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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Bimetallic NiCu catalysts supported on a Metal-Organic framework for Non-oxidative ethanol dehydrogenation

Non-oxidative ethanol dehydrogenation is a promising route to produce acetaldehyde and hydrogen from sustainable feedstock. Bimetallic NiCu catalysts have shown high efficiency and selectivity for this chemical transformation. In this study, we leverage the high porosity and uniform catalyst deposition sites on a Zr-based metal–organic framework (MOF) catalyst support, NU-1000, to understand how the changes in Cu:Ni ratio affects the reactivity for non-oxidative ethanol dehydrogenation. We found that increasing the Ni 2+ concentration significantly reduces the activation energy of the reaction due to the role of Ni 2+ in suppressing the onset of Cu reduction. Furthermore, this study illustrates how MOFs can be used as catalyst supports to fine-tune the catalyst compositions and understand their effect on the overall catalytic performances.

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

Supported Single‐Atom Manganese Catalysts for the Trimerization of Ethylene

Selective ethylene oligomerization via oxidative cyclization, forming metallacyclic intermediates, is typically catalyzed by molecular titanium and chromium complexes to produce butenes, hexenes, or octenes, depending on the supporting ligand framework. However, this mechanism requires significant electron density at the metal active site and is not known to be generalizable to other first-row transition metals. In this work, we computationally investigate the electronic modulation of five transition metals (Mn, Fe, Co, Ni, and Cu) supported on titania (TiO₂) through reductive lithium intercalation to promote selective oligomerization via oxidative cyclization, using density functional theory (DFT). Our findings predict that Mn/LiTiO₂ exhibits high catalytic activity due to the exergonic nature of oxidative cyclization with two ethylene molecules. Additionally, lithium titanate (LiTiO₂) supports enhance catalytic performance compared to TiO₂. Experimental validation confirms that Mn/LiTiO₂ achieves higher conversion rates and improved selectivity toward hexene (C₄:C₆ = 1:2.6). The enhanced activity is attributed to lithiation, which alters the electronic environment around Mn active sites. Mechanistic studies reveal that the formation of a seven-membered ring, a key intermediate for hexene formation, is more favorable on LiTiO₂ than TiO₂. This work provides the first evidence of Mn catalyzing selective ethylene oligomerization via oxidative cyclization in either homogeneous or heterogeneous catalysis.

Kim, Yu Lim [Argonne National Laboratory (ANL), Ar↗
DOE OSTI2025

Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C–C bonds

Current methods of processing accumulated polyolefin waste typically require harsh conditions, precious metals or high metal loadings to achieve appreciable activities. Here, in this work, we examined supported, single-site organonickel catalysts for polyolefin upcycling. Chemisorption of Ni(COD) 2 (COD, 1,5-cyclooctadiene) onto Brønsted acidic sulfated alumina (AlS) yields a highly electrophilic Ni(I) precatalyst, AlS/Ni(COD) 2 , which is converted under H 2 to the active AlS/Ni II H catalyst. This single-site system exhibits unique hydrogenolysis selectivity that favours cleaving branched polyolefin C–C linkages, enabling the hydrogenolytic separation of polyethylene and isotactic polypropylene (iPP) mixtures. Moreover, AlS/Ni II H remains highly selective and active for hydrogenolysis of iPP admixed with polyvinyl chloride, and the spent catalyst can be repeatedly regenerated by AlEt3 treatment. Experimental mechanistic analysis and density functional theory modelling reveal a turnover-limiting C–C scission pathway featuring β-alkyl transfer and strong olefin binding. These results highlight the potential of nickel-based systems for the selective upcycling of complex plastic waste streams.

green chemistry↗
DOE OSTI2021

Rationalization of promoted reverse water gas shift reaction by Pt 3 Ni alloy: Essential contribution from ensemble effect

Bimetallic alloys have attracted considerable attention due to the tunable catalytic activity and selectivity that can be different from those of pure metals. Here, we study the superior catalytic behaviors of the Pt 3 Ni nanowire (NW) over each individual, Pt and Ni NWs during the reverse Water Gas Shift (rWGS) reaction, using density functional theory. The results show that the promoted rWGS activity by Pt3Ni strongly depends on the ensemble effect (a particular arrangement of active sites introduced by alloying), while the contributions from ligand and strain effects, which are of great importance in electrocatalysis, are rather subtle. As a result, a unique Ni–Pt hybrid ensemble is observed at the 110/111 edge of the Pt 3 Ni NW, where the synergy between Ni and Pt sites is active enough to stabilize carbon dioxide on the surface readily for the rWGS reaction but moderate enough to allow for the facile removal of carbon monoxide and hydrogenation of hydroxyl species. Furthermore, our study highlights the importance of the ensemble effect in heterogeneous catalysis of metal alloys, enabling selective binding–tuning and promotion of catalytic activity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Atomic layer deposition for surface area determination of solid oxide electrodes

Surface area measurements are important for characterizing porous solids, but commonly used methods such as Brunauer–Emmett–Teller (BET) gas adsorption and computed nanotomography are lacking for certain applications such as the development of solid oxide fuel cell electrodes, which often have absolute surface areas <1 m 2 and contain nanoscale features. Presented is a novel method for the surface area determination of samples with total measurable areas of 1–1000 cm 2 with a standard deviation ± 1 cm 2 , utilizing the atomic layer deposition (ALD) of Al 2 O 3 over microstructurally complex internal porosity. The volume of alumina is then quantified using plasma spectroscopy and converted to an area using the known ALD layer thickness. Under the modest ALD reactor soak times used (8.5 s), the precursor penetration depth is found to be ~50 μm, exceeding the requirement for uniformly coating SOFC functional layers. A model system, (La 0.8 Sr 0.2 ) 0.98 MnO 3–δ /Ce 0.9 Gd 0.1 O 1.95 (LSM/GDC) scaffolds of ~2.7 m 2 g –1 , was measured using the technique and compared against the BET method, and comparable results were obtained but with 1000 times less material needed. The technique is demonstrated for measurements in two example areas of active SOFC research: exsolved (Ni, Fe) nanoparticles on an Sr(Ti, Fe, Ni)O 3–δ electrode and PrO x catalyst nanoparticles infiltrated onto LSM/GDC scaffolds. Finally, the technique may be broadly useful wherever the accurate surface area determination of small absolute quantities of porous ceramic structures on the order of 0.1–50 m 2 g –1 is sought.

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

Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition

Hydrogen bonding accelerates many catalytic reactions by orienting intermediates, stabilizing transition states, and even opening reaction pathways. However, most mechanistic studies regarding the decomposition of formic acid (FA), a promising hydrogen storage material, neglect hydrogen-bonding interactions even though FA is a strong hydrogen-bond donor and acceptor. Here, we probe the formation of bimolecular hydrogen-bonded complexes between FA and formate (FA–HCOO complexes) adsorbed on metal surfaces and how these complexes affect HCOO* decomposition. Using first-principles density functional theory (DFT) calculations on 12 close-packed (111)/(0001) and 8 open (100) surfaces of 12 transition metals—Ag, Au, Co, Cu, Ir, Ni, Os, Re, Pd, Pt, Rh, and Ru, we—show that FA–HCOO complexes are generally thermodynamically stable, even at elevated temperatures and pressures. We then illustrate that these complexes produce infrared spectroscopic signatures consistent with as yet unassigned experimental peaks. We last demonstrate that by stabilizing the dangling bond of monodentate HCOO*, these complexes significantly lower the barriers for rotation of HCOO* from a bidentate to a monodentate configuration, the rate-limiting step for HCOO* decomposition on many surfaces. FA thus acts as a cocatalyst for HCOO* decomposition. Our results may guide the community toward improved catalysts for reactions involving HCOO* such as FA decomposition, methanol steam reforming, and the water gas shift reaction. More broadly, our work highlights the ability of hydrogen bonding to modify the adsorbed structures of intermediates and lower the barriers for their reaction on heterogeneous catalysts. Lastly, this phenomenon can be relevant for other reactions involving ammonia, alcohols, and carboxylic acids.

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

High-Temperature Rotating Disk Electrode Study of Platinum Bimetallic Catalysts in Phosphoric Acid

Understanding the H 3 PO 4 effect on the catalyst’s activity under a relevant condition is important for high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) catalyst research. Here, we report a high-temperature rotating disk electrode (HT-RDE) study of oxygen reduction reaction (ORR) in H 3 PO 4 . With the regular electrochemical protocol, we found that H 3 PO 4 reduction could occur during cyclic voltammetry study and form a reductive species—phosphorus acid (H 3 PO 3 ). Further, to obtain reliable ORR measurement, we optimized the protocol to avoid the H 3 PO 3 generation. The ORR activity of carbon-supported PtM (M = Fe, Co, Ni, Ru, Pd, and Ir) bimetallic alloy catalysts measured with this HT-RDE method showed higher ORR activity than Pt. To understand the alloying effect, we combine experiments in diluted solutions to distinguish the alloying effect on Pt–O binding and Pt–H 3 PO 4 binding. The results indicate that H 3 PO 4 mainly reduces available sites for ORR, with little effect on neighboring site’s Pt–O binding via Pt–H 3 PO 4 interaction, which is also supported by the density functional theory calculation of the Pt–O binding energy with/without H 2 PO 4 . Further study in a phosphoric acid-doped quaternary ammonium-biphosphate ion pair coordinated polyphenylene (PA-QAPOH) membrane electrode assembly (MEA) shows that the active alloy catalyst has better performance in both the HT-RDE and MEA. Also, the MEA gives higher ORR activity than the HT-RDE because of the higher pressure and less phosphoric acid content of the MEA. Yet, the gap between the HT-RDE and MEA is significantly smaller than that between the room temperature (RT)-RDE and MEA, suggesting the importance of temperature and H 3 PO 4 concentration in understanding ORR in HT-PEMFCs.

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

A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation

High-entropy materials are an emerging pathway in the development of high-activity (electro)catalysts because of the inherent tunability and coexistence of multiple potential active sites, which may lead to earth-abundant catalyst materials for energy-efficient electrochemical energy storage. In this report, we identify how the multication composition in high-entropy perovskite oxides (HEO) contributes to high catalytic activity for the oxygen evolution reaction (OER), i.e., the key kinetically limiting half-reaction in several electrochemical energy conversion technologies, including green hydrogen generation. We compare the activity of the (001) facet of LaCr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 O 3-δ with the parent compounds (single B-site in the ABO 3 perovskite). While the single B-site perovskites roughly follow the expected volcano-type activity trends, the HEO clearly outperforms all of its parent compounds with 17 to 680 times higher currents at a fixed overpotential. As all samples were grown as an epitaxial layer, our results indicate an intrinsic composition–function relationship, avoiding the effects of complex geometries or unknown surface composition. In-depth X-ray photoemission studies reveal a synergistic effect of simultaneous oxidation and reduction of different transition metal cations during the adsorption of reaction intermediates. The surprisingly high OER activity demonstrates that HEOs are a highly attractive, earth-abundant material class for high-activity OER electrocatalysts, possibly allowing the activity to be fine-tuned beyond the scaling limits of mono- or bimetallic oxides.

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

Highly Efficient Urea Oxidation via Nesting Nano-Nickel Oxide in Eggshell Membrane-Derived Carbon

Here, we reported a strategy of using an eggshell membrane to produce hierarchically porous carbon as a low-cost substrate for synthesizing a nano-nickel oxide catalyst (C@NiO), which can effectively turn biowaste—urea—into energy through an electrochemical approach. Here, the interwoven carbon networks within NiO led to highly efficient urea oxidation due to the strong synergistic effect. The as-prepared electrode only needed 1.36 V versus reversible hydrogen electrode to realize a high efficiency of 10 mA cm –2 in 1.0 M KOH with 0.33 M urea and delivered an even higher current density of 25 mA cm –2 at 1.46 V, which is smaller than that of the porous carbon and commercial Pt/C catalyst. Benefiting from theoretical calculations, Ni(III) active species and the porous carbon further enabled the electrocatalyst to effectively inhibit the “CO 2 poisoning” of electrocatalysts, as well as ensuring its superior performance for urea oxidation.

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

Solvent-free synthesis of Co single atom and nanocluster decorated N-doped carbon for efficient oxygen reduction

The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. Here, the solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.

Nitrogen-doped carbon↗
DOE OSTI2024

Revealing Structural Evolution of Nickel Phosphide-Iron Oxide Core–Shell Nanocatalysts in Alkaline Medium for the Oxygen Evolution Reaction

Metal phosphide-containing materials have emerged as a potential candidate of non-precious metal-based catalysts for alkaline oxygen evolution reaction (OER). While it is known that metal phosphide undergoes structural evolution, considerable debate persists regarding the effects of dynamics on the surface activation and morphological stability of the catalysts. In this study, we synthesize NiP x -FeO x core-shell nanocatalysts with an amorphous NiP x core designed for enhanced OER activity. Using ex-situ X-ray absorption spectroscopy, we elucidate the local structural changes as a function of cyclic voltammetry cycles. Our studies suggest that the presence of corner-sharing octahedra in the FeO x shell improves structural rigidity through interlayer cross-linking, thereby inhibiting the diffusion of OH - /H 2 O. Thus, the FeO x shell preserves the amorphous NiP x core from rapid oxidation to Ni 3 (PO 4 ) 2 and Ni(OH) 2 . On the other hand, the incorporation of Ni from the core into the FeO x shell facilitates absorption of hydroxide ions for OER. As a result, the Ni/Fe(OH) x at the surface oxidizes to the active γ-(oxy)hydroxide phase under the applied potentials, promoting OER. This intriguing synergistic behavior holds significance as such synthetic route involving the FeO x shell can be extended to other systems, enabling manipulation of surface adsorption and diffusion of hydroxide ions. These findings also demonstrate that nanomaterials with core-shell morphology can be tuned to leverage the strength of each metallic component for improved electrochemical activities.

25 ENERGY STORAGE↗
DOE OSTI2026

Metal Identity and Coordination Environment Modulate Single-Atom Catalyst Stability During Electrocatalysis

A major hurdle to the implementation of single-atom catalysts (SACs) in real-world systems is a poor understanding of their stability under operating conditions, which is particularly relevant due to the high surface free energy of SACs. Here, we evaluated the aggregation behavior of a suite of SACs varied by metal identity (Fe, Co, Ni, and Cu) during electrocatalytic nitrate reduction using in situ X-ray absorption spectroscopy. The metal center had significant influence on reconstruction, where under identical applied reductive potentials, SACs underwent varying levels of reconstruction, ranging from no discernible change to complete reduction into metallic nanoparticles. Such in situ experiments revealed Cu SACs to be the most susceptible to aggregation, prompting a deeper investigation into how coordination environment (O-, B-, and N-graphene) affected Cu SAC aggregation. We further conducted density functional theory calculations to elucidate the relationship between Cu SAC structure and stability. This work deconvolutes the relationship between SAC architecture and stability, which is essential to evaluate and explain for the realization of SACs for electrocatalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhanced Hydrogen Evolution Catalysis of Pentlandite due to the Increases in Coordination Number and Sulfur Vacancy during Cubic‐Hexagonal Phase Transition

Abstract The search for new phases is an important direction in materials science. The phase transition of sulfides results in significant changes in catalytic performance, such as MoS 2 and WS 2 . Cubic pentlandite [cPn, (Fe, Ni) 9 S 8 ] can be a functional material in batteries, solar cells, and catalytic fields. However, no report about the material properties of other phases of pentlandite exists. In this study, the unit‐cell parameters of a new phase of pentlandite, sulfur‐vacancy enriched hexagonal pentlandite (hPn), and the phase boundary between cPn and hPn are determined for the first time. Compared to cPn, the hPn shows a high coordination number, more sulfur vacancies, and high conductivity, which result in significantly higher hydrogen evolution performance of hPn than that of cPn and make the non‐nano rock catalyst hPn superior to other most known nanosulfide catalysts. The increase of sulfur vacancies during phase transition provides a new approach to designing functional materials.

Chemistry↗
DOE OSTI2022

Promoting the water dissociation of nickel sulfide electrocatalyst through introducing cationic vacancies for accelerated hydrogen evolution kinetics in alkaline media

Developing cost-effective non-precious electrocatalysts with excellent HER performance in alkaline media is of significance for industrial hydrogen production. Herein, we successfully endow Ni 3 S 2 with unprecedentedly enhanced alkaline HER activities by introducing nickel vacancies. The Ni 3 S 2 catalyst with nickel vacancies exhibits an ultralow overpotential of 35 mV at 10 mA cm –2 in 1 M KOH electrolyte, outperforming commercial Pt/C (56 mV) and most reported non-precious electrocatalysts. The electron paramagnetic resonance and X-ray absorption fine structure etc. validates the formation of Ni vacancies and the change of the geometric/electronic structure of Ni 3 S 2 . Additionally, the theoretical calculations reveal that the Ni sites with higher valence state neighbouring the Ni vacancies can promote the water dissociation, playing a vital role in accelerating HER kinetics in alkaline media. Finally, this work may provide a universal strategy to enhance the HER activity of transition-metal compound catalysts in alkaline media by means of cationic defect engineering.

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

Template-free fabrication of fractal porous Y 2 O 3 monolithic foam and its functional modification by Ni-doping

Fractal structures which display nearly the same character at every scale exist widely in nature, however, it is still a great challenge to fabricate a fractal nanostructure. Herein, a Y 2 O 3 monolith with unique hierarchically fractal porous structure was fabricated via calcination of a fractal porous coordination polymer precursor. The monolith exhibits porous feature with the pore-size ranging from micrometers to nanometers. Interestingly, each level of the pore-wall is composed of secondary porous structures, whose pore-wall is composed of sub-level self-similar porous feature. Moreover, by Ni-doping in the coordination polymer precursor, fractal porous Ni@Y 2 O 3 was prepared, and exhibited enhanced activity in ethanol steam reforming compared with that of a common supported NiO catalyst.

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

Breaking Simple Scaling Relations through Metal–Oxide Interactions: Understanding Room-Temperature Activation of Methane on M/CeO 2 (M = Pt, Ni, or Co) Interfaces

The clean activation of methane at low temperatures remains an eminent challenge and a field of competitive research. In particular, on late transition metal surfaces such as Pt(111) or Ni(111), higher temperatures are necessary to activate the hydrocarbon molecule, but a massive deposition of carbon makes the metal surface useless for catalytic activity. However, on very low-loaded M/CeO 2 (M = Pt, Ni, or Co) surfaces, the dissociation of methane occurs at room temperature, which is unexpected considering simple linear scaling relationships. This intriguing phenomenon has been studied using a combination of experimental techniques (ambient-pressure X-ray photoelectron spectroscopy, time-resolved X-ray diffraction, and X-ray absorption spectroscopy) and density functional theory-based calculations. The experimental and theoretical studies show that the size and morphology of the supported nanoparticles together with strong metal–support interactions are behind the deviations from the scaling relations. These findings point toward a possible strategy for circumventing scaling relations, producing active and stable catalysts that can be employed for methane activation and conversion.

03 NATURAL GAS↗
DOE OSTI2021

The role of sub-surface hydrogen on CO 2 reduction and dynamics on Ni(110): An ab initio molecular dynamics study

The catalytic reduction of carbon dioxide is a crucial step in many chemical industrial reactions, such as methanol synthesis, the reverse water-gas shift reaction (rWGS) and formic acid synthesis. Here, we investigate the role of bulk hydrogen, where hydrogen atoms are found deep inside a metal surface as opposed to subsurface ones, upon CO 2 reduction over a Ni(110) surface using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. While it has previously been shown that subsurface hydrogen stabilizes CO 2 and can aid in overcoming reaction barriers, the role of bulk hydrogen is less studied and thus unknown with regard to CO 2 reduction. Furthermore, we find that the presence of bulk hydrogen can significantly alter the electronic structure of the Ni(110) surface, particularly the work function and d-band center, such that CO 2 adsorbs more strongly to the surface and is more easily reduced. Our results show an enhanced CO 2 dissociation in the presence of bulk hydrogen, shedding light on a hitherto underappreciated mechanistic pathway for CO 2 reduction on metal surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗