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.

Atomistic Insights into the Stability of Pt Single-Atom Electrocatalysts.

Single-atom catalysts (SACs) have quickly emerged as a new class of catalytic materials. When confronted with classical carbon-supported nanoparticulated catalysts (Pt/C), SACs are often claimed to have superior electrocatalytic properties, e.g., stability. In this study, we critically assess this statement by investigating S-doped carbon-supported Pt SACs as a representative example of noble-metal-based SACs. We use a set of complementary techniques, which includes online inductively coupled plasma mass spectrometry (online ICP-MS), identical location transmission electron microscopy (IL-TEM), and X-ray photoelectron spectroscopy (XPS). It is shown by online ICP-MS that the dissolution behavior of as-synthesized Pt SACs is significantly different from that of metallic Pt/C. Moreover, Pt SACs are, indeed, confirmed to be more stable toward Pt dissolution. When cycled to potentials of up to 1.5 VRHE, however, the dissolution profiles of Pt SACs and Pt/C become similar. IL-TEM and XPS show that this transition is due to morphological and chemical changes caused by cycling. The latter, in turn, is a consequence of the relatively poor stability of S ligands. As monitored by online ICP-MS and XPS, significant amounts of sulfur leave the catalyst during oxidation. Hence, in case catalysts with improved stability in the anodic potential region are desired, more robust supports and ligands must be developed.

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.

Recent developments in the sonoelectrochemical synthesis of nanomaterials.

In recent years, the synthesis and use of nanoparticles have been of special interest among the scientific communities due to their unique properties and applications in various advanced technologies. The production of these materials at industrial scale can be difficult to achieve due to high cost, intense labour and use of hazardous solvents that are often required by traditional chemical synthetic methods. Sonoelectrochemistry is a hybrid technique that combines ultrasound and electrochemistry in a specially designed electrochemical setup. This technique can be used to produce nanomaterials with controlled sizes and shapes. The production of nanoparticles by sonoelectrochemistry as a technique offers many advantages: (i) a great enhancement in mass transport near the electrode, thereby altering the rate, and sometimes the mechanism of the electrochemical reactions, (ii) a modification of surface morphology through cavitation jets at the electrode-electrolyte interface, usually causing an increase of the surface area and (iii) a thinning of the electrode diffusion layer thickness and therefore ion depletion. The scalability of sonoelectrochemistry for producing nanomaterials at industrial scale is also very plausible due to its "one-pot" synthetic approach. Recent advancements in sonoelectrochemistry for producing various types of nanomaterials are briefly reviewed in this article. It is with hope that the presentation of these studies therein can generate more interest in the field to "catalyze" future investigations in novel nanomaterial development and industrial scale-up studies.

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.

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.

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.

Self-assembly of nanoparticles onto the surfaces of polystyrene spheres with a tunable composition and loading.

Functional colloidal materials were prepared by design through the self-assembly of nanoparticles (NPs) on the surfaces of polystyrene (PS) spheres with control over NP surface coverage, NP-to-NP spacing, and NP composition. The ability to control and fine tune the coating was extended to the first demonstration of the co-assembly of NPs of dissimilar composition onto the same PS sphere, forming a multi-component coating. A broad range of NP decorated PS (PS@NPs) spheres were prepared with uniform coatings attributed to electrostatic and hydrogen bonding interactions between stabilizing groups on the NPs and the functionalized surfaces of the PS spheres. This versatile two-step method provides more fine control than methods previously demonstrated in the literature. These decorated PS spheres are of interest for a number of applications, such as catalytic reactions where the PS spheres provide a support for the dispersion, stabilization, and recovery of NP catalysts. The catalytic properties of these PS@NPs spheres were assessed by studying the catalytic degradation of azo dyes, an environmental contaminant detrimental to eye health. The PS@NPs spheres were used in multiple, sequential catalytic reactions while largely retaining the NP coating.