + –H + pair sites and isolated Ga + sites to be 90.8 ± 1.5 and 117 ± 4.7 kJ·mol –1 , respectively. These results demonstrate that Ga+–H+ pair sites are much more active in the PDH than isolated Ga + sites. The activation energy of GaH x decomposition to form H 2 was determined to be 40–60 kJ·mol –1 higher than that of the PDH on Ga species, suggesting that the GaH x decomposition is unlikely to be part of the PDH mechanism. Although both Brønsted acid and Ga sites interact with propane, Fourier transform infrared spectroscopy results provide strong evidence suggesting that the alkyl mechanism is more likely in the PDH on Ga/H-ZSM-5 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Highly Selective Oxygen Reduction to Hydrogen Peroxide on a Carbon-Supported Single-Atom Pd Electrocatalyst

Selective electrochemical two-electron oxygen reduction is a promising route for renewable and on-site H 2 O 2 generation as an alternative to the anthraquinone process. In this study, we report a high-performance nitrogen-coordinated single-atom Pd electrocatalyst, which is derived from Pd-doped zeolitic imidazolate frameworks (ZIFs) through one-step thermolysis. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with X-ray absorption spectroscopy verifies atomically dispersed Pd atoms on nitrogen-doped carbon (Pd-NC). The single-atom Pd-NC catalyst exhibits excellent electrocatalytic performance for two-electron oxygen reduction to H 2 O 2 , which shows ~95% selectivity toward H 2 O 2 and an unprecedented onset potential of ~0.8 V versus revisable hydrogen electrode (RHE) in 0.1 M KOH. Density functional theory (DFT) calculations demonstrate that the Pd-N 4 catalytic sites thermodynamically prefer *–O bond breaking to O–O bond breaking, corresponding to a high selectivity for H 2 O 2 production. This work provides a deep insight into the understanding of the catalytic process and design of high-performance 2e– ORR catalysts.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Copper Single Atom-Triggered Niobia–Ceria Catalyst for Efficient Low-Temperature Reduction of Nitrogen Oxides

To reduce nitrogen oxide (NO x ) emission from diesel engines in the cold-start process benefitting the atmospheric environment, catalysts with superior low-temperature NO x removal efficiency are highly demanded. Herein, we report an efficient Nb 2 O 5 /CuO/CeO 2 (NbCuCe) oxide catalyst for the selective catalytic reduction (SCR) of NO x , showing much higher DeNO x activity below 200 °C, superior sulfur resistance, faster response, and much less NH 3 slip than the state-of-the-art Cu-CHA zeolite catalyst. Additionally, atomically dispersed Cu species facilitate the strong interaction between Cu and the Nb/Ce base catalyst, which significantly improves the low-temperature redox properties at Cu–O–Ce sites and NH 3 adsorption/activation at Nb–O–Cu sites, thus contributing to the superior SCR performance of NbCuCe at low temperatures. The developed NbCuCe catalyst is highly promising for efficient DeNO x from cold-start diesel engines and can be coupled with Cu-CHA to achieve a broad operation temperature window.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Effect of Co/SiO 2 Single-Site Heterogeneity on Small Alkane Dehydrogenation Kinetics

Atomically dispersed, high-spin Co(II) atoms in distorted tetrahedral coordination to an amorphous silica (am-SiO 2 ) 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-SiO 2 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Effect of Strength of Soluble and Solid Acid Catalysts on Selectivity in Aldol Reactions

Aldol reactions can follow the classical condensation path and produce an α,β-unsaturated carbonyl compound and water, however in some cases, aldol chemistry may be steered towards a fission that gives an olefin and a carboxylic acid. This investigation examines how the strength of Brønsted acid sites—both in homogeneous and heterogeneous catalysis—controls these two pathways and their kinetics. The cross-aldol reaction between benzaldehyde and 3-pentanone served as test case. Batch reactions, conducted in toluene as solvent at a temperature of 140 °C under autogenous pressure, were analyzed by GC and in situ ATR-FTIR spectroscopy to determine product distributions and rate constants for condensation and fission pathways. A series of soluble acids including a family of sulfonic acids mostly favored the condensation pathway, with formic acid as the weakest in the series by its pKa being inactive for aldol chemistry. Significant amounts of fission products were rare except for the known selectivity of phosphoric acid, and the circumstances were difficult to delineate. For the sulfonic acid family, the logarithm of the first-order condensation rate constants scaled only roughly with pKa (water) values, whereas a good correlation was obtained with calculated deprotonation Gibbs energies in toluene. A series of H-forms of isomorphously substituted beta zeolites, HESiBEA with E = Al, Ga, Fe, or B, favored the fission pathway. Site density and site strength were characterized by calorimetric measurements of the heats of adsorption of isopropylamine, which decreased in the order Al > Ga, Fe > B. The logarithm of the site-normalized first-order fission rate constants scaled roughly with the heats of adsorption and correlated excellently with reported deprotonation energies. In conclusion, acid strength mainly affects activity and can be seen as a pre-requisite for either aldol condensation or fission chemistry, whereas additional, yet to be full clarified catalyst properties and reaction conditions are required to steer aldol chemistry towards fission selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Pore-Scale Microenvironments Control Anthropogenic Carbon Mineralization Outcomes in Basalt

Thin sections and hand samples from 50 sidewall cores from the Wallula Basalt Pilot Demonstration, a basaltic carbon sequestration demonstration, provided the opportunity for the in-depth analysis of carbon mineralization induced by the injection of supercritical CO 2 . In this study, we used optical petrography and scanning electron microscopy to characterize the physical and chemical characteristics of the basalt components influenced by carbon mineralization reactions from all available hand samples and thin sections within the three CO 2 injection zones and caprock flow interiors. We found extensive carbonate mineralization, mostly in the form of nodules that were shown to be chemically zoned: Ca-dominant in the core regions and Ca-bearing Fe-dominant in the outer regions. Carbonate mineralization also took the form of fracture-filling carbonate cement, and acicular aragonite was also observed. Overall, we clarified the structural and paragenetic relationships between newly formed minerals, identifying a new fibro-palagonite-like, poorly crystalline silicate phase that grew on the carbonate nodules and pore-lining zeolites. Here we observed Fe-dominant carbonate precipitates surrounding acicular aragonite and rhombohedral Ca-carbonate cores, whereas previous studies of these zoned nodules did not observe these structures. A comprehensive accounting of the carbon mineralization products is vital to understand and predict the behavior of supercritical CO 2 in the subsurface given both the diversity of the host rock between and within injection zones, especially considering that the morphology and chemistry of the diverse precipitates are influenced by the pore-scale microenvironments of the basalt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Decadal-Scale Hydrothermal Alteration of Basalt: Implications for Long-Term Reactivity in Subsurface Technologies

Global demands to secure critical mineral supply chains and managing water resources require innovative resource management strategies. Subsurface basalt reservoirs offer a dual-purpose application, where CO2 enhanced critical metal recovery can be coupled with water remediation strategies for the extraction of economically important and environmentally relevant elements. This study utilizes static batch experiments conducted on Columbia River Basalt Group samples to evaluate long-term fluid–rock interactions relevant to coupled subsurface applications. Samples were reacted under elevated temperature and pressure conditions, for 296 and 4,061 days, providing a unique dataset to assess geochemical evolution, element partitioning, and aqueous chemistry over decadal timescales. The alteration was dominated by silicate, aluminosilicate, and oxide phases. Progressive hydrothermal alteration increased the cation exchange capacity through the formation of secondary minerals (e.g. clays and zeolites), influencing solute retention, ion exchange behavior, and aqueous chemistry. Grain-scale and bulk analyses revealed selective cation release and retention patterns, establishing a mechanistic baseline for predicting element mobility. These geochemical constraints inform the prospective use of CO2-enhanced metal recovery for critical resources (e.g. Co, Ni, Mn, Mg, Ti, Fe) and associated water-quality impacts, providing a foundation for the design and management of engineered fluid–rock systems in basalt reservoirs.

Gibson, Marie N.↗

DOE OSTI2024

Tandem Electrocatalytic–Thermocatalytic Conversion of CO 2 to Aromatic Hydrocarbons

The reaction of CO 2 with H 2 O to produce aromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylene isomers) (BTEX) represents a promising pathway for converting CO 2 to value-added liquid products. However, this reaction cannot be achieved in a single electrochemical or thermochemical process. This work utilizes tandem electrochemical-thermochemical reactors as a new paradigm by starting with CO 2 and H 2 O as the feed in a membrane electrode assembly (MEA) to produce C 2 H 4 , which subsequently undergoes thermochemical aromatization using a Gallium- and Phosphorus-modified zeolite ZSM-5 catalyst (Ga/ZSM-5/P) at ambient pressure to produce BTEX. The current study also demonstrates the potential advantage of the tandem strategy in mitigating negative effects of water by testing the tandem reactor system under different hydration conditions and by performing in-situ X-ray diffraction (XRD) and X-ray absorption (XAS) characterization of the aromatization catalysts. Finally, these results highlight the advantage of using the tandem process with the use of a water trap before the thermochemical reactor.

10 SYNTHETIC FUELS↗

DOE OSTI2024

Tailoring-Orientated Deposition of Li 2 S for Extreme Fast-Charging Lithium–Sulfur Batteries

Precipitation/dissolution of insulating Li 2 S has long been recognized as the rate-determining step in lithium-sulfur (Li-S) batteries, which dramatically undermines sulfur utilization at elevated charging rates. Herein, we present an orientated Li 2 S deposition strategy to achieve extreme fast charging (XFC, ≤15 min) through synergistic control of porosity, electronic conductivity, and anchoring sites of electrode substrate. Via magnesiothermic reduction of a zeolitic imidazolate framework, a nitrogen-doped and hierarchical porous carbon with highly graphitic phase was developed. This design effectively reduces interfacial resistance and ensures efficient sequestration of polysulfides during deposition, leading to (110)-preferred growth of Li 2 S nanocrystalline between (002)-dominated graphitic layers. Our approach directs an alternative Li 2 S deposition pathway to the commonly reported lateral growth and 3D thickening growth mode, ameliorating the electrode passivation. Therefore, a Li-S cell capable of charging/discharging at 5C (12 min) while maintaining excellent cycling stability (82% capacity retention) for 1000 cycles is demonstrated. In conclusion, even under high S loading (8.3 mg cm -2 ) and low electrolyte/sulfur ratio (3.8 mL mg -1 ), the sulfur cathode still delivers a high areal capacity of >7 mAh cm -2 for 80 cycles.

25 ENERGY STORAGE↗

DOE OSTI2026

Polymer-Derived Amorphous Aluminosilicate Nanomembranes for H 2 Purification

Aluminosilicate zeolite membranes with robust microporous crystalline structures are attractive for the molecular separation of H 2 from light gases, but their large-scale fabrication is complicated and costly, hindering their practical applications. Herein, we present polymer-derived amorphous aluminosilicate nanomembranes that combine the exceptional processability of polymers with the superior gas separation properties of aluminosilicates. Specifically, thin-film composite membranes comprising 150 nm polydimethylsiloxane were first treated with oxygen plasma to generate 10 nm polyorganosilica (POSi) on the surface, which were then subjected to few-cycle atomic layer deposition (ALD) using trimethylaluminum as a metal precursor and water vapor as a coreactant. This scalable two-step process yields few-nanometer amorphous aluminosilicates with strong size-sieving ability. For example, three-cycle ALD treatment of POSi increases H 2 /CO 2 selectivity from 39 to 200 and H 2 /CH 4 selectivity from 190 to 500, while decreasing H 2 permeance from 990 to 210 GPU at 150 °C, superior to the state-of-the-art membranes. In conclusion, rapid and scalable manufacturing of amorphous aluminosilicate nanolayers can also be of interest for catalysis and adsorption applications.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Renewable Activated Carbon Sorbent for the Desulfurization of Liquid Fuels

In recent years, significant efforts have been devoted to the reduction of sulfur levels in transportation fuels in order to reach regulatory limits and reduce the emission of harmful SO x into the atmosphere. In particular, adsorptive desulfurization (ADS) has the potential to produce zero-sulfur fuels without the need for a high energy intensity process, high H 2 pressure, and long process times as in the case of other technologies such as hydrodesulfurization. In this work, we have demonstrated the effectiveness of renewable activated carbons derived from food waste (FWAC) for the ADS of model jet and diesel fuels. The optimal FWAC materials were those fabricated to maximize the micropore volume, providing available sites for the adsorption of dibenzothiophene (DBT) and dimethyldibenzothiophene (DMDBT). The FWAC had a greater sulfur adsorption capacity than commercial AC, Y zeolite sorbents, and AC derived from other biomass sources including miscanthus, coconut shell, and walnut shell. Elemental analysis suggests that the inorganic impurities inherent in food waste, notably K, Ca, P, and Na, may contribute to its improved sulfur adsorption compared to other AC materials. Microscopy and X-ray diffraction studies further demonstrated the presence of inorganic species on FWAC that may provide active sites for the chemisorption of sulfur molecules.

Adsorption↗

DOE OSTI2024

Catalytic Deconstruction of Ethylene Vinyl Acetate Copolymer and Polyethylene Mixtures via Hydroconversion: Challenges and Solutions

We explore hydrogenolysis over ruthenium supported on zirconia (Ru/ZrO 2 ) and hydrocracking over platinum (Pt) supported on zeolites as an effective end-of-life strategy for ethylene vinyl acetate (EVA)–a widely used performance heat sealant in hard-to-recycle multilayer packaging. For Ru/ZrO 2 hydrogenolysis, EVA reacts slower than low-density polyethylene (LDPE) and the catalyst deactivates due to carbonaceous deposits originating from polyenes generated in situ during EVA thermal degradation. High H 2 pressures and temperatures can overcome catalyst deactivation; however, CH 4 yields are excessive due to cascade hydrogenolysis stemming from strong C=C/metal interactions. Polyene hydrogenation allows chains anchored by C=C to desorb from Ru, shifting product selectivity from CH 4 to higher-value liquids. Hydrogenolysis of mixed EVA and linear low-density polyethylene (LLDPE), mirroring typical frozen food packaging formulations, results in comparable catalyst activity and CH 4 yield as the pure EVA resin. For Pt/zeolite hydrocracking, pure EVA and EVA:LLDPE mixtures are deconstructed to propane or light naphtha with minimal CH 4 production. Among catalysts tested, Pt/HY gives the highest liquid productivity (g C5+products /g cat ·h). Furthermore, these findings showcase the recalcitrant nature of EVA and its associated mixtures for Ru/ZrO 2 hydrogenolysis, highlighting that hydrocracking catalysts may be superior for complex packaging waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Techno-Economic and Life Cycle Assessment of Chemical Recycling and Upcycling of Mixed Plastics Waste Containing Poly-vinyl-chloride

Developing technologies that completely remove chlorine from plastic waste can allow its chemical recycling and upcycling with catalytic methods. Here, this study compares eight processes involving different dechlorination methods (absorption columns, adsorption in beds of zeolites, catalytic dechlorination, and dissolution in ionic liquids) and chemical conversion technologies (incineration, pyrolysis, hydrogenolysis) to upgrade mixed plastics waste to various products (e.g., electricity, fuels, virgin polymers, and lubricant oil). The analysis determines that the absorption of chlorine in columns with basic aqueous solutions is limited to plastics waste with PVC concentrations below 0.1%. Dissolution in ionic liquids is not cost-competitive. On the contrary, two-step processes with catalytic dechlorination followed by thermochemical catalytic depolymerization, either pyrolysis or hydrogenolysis, significantly improve process economics and emissions. The most economically viable alternative is hydrogenolysis for producing lubricants, while the technology with the lowest global warming potential is chemical recycling via catalytic pyrolysis.

circular economy↗

DOE OSTI2020

Isotopic Studies for Tracking Biogenic Carbon during Co-processing of Biomass and Vacuum Gas Oil

Co-processing bio-oils with petroleum-derived feeds in the existing multitrillion dollar refining and distribution infrastructure is an attractive option for introducing renewable energy into the fuels marketplace. Considerable research on co-processing bio-oils and vacuum gas oil (VGO) in fluid catalytic cracking units (FCC) using equilibrium catalysts (E-Cats) demonstrated that biomass-derived molecules decreased activity of and increased carbon laydown on E-Cat. In this work, 13 C-labeled biomass was co-processed with VGO using either an E-Cat or a proprietary zeolite Johnson Matthey catalyst (CP758), which is optimzed for upgrading biomass vapors in a riser reactor, to evaluate the fate of biogenic carbon in FCC products. The results from both catalysts indicate that biogenic carbon was incorporated into alkenes and aromatic hydrocarbons. While no biogenic carbon was found in linear alkanes, it was observed in cycloalkanes during experiments with E-Cat but not with CP758. All produced CO2 was biogenic as was most of the carbon laydown on the catalysts. Several partially deoxygenated biomass compounds, such as alkylphenols and benzofurans, unexpectedly contained small amounts of carbon from VGO. Although this study was conducted with labeled biomass and not bio-oil, it provides insights to reaction mechanisms for co-processing bio-oil and VGO in an FCC, which is required to develop catalysts that efficiently convert bio-oil components during FCC co-processing. This work also demonstrates that comprehensive catalyst development utilizing both biomass- and fossil-derived feeds is required to maximize the incorporation of biogenic carbon into transportation fuels.

09 BIOMASS FUELS↗

DOE OSTI2021

Observation of an Intermediate to H 2 Binding in a Metal–Organic Framework

Coordinatively unsaturated metal sites within certain zeolites and metal–organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H 2 at the trigonal pyramidal Cu + sites in the metal–organic framework Cu I -MFU- 4 l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. Here, the activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu + coordination environment that enhances p-backbonding with H 2 . Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores—referred to as “microporous water”—enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components—including catalysts, proteins, and cells—while retaining as much of their internal pore volume as possible. Here, in this work, we establish design principles for the noncovalent surface functionalization of hydrophobic metal–organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O 2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal–organic framework particles in aqueous environments to augment the properties of microporous water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Effects of Cofeeding Hydrogen on Propane Dehydrogenation Catalyzed by Isolated Iron Sites Incorporated into Dealuminated BEA

Iron sites dispersed on nonacidic siliceous supports have been reported to be catalytically active for propane dehydrogenation (PDH), yet the precise relationship between site structure and catalytic activity remains elusive. Here, this study provides a comprehensive understanding of the catalytic performance of iron supported on dealuminated BEA (DeAlBEA) zeolites for PDH. Using XAS, UV-vis, and IR spectroscopy of adsorbed pyridine and deuterated acetonitrile, it was found that, at an Fe/Al 0 of 0.04, isolated Fe sites form. These isolated sites exhibit a forward rate of PDH of 213 mol propene/mol Fe·h at 823 K and a feed containing 15 kPa propane. When 15 kPa of H 2 is added to the feed, the forward rate of PDH rises to 391 mol of propene/mol of Fe·h. In both cases, the propene selectivity is over 99%. IR spectroscopy of d 3 -acetonitrile suggests that the open Lewis acid site ((-Si-O-) 2 Fe 3+ -OH) serves as the active site responsible for PDH, while Brønsted acid sites (≡Fe 3+ -O(H)-Si≡) contribute to propane cracking with increasing Fe/Al 0 ratios. Kinetic analysis of the effects of H 2 addition to the propane feed on PDH kinetics shows that H 2 enhances the activity of 0.04FeDeAlBEA primarily by enhancing the strength of the propane adsorption.

Alghannam, Afnan [University of California, Berkel↗