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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Comparison of direct and CO 2 -oxidative dehydrogenation of propane

Propane dehydrogenation to propylene has received increasing attention due to the fast growth in propylene demand and the exploration of shale gas containing propane. Direct dehydrogenation of propane (DDHP) offers high propylene selectivity but is limited by quick deactivation due to coke formation. CO 2 -assisted oxidative dehydrogenation of propane (CO 2 -ODHP) can consume CO 2 and meanwhile reduce coke deposition via the reverse Boudouard reaction. Here in the current review, direct and CO 2 -assisted dehydrogenation of propane has been compared from three aspects: reaction mechanisms, catalyst compositions, and CO 2 footprint analysis. As the average CO 2 emissions from electricity generation decrease due to the utilization of renewable energy, CO 2 -ODHP potentially leads to a net-negative CO 2 footprint while DDHP cannot.

58 GEOSCIENCES↗
DOE OSTI2020

Boron-hyperdoped silicon for the selective oxidative dehydrogenation of propane to propylene

Boron containing catalysts have great potential in the oxidative dehydrogenation of propane. Herein, a series of 15, 25 and 42 at% boron-hyperdoped silicon catalysts synthesized by laser pyrolysis was studied. Here, boron-hyperdoped silicon samples showed >6 times higher propylene productivity than commercial h-BN at 450 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhancement of oxidative dehydrogenation over cerium-doped nickel niobium catalysts and analysis of batch-to-batch variability

Nickel based catalysts are inexpensive and efficient for use in the oxidative dehydrogenation of ethane. NiO doped with niobium and cerium shows increased ethylene production. Small amounts of Ce doped onto a NiNb catalyst led to increased Ni activity. The catalyst that had the highest ethylene production rate per g of catalyst had 1 atom% Ce, 86 at% Ni, and 13 at% Nb (1CeNiNb) while, if surface area is incorporated into the calculation, the catalyst that had the highest ethylene production rate per m 2 was the 0.5CeNiNb catalyst. The ethylene production rates of these Ce-containing catalysts are 27 %-127 % higher than those with NiNb alone previously reported in the literature. Here, to fully understand how cerium affects the NiNb catalyst, the Ce content and effect on active sites has been fully characterized over multiple batches. In doing this, light has been shed on batch-to-batch variability. Characterization techniques such as powder X-ray diffraction, hydrogen temperature programmed reduction, X-ray photoelectron spectroscopy, synchrotron X-ray absorption spectroscopy, and methanol adsorption were used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Preventing Loss of Selectivity during the Oxidative Dehydrogenation of Propane over Supported Vanadium Catalysts

Supported vanadium materials are promising catalysts for the oxidative dehydrogenation of propane to propylene (ODHP), but a lack of mechanistic understanding limits the rational design of catalysts with improved propylene selectivity. Adding Ta to V/SiO 2 increases the propylene selectivity, as well as the activity, leading to superior performance compared to state-of-the-art boron-based systems. In this contribution, we utilize this surprising promotional effect of Ta to elucidate key elements of the mechanistic cycle. Through a combination of characterization techniques, computational modeling, and kinetic experiments, we show that the catalytic cycle over V/SiO 2 likely involves the formation of an isopropyl alcohol intermediate, the fate of which is in kinetic competition between subsequent dehydration to propylene or further oxidation. Furthermore, we show that the relatively facile propylene overoxidation observed for these materials occurs via the epoxidation of propylene by a proposed peroxovanadium intermediate, rather than the abstraction of propylene’s allylic C–H bond as previously assumed. Using these key mechanistic features, we rationalize the enhanced selectivity and activity of Ta promotion. In conclusion, our mechanistic framework offers avenues for future catalyst development to improve supported vanadium materials for ODHP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Effect of the Molecular Structure of Surface Vanadia on Activity and Regenerability of VO $x$ /In 2 O 3 Catalysts for CO 2 -Assisted Oxidative Dehydrogenation of Propane

Our recent work has reported that higher propylene selectivity and improved stability can be achieved by combining redox-active VO $x$ and basic In 2 O 3 for CO 2 -assisted oxidative dehydrogenation of propane (CO 2 -ODHP). In the present work, we continued to explore the stability and regenerability of V/In catalysts. In particular, our interest lies in identifying the effect of mono- and polyvanadate on catalytic performance and regenerability. A V/In catalyst with an increased proportion of monovanadate was prepared using the Schlenk line under moisture-free conditions (V/In–S), while the fully polymerized vanadate catalyst was prepared through a regular impregnation (V/In) for comparison. The Schlenk-line-prepared catalyst, namely, V/In–S, not only exhibits a 17–30% enhanced propylene yield at high temperatures (500–540 °C) over V/In but also presents improved stability and regenerability with nearly 88% activity recovered after regeneration in O 2 . Detailed characterizations have been performed to reveal the catalyst structure–performance relationship, including chemisorption (NH 3 /CO 2 -temperature-programmed desorption, NH 3 /CO 2 -TPD), H 2 -temperature-programmed reduction (H 2 -TPR), and spectroscopic studies [Raman spectroscopy, UV–vis diffuse reflectance spectroscopy (UV–vis DRS), near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS), and high-sensitivity low-energy ion scattering (HS-LEIS)]. Characterization results demonstrate that compared with polyvanadates, monovanadates lead to strengthened interaction with In 2 O 3 and a more stabilized V/In surface and subsurface, as well as improved redox properties of VO $x$ . These advantages give rise to the observed enhancement in activity, stability, and regenerability. In conclusion, these findings advance the understanding of the relationship between the activity/stability and the molecular structure of surface oxide species (vanadia) and the interplay between acid–base interactions and redox properties of mixed metal-oxide catalysts for efficient CO 2 -ODHP.

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

Molten‐Salt‐Mediated Chemical Looping Oxidative Dehydrogenation of Ethane with In‐Situ Carbon Capture and Utilization

Abstract The molten‐salt‐mediated oxidative dehydrogenation (MM‐ODH) of ethane (C 2 H 6 ) via a chemical looping scheme represents an effective carbon capture and utilization (CCU) method for the valorization of ethane‐rich shale gas and concurrent mitigation of carbon dioxide (CO 2 ) emissions. Here, stepwise experimentation with Li 2 CO 3 ‐Na 2 CO 3 ‐K 2 CO 3 (LNK) ternary salts (i) assessed how each component of the LNK mixture impacted ethane MM‐ODH performance and (ii) explored physicochemical and thermodynamic mechanisms behind melt‐induced changes to ethylene (C 2 H 4 ) and carbon monoxide (CO) yields. Of fifteen screened LNK compositions, nine exhibited ethylene yields greater than 50 % at 800 °C while maintaining C 2 H 4 selectivities of 85 % or higher. LNK salts rich in Li 2 CO 3 content yielded more ethylene and CO on average than their counterparts, and net CO 2 capture per cycle reached a maximum of ~75 %. Extended MM‐ODH cycling also demonstrated long‐term stability of a high‐performing LNK medium. Density functional theory (DFT) calculations andab initiomolecular dynamics (AIMD) simulations suggested that the molten salt does not directly activate C 2 H 6 . Meanwhile, an empirical model informed by experimental data and reaction thermodynamics adequately predicted overall MM‐ODH performance from LNK composition and provided insights into the system′s primary drivers.

Chemistry↗
DOE OSTI2022

CaMn 0.9 Ti 0.1 O 3 based redox catalysts for chemical looping – Oxidative dehydrogenation of ethane: Effects of Na 2 MoO 4 promoter and degree of reduction on the reaction kinetics

Reduction kinetics and stability of 20 wt% Na 2 MoO 4 -promoted CaMn 0.9 Ti 0.1 O 3 were investigated for its applications in Chemical Looping – Oxidative Dehydrogenation (CL-ODH) of ethane, a potential alternative for ethylene production with higher efficiency and lower emissions. Here, the present work reports a kinetics model and parameters for a Na 2 MoO 4 -promoted, Ti-doped CaMnO 3 (CaMn 0.9 Ti 0.1 O 3 ) redox catalyst under H 2 and C 2 H 4 . A first-order reaction model provides the best fit for the reduction of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 , while the C 2 H 4 reduction is well described by an Avrami–Erofe’ev model. The activation energy for C 2 H 4 oxidation is approximately three times higher than that for H 2 conversion, showing that the activation of C 2 H 4 is significantly more difficult on the surface of the redox catalyst. The reduction rate of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 at 750 °C is more than two orders of magnitude greater than that under C 2 H 4 , while the reduction rate of unpromoted CaMn 0.9 Ti 0.1 O 3 is comparable under H 2 and C 2 H 4 , showing that the addition of Na 2 MoO 4 effectively suppresses C 2 H 4 combustion relative to H 2 oxidation. The kinetics results for Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 confirm its excellent selectivity towards hydrogen combustion, making it a promising candidate under CL-ODH. Additionally, the stability of the CaMn 0.9 Ti 0.1 O 3 @ Na 2 MoO 4 core-shell structure, which was the underlying reason for the excellent selectivity, was examined under both shallow and deep reductions. It was determined that deep reduction of the redox catalyst, e.g. higher than 80% solid conversion, would lead to loss of sodium and hence to decreased selectivity for hydrogen combustion. In contrast, the core-shell structure was well-maintained, exhibiting excellent performance after 50 redox cycles when deep reduction of the redox catalyst was avoided. This study offers a basis for both the CL-ODH reactor design and redox catalyst optimizations.

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

Chemical Grafting of Highly Dispersed VO x /CeO 2 for Increased Catalytic Activity in Methanol Oxidative Dehydrogenation

Vanadia supported on well-defned ceria nanocubes are synthesized at various loadings using a liquid-phase chemical grafting technique and are compared to those prepared using traditional incipient wetness impregnation. Raman and IR characterization reveal that, as vanadia loading is increased to near monolayer coverage, vanadia deposited using grafting shows greatly enhanced dispersion (i.e., improved VO x monomer/dimer distribution). Methanol is used as a probe molecule to explore the redox behavior of the catalysts. IR and temperature programmed desorption of methanol show increased CO 2 formation occurs on the bare ceria support and increasing the dispersion of vanadia promotes dehydrogenation to formaldehyde due to the inhibited oxygen vacancy formation on VO x /CeO 2 . Hydrogen temperature programmed reduction demonstrates that the catalyst reducibility and formation of surface oxygen vacancy are directly related to the degree of vanadia oligomerization. In conclusion, the samples prepared using grafting exhibit superior catalytic performance for methanol oxidative dehydrogenation to formaldehyde compared to the impregnated samples, due to the presence of highly dispersed VO x species (i.e., monomers and dimers).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane

Boron–containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. Here, we combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface–mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure–dependent relative formation of the main product propylene and by–product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium–based catalysts.

03 NATURAL GAS↗
DOE OSTI2023

Tracking Active Phase Behavior on Boron Nitride during the Oxidative Dehydrogenation of Propane Using Operando X-ray Raman Spectroscopy

Hexagonal boron nitride (hBN) is a highly selective catalyst for the oxidative dehydrogenation of propane (ODHP) to propylene. Using a variety of ex situ characterization techniques, the activity of the catalyst has been attributed to the formation of an amorphous boron oxyhydroxide surface layer. The ODHP reaction mechanism proceeds via a combination of surface mediated and gas phase propagated radical reactions with the relative importance of both depending on the surface-to-void-volume ratio. Here we demonstrate the unique capability of operando X-ray Raman spectroscopy (XRS) to investigate the oxyfunctionalization of the catalyst under reaction conditions (1 mm outer diameter reactor, 500 to 550 °C, P = 30 kPa C 3 H 8 , 15 kPa O 2 , 56 kPa He). We probe the effect of a water cofeed on the surface of the activated catalyst and find that water removes boron oxyhydroxide from the surface, resulting in a lower reaction rate when the surface reaction dominates and an enhanced reaction rate when the gas phase contribution dominates. Computational description of the surface transformations at an atomic-level combined with high precision XRS spectra simulations with the OCEAN code rationalize the experimental observations. Finally, this work establishes XRS as a powerful technique for the investigation of light element-containing catalysts under working conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane

Abstract Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface‐mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure‐dependent relative formation of the main product propylene and by‐product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium‐based catalysts.

Venegas, Juan M.↗
DOE OSTI2020

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Abstract Although hexagonal boron nitride (h‐BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas‐phase methyl radicals (CH 3 . ) in the ODHP reaction over boron‐based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV‐PIMS), which uncovers the existence of gas‐phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C 2 and C 1 products can be formed via both surface‐mediated and gas‐phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron‐based catalysts.

Zhang, Xuanyu↗
DOE OSTI2020

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH 3 . ) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C-H activation of propane, while C 2 and C 1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Off-Stoichiometric Restructuring and Sliding Dynamics of Hexagonal Boron Nitride Edges in Conditions of Oxidative Dehydrogenation of Propane

Boron-containing materials, such as hexagonal boron nitride (h-BN), recently shown to be active and selective catalysts for the oxidative dehydrogenation of propane (ODHP), have been shown to undergo significant surface oxyfunctionalization and restructuring. Although experimental ex situ studies have probed the change in chemical environment on the surface, the structural evolution of it under varying reaction conditions has not been established. Herein, we perform global optimization structure search with a grand canonical genetic algorithm to explore the chemical space of off-stoichiometric restructuring of the h-BN surface under ambient as well as ODHP-relevant conditions. A grand canonical ensemble representation of the surface is established, and the predicted 11B solid-state NMR spectra are consistent with previous experimental reports. In addition, we investigated the relative sliding of h-BN sheets and how it influences the surface chemistry with ab initio molecular dynamics simulations. Furthermore, the B–O linkages on the edges are found to be significantly strained during the sliding, causing the metastable sliding configurations to have higher reactivity toward the activation of propane and water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Oxidative dehydrogenation of propane on the oxygen adsorbed edges of boron nitride nanoribbons

Metal-free boron nitride has recently been reported to exhibit high catalytic activity and selectivity towards oxidative dehydrogenation of propane (ODHP). Despite several experimental studies, the exact nature and function of the active sites in this emerging catalyst are unknown. In the present work, density functional theory calculations are combined with microkinetic modeling to systematically explore the ODHP on oxygen passivated boron nitride nanoribbons (BNNRs). Here, the relative stabilities of different edge structures of BNNR were examined using ab initio thermodynamic analysis, and the most stable oxygen passivated edge structure was used for a mechanistic study. Microkinetic analysis revealed that a N 2 O or NO x -type active site is active and selective for the conversion of propane to propene. In addition to a heterogeneous catalytic cycle, the proposed N 2 O/NO x -type active sites are expected to be able to generate gas phase C 3 H 7 ˙, which in turn can trigger gas phase reactions of ODHP as experimentally speculated.

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

Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size

Supported subnano-cluster catalysts are highly dynamic, developing true active sites only under the pressures and temperatures of reaction conditions. Operando X-ray absorption near-edge structure (XANES) spectroscopy can track changes in the oxidation state and the local environment of cluster atoms, providing insight into the development of these active sites. While bulk metal, oxide, and hydroxide standards are often used for fitting experimental XANES spectra to obtain average oxidation states, we recently showed that computed cluster standards of relevant compositions are a more suitable basis, producing more accurate fits. Here, we theoretically interpret the operando XANES of supported Cu 3 Pd and Cu 4 clusters during temperature-programmed reaction (TPRx) of oxidative dehydrogenation of propane. We use an expanded basis set including both globally optimized computed clusters and bulk standards. Not only can we track reversible composition/oxidation state change with temperature, but also the irreversible growth of the bulk fraction upon heating, which we attribute to cluster sintering. This has important implications for the mechanism of the catalyzed reaction and the nature of the available active sites. Here, we propose that operando XANES provides most significant insight into the nature of supported cluster catalysts in reaction conditions when interpreted using mixed computed cluster and bulk standards.

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

Experimental Combustion and Flame Characterization of a Chemical Looping-Based Oxidative Dehydrogenation Byproduct Fuel Mixture Containing High CO2 Dilution

Abstract This study investigates the combustion performance of a CO2-rich fuel mixture containing ethane and methane as active species using a constant volume combustion chamber. This fuel is obtained as a byproduct of a chemical looping-based oxidative dehydrogenation (Cl-ODH) process ethylene production. The byproduct gas mixture has 40.79% CO2, 39.49% ethane, and 4.88% methane by weight with other minor compounds. Using this fuel for energy extraction would improve the process efficiency of the ethane to ethylene conversion. After initial combustion modeling, the gas fuel mixture was reduced to just the major species: CO2, ethane, and methane. The mixture was then tested for flammability limits and combustion performance under spark-ignition conditions. Effects of ambient conditions like temperatures between 300 and 400 K with initial pressures from 1 to 10 bar were tested. The effects of stoichiometry were tested to understand flame velocities and heat release. The fuel mixture showed an overall reduced flame velocity compared to gasoline. Instability in combustion was believed to be caused by the dissociation of ethane under elevated conditions. At higher pressures, the flame produces lower cumulative heat release. Simulations were also performed using a model tuned to replicate the operations of the combustion chamber used in the experiments. Heat release and unburnt fuel mass data were calculated to identify the discrepancies in the combustion completeness at elevated pressures. The effects of CO2 quenching the flame coupled with the increased dissociation of the fuel species can lead to up to more than 75% of the fuel mixture being unburnt. Data from this study were used to modify a small-scale spark-ignition engine to use this fuel and produce usable energy.

Energy & Fuels↗