Nanoparticle design and assembly for p-type metal oxide gas sensors.

Metal oxide semiconductors have wide band gaps with tailorable electrical properties and high stability, suitable for chemiresistive gas sensors. p-Type oxide semiconductors generally have less sensitivity than their n-type counterparts but provide unique functionality with low humidity dependence. Among various approaches to enhance the p-type characteristics, nanostructuring of active materials is essential to exhibit high sensing performances comparable to n-type materials. Moreover, p-n heterojunction formation can achieve superior sensitivity at low operating temperatures. The representative examples are hollow and urchin-like particles, mesoporous structures, and nanowire networks. These morphologies can generate abundant active surface sites with a high surface area and induce rapid gas diffusion and facile charge transport. For growing interests in environmental and healthcare monitoring, p-type oxide semiconductors and their heterojunctions with well-designed nanostructures gain much attention as advanced gas sensing materials for practical applications. In addition to precise nanostructure design, the combination with other strategies, e.g. light activation and multiple gas sensing analysis using sensor arrays will be able to fabricate the desired gas sensors with exclusive gas detection at ultra-low concentrations operating even at room temperature.

Structural complexity induced by {110} blocking of cysteine in electrochemical copper deposition on silver nanocubes.

Morphology evolution into intricate structures at the nanoscale is hard to understand, but we can get critical information from the combination of ex situ and in situ spectroelectrochemical techniques. In this study, we investigated the structural complexity generated during electrochemical Cu deposition on individual Ag nanocubes, which was driven by surface regulating cysteine molecules. During the deposition process, selective nucleation occurred on the Ag nanocubes by underpotential deposition, and then sequential structural evolution to a windmill morphology was observed. By adjusting the cysteine coverage, diverse structures were yielded, including face-overgrown, four-leaf clover, and octapod-like structures. Structural analysis along the crystallographic directions demonstrated that cysteine molecules exclusively blocked the growth along 110 and relatively promoted the growth along 100 and 111, respectively. Interestingly, all morphologies maintained a highly symmetric nature from the pristine cube, despite being diverse and sophisticated. These findings would be essential to design complex morphologies and achieve desirable optical and catalytic properties.

ZnO-CuO Core-Hollow Cube Nanostructures for Highly Sensitive Acetone Gas Sensors at the ppb Level.

This paper presents a ZnO-CuO p-n heterojunction chemiresistive sensor that comprises CuO hollow nanocubes attached to ZnO spherical cores as active materials. These ZnO-CuO core-hollow cube nanostructures exhibit a remarkable response of 11.14 at 1 ppm acetone and 200 °C, which is a superior result to those reported by other metal-oxide-based sensors. The response can be measured up to 40 ppb, and the limit of detection is estimated as 9 ppb. ZnO-CuO core-hollow cube nanostructures also present high selectivity toward acetone against other volatile organic compounds and demonstrate excellent stability for up to 40 days. The outstanding gas-sensing performance of the developed nanocubes is attributed to their uniform and unique morphology. Their core-shell-like structures allow the main charge transfer pathways to pass the interparticle p-p junctions, and the p-n junctions in each particle increase the sensitivity of the reactions to gas molecules. The small grain size and high surface area of each domain also enhance the surface gas adsorption.

Branched Copper Oxide Nanoparticles Induce Highly Selective Ethylene Production by Electrochemical Carbon Dioxide Reduction.

For long-term storage of renewable energy, the electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising option for converting electricity to permanent forms of chemical energy. In this work, we present highly selective ethylene production dependent upon the catalyst morphology using copper oxide nanoparticles. The branched CuO nanoparticles were synthesized and then deposited on conductive carbon materials. After activation, the major copper species changed to Cu+, and the resulting electrocatalyst exhibited a high Faradaic efficiency (FE) of ethylene reaching over 70% and a hydrogen FE of 30% without any byproducts in a neutral aqueous solution. The catalyst also showed high durability (up to 12 h) with the ethylene FE over 65%. Compared to cubic morphology, the initial branched copper oxide structure formed highly active domains with interfaces and junctions in-between during activation, which caused large surface area with high local pH leading to high selectivity and activity for ethylene production.

Single-Molecule Rotation for EGFR Conformational Dynamics in Live Cells.

Monitoring the dynamics of proteins in live cells on appropriate spatiotemporal scales may provide key information regarding long-standing questions in molecular and cellular regulatory mechanisms. However, tools capable of imaging the conformational changes over time have been elusive. Here, we present a single-molecule stroboscopic imaging probes by developing gyroscopic plasmonic nanoparticles, allowing for replication of protein-protein interactions and the conformational dynamics based on rotational and lateral velocities. This study fundamentally monitors the rotational motion of a membrane protein, epidermal growth factor receptor (EGFR), to decipher undiscovered structural dynamics in live cells without any molecular perturbations. This method offers a strategy to visualize assemblies and conformational changes, and provides unique insights into the mechanism underlying the molecular dynamics for receptors.

Nonstoichiometric Co-rich ZnCo2O4 Hollow Nanospheres for High Performance Formaldehyde Detection at ppb Levels.

Since metal oxide semiconductors were investigated as chemiresistors, rapid advances have been reported in this field. However, better performance metrics are still required, such as higher sensitivity and selectivity levels for practical applications. To improve the sensing performance, we discuss an optimal composition of the active sensing material, nonstoichiometric Co-rich ZnCo2O4, prepared by the partial substitution of Co(2+) into Zn(2+) in Co3O4 without altering a hollow sphere morphology. Remarkably, this Co-rich ZnCo2O4 phase achieved detection limits for formaldehyde as low as 13 ppb in experimental measurements and 2 ppb in theory, which were the lowest values ever reported from actual measurements at a working temperature of 225 °C. It was also unprecedented that the selectivity for formaldehyde was greatly enhanced with respect to the selectivity levels against other volatile organic compounds (VOCs). These excellent sensing performances are due to the optimal composition of the Co-rich ZnCo2O4 material with a proper hole concentration and well-organized conductive network.

Poly(ethylene glycol)- and carboxylate-functionalized gold nanoparticles using polymer linkages: single-step synthesis, high stability, and plasmonic detection of proteins.

Gold nanoparticles with suitable surface functionalities have been widely used as a versatile nanobioplatform. However, functionalized gold nanoparticles using thiol-terminated ligands have a tendency to aggregate, particularly in many enzymatic reaction buffers containing biological thiols, because of ligand exchange reactions. In the present study, we developed a one-step synthesis of poly(ethylene glycol) (PEG)ylated gold nanoparticles using poly(dimethylaminoethyl methacrylate) (PDMAEMA) in PEG as a polyol solvent. Because of the chelate effect of polymeric functionalities on the gold surface, the resulting PEGylated gold nanoparticles (Au@P-PEG) are very stable under the extreme conditions at which the thiol-monolayer-protected gold nanoparticles are easily coagulated. Using the solvent mixture of PEG and ethylene glycol (EG) and subsequent hydrolysis, gold nanoparticles bearing mixed functionalities of PEG and carboxylate are generated. The resulting particles exhibit selective adsorption of positively charged chymotrypsin (ChT) without nonselective adsorption of bovine serum albumin (BSA). The present nanoparticle system has many advantages, including high stability, simple one-step synthesis, biocompatibility, and excellent binding specificity; thus, this system can be used as a versatile platform for potential bio-related applications, such as separation, sensing, imaging, and assays.

Azide-alkyne Huisgen [3+2] cycloaddition using CuO nanoparticles.

Recent developments in the synthesis of CuO nanoparticles (NPs) and their application to the [3+2] cycloaddition of azides with terminal alkynes are reviewed. With respect to the importance of click chemistry, CuO hollow NPs, CuO hollow NPs on acetylene black, water-soluble double-hydrophilic block copolymer (DHBC) nanoreactors and ZnO–CuO hybrid NPs were synthesized. Non-conventional energy sources such as microwaves and ultrasound were also applied to these click reactions, and good catalytic activity with high regioselectivity was observed. CuO hollow NPs on acetylene black can be recycled nine times without any loss of activity, and water-soluble DHBC nanoreactors have been developed for an environmentally friendly process.

Porosity control of Pd@SiO2 yolk-shell nanocatalysts by the formation of nickel phyllosilicate and its influence on Suzuki coupling reactions.

The surface of Pd@SiO(2) core-shell nanoparticles (1) was simply modified by the formation of nickel phyllosilicate. The addition of nickel salts formed branched nickel phyllosilicates and generated pores in the silica shells, yielding Pd@SiO(2)-Niphy nanoparticles (Niphy = nickel phyllosilicate; 2, 3). By removal of the silica residue, Pd@Niphy yolk-shell nanoparticles (4) was uniformly obtained. The four distinct nanostructures (1-4) were employed as catalysts for Suzuki coupling reactions with aryl bromide and phenylboronic acid, and the conversion yields were in the order of 1 < 2 < 3 < 4 as the pore volume and surface area of the catalysts increased. The reaction rates were strongly correlated with shell porosity and surface exposure of the metal cores. The chemical inertness of nickel phyllosilicate under the basic conditions rendered the catalysts reusable for more than five times without loss of activity.

Platinum-centered yolk-shell nanostructure formation by sacrificial nickel spacers.

We have synthesized Pt@silica/nickel phyllosilicate and Pt@silica yolk-shell nanostructures from NiPt@silica core-shell particles by simple chemical treatments. Silica coating of the NiPt alloy nanoparticles via the microemulsion method yielded spherical NiPt@silica core-shell nanoparticles with an average core diameter of 6.5 nm. Under a reflux condition in water, the core-shell structure transformed into Pt@silica yolk-shell nanoparticles with branched nickel phyllosilicate, which exhibited high surface area and large pore volume. The addition of hydrochloric acid selectively etched the nickel component from the NiPt cores and yielded Pt@silica yolk-shell nanoparticles with single-crystalline platinum cores. The average diameter of the metal cores was reduced to 4.5 nm. In both cases, the nickel components behaved as sacrificial spacers and successfully formed a vacancy between the metal cores and the silica hollow shells.

Chemical transformation and morphology change of nickel-silica hybrid nanostructures via nickel phyllosilicates.

Ni@SiO(2) core-shell nanoparticles were transformed to Ni particles on silica spheres via a branched nickel phyllosilicate phase by hydrothermal and hydrogen reduction reactions; the final morphology was successfully employed as an active nanocatalyst for the hydrogen transfer reaction of acetophenone.

Adsorption and co-adsorption of ethylene and carbon monoxide on silica-supported monodisperse Pt nanoparticles: volumetric adsorption and infrared spectroscopy studies.

The adsorption of carbon monoxide and ethylene, and their sequential adsorption, was studied over a series of Pt/SBA-15 catalysts with monodisperse particle sizes ranging from 1.7 to 7.1 nm by diffuse-reflectance infrared spectroscopy and chemisorption. Gas adsorption was dependent on the Pt particle size, temperature, and sequence of gas exposure. Adsorption of CO at room temperature on Pt/SBA-15 gives rise to a spectroscopic feature assigned to the C-O stretch: nu(CO) = 2075 cm-1 (1.9 nm); 2079 cm-1 (2.9 nm); 2082 cm-1 (3.6 nm); and 2090 cm-1 (7.1 nm). The intensity of the signal decreased in a sigmoidal fashion with increasing temperature, thereby providing semiquantitative surface coverage information. Adsorption of ethylene on Pt/SBA-15 gave rise to spectroscopic features at approximately 1340, approximately 1420, and approximately 1500 cm-1 assigned to ethylidyne, di-sigma-bonded ethylene, and pi-bonded ethylene, respectively. The ratio of these surface species is highly dependent on the Pt particle size. At room temperature, Pt particles stabilize ethylidyne as well as di-sigma- and pi-bonded ethylene; however, ethylidyne predominated on the surfaces of larger particles. Ethylidyne was the only identifiable species at 403 K, with its formation being more facile on larger particles. Co-adsorption experiments reveal that the composition of the surface layer is dependent on the order of exposure to gases. Exposure of a C2H4-covered Pt surface to CO resulted in an approximately 50% decrease in chemisorbed CO compared to a fresh Pt surface. The nu(CO) appeared at 2050 cm-1 on Pt/SBA-15 pretreated with C2H4 at room temperature. The di-sigma-bonded and pi-bonded species are the most susceptible to displacement from the surface by CO. The formation of ethylidyne appeared to be less sensitive to the presence of adsorbed carbon monoxide, especially on larger particles. Upon exposure of C2H4 to a CO-covered Pt surface, little irreversible uptake occurred due to nearly 100% site blocking. These results demonstrate that carbon monoxide competes directly with ethylene for surface sites, which will have direct implications on the poisoning of the heterogeneously catalyzed conversion of hydrocarbons.