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NASA NTRS1999

Z-Scan Measurement of the Nonlinear Absorption of a Thin Gold Film

We have used the z-scan technique at a wavelength (532 nm) near the transmission window of bulk gold to measure the nonlinear absorption coefficient of continuous approximately 50-Angstrom-thick gold films, deposited onto surface-modified quartz substrates. For highly absorbing media such as metals, we demonstrate that determination of either the real or imaginary part of the third-order susceptibility requires a measurement of both nonlinear absorption and nonlinear refraction, i.e. both open- and closed-aperture z-scans must be performed. Closed-aperture z-scans did not yield a sufficient signal for the determination of the nonlinear refraction. However, open-aperture z-scans yielded values ranging from Beta = 1.9 x 10(exp -3) to 5.3 x 10(exp -3) cm/W in good agreement with predictions which ascribe the nonlinear response to a Fermi smearing mechanism. We note that the sign of the nonlinearity is reversed from that of gold nanoparticle composites, in accordance with the predictions of mean field theories.

Smith, David D.↗

DOE OSTI2026

Pulsed laser synthesis of mesoporous metal chalcogenide thin films

Mesoporous films of the metal chalcogenide B-FeSe were grown on MgO substrates by KrF pulsed laser deposition (PLD) in an argon background. At 100 mTorr, gated intensified charge-coupled device imaging and ion probe measurements showed that the plasma plume responsible for crystal growth initially comprised three components, with distinct expansion velocities. Plume interactions with the substrate heater and ablation target gave rise to complex dynamics, including collisions between the charged leading edge—rebounding between the substrate and the target—and slower-moving species in the plume interior. Film growth was dominated by species with kinetic energies ≤0.5 eV/atom. X-ray reflectivity revealed that films grown in this environment—with a substrate temperature of 350 ° C, a laser fluence of 1.0 J cm −2 , and a 7.5 mm 2 spot area—formed a porous framework with 15% porosity. Atomic force microscopy showed surface features that suggest pore sizes below 100 nm. X-ray diffraction indicated that the porous films were epitaxial with respect to the substrate and likely grew by oriented-attachment of gas-phase molecular clusters or very small nanoparticles, in contrast to the conventional epitaxy of vacuum films from atomic constituents. The in-plane orientation of the mesoporous films was B-FeSe [100]||[110] MgO, attributed to the soft landing of pre-formed crystallites on the MgO substrates, where protruding Se rows of B-FeSe aligned with corrugations of the MgO surface. In conclusion, this work implies that growth of candidate electrocatalyst materials by PLD in inert gas background may allow mesoporous frameworks with a single crystallographic orientation that expose specific crystal facets for electrochemical reactions and active site engineering.

cluster epitaxy↗

DOE OSTI2025

Solvation directed morphological control in metal oxide nanostructures

The development of structural hierarchy on various length scales during the crystallization process is ubiquitous in biological systems and minerals and is common in synthetic nanomaterials. The driving forces for the formation of complex architectures range from local interfacial interactions, that modify interfacial speciation, local supersaturation, and nucleation barriers, to macroscopic interparticle forces. Although it is enticing to interpret the formation of hierarchical architectures as the assembly of independently nucleated building blocks, crystallization pathways often follow monomer-by-monomer addition with structural complexity arising from interfacial chemical coupling and strongly correlated fluctuation dynamics in the electric double layers. Here, we show that the development of structural hierarchy through heterogeneous nucleation is driven by dipolar and solvation forces. Specifically, coupled simulations and experimental studies revealed that dipole build-up along the slow growth direction can trigger twinning and the development of branched architectures. Enthalpic solvation interactions were shown to either enhance or reduce the dipole moment of the nanoparticles and, thereby, control crystal morphology and architecture. The systematic studies of chemical coupling between different solvents and undercoordinated surface atoms of the growing nanocrystals revealed the mechanism of dimensionality control and the development of structural hierarchy without ligands or structure-directing agents.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2025

Facet-Dependent Cold Welding of Au Nanorods Revealed by Liquid Cell Transmission Electron Microscopy

Cold welding of metals at the nanoscale has been demonstrated to play a significant role in bottom-up manufacturing and self-healing processes of nanostructures and nanodevices. However, the welding mechanism at the nanoscale is not well understood. In this study, a comprehensive demonstration of the cold welding process of gold nanorods with different modes is presented through in situ liquid cell transmission electron microscopy. The experimental results and molecular dynamics simulations reveal that the nanorods are welded through the facet-dependent atomic surface diffusion and rearrangement along {100} facets. The density functional theory calculations indicate that the preferred coalescence of two {100} surfaces is thermodynamically favorable. Unlike the prevalent “oriented attachment” in the nanoparticle coalescence, the misalignment of nanorod orientations and local stresses can induce grain boundaries and stacking faults in the welded interface.

42 ENGINEERING↗

DOE OSTI2023

Structural and Chemical Evolution of an Inverse CeO x /Cu Catalyst under CO 2 Hydrogenation: Tunning Oxide Morphology to Improve Activity and Selectivity

Small nanoparticles of ceria deposited on a powder of CuO display a very high selectivity for the production of methanol via CO 2 hydrogenation. CeO 2 /CuO catalysts with ceria loadings of 5%, 20%, and 50% were investigated. Among these, the system with 5% CeO x showed the best catalytic performance at temperatures between 200 and 350 °C. The evolution of this system under reaction conditions was studied using a combination of environmental transmission electron microscopy (E-TEM), in situ X-ray absorption spectroscopy (XAS), and time-resolved X-ray diffraction (TR-XRD). For 5% CeO x /Cu, the in situ studies pointed to a full conversion of CuO into metallic copper, with a complete transformation of Ce 4+ into Ce 3+ . Images from E-TEM showed drastic changes in the morphology of the catalyst when it was exposed to H 2 , CO 2 , and CO 2 /H 2 mixtures. Under a CO 2 /H 2 feed, there was a redispersion of the ceria particles that was detected by E-TEM and in situ TR-XRD. Finally, these morphological changes were made possible by the inverse oxide/metal configuration and facilitate the binding and selective conversion of CO 2 to methanol.

03 NATURAL GAS↗

NASA NTRS2019

Fabrication and Performance of NiCuCoFeMn High Entropy Alloy Nanopastes for Brazing Inconel 718

Overview: High entropy alloys (HEAs) are a class of metallic alloys consisting of 5 plus elemental components and have four core effects - 1. High mixing entropy - 2. Sluggish diffusion kinetics - 3. High lattice distortion - 4. Cocktail effect; Boron-free, silicon-free brazing materials for nickel superalloys to avoid brittle intermetallic and eutectic phase formation; Size-dependent melting point depression can eliminate the need for boron, silicon and other melting point depressants; A Ni-Mn-Fe-Co-Cu HEA with low solidus and liquidus temperatures (1080 °C and 1150 °C) was developed; Low solidus and liquidus temperatures of the HEA combined with the nanoscale melting point depression in this study; Bulk HEA fabricated by induction melting of elemental powders; HEA nanoparticles (NPs) fabricated by ball milling of the HEA micropowder; Inconel 718 was laser brazed in air using the HEA and bulk and NP performances are compared.

Bridges, Denzel↗

DOE OSTI2019

Early Career Award: Decoupling the Electronic and Geometric Parameters of Metal Nanocatalysts

Central in many industrial processes (e.g., petroleum refining) and the realization of new energy platforms (e.g., fuel cells and biomass conversion) is heterogeneous catalysis. The performance of a catalyst is governed by interplay between electronic and geometric factors, but controlling these parameters to achieve efficient catalysis remains a grand challenge. The overall goal of this project was to decouple the electronic and geometric parameters of nanoscale metal catalysts for independent manipulation through the design and use of new architecturally controlled bimetallic nanocrystals. Specifically, shape-controlled core@shell nanocrystals were studied as catalysts. The binary composition of these structures provided a means of electronic control while the shape of the nanocrystals provided geometric control. Through a series of experiments with nanocrystals of different shapes and bimetallic compositions, the electronic and geometric parameters of such metal nanocatalysts were effectively decoupled for independent manipulation of catalyst performance. These concepts were applied toward new nanocatalysts for semihydrogenation, formic acid electrooxidation and for the oxygen reduction reaction. Ultimately, with the development of new synthetic strategies toward bimetallic nanocrystals, this research has advanced the design and synthesis of bimetallic nanocrystals as catalysts for diverse chemical transformations.

36 MATERIALS SCIENCE↗

DOE OSTI2026

In Situ EXAFS Study of Mo–P Bond Dynamics in Molybdenum Phosphide during CO 2 Reduction and Hydrogen Evolution

Transition Metal Phosphides (TMPs) are widely studied as catalysts in reactions like hydrogen evolution, oxygen reduction, and hydrodesulfurization. TMPs have demonstrated remarkable efficiency in accelerating reactions by providing active sites for adsorption and facilitating the transformation of reaction intermediates, a feature that has increased the interest of TMPs in the electrochemical carbon dioxide reduction reaction (eCO 2 RR). Despite their growing use, the potential-dependent structural behavior of TMPs under operating electrochemical conditions remains insufficiently understood. This work investigates the dynamics of the Mo−P bond during eCO 2 RR and hydrogen evolution reaction (HER) using in situ extended X-ray absorption spectroscopy (EXAFS) studies at the Mo−K edge. Structural characterization of the synthesized MoP nanoparticles was performed by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results of the overall electrochemical activity of MoP are presented through linear sweep voltammetry (LSV) experiments in the potential range of 0 to −1.5 V versus Ag/AgCl and chronoamperometry (CA). Liquid products were analyzed by 1 H NMR spectroscopy. The synthesized catalyst showed increasing activity with the highest Faradaic efficiency of 11.75% for C 2+ products at −1.3 V vs Ag/AgCl. In situ EXAFS revealed a change in the average Mo−P bond distance during eCO 2 RR, whereas no such change was observed during the hydrogen evolution reaction (HER). This finding suggests that phosphorus, particularly through modulation of the Mo−P bond length, plays an important role in the eCO 2 RR and demonstrates how in situ EXAFS can track local structural perturbations in MoP catalysts during electrochemical operation, providing complementary structural insight that correlates with electrochemical behavior.

Catalysts↗

DOE OSTI2021

Advanced Nanocarbons for Enhanced Performance and Durability of Platinum Catalysts in Proton Exchange Membrane Fuel Cells

Insufficient stability of current carbon supported Pt and Pt alloy catalysts is a significant barrier for proton-exchange membrane fuel cells (PEMFCs). As a primary degradation cause to trigger Pt nanoparticle migration, dissolution, and aggregation, carbon corrosion remains a significant challenge. Compared with enhancing Pt and PtM alloy particle stability, improving support stability is rather challenging due to carbon's thermodynamic instability under fuel cell operation. In recent years, significant efforts have been made to develop highly durable carbon-based supports concerning innovative nanostructure design and synthesis along with mechanistic understanding. Here, this review critically discusses recent progress in developing carbon-based materials for Pt catalysts and provides synthesis–structure–performance correlations to elucidate underlying stability enhancement mechanisms. The mechanisms and impacts of carbon support degradation on Pt catalyst performance are first discussed. The general strategies are summarized to tailor the carbon structures and strengthen the metal–support interactions, followed by discussions on how these designs lead to enhanced support stability. Based on current experimental and theoretical studies, the critical features of carbon supports are analyzed concerning their impacts on the performance and durability of Pt catalysts in fuel cells. Finally, the perspectives are shared on future directions to develop advanced carbon materials with favorable morphologies and nanostructures to increase Pt utilization, strengthen metal-support interactions, facilitate mass/charge transfer, and enhance corrosion resistance.

25 ENERGY STORAGE↗

DOE OSTI2023

Speciation of Nanocatalysts Using X-ray Absorption Spectroscopy Assisted by Machine Learning

Structure and morphology of supported nanoparticle catalysts play important roles in many industrial reactions. Recent progress has identified key aspects of structure-activity relationships at nanoscale and novel methods to study the local environment of the active sites. X-ray absorption fine structure (XAFS) spectroscopy, despite being a leading technique for this purpose, is hampered significantly by its ensemble-averaging nature which often leads to a bias towards a single "representative" structure. Learning heterogeneous distributions of nanostructures at the inter- and intra-particle level from the average XAFS spectrum is a formidable challenge that can be overcome in some cases, described in this Perspective. Here we also discuss emerging machine learning techniques for extracting the information about heterogeneity of metal species from XAFS data.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Template-Assisted, Seed-Mediated Synthesis of Hierarchically Mesoporous Core–Shell UiO-66: Enhancing Adsorption Capacity and Catalytic Activity through Iterative Growth

A hierarchically mesoporous (HM) UiO-66-F 4 shell with ~8 nm mesopores can be iteratively grown on top of UiO-66 nanoparticle (NP) seeds over several cycles templated by Pluronic F-127 micelles. Presumably, the Pluronic micelles that were formed in water can surround UiO-66 NPs to facilitate the overgrowth of an HM-UiO-66-F 4 shell in the presence of Zr IV precursors and BDC-F 4 linkers. The UiO-66 NP seeds play an important role in directing the continuous growth of the HM-UiO-66-F 4 shell, as only a nonporous phase was obtained in their absence. Furthermore, this template-assisted, seed-mediated method can be extended to produce other UiO-66-X (X = (OH) 2 , (COOH) 2 , etc.) shells, demonstrating its generality for the UiO-66 family of metal–organic frameworks. Notably, the incorporation of mesopores into the thrice-overgrown UiO-66@HM|3rd-UiO-66-F 4 materials leads to impressive enhancements in the per-mass uptake capacity of Direct Blue 86, a large anionic dye: 320% better than the parent UiO-66 seeds and 150% better than that for a [UiO-66 + UiO-66-F 4 ] physical mixture at the same mass proportion. Similar enhancements were also observed in the catalyzed oxidation of thioanisole.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Liquid crystalline behavior and photoluminescence of lanthanide decanoate nanoparticles synthesized by microwave radiation

Luminescent lanthanide decanoate nanoparticles (LnC 10 NPs; Ln = Pr, Nd, Sm, Eu, Gd, Er) with spherical morphology (<100 nm) have been synthesized via a facile microwave (MWV) method using Ln(NO 3 ) 3 ·xH 2 O, ethanol/water, and decanoic acid. These hybrid nanomaterials adopt a lamellar structure consisting of inorganic Ln 3+ layers separated by a decanoate anion bilayer and exhibit liquid crystalline (LC) phases during melting. The particle size, crystalline structure, and LC behavior were characterized using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (ambient and heated). Thermal analysis indicated the formation of Smectic A LC phases by LnC 10 nanoparticles, with the smaller lanthanides (Ln = Sm, Gd, Er) displaying additional solid intermediate and Smectic C phases. The formation of LC phases by the smaller Ln 3+ suggests that these nanoscale materials have vastly different thermal properties than their bulk counterparts, which do not exhibit LC behavior. In this work, photoluminescence spectroscopy revealed the LnC 10 NPs to be highly optically active, producing strong visible emissions that corresponded to expected electronic transitions by the various Ln 3+ ions. Under long-wave UV irradiation (λ = 365 nm), bright visible luminescence was observed for colloidal suspensions of Nd, Sm, Eu, Gd, and ErC 10 NPs. To the best of the authors’ knowledge, this is the first reported synthesis of nanoscale metal alkanoates, the first report of liquid crystalline behavior by any decanoate of lanthanides smaller than Nd, and the first observation of strong visible luminescence by non-vitrified lanthanide alkanoates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Selective Hydroxylation of In 2 O 3 as A Route to Site-Selective Atomic Layer Deposition

We report that several atomic layer deposition (ALD) processes are now known that leverage the distinct surface chemistry of two disparate substrates (e.g., metal vs oxide) to realize markedly different ALD nucleation rates in an approach referred to as area-selective ALD. In contrast, few ALD processes have been identified that allow selective reaction at distinct surface sites of a single material surface, in a process that might be called site-selective ALD (SS-ALD). We describe one potential strategy to discriminate among several distinct surface sites on bixbyite In 2 O 3 to achieve site selectivity. Using density functional theory, we predict the discriminant hydration and hydroxylation of In 2 O 3 terrace and step-edge sites that depend strongly on the substrate temperature at low water coverage. Infrared measurement of surface hydroxyls on In 2 O 3 nanoparticles supports the predicted temperature dependence. The in situ examination of MgO ALD nucleation also shows results consistent with the predicted temperature dependence of In 2 O 3 hydroxylation. Together, these findings suggest that a selective hydroxylation approach may be a viable route to SS-ALD on In 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Reforming of methane with carbon dioxide over cerium oxide promoted nickel nanoparticles deposited on 4-channel hollow fibers by atomic layer deposition

Ni nanoparticles were deposited on four-channel structured α-Al2O3 hollow fibers by atomic layer deposition (ALD). CeO 2 was loaded by a liquid phase incipient wetness method to promote Ni catalysts for dry reforming of methane. For Ni/Al 2 O 3 prepared by ALD, inactive NiAl2O4 that originated from the Ni ALD process was incompletely reduced. The introduced CeO 2 was found to weaken the NiO–Al 2 O 3 interaction, free NiO from NiO–Al 2 O 3 or NiAl 2 O 4 , and improve the reducibility of NiO. The higher reducibility of NiAl 2 O 4 , tuned by CeO 2 , further activated the catalyst during DRM, because a larger proportion of NiAl 2 O 4 was gradually reduced to metallic nickel by the reaction products. The optimal catalytic performance reached a methane reforming rate of 2410 L h -1 gNi -1 at 850 °C. The CeO 2 promoted catalyst also exhibited an excellent performance after regeneration. In addition, the inhibition effect of CeO 2 on coke formation was observed, due to the enhanced CO 2 dissociative adsorption by CeO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Surface Ligand Effects on Energetics, Charge Transfer, and Stability at Interfaces Between Metal Halide Perovskites and Organic Semiconductors

Chemistry at organic-inorganic interfaces plays a major role in determining the performance of electronic and optoelectronic devices. Understanding, developing, and using surface chemistry is thus essential for creating improved and novel materials and devices. Organic metal halide perovskites (HPs) are inexpensive semiconductors that can be printed from solution to make efficient photovoltaic cells for harvesting solar energy, light emitting diodes for energy efficient solid-state lighting applications, solid-state lasers, and even spin selective devices with applications to quantum computing. To realize the potential of HPs, their surface chemistry and interfacial properties must be better understood and appropriately adjusted to meet the needs of the targeted application. For example, surface chemistry influences non-radiative recombination, which influences the efficiency of light emission and solar energy conversion, charge-carrier injection and extraction from optoelectronic devices, and material and device stability. This research project centered around determining how the surface chemistry of HP thin films and nanoparticles influences optical properties, charge transfer processes, energetics, and stability. In this project we characterized ligand binding strengths to HPs; determined how surface ligand chemistry influences photoluminescence properties, energetics, and charge transfer processes; determined that surface ligands often penetrate into HPs and uncovered methods of reducing surface ligand penetration through structural modifications; and discovered how interfacial energetics impact charge transfer processes and photovoltaic performance parameters. Overall, this research established important insights into how surface ligands interact with HPs to influence their optical properties, electronic properties, stability, and device level performance.

14 SOLAR ENERGY↗

DOE OSTI2025

Rapid Screening of Single-Atom Catalyst Synthesis Conditions Using ToF-SIMS and Facet-Dependent Single-Crystal Substrates

Single-atom catalysts (SACs) offer superior catalytic performance compared to traditional nanoparticle catalysts but are challenging to develop because of the need for extensive optimization and specialized characterization techniques. Here, this study presents a rapid and versatile method for detecting synthesis conditions and elucidating deposition mechanisms of SACs on various substrates. By depositing active elements (Au, Cu, Ni and Rh) on facet-specific single-crystalline substrates (CeO 2 , TiO 2 , MgO and Al 2 O 3 ) and employing time-of-flight secondary ion mass spectroscopy (ToF-SIMS), we assessed facet-dependent deposition behaviors and identified optimal conditions for solution-based SAC synthesis. On CeO 2 and TiO 2 , we confirmed facet-dependent deposition, primarily influenced by oxygen vacancy density and photocatalytic activity, respectively. MgO exhibited the formation of metal oxide/hydroxide clusters for all active elements, and the degree of clustering for Cu and Ni was correlated with the facet hydrolysis susceptibility. Notably, Au and Rh deposition on MgO was facet-independent, attributed to the formation of hydroxide species in solution. Al 2 O 3 , due to its chemical stability and lack of surface defects, did not show active element deposition. This study not only provides a time and cost-efficient method for prescreening SAC synthesis conditions, but it also provides valuable insights into the various deposition mechanisms governing SAC formation on different substrates, paving the way for the rational design of tailored SACs for various catalytic applications.

ToF-SIMS↗

DOE OSTI2023

Understanding the Polymorphism of Cobalt Nanoparticles Formed in Electrodeposition–An In Situ XRD Study

An advanced synchrotron-based in situ X-ray diffraction (XRD) technique is successfully developed and employed to track and monitor the formation and phase selection of cobalt (Co) in electrodeposition in real time and verify DFT computational results. The impacts of a number of controlling factors including the pH of the electrolyte and deposition overpotential are systematically studied. The results show that the yielded phase of the electrodeposited Co is controlled by both thermodynamics and kinetics. The low pH low overpotential condition favors the formation of the thermodynamically stable fcc phase. While the high pH high overpotential condition promotes the formation of the metastable hcp phase. The experimental results agree well with the nanometric phase diagram computed with DFT. Layer-by-layer alternative stacking of fcc-hcp polymorphic phases can be facilely fabricated by just varying the overpotential. This work not only offers an effective means to control the phase of electroplating of Co but also presents a new approach to reveal the fundamental insights of the formation of metals under electrochemical reduction driving force.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Effect of dilute Rh on oxygen dissociation, spillover, and the oxidation of Cu across many orders of magnitude pressure

Knowledge of how trace amounts of more reactive metals influence the oxidation rate and mechanism of Cu surfaces is essential for developing strategies to optimize the performance of Cu-based catalysts. We find that the addition of 1% Rh to Cu(111) increases the initial O 2 dissociation rate by approximately 9-fold. CO poisoning experiments reveal that single Rh atoms activate O 2 and facilitate the spillover of atomic oxygen to Cu sites. Scanning tunneling microscopy (STM) and in situ X-ray photoelectron spectroscopy (XPS) support this mechanism, showing enhanced surface oxygen near Rh atoms. Here, a density functional theory (DFT)-based model demonstrates that Rh binds the O 2 precursor 0.15 eV more strongly than Cu(111) and lowers the O 2 dissociation barrier by 0.02 eV. Both single-crystal and nanoparticle experiments show that at low oxygen pressures, Rh enhances Cu oxidation, whereas at higher pressures, it inhibits deeper oxidation, as evidenced by in situ ultraviolet-visible (UV-vis) spectra.

36 MATERIALS SCIENCE↗