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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Atomic Layer Deposition Overcoating Improves Catalyst Selectivity and Longevity in Propane Dehydrogenation

Propylene, a precursor for commodity chemicals and plastics, is produced by propane dehydrogenation (PDH). An increase in PDH yield via added catalyst activity, lifetime, or selectivity represents significant energy and economic savings. Using Pt dispersed on Al2O3 extrudate supports as a commercially relevant model system, we demonstrate that atomic layer deposition (ALD) metal oxide overcoats, used to tailor metal-active sites, can increase PDH yield and selectivity. We investigate the interplay of Pt loading, ALD overcoat thickness, and Al 2 O 3 support surface area on PDH activity, selectivity, and catalyst stability to show that applying a 6-8 A thick layer of Al 2 O 3 on low-surface area Al 2 O 3 supports of similar to 90 m 2 /g surface area yields the optimal combination of stability and activity, while increasing propylene selectivity from 91 to 96%. Increased stability upon steaming deactivation occurs because the Al 2 O 3 overcoat prevents the Pt nanoparticles from sintering. We speculate that the ALD overcoat selectively binds to the undercoordinated sites on the Pt nanoparticles, while leaving the more selective terrace sites available for dehydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Single-Atom Manganese-Based Catalysts for the Oxidative Dehydrogenation of Propane

Combinatorial screening of 150 supported metal oxide (manganese and additives) catalysts was carried out via a high-throughput synthesis platform and parallel reactors for the oxidative dehydrogenation (ODH) of propane to propylene. Specifically, an organomanganese (0.05-2.5 Mn atoms/nm 2 ) complex was grafted on metal oxide supports (Al 2 O 3 , SiO 2 , TiO 2 , and ZrO 2 ) premodified with either Lewis acid (Al, Ti, Zn, and Zr) or redox-active (Cu, Cr, Ga Ni, V) additives at various surface coverages (25, 50, and 75%). Catalysts were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and UV-vis spectroscopy. Catalysts 0.05 Mn/V(50%)/Al 2 O 3 and 0.05 Mn/Ni(50%)/ZrO 2 showed the highest combined propane conversion and propylene selectivities (31/41% and 15/85%), with excellent stability at 500 degrees C for 25 h. The presence of Ni in Mn/Ni/ZrO 2 resulted in a 6-fold increase in turnover frequency (TOF) over the Mn/ZrO 2 . HRTEM identified single Mn atoms after 500 degrees C heat treatment. For the Mn/Ni/ZrO 2 system, Mn was incorporated into the support lattice due to the similar ionic radius of Mn 2+ and Zr 4+ , which was also enhanced by the presence of Ni. For the Mn/V/Al 2 O 3 system, highly active MnO was prevalent as observed by Raman. Both V and Mn contributed to an increase in mutual dispersion, but both species remained on the surface. Finally, it is proposed that the highly dispersed atom and interactions between Mn with either Ni or V are responsible for the ODH performance and stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Dynamic Behavior of Pt Multimetallic Alloys for Active and Stable Propane Dehydrogenation Catalysts

Improving the use of platinum in propane dehydrogenation catalysts is a crucial aspect to increasing the efficiency and sustainability of propylene production. A known and practiced strategy involves incorporating more abundant metals in supported platinum catalysts, increasing its activity and stability while decreasing the overall loading. Here, using colloidal techniques to control the size and composition of the active phase, we show that Pt/Cu alloy nanoparticles supported on alumina (Pt/Cu/Al 2 O 3 ) displayed elevated rates for propane dehydrogenation at low temperature compared to a monometallic Pt/Al 2 O 3 catalyst. We demonstrate that the enhanced catalytic activity is correlated with a higher surface Cu content and formation of a Pt-rich core and Cu-rich shell that isolates Pt sites and increases their intrinsic activity. However, rates declined on stream because of dynamic metal diffusion processes that led to a more uniform alloy structure. This transformation was only partially inhibited by adding excess hydrogen to the feed stream. Instead, cobalt was introduced to provide trimetallic Pt/Cu/Co catalysts with stabilized surface structure and stable activity and higher rates than the original Pt/Cu system. In conclusion, the structure–activity relationship insights in this work offer improved knowledge of propane dehydrogenation catalyst development featuring reduced Pt loadings and notable thermal stability for propylene production.

Alloys↗
DOE OSTI2026

Systematic Catalyst Variation for Improved Stereoselective Epoxide Polymerization: Subtle Modifications Resulting in Superior Efficiency

Isotactic poly(propylene oxide) (iPPO) is a semicrystalline polyether that has emerged as a high-strength, photodegradable material for marine applications. To improve the accessibility of i PPO, catalysts with higher activity and selectivity are required. Using rational catalyst design informed by computational insights, we developed a flexibly tethered, bimetallic chromium catalyst exhibiting high enantioselectivity ( k rel ∼ 100) and unprecedented activity (TOF ∼ 50,000 h −1 ) for propylene oxide (PO) polymerization. Mechanistic studies reveal that high enantioselectivity originates from increased steric bulk at the ortho position of the salicylimine moiety, which increases steric repulsion between the alkoxide chain end and the ligand in the disfavored transition state. Furthermore, introducing geminal dimethyl groups that rigidify the flexible tether between the two ligand moieties significantly enhances catalyst activity by destabilizing the resting state during polymerization. The catalyst remains active at loadings as low as 0.5 ppm, enabling the synthesis of colorless, tough i PPO.

Ren, Bai-Hao [Cornell Univ., Ithaca, NY (United St↗
DOE OSTI2024

Confining platinum clusters in indium-modified ZSM-5 zeolite to promote propane dehydrogenation

Designing highly active and stable catalytic sites is often challenging due to the complex synthesis procedure and the agglomeration of active sites during high-temperature reactions. Here, we report a facile two-step method to synthesize Pt clusters confined by In-modified ZSM-5 zeolite. In-situ characterization confirms that In is located at the extra-framework position of ZSM-5 as In + , and the Pt clusters are stabilized by the In-ZSM-5 zeolite. The resulting Pt clusters confined in In-ZSM-5 show excellent propane conversion, propylene selectivity, and catalytic stability, outperforming monometallic Pt, In, and bimetallic PtIn alloys. The incorporation of In + in ZSM-5 neutralizes Brønsted acid sites to inhibit side reactions, as well as tunes the electronic properties of Pt clusters to facilitate propane activation and propylene desorption. The strategy of combining precious metal clusters with metal cation-exchanged zeolites opens the avenue to develop stable heterogeneous catalysts for other reaction systems.

58 GEOSCIENCES↗
DOE OSTI2020

Structural trends in the dehydrogenation selectivity of palladium alloys

Alloying is well-known to improve the dehydrogenation selectivity of pure metals, but there remains considerable debate about the structural and electronic features of alloy surfaces that give rise to this behavior. To provide molecular-level insights into these effects, a series of Pd intermetallic alloy catalysts with Zn, Ga, In, Fe and Mn promoter elements was synthesized, and the structures were determined using in situ X-ray absorption spectroscopy (XAS) and synchrotron X-ray diffraction (XRD). The alloys all showed propane dehydrogenation turnover rates 5–8 times higher than monometallic Pd and selectivity to propylene of over 90%. Moreover, among the synthesized alloys, Pd 3 M alloy structures were less olefin selective than PdM alloys which were, in turn, almost 100% selective to propylene. This selectivity improvement was interpreted by changes in the DFT-calculated binding energies and activation energies for C–C and C–H bond activation, which are ultimately influenced by perturbation of the most stable adsorption site and changes to the d-band density of states. Furthermore, transition state analysis showed that the C–C bond breaking reactions require 4-fold ensemble sites, which are suggested to be required for non-selective, alkane hydrogenolysis reactions. These sites, which are not present on alloys with PdM structures, could be formed in the Pd 3 M alloy through substitution of one M atom with Pd, and this effect is suggested to be partially responsible for their slightly lower selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Overcoming limitations in propanedehydrogenation by codesigning catalyst-membrane systems

Propylene production through propane dehydrogenation (PDH) is endothermic, and high temperatures required to achieve acceptable propane conversions lead to low selectivity and severe carbon-induced deactivation of conventional catalysts. We developed a catalyst-membrane system that removes the hydrogen by-product and can thus achieve propane conversions that exceed equilibrium limits. In this codesigned system, a silica/alumina (SiO 2 /Al 2 O 3 ) hollow-fiber hydrogen membrane was packed with a selective platinum-tin (Pt 1 Sn 1 /SiO 2 ) PDH catalyst on the tube side with hydrogen diffusing from the tube to the shell side. We demonstrate that the catalyst-membrane system can achieve propane conversions >140% of the nominal equilibrium conversion with a propylene selectivity >98% without deactivation of the system components. Here, we also show that by introducing oxygen on the shell side of the catalyst-membrane system, we can couple the endothermic PDH reaction on the tube side with exothermic hydrogen oxidation on the shell side. This coupling results in higher rates of hydrogen transport, leading to further enhancements in the propane conversion as well as desired thermoneutral system operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Zeolitic Imidazolate Framework Membranes: Novel Synthesis Methods and Progress Toward Industrial Use

In the last decade, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes. In this review, we highlight unique structural properties of ZIFs that allow them to achieve certain important separations, like that of propylene from propane, and summarize the state of the art in ZIF thin-film deposition on porous substrates and their modification by postsynthesis treatments. We also review the reported membrane performance for representative membrane synthesis approaches and attempt to rank the synthesis methods with respect to potential for scalability. To compare the dependence of membrane performance on membrane synthesis methods and operating conditions, we map out fluxes and separation factors of selected ZIF-8 membranes for propylene/propane separation. Finally, we provide future directions considering the importance of further improvements in scalability, cost effectiveness, and stable performance under industrially relevant conditions.

Chemistry↗
DOE OSTI2021

A Theoretical Model for Computing Freezing Point Depression of Lithium-Ion Battery Electrolytes

Reliable prediction of freezing point depression in liquid electrolytes will accelerate the development of improved Li-ion batteries which can operate in low temperature environments. In this work we establish a computational methodology to calculate activity coefficients and liquidus lines for battery-relevant liquid electrolytes. Electronic structure methods are used in conjuction with classical molecular dynamics simulations and theoretical expressions for Born solvation energy, ion-atmosphere effects from Debye-Hückel theory and solvent entropic effects. The framework uses no a priori knowledge beyond neat solvent properties and the concentration of salt. LiPF 6 in propylene carbonate (PC), LiPF 6 in dimethyl carbonate (DMC) and LiClO 4 in DMC are investigated up to 1 molal with accuracy better than 3 °C when compared to experimental freezing point measurements. Finally, we find that the difference in freezing point depression between the propylene carbonate-based electrolyte and the dimethyl carbonate electrolytes originates from the difference in the solvent dielectric constant.

25 ENERGY STORAGE↗
DOE OSTI2024

Liquid Piston with Spray Cooling Near-Isothermal Compressor

The goal of this project was to prototype and characterize the performance of a liquid-piston spray-cooled gas compressor. The working principle of the compressor enables optimized high-efficiency operation over a very wide range of operating conditions, unlike conventional compressors that are optimized for a narrow range of operating conditions. The compressor technology is suitable for many applications, such as gas pipeline transport, gas storage, and commercial and residential heat pumps. Both physical testing and computational fluid dynamics (CFD) modeling of the processes using the Oak Ridge National Laboratory high-performance computing center were completed. The experimental and CFD studies focused on a near-isothermal liquid-piston compressor (LPC) that uses propylene glycol to compress CO 2 . The first prototype demonstrated isothermal operation during several sequentially executed cycles of CO 2 compression and raised the temperature of the compressed CO 2 by only 2 K, compared with approximately 6 K when the gas was compressed non-isothermally. Isothermal operation was demonstrated at CO 2 flow rates of up to 2 L/min. The second prototype was designed with two compression chambers to allow continuous flow of high-pressure CO 2 . However, the design of the valve train to direct flow between the compression chambers was not sufficient to allow demonstration of CO 2 compression. Numerical simulations of the LPC in which the compression chamber was filled with propylene glycol injected from the bottom inlet were performed using large eddy simulation (LES) with the wall-adapting local eddy-viscosity subgrid-scale model coupled with the multiphase volume of fluid (VOF) model to simulate the transient interface between gas and liquid and to capture the heat and mass transfers within the compression chamber. In this effort, the effects of boundary conditions applied to the LES-VOF calculations (i.e., no wall, an adiabatic wall, and a wall with a heat flux subscribed) on the overall pressure and temperature of the CO 2 gas as well as the transient evolution of flow and heat transfer within the compression chamber were investigated and are discussed in this report. The LES calculation with no wall showed no dynamical flow patterns, and the volume-averaged temperature of CO 2 increased from 305 to 392.7 K, whereas LES calculations with a constant wall temperature or a wall heat flux had similar increases of CO 2 temperatures. The results of the LES simulation using a wall heat flux showed different stages in the compression process and revealed dynamical formation and interaction of CO 2 gas layers and circulation flow patterns within the chamber that contributed to the overall heat transfer between the solid wall, gas, and liquid surface in the compressor. Though an industrial partnership for commercializing the compressor was not secured, the technology was attractive for an industrial partner to use in two research proposals in response to US Department of Energy funding opportunity announcements.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Kinetic and Mechanistic Understanding of Boron-Containing Catalysts for the Production of Light Olefins through Selective Oxidation

In recent years, an abundance of natural gas obtained from shale deposits has created opportunities for the US chemical industry to establish new and more efficient processes for the production of chemical intermediates and polymers. For example, the replacement of petroleum-derived naphtha as a to shale-derived ethane as feedstocks has made the production of ethylene/polyethylene less costly. However, this shift in feedstock has led to lower production of propylene from steam crackers, and new “on-purpose” light olefin production technologies have been implemented to bridge the gap between propylene supply and demand. The most important of these processes is direct propane dehydrogenation (PDH), but catalyst deactivation and high temperatures lead to high capital and operating costs. Oxidative dehydrogenation of propane (ODHP) is an efficient alternative to PDH, but high selectivity to CO2 from previous metal oxide catalyst prevents implementation. Hexagonal boron nitride (hBN) and other boron-containing materials have been recently developed as highly selective catalysts for both ODHP and oxidative cracking, surpassing previous systems. Much is still unknown in regard to the mechanism and the dynamic surface changes that occur under reaction conditions. This research project aims to combine in situ/operando spectroscopic investigation and kinetic studies to elucidate the interplay between the proposed gas-phase mechanism and the surface structures on the working catalyst. These insights will be leveraged to create a framework for optimizing reaction conditions and material synthesis for the next generation of boron-containing selective oxidation catalysts.

02 PETROLEUM↗
DOE OSTI2022

Initial Design and Experimental Results of a Novel Near-Isothermal Compressor for Heat Pump Applications

In efforts to increase the efficiency of residential and commercial air conditioners and heat pumps, it is found that the compressor has the highest electrical energy usage of the system. Therefore, it is appropriate to try to increase the efficiency of this component to reduce its energy usage. Another challenge with heat pump design is that some compressor types have drawbacks that make modulation difficult. To answer these challenges, we are developing an isothermal liquid compressor. The compressor uses propylene glycol to compress carbon dioxide. In the compression chamber the propylene glycol can enter either from the bottom to create a liquid piston for compression or it can enter through a spray nozzle at the top of the chamber. In the latter case, heat transfer from the gas to be compressed to the liquid droplets is high. This allows near isothermal operation of the compressor, which increases the efficiency by 17% to 30%, compared to adiabatic compression. In addition, the isothermal liquid compressor enables very efficient and simple part load modulation.Experimental results demonstrating the operation of the liquid compressor are presented. Initial data demonstrated a temperature rise of 7 K at pressure ratios of almost 4. For comparison at the same initial pressure, temperature, and pressure ratio, adiabatic compression would result in a temperature increase of approximately 70 K. Plotting data on a P-h diagram demonstrates that the compression started at superheated state and ended in supercritical state. Testing was later performed with repeated compressions in the superheated region of the P-h diagram at liquid flow rates of 2 x 10-3 m3/min and 2 x 10-3 m3/min to understand the limitations of the prototype for use with an actual heat pump system. This work demonstrated a novel cycle on a T-s diagram. Results from this work will be used to develop a second-generation prototype where more rapid cycling is possible.

Kowalski, Steve↗
DOE OSTI2020

Accelerated Aging and Evaluation of Hose-In-Hose Transfer Lines in the Hanford Waste Transfer System - 20312

Nonmetallic materials are used in the United States Department of Energy's Hanford Site Tank Farm waste transfer system. These materials include the inner primary hoses in the hose-in-hose transfer lines (HIHTLs), Garlock{sup R} gaskets, ethylene propylene diene monomer (EPDM) O-rings, and other nonmetallic materials. These nonmetallic materials are exposed to β and γ radiation, caustic solutions as well as high temperature and pressure stressors. How the nonmetallic components react to each of these stressors individually has been well established. However, simultaneous exposure of these stressors has not been evaluated and is of great concern to Hanford Site engineers. Florida International University's Applied Research Center engineers worked closely with key Hanford's Washington River Protection Solutions personnel to develop an experimental test plan that determines how these nonmetallic components react to various simultaneous stressor exposures. In this paper, research on the experimental testing of the hose-in-hose transfer lines used in the Hanford tank farm waste transfer system under simultaneous stressor exposures is presented. The stressor exposure experiments consisted of various combinations of simultaneous stressor exposure of caustic solution, high temperature and high pressure stressors. Research efforts focused on evaluating the aging behavior of EPDM by exposing samples of HIHTLs as well as EPDM dog bone shaped specimens to a 25% NaOH solution at (38 deg. C), operating (54 deg. C) and design temperatures (77 deg. C) for 6 months and 12 months. In addition, HIHTL and the EPDM dog-bone specimens were exposed to only hot water at 77 deg. C for a duration of one year. The mechanical and material properties of the samples were characterized and compared with those of the unexposed samples (baseline). Evaluations included burst pressure tests of the EPDM hose-in-hose transfer lines and material tensile strength test of EPDM dog-bone coupons. Both the tensile strength of the EPDM material dog bones and the burst pressure of the HIHTLs significantly decreased with the increasing temperature and increasing exposure time. When compared with the baseline samples, the burst pressure decreased by 28.75% for the sample aged at 77 deg. C after 12 months, in comparison to sample aged at 38 deg. C and 54 deg. C which had about 1.34% and 5.70% loss in burst pressures, respectively, after 12-month exposure. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Long-term cyclability of Li 4 Ti 5 O 12 /LiMn 2 O 4 cells using carbonate-based electrolytes for behind-the-meter storage applications

Li 4 Ti 5 O 12 /LiMn 2 O 4 (LTO/LMO) chemistry was evaluated as a potential candidate for behind-the-meter storage (BTMS) applications. Its long-term cycle performance at 45 °C was tested using ethylene carbonate (EC) and propylene carbonate (PC) solvent electrolytes. Over 1000 cycles, LTO/LMO cells exhibited ~80% capacity retention and Coulombic efficiency higher than 99.96%. Electrochemical test results showed the major degradation mode of LTO/LMO cells arises from continuous electrolyte decomposition at the LTO anode and loss of Li inventory. EC and PC electrolytes created distinct surface layers, where the EC reduction products were more effective in passivating the LTO electrode surface. Dissolution and migration of Mn from the cathode was probed as Mn 2+ species distributed throughout the surface layer at the anode. By utilizing a prelithiated LTO electrode, the LTO/LMO cell performance was significantly enhanced with EC electrolyte. On the other hand, PC electrolyte resulted in accelerated electrolyte decomposition at the lithiated LTO surface due to the lack of surface passivation. Thus, mitigating parasitic reactions at the LTO electrode is the key to developing successful LTO/LMO cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry

Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. In this paper, we report a series of silica-supported tungsten and molybdenum dimers (X 3 M≡MX 3, where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the M≡M triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers become active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Pore-Space Partition and Optimization for Propane-Selective High-Performance Propane/Propylene Separation

The development of effective propane (C 3 H 8 )-selective adsorbents for the purification of propylene (C 3 H 6 ) from C 3 H 8 /C 3 H 6 mixture is a promising alternative to replace the energy-intensive cryogenic distillation. However, few materials possess the dual desirable features of propane selectivity and high uptake capacity. Here, we report a family of pore-space-partitioned crystalline porous materials (CPM) with remarkable C 3 H 8 uptake capacity (up to 10.9 mmol/g) and the highly desirable, yet uncommon C 3 H 8 selectivity (up to 1.54 at 0.1 bar and 1.44 at 1bar). The selectivity-capacity synergy endows them with record-performing C 3 H 8 /C 3 H 6 separation potential (i.e., C 3 H 6 recovered from the mixture). Moreover, these CPMs exhibit outstanding properties including high stability, low regeneration energy, and multi-modular chemical and geometrical tunability within the same isoreticular framework. Furthermore, the high C 3 H 8 /C 3 H 6 separation performance was further confirmed by the breakthrough experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Identifying Boron Active Sites for the Oxidative Dehydrogenation of Propane

Oxidative dehydrogenation of propane (ODHP) to propylene could have a significant impact on the production of this critical chemical intermediate, if appropriate catalysts can be discovered. Recently, heterogeneous catalysts based on boron (oxides and nitrides) have been demonstrated to be promising for ODHP, but their active sites have not been conclusively identified. Here, we report that the deposition of differently sized boronic acids into the micropores of silica supports results in different distributions of surface borate species after calcination. Furthermore, these materials, in turn, display a wide range of rates in ODHP but similar selectivity, suggesting that they differ only in the numbers of active sites. Features identified by in situ Raman, IR, and magic-angle-spinning 11 B solid-state NMR spectroscopies are compared to catalyst activity. This correlation identifies the S2 borate species, a hydroxylated nonring boron, as the likely active site and provides a target for directed syntheses of future catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ga + -Chabazite Zeolite: A Highly Selective Catalyst for Nonoxidative Propane Dehydrogenation

Ga-chabazite zeolites (Ga-CHA) have been found to efficiently catalyze propane dehydrogenation with high propylene selectivity (96%). In situ FTIR spectroscopy and pulse titrations are employed to determine that upon reduction, surface Ga 2 O 3 is reduced and diffuses into the zeolite pores, displacing the Brønsted acid sites (BAS) and forming extra-framework Ga + sites. This isolated Ga + site reacts reversibly with H 2 to form GaHx (2034 cm -1 ) with an enthalpy of formation of ~ -51.2 kJ·mol -1 , a result supported by Density functional theory (DFT) calculations. The initial C 3 H 6 dehydrogenation rates decrease rapidly (40%) during the first 100 min and then decline slowly afterward, while the C 3 H 6 selectivity is stable at ~ 96%. The reduction in the reaction rate is correlated with the formation of polycyclic aromatics inside the zeolite (using UV-vis spectroscopy) indicating that the accumulation of polycyclic aromatics is the main cause of the deactivation. The carbon species formed can be easily oxidized at 600 °C with complete recovery of the PDH catalytic properties. The correlations between GaH x vs. Ga/Al ratio, and PDH rates vs. Ga/Al ratio show that extra-framework Ga + is the active center catalyzing propane dehydrogenation. The higher reaction rate on Ga + than In + in CHA zeolites, by a factor of 43, is the result of differences in the stabilization of the transition state due to the higher stability of Ga 3+ vs. In 3+ . The uniformity of the Ga + sites in this material makes it an excellent model for the molecular understanding of metal cation exchanged hydrocarbon interactions in zeolites.

10 SYNTHETIC FUELS↗