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At least 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells (Final Report)

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co2O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly 4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Sulfur-Reducing Additives Based on Aluminosilicates Al-SBA-15 and Al-SBA-16 for Cracking catalysts

Sulfur-reducing additives for fluid catalytic cracking (FCC) catalysts based on mesoporous aluminosilicates Al-SBA-15 and Al-SBA-16 were synthesized and characterized using FTIR spectroscopy, transmission electron microscopy, low-temperature N{sub 2} adsorption/desorption, and thermally programmed desorption of NH3. Catalytic experiments were performed using a commercial zeolite-containing FCC catalyst and the additives (10 wt.%). It was found that all synthesized materials were active for reducing sulfur in liquid catalytic cracking products. The S content in the liquid cracking products obtained using an additive of 3% La-Al-SBA-15/Al{sub 2}O{sub 3} (50:50) decreased by 36% as compared to the same parameter obtained using the commercial catalyst with no additive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Elucidation of the Reaction Mechanism for High-Temperature Water Gas Shift over an Industrial-Type Copper–Chromium–Iron Oxide Catalyst

The water gas shift (WGS) reaction is of critical importance for the chemical industry, as it constitutes, coupled with methane reforming, the main industrial route to produce hydrogen. Copper–chromium–iron oxide-based catalysts have been widely used for the high-temperature WGS reaction industrially. The WGS reaction mechanism by the CuCrFeO x catalyst has been debated for years, mainly between a “redox” mechanism involving the participation of atomic oxygen from the catalyst and an “associative” mechanism proceeding via a surface formate-like intermediate. Here, advanced in situ characterization techniques (infrared spectroscopy, temperature-programmed surface reaction (TPSR), near-ambient pressure XPS (NAP-XPS), and inelastic neutron scattering (INS)) were applied to determine the nature of the catalyst surface and identify surface intermediate species under WGS reaction conditions. The surface of the CuCrFeO x catalyst is found to be dynamic and becomes partially reduced under WGS reaction conditions, forming metallic Cu nanoparticles on Fe 3 O 4 . Neither in situ IR not INS spectroscopy detect the presence of surface formate species during WGS. TPSR experiments demonstrate that the evolution of CO 2 and H 2 from the CO/H 2 O reactants follows different kinetics than the evolution of CO 2 and H 2 from HCOOH decomposition (molecule mimicking the associative mechanism). Steady-state isotopic transient kinetic analysis (SSITKA) (CO + H 2 16 O → CO + H 2 18 O) exhibited significant 16 O/ 18 O scrambling, characteristic of a redox mechanism. Computed activation energies for elementary steps for the redox and associative mechanism by density functional theory (DFT) simulations indicate that the redox mechanism is favored over the associative mechanism. The combined spectroscopic, computational, and kinetic evidence in the present study finally resolves the WGS reaction mechanism on the industrial-type high-temperature CuCrFeO x catalyst that is shown to proceed via the redox mechanism.

SSITKA↗
DOE OSTI2017

Al-doped TiO{sub 2} mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

Pd catalysts supported on Al-doped TiO{sub 2} mesoporous materials were evaluated in complete oxidation of ethanol. The catalysts synthesized by wet impregnation based on evaporation-induced self-assembly were characterized by X-ray diffraction, measurement of pore structure, XPS, FT-IR, temperature programmed reduction and TEM. Characteristic results showed that the aluminium was doped into the lattice of mesoporous anatase TiO{sub 2} to form Al-O-Ti defect structure. Catalytic results revealed that Al-doped catalysts were much more active than the pristine one, especially at low temperature (≤200 °C). This should be ascribed to the introduction of aluminium ions that suppressed the strong metal-support interaction and increased the active sites of Pd oxides, enhanced the stabilized anatase TiO{sub 2}, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen. - Graphical abstract: Al-doped Pd/TiO{sub 2} exhibited optimal catalytic performance for ethanol oxidation and CO{sub 2} yield by the suppression of SMSI. - Highlights: • Palladium catalysts supported on Al-doped TiO{sub 2} mesoporous materials were studied. • The introduction of Al can enhance anatase stabilization and increase defect TiO{sub 2}. • The Pd/Al-TiO{sub 2} catalysts show higher ethanol conversion and CO{sub 2} yield than Pd/TiO{sub 2}. • The influence of Al on SMSI and catalytic performance were evaluated by TPR and XPS.

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

Co-hydrotreatment of Bio-oil and Waste Cooking Oil to Produce Transportation Fuels

This paper reports the co-hydrotreatment of the heavy bio-oil fraction with waste cooking oil (WCO) using NiMo/γ-Al 2 O 3 catalyst, followed by the distillation of resulting deoxygenated oil and the characterization of resulting fuel cuts. The heavy BTG bio-oil fraction was obtained by removing the very reactive light-oxygenated compounds via rotary evaporation, subsequently mixed with 1-butanol. The resulting oil was blended with WCO and subjected to a two-step co-hydrotreatment process. The first step, called “stabilization,” is aimed at saturating highly reactive hydrogen-deficient compounds. The second step, called “deoxygenation,” aimed to remove bio-oil oxygen, primarily as H 2 O. This study examined the impact of varying bio-oil concentrations (0, 10, 20, 30, 40 wt.% of WCO) on the upgraded oil's yield, composition, and fuel properties. The resulting hydrotreated oil was distilled into gasoline-range, kerosene-range, and diesel-range hydrocarbons at <150 °C, 150 to 250 °C, and 250 to 350 °C, respectively. The yield of the hydrotreated oil indicates that as the bio-oil concentration increases, the amounts of coke (0.7 to 2.4 %) and water (2 to 10 wt. %) increase while the organic layer yields decrease (80 to 63 %). The coke yield was comparable to the coke yield obtained when co-processing the pyrolytic lignin fraction. This suggests that coke is formed from both the sugar oligomers and the lignin-derived oligomers. The UV-fluorescence analysis on the hydrotreated oil shows that more polycondensed and conjugated ring compounds formed as the bio-oil concentration is increased. These compounds are precursors of coke. FTIR results showed that most raw materials were converted to biofuels after the hydrotreatment. To achieve less than 1 wt. % of coke yield, blends with up to 20 wt. % pyrolysis oil should be used. An increase in bio-oil concentration leads to a slight increase in gasoline yield and a decrease in kerosene and diesel yields. The identified carbon species found in the fuel cuts include n-paraffin, iso-paraffin, cycloparaffin, and aromatics. Further, the jet fuel cut (kerosene) was characterized by density, surface tension, and viscosity. Our product conforms to the standard specifications for sustainable aviation fuels (Jet A-1). Further research is suggested to fine-tune the operating parameters for achieving reduced coke yield and enhanced kerosene yield.

09 BIOMASS FUELS↗
DOE OSTI2016

Dipole-Oriented Molecular Solids Can Undergo a Phase Change and Still Maintain Electrical Polarization

It has recently been demonstrated that nanoscale molecular films can spontaneously assemble to self-generate intrinsic electric fields that can exceed 10 8 V/m. These electric fields originate from polarization charges in the material that arise because the films self-assemble to orient molecular dipole moments. This has been called the spontelectric effect. Such growth of spontaneously polarized layers of molecular solids has implications for our understanding of how intermolecular interactions dictate the structure of molecular materials used in a range of applications, for example, molecular semiconductors, sensors, and catalysts. In this paper, we present the first in situ structural characterization of a representative spontelectric solid, nitrous oxide. Infrared spectroscopy, temperature-programmed desorption, and neutron reflectivity measurements demonstrate that polarized films of nitrous oxide undergo a structural phase transformation upon heating above 48 K. A mean-field model can be used to describe quantitatively the magnitude of the spontaneously generated field as a function of film-growth temperature, and this model also recreates the phase change. Finally, this reinforces the spontelectric model as a means of describing long-range dipole–dipole interactions and points to a new type of ordering in molecular thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Direct spectroscopic evidence for isolated silanols in SiO x /Al 2 O 3 and their formation mechanism

Here, the preparation and unambiguous characterization of isolated Brønsted-acidic silanol species on silica–alumina catalysts presents a key challenge in the rational design of solid acid catalysts. In this report, atomic layer deposition (ALD) and liquid-phase preparation (chemical liquid deposition, CLD) are used to install the SiO x sites on Al 2 O 3 catalysts using the same Si source (tetraethylorthosilicate, TEOS). The ALD-derived and CLD-derived SiO x sites are probed with dynamic nuclear polarization (DNP)-enhanced 29 Si– 29 Si double-quantum/single-quantum (DQ/SQ) correlation NMR spectroscopy. The investigation reveals conclusively that the SiO x /Al 2 O 3 material prepared by ALD and CLD, followed by calcination under an O 2 stream, contains fully spatially isolated Si species, in contrast with those resulting from the calcination under static air, which is widely accepted as a postgrafting treatment for CLD. Insight into the formation mechanism of these sites is obtained via in situ monitoring of the TEOS + γ-Al 2 O 3 reaction in an environmental diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) cell. Upon calcination, the DRIFTS spectra of SiO x /Al 2 O 3 reveal a signature unambiguously assignable to isolated Brønsted-acidic silanol species. Surprisingly, the results of this study indicate that the method of preparing SiO x /Al 2 O 3 catalysts is less important to the final structure of the silanol sites than the post-treatment conditions. This finding should greatly simplify the methods for synthesizing site-isolated, Brønsted-acidic SiO x /Al 2 O 3 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Hybrid Catalytic Biorefining of Hardwood Biomass to Methylated Furans and Depolymerized Technical Lignin

A robust method is needed to achieve high yield all-catalytic conversion of recalcitrant lignocellulosic biomass to transportation fuels while maximizing carbon utilization from raw substrates. In this paper, to accomplish this, we developed an integrated strategy that combines homogeneous and heterogeneous reactions with a treatment-extraction step to coproduce 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) directly from hardwood poplar while maintaining high catalyst activity. In the first step, poplar wood chips were treated with dilute FeCl 3 in THF–water at subpyrolytic temperature to yield 93.5% furfural (FF) from xylan and 66.0% 5-hydroxymethylfurfural (HMF) from glucan. Concurrently, a highly pure lignin powder was obtained from the liquor by precipitation upon room temperature vacuum recovery of THF from the water. Afterward, FF and HMF were extracted from water into an organic phase consisting of toluene and 1,4-dioxane treated with Ca(OH) 2 . A second hydrodeoxygenation reaction using Cu–Ni/TiO 2 catalyst yielded 87.8% MF from FF and 85.6% DMF from HMF. Characterization of the lignin product showed its molecular weight to be reduced by an order of magnitude from its native state as well as complete removal of its native β-aryl ether linkages without hydrogen input or further heterogeneous catalytic processing. Finally, a 60% cumulative yield of MF, DMF, and lignin products from the available carbon (xylan+glucan+lignin) in poplar was achieved, rivaling more mature cellulosic ethanol strategies.

09 BIOMASS FUELS↗
DOE OSTI2021

Structure evolution of single-site Pt in a metal–organic framework

Heterogeneous single-metal-site catalyst or single-atom catalyst research has grown rapidly due to the accessibility of modern characterization techniques that can provide invaluable information at the atomic-scale. Herein, we study the structural evolution of isolated single Pt sites incorporated in a metal–organic framework containing bipyridine functional groups using in situ diffuse reflectance infrared Fourier transform spectroscopy with CO as the probe molecule. The structure and electronic properties of the isolated Pt sites are further corroborated by x-ray photoelectron spectroscopy and aberration-corrected scanning transmission electron microscopy. Here, we find the prerequisite of high temperature He treatment for Pt activation and CO insertion and inquire into the structural transformation of Pt site process by dynamic nuclear polarization-enhanced solid-state nuclear magnetic resonance spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Molecular basis for enantioselective herbicide degradation imparted by aryloxyalkanoate dioxygenases in transgenic plants

The synthetic auxin 2,4-dichlorophenoxyacetic acid (2,4-D) is an active ingredient of thousands of commercial herbicides. Multiple species of bacteria degrade 2,4-D via a pathway initiated by the Fe(II) and α-ketoglutarate (Fe/αKG)-dependent aryloxyalkanoate dioxygenases (AADs). Recently, genes encoding 2 AADs have been deployed commercially in herbicide-tolerant crops. Some AADs can also inactivate chiral phenoxypropionate and aryloxyphenoxypropionate (AOPP) herbicides, albeit with varying substrate enantioselectivities. Certain AAD enzymes, such as AAD-1, have expanded utility in weed control systems by enabling the use of diverse modes of action with a single trait. Here, we report 1) the use of a genomic context-based approach to identify 59 additional members of the AAD class, 2) the biochemical characterization of AAD-2 from Bradyrhizobium diazoefficiens USDA 110 as a catalyst to degrade (S)-stereoisomers of chiral synthetic auxins and AOPP herbicides, 3) spectroscopic data that demonstrate the canonical ferryl complex in the AAD-1 reaction, and 4) crystal structures of representatives of the AAD class. Structures of AAD-1, an (R)-enantiomer substrate-specific enzyme, in complexes with a phenoxypropionate synthetic auxin or with AOPP herbicides and of AAD-2, which has the opposite (S)-enantiomeric substrate specificity, reveal the structural basis for stereoselectivity and provide insights into a common catalytic mechanism.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Improving Cost and Efficiency of the Scalable Solid Oxide Fuel Cells Power System

The objective of this project was to design and develop a 20kW range small-scale solid oxide fuel cells (SOFC) power system for applications such as data centers and commercial buildings. The original plan included a 5,000 hours demonstration and a Techno-Economic Analysis (TEA) which were dropped as part of project termination. The original project plan was to use a stack with a cross-flow cell design which had previously been tested for 500 hours at a community college in Malta, NY. However, it was decided to move to the advanced R-SOFC co-flow cell developed under Department of Energy Award DE-FE0031971. The advanced cell design has the advantage of a larger active area for the same manufacturing footprint which results in fewer required cells for the same stack power, hence a higher volumetric power density (kW/L) and lower cost per kW than the original cross-flow cell design. A full SOFC system Simulink model was developed and calibrated with testing data from a fuel cell stack and BOP (balance of plant) components. The simulation results from the calibrated model showed an acceptable match with the experimental data. A structural analysis conducted for various load scenarios indicated no high stress areas for all spatial directions. Major electrical system components were acquired, built and successfully tested. System sensors were verified and validated against controls. Safety checks, a diagnostic check, PID tuning, and control software commissioning tasks were also conducted. The power electronics prototype was delivered and trial testing completed. Balance of Plant component testing and simulation work was conducted to characterize Reformer-Heat Exchanger heat transfer and backpressure and reformer catalyst methane conversion and product selectivity. Simulations were conducted to design the Anode and Cathode fluid passages and size the air-air and fuel-fuel heat exchangers. A Burner operation map was created from test data and the Anode Gas Recirculation blower was tested to evaluate its durability. The SOFC system used a horizontal style design where components sit directly on a casting with a direct connection to the skid. This design has efficient packaging and a small footprint with approximate dimensions of 750 mm x 700 mm x 1700 mm. An SOFC system was built and successfully tested at the Malta, NY facility The system for over 500 hours under load of which over 300 hours was at full load of 20 kW.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Technoeconomic analysis of hydrogen storage using 1,4-butanediol (BDO)/γ-butyrolactone (GBL) as a stationary backup power system

Liquid organic hydrogen carriers (LOHCs) are compounds that store and release hydrogen in stable forms at high density. While one-way carriers such as methanol and ammonia have gained attention, their economic advantages are often realized from their use as an export product and direct use as a fuel. Liquid carrier materials that can instead be cycled for energy storage have promise for stationary power applications. In particular, the reversible LOHC system 1,4-butanediol (BDO, H 2 -rich) and gamma-butyrolactone (GBL, H 2 -lean) has a lower enthalpy of dehydrogenation compared to conventional cyclic hydrocarbons and can utilize non-precious metal copper-based catalysts. Here, in this study, BDO/GBL system capital and operating expenses are characterized for vapor phase versus liquid phase hydrogenation and dehydrogenation in a 10 MW backup power application corresponding to sizing of Tier 2 datacenters as well as other critical infrastructure such as hospitals. Costs are benchmarked against two incumbent technologies: a well-established methylcyclohexane/toluene carrier system and compressed gas storage. BDO/GBL storage costs are found to differ substantially between operating modes, with liquid phase hydrogenation coupled with liquid phase dehydrogenation leading to the lowest LCOS of $\$$4.58/kg H 2 in the absence of byproduct formation. In this bounding case, LCOS for the BDO/GBL system is lower than for MCH/TOL ($\$$6.97/kg H 2 ) and compressed gas ($\$$8.48/kg H 2 at 170 bara and $\$$12.05/kg H 2 at 350 bara). However, escalating costs of carrier replacement due to byproduct formation (ranging from an added $\$$6–11/kg H 2 ) illustrate the need for highly selective catalysts to ensure BDO/GBL carrier viability.

BDO/GBL↗
DOE OSTI2023

Assessing factors that determine adatom migration and clustering on a thin film oxide; Pt 1 and Rh 1 on the “29” Cu x O/Cu(1 1 1) surface

The dynamical nature of single-site catalysts under non-equilibrium conditions poses significant challenges in the full characterization of their active sites. The “29” oxide is a thin Cu x O film grown on Cu(111) which provides a well-defined surface on which to study the structure and chemistry of atomically dispersed precious metals. A combination of experimental and first-principles approaches is used to investigate the factors that influence the mobility of metal adatoms and their clustering tendencies. Our work elucidates how a homogenous coordination environment of neutral single-atoms can be obtained when its tendency to break oxide bonds within its vicinity is low. Herein we demonstrate that this in turn affects the chemical atomically dispersed species on thin-film oxides, as defects on the oxide would in fact allow such species to be more accessible to CO. We thus highlight the importance of understanding the relationship between defects and atomically dispersed active sites upon designing single-site catalysts.

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

Acid-Catalyst is Required for Hydrogenolysis of a Late Metal Hydroxo Complex

The cationic AuIII pincer complex [(tBuPCP)AuIII -OH]OTf (AuOH, tBuPCP = 2,6-(CH2PtBu2)2C6H3) was prepared and characterized. In contrast to hydrogenolysis reactions of other late metal-hydroxides, the hydrogenolysis of AuOH to form the corresponding AuIII -H and water is shown to require an acid catalyst. The kinetic data, collected in acetone-d6, are consistent with a reaction mechanism involving initial protonation to form the AuIII aquo complex, [(tBuPCP)AuIII -OH2](OTf)2 (AuOH2), which was isolated and characterized. Following substitution of the water by coordinating solvent, the dicationic AuIII center undergoes electrophilic activation of H2 to generate the [(tBuPCP)AuIII -H]OTf product (AuH). The mechanism of hydrogenolysis is supported by experimental and computational (DFT) results. A AuIII dihydrogen complex (Au(H2)) was located along the potential energy surface for the reaction and computations indicate that deprotonation of Au(H2) by acetone solvent is barrierless. The bonding and properties of the proposed AuIII -H2 complex are consistent with predictions made for high-valent, electrophilic metal-dihydrogen complexes.

Ardon, Yotam [University of Pennsylvania] (ORCID:0↗
DOE OSTI2021

Synthesis and Structure–Activity Characterization of a Single-Site MoO 2 Catalytic Center Anchored on Reduced Graphene Oxide

Molecularly derived single-site heterogeneous catalysts can bridge the understanding and performance gaps between conventional homogeneous and heterogeneous catalysis, guiding the rational design of next-generation catalysts. While impressive advances have been made with well-defined oxide supports, the structural complexity of other supports and the nature of the grafted surface species present an intriguing challenge. In this study, single-site Mo(=O) 2 species grafted onto reduced graphene oxide (rGO/MoO 2 ) are characterized by XPS, DRIFTS, powder XRD, N 2 physisorption, NH 3 -TPD, aqueous contact angle, active site poisoning assay, Mo EXAFS, model compound single-crystal XRD, DFT, and catalytic performance. NH 3 -TPD reveals that the anchored MoO 2 moiety is not strongly acidic, while Mo 3d 5/2 XPS assigns the oxidation state as Mo(VI), and XRD shows little rGO periodicity change on MoO 2 grafting. Contact angle analysis shows that MoO 2 grafting consumes rGO surface polar groups, yielding a more hydrophobic surface. The rGO/MoO 2 DRIFTS assigns features at 959 and 927 cm –1 to the symmetric and antisymmetric Mo=O stretching modes, respectively, of an isolated cis-(O=Mo=O) moiety, in agreement with DFT computation. Moreover, the Mo EXAFS rGO/MoO 2 structural data are consistent with isolated (C–O) 2– Mo(=O) 2 species having two Mo=O bonds and two Mo–O bonds at distances of 1.69(3) and 1.90(3) Å, respectively. rGO/MoO 2 is also more active than the previously reported AC/MoO 2 catalyst, with reductive carbonyl coupling TOFs approaching 1.81 × 10 3 h –1 . rGO/MoO 2 is environmentally robust and multiply recyclable with 69 ± 2% of the Mo sites catalytically significant. Altogether, rGO/MoO 2 is a structurally well-defined and versatile single-site Mo(VI) dioxo heterogeneous catalytic system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗