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At least 703 records · Page 39

Nano-Engineered Catalysts for Direct Methanol Fuel Cells

Nano-engineered catalysts, and a method of fabricating them, have been developed in a continuing effort to improve the performances of direct methanol fuel cells as candidate power sources to supplant primary and secondary batteries in a variety of portable electronic products. In order to realize the potential for high energy densities (as much as 1.5 W h/g) of direct methanol fuel cells, it will be necessary to optimize the chemical compositions and geometric configurations of catalyst layers and electrode structures. High performance can be achieved when catalyst particles and electrode structures have the necessary small feature sizes (typically of the order of nanometers), large surface areas, optimal metal compositions, high porosity, and hydrophobicity. The present method involves electrodeposition of one or more catalytic metal(s) or a catalytic-metal/polytetrafluoroethylene nanocomposite on an alumina nanotemplate. The alumina nanotemplate is then dissolved, leaving the desired metal or metal/polytetrafluoroethylene-composite catalyst layer. Unlike some prior methods of making fine metal catalysts, this method does not involve processing at elevated temperature; all processing can be done at room temperature. In addition, this method involves fewer steps and is more amenable to scaling up for mass production. Alumina nanotemplates are porous alumina membranes that have been fabricated, variously, by anodizing either pure aluminum or aluminum that has been deposited on silicon by electronbeam evaporation. The diameters of the pores (7 to 300 nm), areal densities of pores (as much as 7 x 10(exp 10)sq cm), and lengths of pores (up to about 100 nm) can be tailored by selection of fabrication conditions. In a given case, the catalytic metal, catalytic metal alloy, or catalytic metal/ polytetrafluoroethylene composite is electrodeposited in the pores of the alumina nanotemplate. The dimensions of the pores, together with the electrodeposition conditions, determine the sizes and surface areas of the catalytic particles. Hence, the small features and large surface areas of the porosity translate to the desired small particle size and large surface area of the catalyst (see figure). When polytetrafluoroethylene is included, it is for the purpose of imparting hydrophobicity in order to prevent water from impeding the desired diffusion of gases through the catalyst layer. To incorporate polytetrafluoroethylene into a catalytic-metal/polytetrafluoroethylene nanocomposite, one suspends polytetrafluoroethylene nanoparticles in the electrodeposition solution. The polytetrafluoroethylene content can be varied to obtain the desired degree of hydrophobicity and permeability by gas.

Myung, Nosang↗

Partial PdAu nanoparticle embedding into TiO 2 support accentuates catalytic contributions from the Au/TiO 2 interface

Despite the broad catalytic relevance of metal–support interfaces, controlling their chemical nature, the interfacial contact perimeter (exposed to reactants), and consequently, their contributions to overall catalytic reactivity, remains challenging, as the nanoparticle and support characteristics are interdependent when catalysts are prepared by impregnation. Here, we decoupled both characteristics by using a raspberry-colloid-templating strategy that yields partially embedded PdAu nanoparticles within well-defined SiO 2 or TiO 2 supports, thereby increasing the metal–support interfacial contact compared to nonembedded catalysts that we prepared by attaching the same nanoparticles onto support surfaces. Between nonembedded PdAu/SiO 2 and PdAu/TiO 2 , we identified a support effect resulting in a 1.4-fold higher activity of PdAu/TiO 2 than PdAu/SiO 2 for benzaldehyde hydrogenation. Notably, partial nanoparticle embedding in the TiO 2 raspberry-colloid-templated support increased the metal–support interfacial perimeter and consequently, the number of Au/TiO 2 interfacial sites by 5.4-fold, which further enhanced the activity of PdAu/TiO 2 by an additional 4.1-fold. Theoretical calculations and in situ surface-sensitive desorption analyses reveal facile benzaldehyde binding at the Au/TiO 2 interface and at Pd ensembles on the nanoparticle surface, explaining the connection between the number of Au/TiO 2 interfacial sites (via the metal–support interfacial perimeter) and catalytic activity. Our results demonstrate partial nanoparticle embedding as a synthetic strategy to produce thermocatalytically stable catalysts and increase the number of catalytically active Au/TiO 2 interfacial sites to augment catalytic contributions arising from metal–support interfaces.

Lim, Kang Rui Garrick (ORCID:0000000321599844)↗

Metallic Cation-Mediated Entrapment of Nucleic Acids on Mesoporous Silica Surface: Application in Castration-Resistant Prostate Cancer

The use of exogenous nucleic acid technologies to modulate aberrant protein expression resulting from genetic mutations is a promising therapeutic approach for the treatment of diseases such as advanced prostate cancer (PC). The promise of nucleic-based therapeutics is dependent on the development of platforms that effectively protect nucleic acids from nuclease degradation and deliver the nucleic acids to the cytosol of target cells. In this work, we present the development of a divalent metal-mediated nucleic acid entrapment strategy with a porous silica matrix. This simple strategy results in efficient loading percentages of both siRNA (>60%) and mRNA (>80%) as well as their release within relevant biological environments (80%). Additionally, our data supports that the current method reduces endosomal entrapment and supports the lipid coating of mesoporous silica nanoparticles (LC-MSNs). Finally, the metal-enhanced nanosystem is assessed for biocompatibility, stability, and circulation within in vitro, ex ovo, and in vivo models of PC.

60 APPLIED LIFE SCIENCES↗

Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction

The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO 2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing Progressive Degradation of Cobalt Oxide Nanoparticles During Thermochemical Redox Cycling via Operando STEM-EELS

Metal oxides are promising materials for long-duration thermochemical energy storage. Efforts to characterize their reaction kinetics, conversion rate, and morphological evolution during thermochemical cycling have largely focused on bulk and microscale measurements. However, the design of nanostructured metal oxides could improve the reaction reversibility and kinetics, warranting the development of platforms to investigate how these materials behave at the nanoscale. Here, we demonstrate the use of correlative, time-resolved electron energy loss spectroscopy and imaging in an environmental transmission electron microscope for studying the thermochemical cyclability of cobalt oxide nanoparticles with high spatial and temporal resolution. The spectroscopic data reveal a striking decrease in reaction kinetics after the first cycle, resulting from sintering-driven nanostructural densification. Comparison between cycling in humid and dry air shows that atmospheric conditions can modulate reaction transition temperatures but have limited effects on sintering over multiple cycles, suggesting long-term durability will instead rely on synthetic and/or nanostructural modifications.

25 ENERGY STORAGE↗

Energy-Resolved Femtosecond Hot Electron Dynamics in Single Plasmonic Nanoparticles

Efficient excitation and harvesting of hot carriers from nanoscale metals is central to many emerging photochemical, photovoltaic, and ultrafast optoelectronic applications. Nevertheless, direct experimental evidence of the energy-dependent femtosecond dynamics in ubiquitous tens-of-nanometer gold structures remains elusive, despite the potentially rich interplay between interfacial and internal plasmonic fields, excitation distributions, and scattering processes. To explore the effects of nanoscale structure on these dynamics, we employ simultaneous time-, angle-, and energy-resolved photoemission spectroscopy of single plasmonic nanoparticles. Photoelectron velocity and electric field distributions reveal bulk-like ballistic hot electron transport in different geometries, lacking any signatures of surface effects. Energy-resolved dynamics are measured in the 1–2 eV range and extrapolated to lower energies via Boltzmann theory, providing a detailed view of hot electron lifetimes within nanoscale gold. Here, we find that particles with relevant dimensions as small as 10 nm serve as exemplary platforms for studying intrinsic metal dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Cr(III) Adsorption on the Dissolution of Boehmite Nanoparticles in Caustic Solution

Incorporation of relatively minor impurity metals onto metal (oxy)hydroxides can strongly impact solubility. In complex highly alkaline multicomponent tank waste such as that at the Hanford Nuclear Reservation, tests indicate that the surface area-normalized dissolution rate of boehmite ($γ$-AlOOH) nanomaterials is at least an order of magnitude lower than that predicted for the pure phase. In this work we examine the dissolution kinetics of boehmite coated by adsorbed Cr(III), which adheres at saturation coverages as sparse chemisorbed monolayer clusters. Using 40 nm boehmite nanoplates as a model system, temperature-dependent dissolution rates of pure versus Cr(III)-adsorbed boehmite showed that the initial rate for the latter is consistently several times lower, with an apparent activation energy 16 kJ·mol -1 higher. Although the surface coverage is only around 50%, solution analytics coupled to multimethod solids characterization reveals a phyicochemical armoring effect by adsorbed Cr(III) that substantially reduces the number of dissolution-active sites on particle surfaces. Such findings could help improve kinetics models of boehmite and/or metal ion adsorbed boehmite nanomaterials, ultimately providing a stronger foundation for the development of more robust complex radioactive liquid waste processing strategies.

54 ENVIRONMENTAL SCIENCES↗

Supported Molybdenum Carbide Nanoparticles as Hot Hydrogen Reservoirs for Catalytic Applications

Transition metal carbides have been long proposed as replacements for expensive Pt-group transition metals as heterogeneous catalysts for hydrogenation reactions, featuring similar to superior activities and selectivities. Combining experimental observations and theoretical calculations, we show that the hydrogenating capabilities of molybdenum carbide can be further improved by nanostructuring, as seen on MoC y nanoclusters anchored on an inert Au(111) support, revealing a more prominent role of Mo active sites in the easier H 2 adsorption, dissociation, H adatom diffusion, and elongated chemisorbed H 2 Kubas moieties formation when compared to the bulk δ-MoC(001) surface, thus explaining the observed stronger H 2 interaction and the larger formation of CH x species, making these systems ideal to catalyse hydrogenation reactions

36 MATERIALS SCIENCE↗

Photothermal behaviour of titanium nitride nanoparticles evaluated by transient X-ray diffraction

The photothermal properties of metal nitrides have recently received significant attention owing to diverse applications in solar energy conversion, photothermal therapies, photoreactions, and thermochromic windows. Here, the photothermal response of titanium nitride nanoparticles is examined using transient X-ray diffraction, in which optical excitation is synchronized with X-ray pulses to characterize dynamic changes in the TiN lattice. Photoinduced diffraction data is quantitatively analyzed to determine increases in the TiN lattice spacing, which are furthermore calibrated against static, temperature-dependent diffraction patterns of the same samples. Measurements of 20 nm and 50 nm diameter TiN nanoparticles reveal transient lattice heating from room temperature up to similar to 175 degrees C for the highest pump fluences investigated here. Increasing excitation intensity drives sublinear increases in lattice temperature, due to increased heat capacity at the higher effective temperatures achieved at higher powers. Temporal dynamics show that higher excitation intensity drives not only higher lattice temperatures, but also unexpectedly slower cooling of the TiN nanoparticles, which is attributed to heating of the solvent proximal to the nanoparticle surface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Lead-lead oxide-carbon nanocomposite for energy storage cells and method of preparation

Lead/lead oxide/carbon (“Pb—O—C”) nanocomposite materials are useful as electrode active materials for electrodes in lithium and sodium batteries. A Pb—O—C nanocomposite as described herein comprises Pb and lead oxide nanoparticles homogeneously dispersed in a carbon nanoparticle matrix. In the nanocomposite, the other element or elements (e.g., transition metals, Al, Si, P, Sn, Sb, and Bi) can be alloyed with the Pb nanoparticles, incorporated as a mixed oxide with the lead oxide nanoparticles, or can be present as distinct elemental or oxide nanoparticles within the carbon nanoparticle matrix. In some embodiments, the additional element or elements are present as alloys and mixed oxides with the Pb materials and as distinct elemental and/or oxide nanoparticles. In a preferred embodiment the Pb nanoparticles surface is oxidized to lead oxide thus creating a shell on core nanostructure.

Johnson, Christopher S.↗

Subsurface hydrogen, curvature, and strain: lessons from electro-reduction of benzaldehyde on nano-structured Pd catalysts

The unique ability of palladium (Pd) to absorb hydrogen and form a bulk hydride is vital for chemical transformations that involve hydrogenation reactions. Nano-structured Pd catalysts offer a promise of tuning these reaction rates by exploiting variations of reactant binding energies depending on the surface structure and morphological constraints that result in inhomogeneous strain. However, the interplay between the nano-structure of Pd and the ability of Pd to adsorb (and absorb) hydrogen as well as other reactive species needs to be better understood for a rational understanding of competitive chemical transformations at Pd surfaces. We consider the effects of the surface corrugation, strain, and subsurface Pd hydride on the reduction of benzaldehyde to benzyl alcohol in two qualitatively different samples – Pd nanoparticles and Pd gels formed by quasi-one-dimensional chains of these nanoparticles. Our electrochemical measurements and computational modelling suggest that surface concave sites, inherent to Pd gels, facilitate hydrogen transfer to the Pd subsurface region, thus weakening benzaldehyde binding to the surface. This effect is further modulated by the strain, depending on the local coordination environment on the corrugated surface. Furthermore, these findings demonstrate how structurally complex samples in the form of gels provide degrees of freedom for controlling the behavior of metal catalysts that are not available in isolated nanoparticles, which paves the way for new approaches in the design of catalytic materials and synthesis of metal hydrides.

Padavala, Sri Krishna Murthy [University of Minnes↗

Inserting a Low-Refractive-Index Dielectric Rear Reflector into PERC Cells: Challenges and Opportunities

One of the simplest and most effective ways to reduce the operating temperature of photovoltaic systems in the field is to reflect unusable, 'sub-bandgap' light with energies below the cell absorber's bandgap energy. In this work, low-refractive index SiO2 nanoparticle films inserted between c-Si wafers and metal electrodes significantly increase the reflectance of sub-bandgap light in fabricated test structures. These films are then integrated into the standard PERC fabrication sequence, revealing that the reflection benefits remains after some processing steps but are lost in certain conditions. The SiO2 nanoparticle films are easily ablated during laser contact opening, but are undesirably etched during post-laser cleaning. After Al metallization, the fully fabricated devices show enhanced sub-bandgap reflection when annealed at moderate temperatures, but energy-dispersive X-ray spectroscopy shows that high-temperature firing causes unwanted Al penetration into the SiO2 nanoparticle film, compromising reflection.

14 SOLAR ENERGY↗

Isolation and Monitoring of Cleanroom-Associated Microbial Contaminates From Geological Collections

Microbial contamination is of particular interest to geological curation as many microorganisms can change mineral composition and produce compounds used as biosignatures used for the detection of life. Microbial cells can change the mineral composition of rocks through organic acid production and direct enzymatic oxidation/reduction of transition metals. Enzymatic oxidation of iron and manganese can occur at a rate several orders of magnitude faster than under abiotic conditions and produce highly reactive nanoparticle- sized oxides that can react and sorb other metals and organic compounds. Many fungi can also produce organic acids that dissolve and chelate mineral matrices chemically reducing and dissolving rock surfaces. Finally, several common soil-associated bacteria and fungi produce secondary metabolites that contain unusual amino acid analogs and non-ribosomal peptides containing both L- and D- chirality used in characterizing carbonaceous chondrites and the detection of extraterrestrial life.

Davis, Richard E.↗

Screen-Printed SHJ Solar Cells with Complex Silver Inks

Metallization using complex metal inks has gained significant research interest due to its cost-effectiveness and ability to achieve performance comparable to traditional nanoparticle pastes. This study introduces the use of complex silver (Ag) inks applied via industrial screen-printing for silicon heterojunction (SHJ) solar cell metallization. The printed Ag lines exhibit a contact resistivity on SHJ tin-doped indium oxide (ITO) surfaces as low as approximately 0.2-12 mO cm2. Photoluminescence imaging reveals minimal surface passivation degradation (iVoc < 3.5 mV), while scanning electron microscopy (SEM) shows a denser structure compared to Ag layer from nanoparticle pastes. The printed Ag grid features thin (approximately 1 micrometer), continuous fingers approximately 100-120 micrometer wide, significantly thinner than conventional approximately 20-30 micrometer fingers produced with nanoparticle-based pastes. Double printing achieves SHJ device efficiencies exceeding 20%, the highest reported for industrial solar cell precursors using this technology. These findings highlight the potential of complex Ag inks as a sustainable alternative to particle-based pastes, reducing Ag consumption and processing temperatures without compromising efficiency.

14 SOLAR ENERGY↗

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.

Chaperonins/chemistry/ultrastructure↗