Atomic-Scale Characterization of Microscale Battery Particles Enabled by a High-Throughput Focused Ion Beam Milling Technique.

The cathode materials in lithium-ion batteries (LIBs) require improvements to address issues such as surface degradation, short-circuiting, and the formation of dendrites. One such method for addressing these issues is using surface coatings. Coatings can be sought to improve the durability of cathode materials, but the characterization of the uniformity and stability of the coating is important to assess the performance and lifetime of these materials. For microscale particles, there are, however, challenges associated with characterizing their surface modifications by transmission electron microscopy (TEM) techniques due to the size of these particles. Often, techniques such as focused ion beam (FIB)-assisted lift-out can be used to prepare thin cross sections to enable TEM analysis, but these techniques are very time-consuming and have a relatively low throughput. The work outlined herein demonstrates a FIB technique with direct support of microscale cathode materials on a TEM grid that increases sample throughput and reduces the processing time by 60-80% (i.e., from >5 to ∼1.5 h). The demonstrated workflow incorporates an air-liquid particle assembly followed by direct particle transfer to a TEM grid, FIB milling, and subsequent TEM analysis, which was illustrated with lithium nickel cobalt aluminum oxide particles and lithium manganese nickel oxide particles. These TEM analyses included mapping the elemental composition of cross sections of the microscale particles using energy-dispersive X-ray spectroscopy. The methods developed in this study can be extended to high-throughput characterization of additional LIB cathode materials (e.g., new compositions, coating, end-of-life studies), as well as to other microparticles and their coatings as prepared for a variety of applications.

Electrodeposition of PdPt Nanoparticles on Edges and S-Vacancies in Exfoliated MoS2 Nanosheets for Enhanced Hydrogen Evolution Activity.

Deposition of metal nanoparticles onto the molybdenum disulfide (MoS2 ) nanosheets is an efficient method to tune the electronic structure of the MoS2 and maximize its catalytic performance towards the hydrogen evolution reaction (HER). Herein, we report the electrodeposition of Pd and Pt nanoparticles onto desulfurized MoS2 nanosheets (MoS2-x ) to achieve an improved HER activity in an acidic electrolyte. The initial MoS2 powder was exfoliated and isolated through centrifugation, followed by electrochemical desulfurization to create defect sites. Subsequently, Pt and Pd nanoparticles were electrodeposited onto the S-vacancies of MoS2-x nanosheets. The resulting PdPt nanoparticles, with a diameter of 3.3 ±1.7 nm, were distributed across the surfaces of the nanosheets. A preferential deposition was evident at the edges of the nanosheets, particularly when Pd was deposited first followed by Pt. Owing to this preferential deposition of Pd and Pt and the synergistic interaction of MoS2-x with Pd and Pt, the prepared catalyst exhibited a low overpotential of 30 mV at 10 mA cm-2 , which is 2.7× lower than the MoS2-x alone. The prepared catalyst exhibited a 1.7× increase in the mass activity at 20 mV overpotential, relative to that of a commercial Pt/C nanocatalyst, showcasing its promising potential as an alternative catalyst.

Near-field enhancement of optical second harmonic generation in hybrid gold-lithium niobate nanostructures.

Nanophotonics research has focused recently on the ability of nonlinear optical processes to mediate and transform optical signals in a myriad of novel devices, including optical modulators, transducers, color filters, photodetectors, photon sources, and ultrafast optical switches. The inherent weakness of optical nonlinearities at smaller scales has, however, hindered the realization of efficient miniaturized devices, and strategies for enhancing both device efficiencies and synthesis throughput via nanoengineering remain limited. Here, we demonstrate a novel mechanism by which second harmonic generation, a prototypical nonlinear optical phenomenon, from individual lithium niobate particles can be significantly enhanced through nonradiative coupling to the localized surface plasmon resonances of embedded gold nanoparticles. A joint experimental and theoretical investigation of single mesoporous lithium niobate particles coated with a dispersed layer of ~10 nm diameter gold nanoparticles shows that a ~32-fold enhancement of second harmonic generation can be achieved without introducing finely tailored radiative nanoantennas to mediate photon transfer to or from the nonlinear material. This work highlights the limitations of current strategies for enhancing nonlinear optical phenomena and proposes a route through which a new class of subwavelength nonlinear optical platforms can be designed to maximize nonlinear efficiencies through near-field energy exchange.

Gold-Protein Composite Nanoparticles for Enhanced X-ray Interactions: A Potential Formulation for Triggered Release.

Drug-delivery vehicles have been used extensively to modulate the biodistribution of drugs for the purpose of maximizing their therapeutic effects while minimizing systemic toxicity. The release characteristics of the vehicle must be balanced with its encapsulation properties to achieve optimal delivery of the drug. An alternative approach is to design a delivery vehicle that preferentially releases its contents under specific endogenous (e.g., tissue pH) or exogenous (e.g., applied temperature) stimuli. In the present manuscript, we report on a novel delivery system with potential for triggered release using external beam radiation. Our group evaluated Zein protein as the basis for the delivery vehicle and used radiation as the exogenous stimulus. Proteins are known to react with free radicals, produced during irradiation in aqueous suspensions, leading to aggregation, fragmentation, amino acid modification, and proteolytic susceptibility. Additionally, we incorporated gold particles into the Zein protein matrix to create hybrid Zein-gold nanoparticles (ZAuNPs). Zein-only nanoparticles (ZNPs) and ZAuNPs were subsequently exposed to kVp radiation (single dose ranging from 2 to 80 Gy; fractionated doses of 2 Gy delivered 10 times) and characterized before and after irradiation. Our data indicated that the presence of gold particles within Zein particles was correlated with significantly higher levels of alterations to the protein, and was associated with higher rates of release of the encapsulated drug compound, Irinotecan. The aggregate results demonstrated a proof-of-principle that radiation can be used with gold nanoparticles to modulate the release rates of protein-based drug-delivery vehicles, such as ZNPs.

Contact transfer of engineered nanomaterials in the workplace.

This study investigates the potential spread of cadmium selenide quantum dots in laboratory environments through contact of gloves with simulated dry spills on laboratory countertops. Secondary transfer of quantum dots from the contaminated gloves to other substrates was initiated by contact of the gloves with different materials found in the laboratory. Transfer of quantum dots to these substrates was qualitatively evaluated by inspection under ultraviolet illumination. This secondary contact resulted in the delivery of quantum dots to all the evaluated substrates. The amount of quantum dots transferred was quantified by elemental analysis. The residue containing quantum dots picked up by the glove was transferred to at least seven additional sections of the pristine substrate through a series of sequential contacts. These results demonstrate the potential for contact transfer as a pathway for spreading nanomaterials throughout the workplace, and that 7-day-old dried spills are susceptible to the propagation of nanomaterials by contact transfer. As research and commercialization of engineered nanomaterials increase worldwide, it is necessary to establish safe practices to protect workers from the potential for chronic exposure to potentially hazardous materials. Similar experimental procedures to those described herein can be adopted by industries or regulatory agencies to guide the development of their nanomaterial safety programmes.

Tuning the Surface Chemistry of Second-Harmonic-Active Lithium Niobate Nanoprobes Using a Silanol-Alcohol Condensation Reaction.

The surface functionalization of nanoparticles (NPs) is of great interest for improving the use of NPs in, for example, therapeutic and diagnostic applications. The conjugation of specific molecules with NPs through the formation of covalent linkages is often sought to provide a high degree of colloidal stability and biocompatibility, as well as to provide functional groups for further surface modification. NPs of lithium niobate (LiNbO3) have been explored for use in second-harmonic-generation (SHG)-based bioimaging, expanding the applications of SHG-based microscopy techniques. The efficient use of SHG-active LiNbO3 NPs as probes will, however, require the functionalization of their surfaces with molecular reagents such as polyethylene glycol and fluorescent molecules to enhance their colloidal and chemical stability and to enable a correlative imaging platform. Herein, we demonstrate the surface functionalization of LiNbO3 NPs through the covalent attachment of alcohol-based reagents through a silanol-alcohol condensation reaction. Alcohol-based reagents are widely available and can have a range of terminal functional groups such as carboxylic acids, amines, and aldehydes. Attaching these molecules to NPs through the silanol-alcohol condensation reaction could diversify the reagents available to modify NPs, but this reaction pathway must first be established as a viable route to modifying NPs. This study focuses on the attachment of a linear alcohol functionalized with carboxylic acid and its use as a reactive group to further tune the surface chemistry of LiNbO3 NPs. These carboxylic acid groups were reacted to covalently attach other molecules to the NPs using copper-free click chemistry. This derivatization of the NPs provided a means to covalently attach polyethylene glycols and fluorescent probes to the NPs, reducing NP aggregation and enabling multimodal tracking of SHG nanoprobes, respectively. This extension of the silanol-alcohol condensation reaction to functionalize the surfaces of LiNbO3 NPs can be extended to other types of nanoprobes for use in bioimaging, biosensing, and photodynamic therapies.

Elucidating the role of precursors in synthesizing single crystalline lithium niobate nanomaterials: a study of effects of lithium precursors on nanoparticle quality.

A number of solution-based procedures have been realized for the synthesis of lithium niobate (LiNbO3) nanoparticles (NPs). Relatively little is, however, known about the influences of the selection of lithium (Li) precursors on the resulting dimensions, shapes, crystallinity, and purity of the products. A comparative study is provided herein on the role of different Li precursors during the synthesis of LiNbO3 NPs. To the best of our knowledge, this study provides the first systematic comparison of the effects of various Li reagents on the preparation of LiNbO3 NPs through solvothermal processes. This solution-phase approach was tuned by the inclusion of Li precursors that either lacked carbon based anions (e.g., F-, Cl-, Br-, I-, OH-, NO3-, or SO42-) or contained carbon-based anions (e.g., C2H5O-, C2H3OO-, C5H7OO-, or CO32-). All other variables were held constant during the synthesis, such as reaction temperature, solvent, niobium precursor, and surfactants. The results of these studies suggest that the type of Li precursor selected plays an important role in nanoparticle formation, such as through controlling the uniformity, crystallinity, and aggregation of LiNbO3 NPs. The average diameter of the resulting NPs can also vary from ∼30 to ∼830 nm as a function of the Li reagent used in the synthesis. The selection of Li precursors also influences the phase purity of the products. This comparative study on the preparation of crystalline LiNbO3 NPs represents a critical step forward to understand the influences and roles of precursors in the design of synthetic processes for the preparation of a variety of alkali metal niobates (e.g., including NaNbO3 and KNbO3) and crystalline metal oxide-based NPs containing other transition metals (e.g., titanium, tantalum).

Arrays of Microscale Linear Ridges with Self-Cleaning Functionality for the Oxygen Evolution Reaction.

Gas management during electrocatalytic water splitting is vital for improving the efficiency of clean hydrogen production. The accumulation of gas bubbles on electrode surfaces prevents electrolyte access and passivates the electrochemically active surface area. Electrode morphologies are sought to assist in the removal of gas from surfaces to achieve higher reaction rates at operational voltages. Herein, regular arrays of linear ridges with specific microscale separations were systematically studied and correlated to the performance of the oxygen evolution reaction (OER). The dimensions of the linear ridges were proportional to the size of the oxygen bubbles, and the mass transfer processes associated with gas evolution at these ridges were monitored using a high-speed camera. Characterization of the adhered bubbles prior to detachment enabled the use of empirical methods to determine the volumetric flux of product gas and the bubble residence times. The linear ridges promoted a self-cleaning effect as one bubble would induce neighboring bubbles to simultaneously release from the electrode surfaces. The linear ridges also provided preferential bubble growth sites, which expedited the detachment of bubbles with similar diameters and shorter residence times. The linear ridges enhanced the OER in comparison to planar electrodes prepared by electrodeposition from the same high-purity nickel (Ni). Linear ridges with a separation distance of 200 µm achieved nearly a 2-fold increase in current density relative to the planar electrode at an operating voltage of 1.8 V (vs Hg/HgO). The electrodes with linear ridges having a separation distance of 200 µm also had the highest sustained current densities over a range of operating conditions for the OER. Self-cleaning surface morphologies could benefit a variety of electrocatalytic gas evolving reactions by improving the efficiency of these processes.

Lithium niobate particles with a tunable diameter and porosity for optical second harmonic generation.

Uniform, porous particles of lithium niobate (LiNbO3) can be used as contrast agents in bioimaging, drug delivery carriers, nonlinear optical emitters, biosensors, photocatalysts and electrode materials in lithium-ion batteries. In this article, we introduce a hydrothermal method to prepare uniform, mesoporous LiNbO3 particles with a tunable diameter and porosity. These properties are each tuned by adjusting the reaction times of the hydrothermal process. This approach forms mesoporous LiNbO3 particles without the addition of organic additives (e.g., surfactants) or hard templates (e.g., silica). Formation of these LiNbO3 particles proceeds through an aqueous sol-gel reaction in which niobium hydroxide species are generated in situ and undergo a condensation reaction in the presence of lithium hydroxide to form a colloidal solution. A hydrothermal reaction using this solution resulted in the formation of uniform, solid, and semi-crystalline particles. A post-calcination step induces crystallinity in the product and transforms the particles into mesoporous materials composed of a rhombohedral LiNbO3 phase. An increase in reaction time results in an increase in the diameter of these particles from 580 to 1850 nm, but also decreases their porosity. These LiNbO3 particles were active towards second harmonic generation (SHG), and their SHG response resembled that of larger crystals of rhombohedral LiNbO3. This work also offers a viable strategy for manufacturing other materials (e.g., tantalates, titanates, niobates) with tunable dimensions and porosity that enable a broad range of applications in photonics, energy, and catalysis.

Size Fractionation of Titania Nanoparticles in Wild Dittrichia viscosa Grown in a Native Environment.

We report a size fractionation of titania (TiO2) nanoparticles absorbed from the environment and found within wild Dittrichia viscosa plants. The nanoparticles were isolated by extraction and isolation from distinct plant organs, as well as from the corresponding rhizosphere of wild, adult plants. The collected nanoparticles were characterized by scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (STEM-EDS). More than 1200 TiO2 nanoparticles were analyzed by these techniques. The results indicated the presence of TiO2 nanoparticles with a wide range of sizes within the inspected plant organs and rhizospheres. Interestingly, a size selective process occurs during the internalization and translocation of these nanoparticles (e.g., foliar and root uptake), which favors the accumulation of mainly TiO2 nanoparticles with diameters <50 nm in the leaves, stems, and roots. In fact, our findings indicate that among the total number of TiO2 nanoparticles analyzed, the fraction of the particles with dimensions <50 nm were 52% of those within the rhizospheres, 88.5% of those within the roots, 90% of those within the stems, and 53% of those within the leaves. This significant difference observed in the size distribution of the TiO2 nanoparticles among the rhizosphere and the plant organs could have impacts on the food chain and further biologicals effects that are dependent on the size of the TiO2.

Differentiation of Nanoparticles Isolated from Distinct Plant Species Naturally Growing in a Heavy Metal Polluted Site.

Leaves harvested from the plants of two different species (Dittrichia viscosa and Cichorium intybus) grown in their autogenous environment near a steel manufacturing company were characterized for naturally accumulated nanoparticles. These plant species are known to accumulate heavy metals. It was, however, unknown if these species would also accumulate these heavy metals in the form of nanoparticles. The isolated solid fractions were analyzed using dynamic light scattering, X-ray fluorescence, and transmission electron microscopy. These analyses revealed the presence of nanoparticles within the plants. The composition of nanoparticles found in each plant species is distinct: (i) for Dittrichia viscosa, the nanoparticle composition matched the heavy metal pollution anticipated from the surrounding industries; (ii) for Cichorium intybus, the nanoparticle composition was similar to the most abundant elements in the soil. The different behavior is a reflection of the phytoaccumulator characteristics of both species. This study provides the first evidence of sequestration of heavy metals in the form of nanoparticles by plants grown autogenously in polluted areas and will have implications in waste management of phytoremediation systems and in understanding the heavy metal life-cycle in the environment.

Tunable functionalization of silica coated iron oxide nanoparticles achieved through a silanol-alcohol condensation reaction.

The surface properties of nanoparticles play an important role in their interactions with their surroundings. Silane reagents have been used for surface modifications to silica shells on iron oxide nanoparticles, but using these reagents presents some challenges. An alternative approach to modifying the surfaces of these silica shells was developed to impart different terminal functional groups, such as a thiol, alcohol, or carboxylic acid, through the use of alcohol-based reagents. This approach to surface functionalization of the core-shell particles was verified through chemical analyses and the attachment of gold nanoparticles. The use of the silanol-alcohol condensation reaction could be extended further to other surface functionalizations through the use of additional alcohol-based reagents.

Mesoporous Platinum Prepared by Electrodeposition for Ultralow Loading Proton Exchange Membrane Fuel Cells.

The porosity and utilization of platinum catalysts have a direct impact on their performance within proton exchange membrane fuel cells. It is desirable to identify methods that can prepare these catalysts with the desired features, and that can be widely implemented using existing and industrially scalable techniques. Through the use of electrodeposition processes, fuel cell testing, and electron microscopy analyses before and after fuel cell testing, we report the preparation and performance of mesoporous platinum catalysts for proton exchange membrane fuel cells. We found that these mesoporous platinum catalysts can be prepared in sufficient quantities through techniques that also enable their direct incorporation into membrane electrode assemblies. We also determined that the mesoporous catalysts achieved a high porosity, which was retained after assembly and utilization within fuel cells. In addition, these mesoporous platinum catalysts exhibited an improved platinum mass specific power over catalysts prepared from commercially available platinum nanocatalysts.

Novel defect-fluorite pyrochlore sodium niobate nanoparticles: solution-phase synthesis and radiation tolerance analysis.

Materials possessing a defect-fluorite pyrochlore structure can have a range of useful properties that are sought after, which include their radiation tolerance, nuclear waste immobilization, and phase stability at elevated temperatures. In this study, we demonstrate for the first time the synthesis and a detailed analysis of defect-fluorite pyrochlore sodium niobate (NaNbO3) nanoparticles. This analysis included an investigation into their stability to elevated temperatures and neutron irradiation. A surfactant-assisted solvothermal method is used to prepare nanoparticles of NaNbO3. This solution-phase approach results in the formation of crystalline nanoparticles of a defect-fluorite pyrochlore NaNbO3 at relatively low temperatures. The products had an average diameter of ∼74 ± 11 nm. The nanoparticles adopted a defect-fluorite pyrochlore phase and matched the cubic Fm3[combining macron]m space group. This pyrochlore form of NaNbO3 was found to be stable up to 500 °C. The nanoparticles transformed into the orthorhombic and rhombohedral perovskite phases of NaNbO3 along with the introduction of a pseudo-hexagonal Nb2O5 at higher temperatures. These defect-fluorite pyrochlore nanoparticles of NaNbO3 also exhibited a resistance to radiation induced amorphization. The dimensions, phase, and crystallinity of the defect-fluorite pyrochlore nanoparticles after exposure to a flux of neutrons were comparable to those of the as-synthesized product. The thermal stability and radiation tolerance of these pyrochlore nanoparticles could be useful in the design of thermally resilient materials, high temperature catalysts, and durable materials for the handling and storage of radioactive waste.

Template assisted preparation of high surface area macroporous supports with uniform and tunable nanocrystal loadings.

The incorporation of catalytic nanocrystals into macroporous support materials has been very attractive due to their increased catalyst mass activity. This increase in catalytic efficiency is attributed in part to the increased surface area to volume ratio of the catalysts and the use of complementary support materials that can enhance their catalytic activity and stability. A uniform and tunable coating of nanocrystals on porous matrices can be difficult to achieve with some techniques such as electrodeposition. More sophisticated techniques for preparing uniform nanocrystal coatings include atomic layer deposition, but it can be difficult to reproduce these processes at commercial scales required for preparing catalyst materials. In this study, catalytic nanocrystals supported on three dimensional (3D) porous structures were prepared. The demonstrated technique utilized scalable approaches for achieving a uniform surface coverage of catalysts through the use of polymeric sacrificial templates. This template assisted technique was demonstrated with a good control over the surface coverage of catalysts, support material composition, and porosities of the support material. A series of regular porous supports were each prepared with a uniform coating of nanocrystals, such as NaYF4 nanocrystals supported by a porous 3D lattice of Ti1-xSixO2, Pt nanocrystals on a 3D porous support of TiO2, Pd nanocrystals on Ni nanobowls, and Pt nanocrystals on 3D assemblies of Au/TiO2 nanobowls. The template assisted preparation of high surface area macroporous supports could be further utilized for optimizing the use of catalytic materials in chemical, electrochemical, and photochemical reactions through increasing their catalytic efficiency and stability.

One-pot synthesis of sub-10 nm LiNbO3 nanocrystals exhibiting a tunable optical second harmonic response.

Nanophotonics, dealing with the properties of light interacting with nanometer scale materials and structures, has emerged as a sought after platform for sensing and imaging applications, and is impacting fields that include advanced information technology, signal processing circuits, and cryptography. Lithium niobate (LiNbO3) is a unique photonic material, often referred to as the "silicon of photonics" due to its excellent optical properties. In this article, we introduce a solution-phase method to prepare single-crystalline LiNbO3 nanoparticles with average diameters of 7 nm. This one-pot approach forms well-dispersed LiNbO3 nanocrystals without additional organic additives (e.g., surfactants) to control growth and aggregation of the nanoparticles. Formation of these LiNbO3 nanocrystals proceeds through a non-aqueous sol-gel reaction, in which lithium hydroxide and niobium hydroxide species were generated in situ. The reaction proceeded through both a condensation and crystallization of these reactants to form the solid nanoparticles. These nanocrystals of LiNbO3 were active for optical second harmonic generation (SHG) with a tunable response from 400 to 500 nm. These nanoparticles could enable further development of non-linear optical techniques such as SHG microscopy for bioimaging, which requires the dimensions of nanoparticles to be well below 100 nm.

Green solvent assisted synthesis of cesium bismuth halide perovskite nanocrystals and the influences of slow and fast anion exchange rates.

Replacing lead in halide perovskites to address the concerns of their toxicity and stability has driven a recent surge in research toward alternative lead-free perovskite materials. Lead-free all inorganic cesium bismuth halide (Cs3Bi2X9) perovskite nanocrystals have attracted attention in recent years due to the air-stability and non-toxic nature of bismuth. Herein, we demonstrate a facile sonication-assisted approach for the preparation of all-inorganic cesium bismuth iodide (Cs3Bi2I9) perovskite nanocrystals (NCs) using propylene carbonate as a green, alternative solvent. The photoluminescence (PL) spectra of the Cs3Bi2X9 NCs have a peak emission that can be tuned from 410 to 550 nm by controlling the composition of the NCs through an anion exchange reaction using tetraalkylammonium halides as a source of halide ions. The rate of this anion exchange reaction is demonstrated to have a significant influence on the dimensions of the NCs obtained from the parent Cs3Bi2I9 NCs. The PL emission of these nanocrystals is predominately due to exciton recombination processes. The NCs also exhibit air-stability for at least 150 days.

Synthesis and Characterization of Tunable, pH-Responsive Nanoparticle-Microgel Composites for Surface-Enhanced Raman Scattering Detection.

The synthesis of microgels with pH-tunable swelling leads to adjustable and pH-responsive substrates for surface-enhanced Raman scattering (SERS)-active nanoparticles (NPs). Sterically stabilized and cross-linked latexes were synthesized from random copolymers of styrene (S) and 2-vinylpyridine (2VP). The pH-dependent latex-to-microgel transition and swellability were tuned based on their hydrophobic-to-hydrophilic content established by the S/2VP ratio. The electrostatic loading of polystyrene/poly(2-vinylpyridine) microgels [PS x P2VP y (M)] with anions such as tetrachloroaurate (AuCl4 -) and borate-capped Ag NPs was quantified. The PS x P2VP y (M) can load ∼0.3 equiv of AuCl4 - and the subsequent photoreduction results in Au NP-loaded PS x P2VP y (M) with NPs located throughout the structure. Loading PS x P2VP y (M) with borate-capped Ag NPs produces PS x P2VP y (M) with NPs located on the surface of the microgels, where the Ag content is set by S/2VP. The pH-responsive SERS activity is also reported for these Ag NP-loaded microgels. Analytical enhancement factors for dissolved crystal violet are high (i.e., 109 to 1010) and are set by S/2VP. The Ag NP-loaded microgels with ∼80 wt % 2VP exhibited the most stable pH dependent response.

Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

Hexagonal Arrays of Cylindrical Nickel Microstructures for Improved Oxygen Evolution Reaction.

Fuel-cell systems are of interest for a wide range of applications, in part for their utility in power generation from nonfossil-fuel sources. However, the generation of these alternative fuels, through electrochemical means, is a relatively inefficient process due to gas passivation of the electrode surfaces. Uniform microstructured nickel surfaces were prepared by photolithographic techniques as a systematic approach to correlating surface morphologies to their performance in the electrochemically driven oxygen evolution reaction (OER) in alkaline media. Hexagonal arrays of microstructured Ni cylinders were prepared with features of proportional dimensions to the oxygen bubbles generated during the OER process. Recessed and pillared features were investigated relative to planar Ni electrodes for their influence on OER performance and, potentially, bubble release. The arrays of cylindrical recesses were found to exhibit an enhanced OER efficiency relative to planar nickel electrodes. These microstructured electrodes had twice the current density of the planar electrodes at an overpotential of 100 mV. The results of these studies have important implications to guide the preparation of more-efficient fuel generation by water electrolysis and related processes.