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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 OSTI2021

Atomic Structure Evolution of Pt–Co Binary Catalysts: Single Metal Sites versus Intermetallic Nanocrystals

Due to their exceptional catalytic properties for the oxygen reduction reaction (ORR) and other crucial electrochemical reactions, PtCo intermetallic nanoparticle (NP) and single atomic (SA) Pt metal site catalysts have received considerable attention. However, their formation mechanisms at the atomic level during high-temperature annealing processes remain elusive. Furthermore, the thermally driven structure evolution of Pt–Co binary catalyst systems is investigated using advanced in situ electron microscopy, including PtCo intermetallic alloys and single Pt/Co metal sites. The pre-doping of CoN 4 sites in carbon supports and the initial Pt NP sizes play essential roles in forming either Pt 3 Co intermetallics or single Pt/Co metal sites. Importantly, the initial Pt NP loadings against the carbon support are critical to whether alloying to L1 2 -ordered Pt 3 Co NPs or atomizing to SA Pt sites at high temperatures. High Pt NP loadings (e.g., 20%) tend to lead to the formation of highly ordered Pt 3 Co intermetallic NPs with excellent activity and enhanced stability toward the ORR. In contrast, at a relatively low Pt loading (<6 wt%), the formation of single Pt sites in the form of PtC 3 N is thermodynamically favorable, in which a synergy between the PtC 3 N and the CoN 4 sites could enhance the catalytic activity for the ORR, but showing insufficient stability.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO 2

Catalysts consisting of atomically dispersed Pt (Pt iso ) species on CeO 2 supports have received recent interest due to their potential for efficient metal utilization in catalytic convertors. However, discrepancies exist between the behavior (reducibility, interaction strength with adsorbates) of high surface area Pt iso /CeO 2 systems and of well-defined surface science and computational model systems, suggesting differences in Pt local coordination in the two classes of materials. Here, we reconcile these differences by demonstrating that high surface area Pt iso /CeO 2 synthesized at low Pt loadings (<0.1% weight) exhibit resistance to reduction and sintering up to 500 °C in 0.05 bar H 2 and minimal interactions with CO—properties previously seen only for model system studies. Alternatively, Pt loadings >0.1 weight % produce a distribution of sub-nanometer Pt structures, which are difficult to distinguish using common characterization techniques, and exhibit strong interactions with CO and weak resistance to sintering, even in 0.05 bar H 2 at 50 °C—properties previously seen for high surface area materials. This work demonstrates that low metal loadings can be used to selectively populate the most thermodynamically stable adsorption sites on high surface area supports with atomically dispersed metals. Further, the site uniformity afforded by this synthetic approach is critical for the development of relationships between atomic scale local coordination and functional properties. Comparisons to recent studies of Pt iso /TiO 2 suggest a general compromise between the stability of atomically dispersed metal catalysts and their ability to interact with and activate molecular species.

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

Dual active site tandem catalysis of metal hydroxyl oxides and single atoms for boosting oxygen evolution reaction

We report the high voltage in oxygen evolution reaction (OER) often causes structural change in electrocatalysts and forms multiple active sites. Therefore, exploring the synergy of various active sites is extremely significant to develop catalysts for OER with multiple elementary steps. Herein, we adopt the physically adsorbed metal ions method to successfully synthesize a highly-efficient electrocatalyst containing the dual active sites of Fe-NiOOH and NiC4 single atoms (marked as Ni SAs/Fe-NiOOH). The Ni SAs/Fe-NiOOH displays outstanding OER performance with an overpotential of 269 mV to deliver current density of 10 mA/cm 2 that shows 55 mV superior to commercial IrO 2 /CB at the same condition. Experiments and density functional theory calculations indicate that the excellent OER activity of Ni SAs/Fe-NiOOH catalyst is attributed to the synergy of dual active sites of NiC 4 SAs and Fe-NiOOH. A tandem catalysis mechanism is also proposed to reveal the synergism of two active centers, which makes the potential-determining step more facile and accordingly decreases the OER overpotential. This work offers a new concept of tandem catalysis to develop the electrocatalysts with many elemental steps, like OER and oxygen reduction reaction catalysts.

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

Combining artificial intelligence and physics-based modeling to directly assess atomic site stabilities: from sub-nanometer clusters to extended surfaces

The performance of functional materials is dictated by chemical and structural properties of individual atomic sites. In catalysts, for instance, the thermodynamic stability of constituting atomic sites is a key descriptor from which more complex properties, such as molecular adsorption energies and reaction rates, can be derived. In this study, we present a widely applicable machine learning (ML) approach to instantaneously compute the stability of individual atomic sites in structurally and electronically complex nano-materials. Conventionally, we determine such site stabilities using computationally intensive first-principles calculations. With our approach, we predict the stability of atomic sites in sub-nanometer metal clusters of 3–55 atoms with mean absolute errors in the range of 0.11–0.14 eV. To extract physical insights from the ML model, we introduce a genetic algorithm (GA) for feature selection. This algorithm distills the key structural and chemical properties governing the stability of atomic sites in size-selected nanoparticles, allowing for physical interpretability of the models and revealing structure–property relationships. The results of the GA are generally model and materials specific. In the limit of large nanoparticles, the GA identifies features consistent with physics-based models for metal–metal interactions. By combining the ML model with the physics-based model, we predict atomic site stabilities in real time for structures ranging from sub-nanometer metal clusters (3–55 atom) to larger nanoparticles (147 to 309 atoms) to extended surfaces using a physically interpretable framework. Finally, we present a proof of principle showcasing how our approach can determine stable and active nanocatalysts across a generic materials space of structure and composition.

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

Metal-Coordinated Phthalocyanines as Platform Molecules for Understanding Isolated Metal Sites in the Electrochemical Reduction of CO 2

Single-atom catalysts (SACs) of non-precious transition metals (TMs) often show unique electrochemical performance, including the electrochemical carbon dioxide reduction reaction (CO 2 RR). However, the inhomogeneity in their structures makes it difficult to directly compare SACs of different TM for their CO 2 RR activity, selectivity, and reaction mechanisms. Here, the comparison of isolated TMs (Fe, Co, Ni, Cu, and Zn) is systematically investigated using a series of crystalline molecular catalysts, namely TM-coordinated phthalocyanines (TMPcs), to directly compare the intrinsic role of the TMs with identical local coordination environments on the CO 2 RR performance. The combined experimental measurements, in situ characterization, and density functional theory calculations of TM-Pc catalysts reveal a TM dependent CO 2 RR activity and selectivity, with the free energy difference of ΔG(*HOCO) - ΔG(*CO) being identified as a descriptor for predicting the CO 2 RR performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Vapor–Phase Synthesis of Electrocatalytic Covalent Organic Frameworks

The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor-phase pathway for the bottom-up synthesis of a class of porphyrin-based COFs is presented. This approach allows integrating electrocatalysts made of metal-ion-containing COFs into the electrodes’ architectures in a single-step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR-COFs is demonstrated. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COFs.

25 ENERGY STORAGE↗
DOE OSTI2023

Dual-site catalysts featuring platinum-group-metal atoms on copper shapes boost hydrocarbon formations in electrocatalytic CO2 reduction

Abstract Copper-based catalyst is uniquely positioned to catalyze the hydrocarbon formations through electrochemical CO 2 reduction. The catalyst design freedom is limited for alloying copper with H-affinitive elements represented by platinum group metals because the latter would easily drive the hydrogen evolution reaction to override CO 2 reduction. We report an adept design of anchoring atomically dispersed platinum group metal species on both polycrystalline and shape-controlled Cu catalysts, which now promote targeted CO 2 reduction reaction while frustrating the undesired hydrogen evolution reaction. Notably, alloys with similar metal formulations but comprising small platinum or palladium clusters would fail this objective. With an appreciable amount of CO-Pd 1 moieties on copper surfaces, facile CO * hydrogenation to CHO * or CO-CHO * coupling is now viable as one of the main pathways on Cu(111) or Cu(100) to selectively produce CH 4 or C 2 H 4 through Pd-Cu dual-site pathways. The work broadens copper alloying choices for CO 2 reduction in aqueous phases.

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

Modifying the Reactivity of Single Pd Sites in a Trimetallic Sn‐Pd‐Ag Surface Alloy: Tuning CO Binding Strength

Abstract Improving control over active‐site reactivity is a grand challenge in catalysis. Single‐atom alloys (SAAs) consisting of a reactive component doped as single atoms into a more inert host metal feature localized and well‐defined active sites, but fine tuning their properties is challenging. Here, a framework is developed for tuning single‐atom site reactivity by alloying in an additional inert metal, which this work terms an alloy‐host SAA. Specifically, this work creates about 5% Pd single‐atom sites in a Pd 33 Ag 67 (111) single crystal surface, and then identifies Sn based on computational screening as a suitable third metal to introduce. Subsequent experimental studies show that introducing Sn indeed modifies the electronic structure and chemical reactivity (measured by CO desorption energies) of the Pd sites. The modifications to both the electronic structure and the CO adsorption energies are in close agreement with the calculations. These results indicate that the use of an alloy host environment to modify the reactivity of single‐atom sites can allow fine‐tuning of catalytic performance and boost resistance against strong‐binding adsorbates such as CO.

Mohrhusen, Lars↗
DOE OSTI2022

The emergence of valency in colloidal crystals through electron equivalents

Colloidal crystal engineering of complex, low-symmetry architectures is challenging when isotropic building blocks are assembled. In this study we describe an approach to generating such structures based upon programmable atom equivalents (nanoparticles functionalized with many DNA strands) and mobile electron equivalents (small particles functionalized with a low number of DNA strands complementary to the programmable atom equivalents). Under appropriate conditions, the spatial distribution of the electron equivalents breaks the symmetry of isotropic programmable atom equivalents, akin to the anisotropic distribution of valence electrons or coordination sites around a metal atom, leading to a set of well-defined coordination geometries and access to three new low-symmetry crystalline phases. All three phases represent the first examples of colloidal crystals, with two of them having elemental analogues (body-centred tetragonal and high-pressure gallium), while the third (triple double-gyroid structure) has no known natural equivalent. This approach enables the creation of complex, low-symmetry colloidal crystals that might find use in various technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Stabilization of Cu 2 O through Site-Selective Formation of a Co 1 Cu Hybrid Single-Atom Catalyst

Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co 1 Cu SAC centers on a Cu 2 O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu 2 O(111) surface, forming a Co 1 Cu SAA with no direct Co–O x bonds. The centers, here referred to as Co 1 Cu hybrid SACs, are found to stabilize the active Cu + sites of the low-cost Cu 2 O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu 2 O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pt Atomic Single-Layer Catalyst Embedded in Defect-Enriched Ceria for Efficient CO Oxidation

The local coordination structure of metal sites essentially determines the performance of supported metal catalysts. Here, using a surface defect enrichment strategy, we successfully fabricated Pt atomic single-layer (Pt ASL ) structures with 100% metal dispersion and precisely controlled local coordination environment (embedded vs adsorbed) derived from Pt single-atoms (Pt 1 ) on ceria-alumina supports. The local coordination environment of Pt 1 not only governs its catalytic activity but also determines the Pt 1 structure evolution upon reduction activation. For CO oxidation, the highest turnover frequency can be achieved on the embedded Pt ASL in the CeO 2 lattice, which is 3.5 times of that on the adsorbed Pt ASL on the CeO 2 surface and 10–70 times of that on Pt1. The favorable CO adsorption on embedded Pt ASL and improved activation/reactivity of lattice oxygen within CeO 2 effectively facilitate the CO oxidation. This work provides new insights for the precise control of the local coordination structure of active metal sites for achieving 100% atomic utilization efficiency and optimal intrinsic catalytic activity for targeted reactions simultaneously.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Insights into Native Single-Atom Electrocatalyst Site Structures

Single-atom electrocatalysts consisting of metal atoms embedded in a carbon matrix are promising next-generation catalysts for green hydrogen production and utilization, CO2 reduction, low-temperature CO oxidation, ammonia production, plastic decomposition, and electrochemical energy storage. The origins of activity and stability for the single-atom sites are still debatable, however, because of constrained insights into their local structure resulting from idealized models and experiments derived from a large number of individual sites. Insights into structural variations around single atomic sites are therefore critical for the continued development of these next-generation catalysts. While electron microscopy commonly provides atomic-scale information about these materials, the beam sensitivity of individual sites makes structural determination by conventional low-voltage (60 keV) techniques challenging. Here, we introduce ultralow-voltage electron ptychography, performed at 30 keV, that enables determination of the lattice structure around individual metal sites in a well-defined single-atom electrocatalyst system while essentially eliminating knock-on structural modifications. Pairing these atomic-scale, site-specific measurements with computational methods will broaden our understanding of the activity and stability of these materials, which will accelerate the development of the next generation of catalysts.

Zachman, Michael [ORNL] (ORCID:0000000319101357)↗
DOE OSTI2020

Supported and coordinated single metal site electrocatalysts

The ever-increasing global environmental and energy crisis issues necessitates technological innovation, especially in the development of renewable energy-related devices, such as electrochemical energy conversion and storage technologies, including fuel cells, water electrolyzers, and CO 2 electrolyzers. Reliable and sustainable energy conversion devices are highly dependent on engineering of electrocatalysts. Furthermore, state-of-the-art electrocatalysts for these electrochemical conversion systems are usually platinum group metal (PGM)-based nanoparticles with high cost, which has sparked intensive research on atomically dispersed single metal site electrocatalysts for decreasing metal loadings and boosting catalytic efficiencies by taking advantage of their inherent electronic effects, quantum size effects, and metal-support interactions. In this review, we first introduced the intrinsic active site identification and stabilization, followed by addressing the mutual metal-support interactions, and most important, their correlations with catalytic properties. Next, the advances in synthetic strategies and characterization techniques for single metal site electrocatalysts are highlighted. Additionally, recent advances in single metal site electrocatalysts designs for applications in electrochemical conversion reactions are also presented. Finally, remaining challenges and a forward-looking perspective on this field of research are provided.

25 ENERGY STORAGE↗
DOE OSTI2021

Atomically dispersed single iron sites for promoting Pt and Pt 3 Co fuel cell catalysts: performance and durability improvements

Significantly reducing platinum group metal (PGM) loading while improving catalytic performance and durability is critical to accelerating proton-exchange membrane fuel cells (PEMFCs) for transportation. In this study, we report an effective strategy to boost PGM catalysts through integrating PGM-free atomically-dispersed single metal active sites in the carbon support toward the cathode oxygen reduction reaction (ORR). We achieved uniform and fine Pt nanoparticle (NP) (~2 nm) dispersion on an already highly ORR-active FeN 4 site-rich carbon (FeN 4 –C). Furthermore, we developed an effective approach to preparing a well-dispersed and highly ordered L1 2 Pt 3 Co intermetallic nanoparticle catalyst on the FeN 4 –C support. DFT calculations predicted a synergistic interaction between Pt clusters and surrounding FeN 4 sites through weakening O 2 adsorption by 0.15 eV on Pt sites and reducing activation energy to break O–O bonds, thereby enhancing the intrinsic activity of Pt. Experimentally, we verified the synergistic effect between Pt or Pt 3 Co NPs and FeN 4 sites, leading to significantly enhanced ORR activity and stability. Especially in a membrane electrode assembly (MEA) with a low cathode Pt loading (0.1 mg Pt cm –2 ), the Pt/FeN 4 –C catalyst achieved a mass activity of 0.451 A mg Pt –1 and retained 80% of the initial values after 30 000 voltage cycles (0.60 to 0.95 V), exceeding DOE 2020 targets. Furthermore, the Pt 3 Co/FeN 4 catalyst achieved significantly enhanced performance and durability concerning initial mass activity (0.72 A mg Pt –1 ), power density (824 mW cm –2 at 0.67 V), and stability (23 mV loss at 1.0 A cm –2 ). The approach to exploring the synergy between PGM and PGM-free Fe–N–C catalysts provides a new direction to design advanced catalysts for hydrogen fuel cells and various electrocatalysis processes.

25 ENERGY STORAGE↗
DOE OSTI2024

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate–Metal–Organic-Framework Architecture

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson–Evans polyoxometalate clusters (POMs, MMo 6 O 24 , M = Rh/Pt) within NU-1000, a Zr-based metal–organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Furthermore, models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.

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

Optimizing Microenvironment of Asymmetric N,S-Coordinated Single-Atom Fe via Axial Fifth Coordination toward Efficient Oxygen Electroreduction

We report single-atom catalysts (SACs) are attractive candidates for oxygen reduction reaction (ORR). The catalytic performances of SACs are mainly determined by the surrounding microenvironment of single metal sites. Microenvironment engineering of SACs and understanding of the structure–activity relation-ship is critical, which remains challenging. Herein, a self-sacrificing strategy is developed to synthesize asymmetric N,S-coordinated single-atom Fe with axial fifth hydroxy (OH) coordination (Fe-N 3 S 1 OH) embedded in N,S codoped porous carbon nanospheres (Fe-N/S-C). Such unique penta-coordination microenvironment is determined by cutting-edge techonologies aiding of systematic simulations. The as-obtained Fe-;N/S-C exhibits superior catalytic ORR activity, and showcases a half-wave potential of 0.882 V surpassing the benchmark Pt/C. Moreover, theoretical calculations confirmed the axial OH in Fe-N 3 S 1 OH can optimize 3d orbitals of Fe center to strengthen O 2 adsorption and enhance O 2 activation on Fe site, thus reducing the ORR barrier and accelerating ORR dynamics. Furthermore, Fe-N/S-C containing H 2 -O 2 fuel cell performs a high peak power density of 512 mW cm -2 , and Fe-N/S-C based Zn-air batteries show the peak power density of 203 and 49 mW cm -2 in liquid and flexible all-solid-state configurations, respectively. This study offers a new platform for fundamentally understand the axial fifth coordination in asymmetrical planar single-atom metal sites for electrocatalysis.

microenvironment↗