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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Metal hybridization in dilute-alloy catalysts promotes sintering resistance by decreasing surface mobility

Dilute-metal-alloy nanoparticles exhibit enhanced catalytic performance compared with monometallic nanoparticles for many reactions. Anecdotal reports indicate that very dilute alloying can also slow the sintering rates of supported nanoparticles, although this has not been rigorously assessed and cannot be explained using bulk descriptors such as metal melting temperature. Here, in this study, we utilize methanol synthesis reactivity, microscopy and in situ spectroscopy measurements to demonstrate that 1 atom% Pt addition to ~1–2-nm-diameter Cu (Pt 1 Cu 100 ) nanoparticles supported on SiO 2 dramatically decreases their sintering rates. Minimal sintering of Pt 1 Cu 100 nanoparticles is observed during aging in H 2 up to 700 °C versus 500 °C for Cu nanoparticles. Scanning tunnelling microscopy reveals that the addition of 0.01 monolayer of Pt to a Cu(110) surface decreases the detachment rate of undercoordinated atoms, demonstrating that dilute dopants can locally decrease the rate of the first step in nanoparticle sintering. Density functional theory calculations quantify the stabilization and predict other sinter-resistant dilute alloys. We find that the degree of host–dopant d-state hybridization correlates with decreased surface mobility, providing a mechanistic framework for designing sinter-resistant catalysts.

Finzel, Jordan [Univ. of California, Santa Barbara↗
DOE OSTI2020

Silver Adsorption on Calcium Niobate(001) Nanosheets: Calorimetric Energies That Explain Sinter-Resistant Support

Metal nanoparticles deposited on oxide supports are essential to many technologies, including catalysts, fuel cells and electronics. Therefore, understanding the chemical bonding strength between metal nanoparticles and oxide surfaces is of great interest. The adsorption energetics, adhesion energy and adsorbate structure of Ag on dehydrated HCa 2 Nb 3 O 10 (001) nanosheets at 300 K have been studied using metal adsorption calorimetry and surface spectroscopies. These dehydrated (“dh”) calcium niobate nanosheets “(dh-HCa 2 Nb 3 O 10 (001))” have stoichiometry Ca 4 Nb 6 O 19 . They impart unusual stability to metal nanoparticles when used as catalyst supports and are easy-to-prepare by Langmuir-Blodgett (LB) techniques, highly ordered, and essentially single-crystal surfaces of mixed oxides with a huge ratio of terrace to edge sites. Below monolayer coverage, Ag grows on dh-HCa 2 Nb 3 O 10 (001) as 2D islands of thickness ~2 layers. The differential heat of Ag adsorption is initially ~303 kJ/mol, increasing slowly to ~338 kJ/mol by 0.8 ML. At higher coverages, Ag atoms mainly add on top of these 2D islands, growing 3D nanoparticles of increasing thickness, as the heat decreases asymptotically towards silver’s heat of sublimation (285 kJ/mol). The adhesion energy of Ag(s) to this Ca niobate surface is estimated to be 4.33 J/m 2 , larger than on any oxide surface previously measured. This explains the sinter resistance reported for metal nanoparticles on this support. Electron transfer from Ag into the calcium niobate is also measured. Furthermore, these results demonstrate an easy way to do singlecrystal-type surface science studies - and especially thermochemical measurements - on the complex surfaces of mixed oxides: using LB-deposited perovskite nanosheets and ultrahigh vacuum annealing in O 2 .

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

Tuning transition metal nanoparticles on a non-traditional support via experimental design

The ability to control metal nanoparticle size and morphology on supported catalysts is crucial for optimizing catalytic performance in targeted applications. Here, this work presents a systematic approach for tuning Ni particle and crystallite size on an unconventional, low-porosity silica fume support through select thermal treatments. The catalyst was synthesized via the deposition of nickelocene onto silica fume, resulting in well-dispersed Ni nanoparticles. A face-centered central composite design was employed to systematically assess the effects of time, temperature, and sintering gas environment on metal particle growth. The results demonstrate that the sintering gas environment is the primary factor governing particle and crystallite evolution, with temperature as the next most significant influence. Nickel nanoparticles sintered at temperatures of 650 °C and above under inert conditions exhibited substantial growth and polycrystalline structures, whereas samples treated in oxidative environments formed NiO, restricting particle mobility. Minimally oxidative (500 ppm O₂) environments facilitated rapid sintering while effectively removing residual ligands from the one-step nickelocene deposition process. Extensive structural characterization via a combination of scanning transmission electron microscopy, X-ray diffraction, hydrogen temperature programmed reduction, and small-angle X-ray scattering revealed that oxidative treatments enhanced metal-support interactions, as evidenced by increased reduction temperatures and narrower particle size distributions. These findings establish quantitative relationships between sintering parameters and Ni nanoparticle characteristics, providing a framework for rational catalyst design through controlled thermal treatments. This methodology is broadly applicable to other catalytic systems and provides a quantitative foundation for catalyst design.

CVD↗
DOE OSTI2022

Templated encapsulation of platinum-based catalysts promotes high-temperature stability to 1,100 °C

Stable catalysts are essential to address energy and environmental challenges, especially for applications in harsh environments (for example, high temperature, oxidizing atmosphere and steam). In such conditions, supported metal catalysts deactivate due to sintering-a process where initially small nanoparticles grow into larger ones with reduced active surface area-but strategies to stabilize them can lead to decreased performance. In this work, we report stable catalysts prepared through the encapsulation of platinum nanoparticles inside an alumina framework, which was formed by depositing an alumina precursor within a separately prepared porous organic framework impregnated with platinum nanoparticles. These catalysts do not sinter at 800 °C in the presence of oxygen and steam, conditions in which conventional catalysts sinter to a large extent, while showing similar reaction rates. Extending this approach to Pd-Pt bimetallic catalysts led to the small particle size being maintained at temperatures as high as 1,100 °C in air and 10% steam. This strategy can be broadly applied to other metal and metal oxides for applications where sintering is a major cause of material deactivation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cost-effective Manufacturing and Morphological Stabilization of Nanostructured Cathodes for Commercial Solid Oxide Fuel Cells (SOFCs) [Slides]

The overall goals of the program were to develop methods for preparing and stabilizing SOFC electrodes by infiltration that can be manufactured on a practical scale, then transfer those methods to cells in stacks. Cathodes prepared by infiltration of nanoparticles into a porous scaffold of the electrolyte have demonstrated outstanding electrochemical performance and mechanical strength but are difficult to manufacture due to the large number of infiltration steps required to produce a conductive composite and show poor stability due to sintering of the nanoparticles. At Penn, the main goal was to develop a fabrication method that uses only a small number of infiltration steps. Infiltration with molten salts and electrodeposition were pursued but deemed impractical. A method in which an electronically conductive scaffold consisted of a composite of a mixed conductor, LSF (La 0.9 Sr 0.1 FeO 3 ), with yttria-stabilized zirconia (YSZ) was found to be promising. While some cation mixing between LSF and YSZ was observed during calcination, there was no evidence for new phases in XRD and incorporation of Zr into the perovskite could be minimized by reducing the Sr content of the LSF. To stabilize nanoparticles infiltrated into the LSF-YSZ composite scaffold, the USC team examined the effects of Atomic Layer Deposition with ZrO 2 and infiltrated nanoparticles. Significantly enhanced stability was observed with the infiltrated nanoparticles. The FuelCell Energy team prepared 4”x4” cells in which an LSF-YSZ composite scaffold was cofired with the YSZ electrolyte and infiltrated with LSCF nanoparticles. Apparently because the LSF-YSZ scaffold layer was very thin in this case, the cation mixing that occurred during calcination resulted in a poor scaffold-electrolyte interface which caused reduced performance.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Ripening of Rh Nanoparticle Catalysts in Reverse Water–Gas Shift via a Data-Driven Model Combining Physics, Theory, and Experiment

Degradation via sintering is an ongoing challenge that impedes the broad commercial success of supported metallic nanoparticle catalysts. To mitigate degradation via informed catalyst design and process operations, here we aim to disambiguate the underlying mechanisms of sintering by combining theory and experiment in a quantitative framework. While mechanistic sintering models exist, they only model a single sintering pathway, even though multiple sintering mechanisms can occur simultaneously or dominate at different stages of the process. Data-driven machine learning models have emerged as a means to represent complex processes through data regression. However, machine learning models have very large data needs and lack mechanistic insights due to their black-box encoding. To develop an interpretive model of catalyst degradation via sintering, we constructed a hybrid model combining mechanistic “physics-based” models and data-driven methods to obtain both reliable predictions and mechanistic insights regarding experimentally observed sintering phenomena. Focusing on nanoparticle sintering in the Rh–TiO 2 catalyst for the reverse water–gas shift (RWGS) reaction, the hybrid model couples a mechanistic term for Ostwald ripening with energy values calculated via density functional theory (DFT) with a parametric, data-driven discrepancy function term for unmodeled mechanisms. The hybrid model is trained using Bayesian inference with data collected from small-angle X-ray scattering (SAXS) in situ experiments wherein average nanoparticle diameter versus time was measured at three relevant operating temperatures. The calibrated hybrid model results show that an Ostwald ripening-only model parameterized with fixed DFT energies does not fully capture the time and temperature dependence of the SAXS-observed sintering kinetics, and that an additional functional contribution, or DFT energy calibration, is required to reconcile simulation and experiment. Analysis of the hybrid-model error confirms that the hybrid model outperforms both the purely mechanistic and purely data-driven alternatives in terms of expected predictive accuracy for time-evolving average particle sizes. Furthermore, the results support the hypothesis that the Ostwald ripening mechanism is less important for explaining the sintering phenomena as operating temperature increases under an assumed fixed DFT parameterization. This could be explained in one of two ways: either latent, unmodeled sintering mechanisms dominate at higher temperatures, or the DFT uncertainty increases with temperature. The proposed modeling approach directly links theory to experiments and simulations via a statistical hybrid modeling framework and can be extended to other catalytic systems to improve predictive models and mechanistic understanding.

Bayesian hybrid modeling↗
DOE OSTI2025

Unravelling Adsorbate-Metal-Oxide Interactions: Water Vapor Chemistry on the Growth and Sintering of Ni over Reducible CeO2(111) Thin Films

The role of water in the growth and sintering of Ni particles over well-ordered CeOx(111) (1.5 < x < 2) thin films was investigated through scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) studies, considering ceria-supported Ni attracts great attention as a promising catalyst for reactions such as steam reforming of ethanol and water gas shift reaction, in which water vapor is used as a key reactant. In the study, both fully oxidized CeO2 and partially reduced CeO1.75 thin films were prepared to examine the effect of the oxygen vacancies/Ce3+ sites in ceria supports. Our STM results revealed that dosing water before or after Ni deposition over the CeOx(111) surfaces at room temperature influenced the sintering behavior of Ni nanoparticles with further heating. Exposure of water to Ni nanoparticles that were deposited over both CeO2 and CeO1.75 at 300 K causes the formation of flatter particles with significantly reduced height when heating to the same temperatures compared to Ni/ceria with no water adsorbates. The flatter Ni particles were also observed when water was first dosed over CeO2 at 300 K followed by Ni deposition at room temperature and further heating. Over a partially reduced CeO1.75 surface with predosed water at 300 K, there is an extensive decrease in the particle density upon subsequent Ni deposition at room temperature and a significant increase in the height for Ni nanoparticles with further heating to higher temperatures compared to Ni over a pristine CeO1.75 surface. This is due to the filling of oxygen vacancies caused by the dissociation of water. This creates fewer nucleation sites for Ni on ceria, weakening the metal-oxide interaction and causing significant metal sintering. Our experimental findings suggest distinct adsorbate-metal-oxide interactions are key to the tuning of sintering of Ni nanoparticles over the CeOx(111) surface caused by water exposure. Such interactions are essential for the further modification of Ni-based catalysts for improved reactivity and stability.

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

Highly dispersed Pt atoms and clusters on hydroxylated indium tin oxide: a view from first-principles calculations

Supported single-atom and small cluster catalysts have become highly popular in heterogeneous catalysis. These catalysts can maximize the metal atom utilization while still showing superior catalytic performance. One of the main challenges in producing these small cluster catalysts is their low binding strength with the support, which causes these small clusters to sinter into larger nanoparticles. We have used first-principles simulations to study small Pt n ( n : 1,2,3) clusters on indium oxide, tin doped indium oxide, and hydroxylated tin doped indium oxide. We report that the Pt n cluster is stabilized in the presence of tin and that this is especially the case for Pt single atoms on the hydroxylated indium tin oxide support, which are anchored to the support via the hydroxyl group. On this support, the Pt single atoms become more stable than Pt 2 and Pt 3 clusters, hence decreasing sintering. These findings provide a promising way to design single-atom catalysts on electrically conducting supports for electrocatalytic applications and to better understand how functional groups on supports can increase the adhesion of cluster catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Temperature-induced hexagonal–orthorhombic phase transition in lutetium ferrite nanoparticles

The x-ray diffraction, Raman, and infrared spectroscopies and magnetic measurements were used to explore the correlated changes of the structure, lattice dynamics, and magnetic properties of the LuFeO3 nanoparticles, which appear in dependence on their sintering temperature. We revealed a gradual substitution of the hexagonal phase by the orthorhombic phase in the nanoparticles, with sintering temperature increasing from 700 to 1100 °C. The origin and stability of the hexagonal phase in the LuFeO3 nanoparticles are of the special interest, because the nanoparticles in the phase can be a room-temperature multiferroic with a weak ferromagnetic and pronounced structural and ferroelectric long-range ordering. The antiferromagnetic and nonpolar orthorhombic phase is more stable in the bulk LuFeO3. To define the ranges of the hexagonal phase stability, we determine the bulk and interface energy densities of different phases from the comparison of the Gibbs model with experimental results. Using effective parameters of the Gibbs model, we predict the influence of size effects and temperature on the structural and polar properties of the LuFeO3 nanoparticles. Analysis of the obtained results shows that the combination of the x-ray diffraction, Raman and infrared spectroscopies, magnetic measurements, and theoretical modeling of structural and polar properties allows us to establish the interplay between the phase composition, lattice dynamics, and multiferroic properties of the LuFeO3 nanoparticles prepared under different conditions.

Materials Science↗
DOE OSTI2021

Persistent Structure and Frustrated Magnetism in High Entropy Rare-Earth Zirconates

The configurational complexity and distinct local atomic environments of high entropy oxides remain largely unexplored, leaving structure-property relationships and the hypothesis that the family offers rich tunability for applications ambiguous. This work investigates the influence of cation size and materials synthesis in determining the resulting structure and magnetic properties of a family of high entropy rare-earth zirconates (HEREZs, nominal composition RE 2 Zr 2 O 7 with RE = rare-earth element combinations including Eu, Gd, Tb, Dy, Ho, La, or Sc). Here, the structural characterization of the series is examined through synchrotron X-ray diffraction and pair distribution function analysis, and electron microscopy, demonstrating average defect-fluorite structures with considerable local disorder, in all samples. The surface morphology and particle sizes are found to vary significantly with preparation method, with irregular micron-sized particles formed by high temperature sintering routes, spherical nanoparticles resulting from chemical co-precipitation methods, and porous nanoparticle agglomerates resulting from polymer steric entrapment synthesis. In agreement with the disordered cation distribution found across all samples, magnetic measurements indicate that all synthesized HEREZs show frustrated magnetic behavior, as seen in a number of single-component RE 2 Zr 2 O 7 pyrochlore oxides. These findings advance the understanding of the local structure of high entropy oxides and demonstrate strategies for designing nanostructured morphologies in the class.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Higher Throughput, Lower Cost Processing of Flexible Perovskite Solar Cells by Photonic Curing

The objectives of this SETO project are to explore whether photonic curing can be used to perform annealing in perovskite solar cell (PSC) fabrication, and if so, whether it can enable high-throughput PSC manufacturing. The successful outcome of the project will reduce manufacturing cost towards realizing the SETO goal of the Levelized cost of electricity (LCOE) $0.03/kWh by 2030. The project is a collaboration between Hsu’s group at the University of Texas at Dallas (UTD) and NovaCentrix, an Austin TX based company that pioneered the PulseForge® photonic curing tools and has expertise in applying this technology to printed electronics. Thin-film synthesis typically involves a thermal annealing step to convert from precursors to final material phases, to obtain the desired crystalline phase, or to improve materials structural or electrical properties. However, thermal annealing typically requires high temperatures that are incompatible with inexpensive plastic substrates and annealing times lasting tens-to-hundreds of minutes, making it incompatible with roll-to-roll (R2R) manufacturing at a desirable web speed. Photonic curing uses a flash Xe lamp to deliver short (20 µs to 100 ms) but high intensity (up to 50 kW/cm 2 ) pulses of broadband light (200 – 1500 nm) to the sample. It has been successfully applied to sinter printed metal nanoparticle inks into conductive patterns. This project aimed to extend the applications of photonic curing to convert halide perovskite films and transparent metal oxide transport layers. Despite the interruption by COVID-19, we have achieved significant accomplishments to establish photonic curing as a viable technology for the high-throughput manufacturing of PSCs. (1) We demonstrated that photonic curing can convert both metal oxide transport layer and halide perovskite absorber in the PSCs and successfully made flexible PSCs on Corning Willow glass® (WG)/ indium tin oxide (ITO) substrates without any thermal annealing steps. These photonically cured devices achieve performance comparable to conventional thermally annealed devices but were fabricated with a total processing time reduced by six orders of magnitude. We also show that photonic curing can achieve desirable web speed (up to 26 m/min) and large-area uniformity. (2) By establishing photonic curing processing phase spaces for the perovskite, we show that the longer pulses are more forgiving in small variation in the photonic curing conditions, making it more suitable for R2R manufacturing. (3) Our results clearly illustrated the importance of improving mechanical and optical properties of transparent electrodes on flexible substrates. (4) We also performed fundamental studies that elucidate the interactions between perovskite absorber and metal oxide transport layer that can undermine the PSC stability. Five refereed journal papers in top journals (ACS Energy Letters, npj Flexible Electronics, ACS Applied Energy Materials, Materials Advances, and Frontiers in Energy Research), one conference proceeding (PVSC-47), six conference presentations (PVSC and Materials Research Society meetings), and a Ph.D. dissertation (Trey B. Daunis) were produced under this project. Energy Materials Corporation (EMC) has forecast that with a 1.5 m wide web moving at a web speed of 30 m/min, R2R processing of PSC could provide up to 4 GW/year for a single R2R assembly line. Replacing thermal annealing with photonic curing, as demonstrated by the accomplishments of this project, is necessary to realize such an energy production goal.

14 SOLAR ENERGY↗
DOE OSTI2023

Nonthermal plasma synthesis of silicon carbonitride

Abstract The use of a low‐temperature plasma for the synthesis of amorphous silicon carbonitride (SiCN) nanoparticles enables the realization of sintered bulk samples with high thermal stability. Amorphous SiCN nanoparticles are produced from a mixture of silane, methane, and ammonia utilizing a mid‐pressure, radio‐frequency, continuous flow reactor. Particle characterization shows that the nanoparticles are largely amorphous with some crystalline silicon and silicon carbide domains <10 nm in size. Compositional tuning, controlled by varying the precursor flow rates, coupled with the uniform mixing of elements at the nanoscale, results in samples that resist crystallization even when sintered at temperatures as high as 2000°C. This study suggests that the low‐temperature plasma synthesis of nanoparticles has great potential to produce bulk structural materials for application in harsh environments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Active and Stable PtPd Diesel Oxidation Catalysts under Industry‐Defined Test Protocols

Nanoparticle-supported Pt and Pd catalysts are employed industrially to convert CO and hydrocarbon residue from incomplete diesel fuel combustion into more environmentally-benign products. However, these catalysts deactivate over time due to sintering, especially for Pt nanoparticles which readily generate volatile species under high operating temperatures. Here, we turned the detrimental vapor-mediated sintering of Pt into an advantage by using a physical mixture of Pt and Pd catalysts prepared using a raspberry-colloid-templating (RCT) method. The RCT method produced Pt/Al 2 O 3 and Pd/Al 2 O 3 catalysts with partially embedded NPs to inhibit surface-mediated sintering pathways. As validated using an industry-defined emission control test protocol, aging a physical mixture of Pt/Al 2 O 3 and Pd/Al 2 O 3 at high temperature produced an alloyed PtPd/Al 2 O 3 catalyst that outperformed the fresh catalyst mixture and both individual catalysts for hydrocarbon conversion, while exhibiting high catalytic stability and resistance to sintering and to SO 2 poisoning. X-ray photoelectron spectroscopy revealed that in the aged catalyst mixture, half of the Pd content existed in the more active metallic state, compared to the less active oxide forms in the fresh mixture and both individual catalysts, explaining the unusual activity enhancement. Our results represent a practical approach to producing active and stable PtPd/Al 2 O 3 diesel oxidation catalysts for emission control applications.

Lim, Kang Rui Garrick [Harvard University, Cambrid↗
DOE OSTI2024

Sintering Mechanism of Pt/Al 2 O 3 in Complex Emission Gases Elucidated via In Situ Environmental STEM

Emission control catalysts are crucial for protecting human health by preventing the release of harmful gases and unburnt fuel into the atmosphere. These catalysts often face deactivation through sintering processes in high-temperature, chemically reactive environments containing multiple gas species. Here, we use in situ environmental scanning transmission electron microscopy to monitor the sintering behavior and transient morphologies of Pt/Al 2 O 3 in various relevant gas environments through controlled experiments. Our results reveal the particle migration and atomic ripening behavior of Pt/Al 2 O 3 at the atomic scale in the presence of water vapor and oxygen, which differs from behaviors observed in single gas environments. We identify an atomic ripening mechanism involving the dissociation and migration of Pt adatom chains from Pt nanoparticles, observed only in combinational gases. Finally, these findings provide valuable insights into catalyst degradation behavior in complex gas environments.

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

Dry Printing Pure Copper with High Conductivity and Adhesion for Flexible Electronics

Additive manufacturing of functional devices on various rigid and flexible substrates is rising rapidly due to their design flexibility, rapid manufacturing, and lower cost. Current printing technologies are ink-based and focused on printing silver (Ag) as conductive lines due to its matured ink formulation process, low sintering temperature, ease of printing, and low oxidation rate. However, Ag is the 68th most abundant element on Earth, while copper (Cu) is the 25th, making it much cheaper (>100×) while having a comparable conductivity to Ag. Therefore, printing Cu has become technologically and economically more attractive than Ag. Nevertheless, Cu printing is still a significant challenge in ink-based printing methods due to the higher sintering temperature relative to the glass-transition temperature of most flexible substrates, the higher oxidation rate, the challenging ink formulation process, and ink stability concerns. Here, we demonstrate printing highly conductive Cu on flexible polyimide substrates using a dry printing technique. Cu nanoparticles (~3–30 nm) are generated by on-demand laser ablation of a solid Cu target inside the printer head and under argon background gas. These Cu nanoparticles are then transported through a nozzle and onto the substrate, where they are laser-sintered in real time. The argon gas plays three critical roles in laser plume condensation for nanoparticle generation, transport, and sheath gas to avoid oxidation during sintering. The sintered nanoparticles thus show high electrical conductivity and mechanical stability under static and cyclic tests. Our dry printing technique can potentially revolutionize how electronic devices and sensors are additively manufactured for earth and space applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗