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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Energetic Tug-of-War between Pt and Leaky TiO 2 : Positive and Negative Effects on the Function of Molecularly-Modified p -Si(111)|TiO 2 |Pt Photocathodes

Photoelectrochemical solar energy conversion to chemical products is a promising avenue towards renewable fuels, and TiO 2 deposition on semiconductor photocathodes is a widespread surface protection strategy. However, the electronic, thermodynamic, and kinetic effects of protection layers on interfacial energetics remains poorly understood. Here, electrochemical data (photocurrent onset and flatband potentials) of p-Si(111)|TiO 2 |Pt is collected in contact with an outer-sphere redox couple. We find that onset potentials shift negatively as a function of increasing oxide thickness, but this effect is not reflected in the flatband potentials. This reveals the mechanism of these shifts is kinetic rather than thermodynamic,and suggests that hole leakage through the TiO 2 is responsible. When Pt nanoparticles are deposited onto the TiO 2 , positive shifts in both the onset and flatband potentials are observed, revealing Pt catalysts are beneficial for more than just increased catalytic rates. These results highlight the importance of understanding the effects of surface modifications on the energetics at the interface in both catalytic and simple electron transfer systems.

14 SOLAR ENERGY↗
DOE OSTI2020

Energetics of CO 2 and H 2 O adsorption on alkaline earth metal doped TiO 2

The process of CO 2 and H 2 O adsorption on the surface of nano-oxide semiconductors is important in the overall performance of artificial photosynthesis and other applications. In this study, we explored the thermodynamics of CO 2 and H 2 O adsorption on TiO 2 as a function of surface chemistry. We applied gas adsorption calorimetry to investigate the energetics of adsorption of those molecules on the surface of anatase nanoparticles. In an attempt to increase TiO 2 surface affinity to CO 2 and H 2 O, TiO 2 was doped with alkaline earth metals (MgO, CaO, SrO, and BaO) by manipulating the chemical synthesis. Adsorption studies using diffuse reflectance infrared spectroscopy at different temperatures indicate that due to the segregation of alkaline earth metals on the surface of TiO 2 nanoparticles, both CO 2 and subsequent H2O adsorption amounts could be increased. CO 2 adsorbs in two different manners, forming carbonates which can be removed at temperatures lower than 700 °C, and a more stable linear adsorption that remains even at 700 °C. Additionally to the surface energetic effects, doping also increased specific surface area, resulting in further improvement in net gas adsorption.

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

Colloidal Quantum Shells: An Emerging 2D Semiconductor for Energy Applications

Low-dimensional semiconductors hold strong promise for future energy applications. These nanomaterials are inexpensive to process and offer a broad spectrum of attractive quantum-mechanical properties. The notorious problem of low-dimensional nanostructures, however, lies in their limited performance under high energetic loads, when more than one exciton per particle is created. Multiple excitons undergo fast annihilation, causing efficiently roll-off in energy-intensive applications, including high-brightness LEDs, X-ray scintillators, and solar cells. In this prospective, we will highlight an emerging type of low-dimensional semiconductors that allows avoiding such multi-exciton (MX) energy losses. Recently demonstrated colloidal quantum shells benefit from the spatial separation of multiple excitons, which leads to extraordinary improvements to MX lifetimes and MX quantum yield. This makes quantum shell morphology an attractive candidate for solution-processed optical and electrical devices. In this Focus Review, we compare the optoelectronic properties of quantum shells against other low-dimensional semiconductors and discuss their emerging opportunities in solid-state lighting and energy-harvesting applications.

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

Low‐Loss Tunable Infrared Plasmons in the High‐Mobility Perovskite (Ba,La)SnO 3

Abstract BaSnO 3 exhibits the highest carrier mobility among perovskite oxides, making it ideal for oxide electronics. Collective charge carrier oscillations known as plasmons are expected to arise in this material, thus providing a tool to control the nanoscale optical field for optoelectronics applications. Here, the existence of relatively long‐lived plasmons supported by high‐mobility charge carriers in La‐doped BaSnO 3 (BLSO) is demonstrated. By exploiting the high spatial and energy resolution of electron energy‐loss spectroscopy with a focused beam in a scanning transmission electron microscope, the dispersion, confinement ratio, and damping of infrared localized surface plasmons (LSPs) in BLSO nanoparticles are systematically investigated. It is found that LSPs in BLSO exhibit a high degree of spatial confinement compared to those sustained by noble metals and have relatively low losses and high quality factors with respect to other doped oxides. Further analysis clarifies the relation between plasmon damping and carrier mobility in BLSO. The results support the use of nanostructured degenerate semiconductors for plasmonic applications in the infrared region and establish a solid alternative to more traditional plasmonic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

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

Shape-Selective Mesoscale Nanoarchitectures: Preparation and Photocatalytic Performance

We create ordered arrays of shape-selective gold-titania composite nanomaterials at the mesoscale (100 µm to 5 mm) by a combination of both bottom-up and top-down approaches for exquisite control of the size, shape, and arrangement of nanomaterials. Lithographic techniques along with wet chemical synthetic methods were combined to create these composite nanomaterials. The photocatalytic activity of these TiO 2, TiO 2 -Au and SiO 2 -TiO 2 -Au nano-composite mesoscale materials was monitored by the photodegradation of a model analyte, methyl orange, under UV and visible (Vis) illumination. Bare TiO 2 - and SiO 2 -TiO 2 -coated pillar arrays showed significant activity toward methyl orange in UV light with degradation rates on the order of 10 −4 –10 −3 min −1 . The photocatalytic activity of these arrays was also found to depend on the nanoparticle shape, in which particles with more edges and corners were found to be more reactive than spherical particles (i.e., the photocatalytic activity decreased as follows: diamonds > squares > triangles > spheres). SiO 2 -TiO 2 -Au nano-composite pillar arrays were tested in both UV and Vis light and showed increased activity in Vis light but decreased activity in UV light as compared to the bare semiconductor arrays. Additionally, the Au nanorod-functionalized nanoarrays exhibit a strong shape-dependence in their photocatalytic activity toward methyl orange degradation in Vis light.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Theoretical and Experimental Advances in High-Pressure Behaviors of Nanoparticles

Using compressive mechanical forces, such as pressure, to induce crystallographic phase transitions and mesostructural changes while modulating material properties in nanoparticles (NPs) is a unique way to discover new phase behaviors, create novel nanostructures, and study emerging properties that are difficult to achieve under conventional conditions. In recent decades, NPs of a plethora of chemical compositions, sizes, shapes, surface ligands, and self-assembled mesostructures have been studied under pressure by in-situ scattering and/or spectroscopy techniques. As a result, the fundamental knowledge of pressure–structure–property relationships has been significantly improved, leading to a better understanding of the design guidelines for nanomaterial synthesis. In the present review, we discuss experimental progress in NP high-pressure research conducted primarily over roughly the past four years on semiconductor NPs, metal and metal oxide NPs, and perovskite NPs. We focus on the pressure-induced behaviors of NPs at both the atomic- and mesoscales, inorganic NP property changes upon compression, and the structural and property transitions of perovskite NPs under pressure. We further discuss in depth progress on molecular modeling, including simulations of ligand behavior, phase-change chalcogenides, layered transition metal dichalcogenides, boron nitride, and inorganic and hybrid organic–inorganic perovskites NPs. These models now provide both mechanistic explanations of experimental observations and predictive guidelines for future experimental design. Here, we conclude with a summary and our insights on future directions for exploration of nanomaterial phase transition, coupling, growth, and nanoelectronic and photonic properties.

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

Shape Control of Colloidal Semiconductor Nanocrystals through Thermodynamically Driven Aggregative Growth

The optoelectronic properties of colloidal semiconductor nanocrystals (NCs) can be manipulated by changing their geometric shapes. The precise synthetic control over particle morphologies, however, has remained elusive. Conventional growth techniques rely on the kinetic assembly of atomic units, where supersaturation and precipitation processes can lead to a broad distribution of particle shapes. In this paper, we demonstrate that replacing atomic precursors with small-size nanocrystals as building blocks for larger colloids offers an easier, more predictive control over nanoparticle shape evolution. The reported growth strategy is illustrated via shape-selective syntheses of CdSe and CdS NC cubes, spheres, rods, as well as unprecedented “donut” and ring-like structures. Growth of desired particle morphologies was achieved by choosing an appropriate reaction solvent that minimizes the surface free energy through a unique shape formation. This so-called "aggregative growth mechanism" is explained using a thermodynamic model for interacting viscous colloids. We expect that this novel growth strategy will offer a viable platform for shape–selective synthesis of many inorganic colloids, providing pathways to optimizable optoelectronic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Biomimetic Catalysts Based on Au@ZnO–Graphene Composites for the Generation of Hydrogen by Water Splitting

For some decades, the scientific community has been looking for alternatives to the use of fossil fuels that allow for the planet’s sustainable and environmentally-friendly development. To do this, attempts have been made to mimic some processes that occur in nature, among which the photosystem-II stands out, which allows water splitting operating with different steps to generate oxygen and hydrogen. This research presents promising results using synthetic catalysts, which try to simulate some natural processes, and which are based on Au@ZnO–graphene compounds. These catalysts were prepared by incorporating different amounts of gold nanoparticles (1 wt.%, 3 wt.%, 5 wt.%, 10 wt.%) and graphene (1 wt.%) on the surface of synthesized zinc oxide nanowires (ZnO NWs), and zinc oxide nanoparticles (ZnO NPs), along with a commercial form (commercial ZnO) for comparison purposes. The highest amount of hydrogen (1127 μmol/hg) was reported by ZnO NWs with a gold and graphene loadings of 10 wt.% and 1 wt.%, respectively, under irradiation at 400 nm. Quantities of 759 μmol/hg and 709 μmol/hg were obtained with catalysts based on ZnO NPs and commercial ZnO, respectively. The photocatalytic activity of all composites increased with respect to the bare semiconductors, being 2.5 times higher in ZnO NWs, 8.8 times higher for ZnO NPs, and 7.5 times higher for commercial ZnO. The high photocatalytic activity of the catalysts is attributed, mainly, to the synergism between the different amount of gold and graphene incorporated, and the surface area of the composites.

Machín, Abniel (ORCID:0000000341343344)↗
DOE OSTI2023

Chapter 14: Surface plasmon resonance enhanced artificial photosynthesis of chemical fuels for energy storage

Nanostructured noble metals such as Au, Ag, and Cu have interesting optical properties because of the oscillation motions of their surface electrons upon strong coupling with light under resonance conditions. This resonant oscillation motion of conduction electrons refers to surface plasmon resonance (SPR) and localized SPR (LSPR) when localized near the surface of a nanoparticle. The extinction spectrum of a solution of plasmonic nanoparticles has tunable wavelength responses from UV to NIR due to strong light scattering and absorption which are highly sensitive to the permittivity of the nanoparticles, their sizes and shapes, and chemical environment. Strong light scattering due to the LSPR of plasmonic nanoparticles creates a strong localized and far-field intensity capable of enhancing light absorption characteristics of a chromophore near a plasmonic surface. Engineering the chromophores’ radiative decay dynamics can be done by 1) increasing its radiative decay rate to increase its photoluminescence intensity and 2) increasing its nonradiative decay rates associated to direct charge transfer to the metal surface. Such interesting photophysical properties of a chromophore can be extended to other light-absorbing materials such as semiconductor thin films and nanostructures. This plasmonic effect on the photophysics of a light-absorbing material can be theoretically and experimentally validated. The phenomenon has also been applied to advanced optoelectronic devices such as organic light-emitting diodes (OLED)1 and organic photovoltaics (OPV).2-4 The local field created by the SPR can provide an intense EM field to enhance photoluminescence emission of an organic chromophore5-8 and Raman scattering of an organic molecule, and single-molecule Raman9-10 can be detected on specially designed LSPR substrate. (Figure 1 on SPR for energy) Recent studies suggest that LSPR can be incorporated in light-harvesting and conversion systems to increase energy conversion in a solar cell and photoelectrochemical cell and chemical transformations of CO2 to chemical fuels.11-12 Plasmonic active metals naturally exhibit catalytic activities for electrochemical fuel conversion that can be enhanced by engineering their structures to form unique catalytic structures such as symmetry-broken Au-Cu Janus nanocrystals.13 These studies are critical to addressing the global challenges of energy14-15 and CO2 emission from nonrenewable sources such as coal, petroleum, and natural gas.16-17 Electrochemical systems comprised of unique photonic structures and functions that enable efficient and affordable energy harvesting/conversion/storage are highly desired for providing safe and environment-friendly energy sources. This chapter reviews our recent work of LSPR enabled photoelectrochemical water splitting and recent advances in LSPR-enabled CO2 reduction and photochemical reactions reported in the literature. Scientific and technical challenges of applying LSPR to enhance these energy conversion and storage systems are discussed at the conclusion of this chapter.

Pan, Shanlin↗
DOE OSTI2025

Rigid cationic ligands enable high-efficiency NIR-II photoluminescence in copper( i ) iodide hybrid semiconductors

Near-infrared (NIR) luminescent materials are pivotal for advanced optoelectronic and biomedical applications, yet attaining efficient emission in the NIR-II region (950-1400 nm) remains challenging. Here, we introduce a ligand cationization strategy for designing copper(i) iodide-organic hybrid materials that emit in the NIR-II region (920-1120 nm) with PLQYs up to 8.58%. By incorporating rigid cationic ligands with CuI modules, we synergistically achieve bandgap narrowing (to 1.51 eV) and structural rigidification via ionic-dative bonding, effectively suppressing non-radiative decay while extending emission beyond 1100 nm. Coupled with solution processability-enabled by the successful synthesis of nanometer-sized nanoparticles in various shapes-and excellent thermal stability (≥210 °C), this work establishes ligand cationization as a universal approach for designing efficient NIR-II emitters.

Chen, Jingwen↗
DOE OSTI2020

Fabrication of field-effect transistors with transfer-free nanostructured carbon as semiconducting channel material

Carbon nanostructures as active channel material in field effect transistors (FETs) are appealing in microelectronics for their improved performance such as high speed and low energy dissipation. However, these devices require the incorporation of nanostructure transfer steps in the fabrication process flow, which makes difficult its application in large scale integration circuits. Here we present a novel method for the fabrication of FETs with nanostructured carbon in the channel with p-type semiconducting properties and intermediate drain-source current (IDS) on/off ratio. The method is based on the use of Ni nanoparticles in the source-drain gap region as seed material for the formation of carbon nanostructures in the FET channel. FETs without Ni nanoparticles in the channel showed no modulation of IDS as a function of gate voltage. The device fabrication process does not require any carbon nanostructure transfer steps since it directly forms carbon nanostructures electrically connected to the device's source and drain electrodes via electron-beam evaporation of carbon and conventional lithographic processes. Since all device fabrication steps are compatible with Si technology processes, they are capable of being further optimized following process development protocols practiced by the semiconductor industry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Nanomorphology of eco-friendly colloidal inks, relating non-fullerene acceptor surface energy to structure formation

Nanoengineered, eco-friendly, solution-processable electroactive materials are in demand for the growing field of printed electronics, and these material requirements can be achieved by the development of waterborne colloidal dispersions. Functionality in these composite materials can be tuned by thermodynamically modifying the material nanomorphology, often by creation of kinetically stabilized aqueous nanoparticle dispersions. In this work we demonstrate that the internal structure of organic nanoparticles is controlled by the surface energy difference between the polymeric donor material and the non-fullerene acceptor (NFA) material. Nanoparticles of the following donor–acceptor combinations, suitable for printed organic photovoltaics, have been synthesized: TQ1:N2200, TQ1:PNDIT10, P3HT:N2200, P3HT:o-IDTBR and P3HT:eh-IDTBR. Advanced synchrotron-based X-ray spectroscopy and microscopy are used to correlate the formation of core–shell nanoparticle morphology to the material surface energy. We subsequently present a viable avenue for customizing the blended nanoparticle structure into (i) core–shell, (ii) molecularly intermixed, or (iii) inverted shell–core structures. Our results showed that TQ1:PNDIT10 and P3HT:o-IDTBR nanoparticles were comprised of a donor-rich shell and an NFA-rich core, however, interestingly we show a reversal to the inverse NFA shell/donor core structure for TQ1:N2200, P3HT:N2200 and P3HT:eh-IDTBR nanoparticles, driven by the low surface energy of N2200 (23.7 mJ m –2 ) and eh-IDTBR (18.3 mJ m –2 ). This article is the first report of a flipped nanoparticle core–shell morphology comprising an NFA-rich shell for the miniemulsion synthesis route. The composition of the shells and cores was able to be controlled by the differential mismatch in the surface energy of the donor and acceptor materials, with ΔG surface > 0, ΔG surface = 0, and ΔG surface < 0 for acceptor core–donor shell, molecularly intermixed, and acceptor shell–donor core, respectively. Accordingly, we introduce an entirely overlooked new figure of merit (FoM) for customizing nanoparticulate colloidal inks: tunable surface energy of non-fullerene-based semiconductors. Finally, the establishment of this FoM opens up electroactive material design to a wide range of functional printing applications with varying device and ink structure requirements, thereby reshaping the nanoengineering toolkit for waterborne colloidal dispersions and hence printed electronics.

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

Molecular Modifications of Crystalline Poly(triazine imide) for Advancing Its Structure–Property Relationships in Light-Driven Catalysis

Carbon-nitride materials represent light-absorbing structures composed of earth-abundant elements capable of being leveraged for semiconductor photocatalysis at their surfaces. This study systematically investigates the addition of molecular modifiers to the synthesis of crystalline carbon nitrides to assess their effects on the materials’ structure, optical bandgap, and photocatalytic activity for hydrogen (H 2 ) and oxygen (O 2 ) evolution under ultraviolet and visible-light irradiation. Melamine and five pyrimidine-centered analogs were employed as building blocks to modify various heteroatoms within the polymeric framework. The modified materials were characterized with attention to the differences introduced by the monomeric modifiers and their influence on the resulting structures and compositions. The findings indicate that these changes significantly broaden the visible-light absorption range, albeit with the gradual loss of the bulk crystalline structure. As the loading of modifiers increased beyond 50%, a predominantly amorphous form of carbon nitride emerged. XPS, 13 C solid-state NMR, and SEM analyses corroborated the changes, which were attributed to modifications of the elemental composition and a reduced amount of Li cations and charge-balancing Cl anions owing to fewer binding sites in the intralayer cavities. In photocatalytic measurements under an ultraviolet 390 nm LED, and aided by photodeposited nanoparticle cocatalysts, the unmodified PTI-LiCl framework demonstrated the highest H 2 evolution rate (HER; 3.44 mmol·g –1 ·h –1 ) with an apparent quantum yield of 5.4%, along with total water splitting at rates of 163 μmol of H 2 ·g –1 ·h –1 and 75.6 μmol·O 2 g –1 ·h –1 . While PTI-LiCl showed trace activity under a visible-light 440 nm LED, all modified materials exhibited enhanced reactivity with as low as 5% molecular modifiers. The photocatalytic rates peaked at a 15% modification level when using 2,4,6-triaminopyrimidine, with rates of 33 μmol·g –1 ·h –1 for HER, along with 19.7 μmol of H 2 ·g –1 ·h –1 and 8.7 μmol of O 2 ·g –1 ·h –1 for total water splitting. Density functional theory calculations were used to probe electronic structure changes resulting from the modifications. Furthermore, these results elucidate the structural, optical, and electronic changes arising from the five selected molecular modifiers and their impact on the semiconductors’ photocatalytic properties.

Electrical conductivity↗
DOE OSTI2026

Single-particle detection of enhanced polarizability in Au-decorated semiconducting nanorods via scanning dielectric microscopy

Hybrid nanostructures that combine semiconducting and metallic components offer great potential for photothermal therapy, optoelectronics, and sensing, by integrating tunable optical properties with enhanced light absorption and charge transport. Boosting the integrated performance of these hybrid systems demands techniques capable of probing local variations of the physical properties inaccessible to bulk analysis. Here, we report the single-particle dielectric characterization of hybrid, semiconducting bismuth sulfide (Bi 2 S 3 ) nanorods (NR) decorated with metallic Au nanoparticles (NP), employing scanning dielectric microscopy, which uses electrostatic force microscopy in combination with finite-element numerical simulations. We reveal a pronounced enhancement in the local dielectric response of Bi2S3 upon Au decoration, attributed to interfacial polarization and electron transfer from Au to the Bi 2 S 3 matrix, thus suggesting a enhanced metallic-like polarizability at the single-particle level. Numerical simulations show that the response is dominated by the vertical component of the permittivity and that the decorating metallic Au NP produce only moderate shielding of the semiconductor Bi 2 S 3 NR core, indicating that the large increase in the dielectric response originates primarily from intrinsic modifications within the NR. Overall, these findings provide direct insight into structure–property relationships at the single-particle level, supporting the rational design of advanced hybrid nanostructures with tailored electronic functionalities.

36 MATERIALS SCIENCE↗
DOE OSTI2024

TiO 2 /TiN Interface Enables Integration of Ni 5 P 4 Electrocatalyst with a III–V Tandem Photoabsorber for Stable Unassisted Solar-Driven Water Splitting

H 2 production by direct photoelectrochemical (PEC) water splitting has remained unachievable commercially, mainly due to rapid failure at the interface between the photoabsorber(s) and catalyst(s). PEC devices made from multijunction III-V semiconductors with platinum group metal (PGM) catalysts have yielded impressive initial solar-to-H 2 (STH) efficiency >19%, which rapidly corrodes in aqueous electrolytes. Here, TiO 2 /TiN layers were fused to create a bifunctional interface between a GaInP 2 /GaAs III-V tandem photoabsorber and a polycrystalline Ni 5 P 4 HER catalyst. Here, the TiO 2 serves as a conducting corrosion barrier, while a thin layer of much denser TiN (1 nm) blocks interlayer diffusion during fabrication. This strategy allows the elevated temperatures needed to crystallize the Ni 5 P 4 nanoparticles and fuse to the TiO 2 /TiN junction to achieve minimal optical loss without damaging the sensitive photoasbsorber. The resulting photocathode exhibits an initial STH efficiency of 11.4%-13.2% in sodium phosphate electrolyte at neutral pH 7. It operated continuously for over 200 h without failure above 10% STH efficiency, exceeding all previous benchmarks. The earth-abundant Ni 5 P 4 catalyst replaces costly PGM catalysts at comparable HER activity in neutral, acidic, or basic pH electrolytes.

08 HYDROGEN↗
DOE OSTI2025

Atomically Precise Nanoclusters as Co‐Catalysts for Light‐Activated Microswimmer Motility

Microswimmers are self-propelled particles that navigate fluid environments, offering significant potential for applications in environmental pollutant decomposition, biosensing, and targeted drug delivery. Their performance relies on engineered catalytic surfaces. Gold nanoclusters (AuNCs), with atomically precise structures, tunable optical properties, and high surface area-to-volume ratio, provide a new optimal catalyst for enhancing microswimmer propulsion. Unlike bulk gold or nanoparticles, AuNCs may deliver tunable photocatalytic activity and increased catalytic specificity, making them ideal co-catalysts for hybrid microswimmers. For the first time, this study combines AuNCs with TiO 2 /Cr 2 O 3 Janus microswimmers, combining the unique properties of both materials. This hybrid system capitalizes on the tuned optical properties of AuNCs and their role as co-catalysts with TiO 2 , driving enhanced photocatalytic performance under ultraviolet (UV) excitation. Using motion analysis, it is shown that the AuNC-microswimmers exhibit significantly greater propulsion and mean squared displacement (MSD) as compared to controls. These findings suggest that the integration of nanoclusters with semiconductor materials enables state of the art, light-switchable microswimmers. These AuNC-microswimmer systems may thus offer new opportunities for environmental catalysis and other applications, providing precise control over catalytic and motile behaviors at the microscale.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Vibronic Excitons and Conical Intersections in Semiconductor Quantum Dots

Surface defects and organic surface-capping ligands affect the photoluminescence properties of semiconductor quantum dots (QDs) by altering the rates of competing nonradiative relaxation processes. In this study, broadband two-dimensional electronic spectroscopy reveals that absorption of light by QDs prepares vibronic excitons, excited states derived from quantum coherent mixing of the core electronic and ligand vibrational states. Rapidly damped coherent wavepacket motions of the ligands are observed during hot-carrier cooling, with vibronic coherence transferred to the photoluminescent state. Furthermore, these findings suggest a many-electron, molecular theory for the electronic structure of QDs, which is supported by calculations of the structures of conical intersections between the exciton potential surfaces of a small ammonia-passivated model CdSe nanoparticle.

36 MATERIALS SCIENCE↗