Rapid Solar Heating of Antimicrobial Ag and Cu2O Nanostructured Plasmonic Textile for Clean Water Production.

Solar steam generation is an attractive method to produce clean water, and high steam generation rates have been achieved using nanostructured light absorbers. However, since it usually takes minutes to reach the temperature for steady-state steam generation under solar illumination, a material that responds quickly to intermittent sunlight is strongly desired. Here, we report an unprecedented heating rate in an ultralight freestanding textile consisting of interconnected Ag and Cu2O nanoparticles. The textile demonstrated high solar absorption with low reflectance and transmittance, which were rationalized using our multiphysics simulations. A commercial polystyrene foam wrapped with this broadband light-absorbing textile showed the fastest response to sunlight together with a good steam generation rate compared to reported inorganic nanostructured steam generators. Furthermore, the textile exhibited antibacterial property, which might lower the risk of the vapor-induced transfer of bacteria during long-term intermittent use and the cost of subsequent water sanitization.

Dynamic viscosity recovery of electrospinning solution for stabilizing elongated ultrafine polymer nanofiber by TEMPO-CNF.

Electrospinning is a widely used production method for nanoscale fine polymer fiber fabrics. An ultrafine fiber made of polymers such as polyvinylpyrrolidone (PVP) polyacrylic acid (PAA) has immense potential for applications in air filters, batteries, and biosensors. However, producing fabrics with long uniformly distributed ultrafine fibers of a mean diameter below ~ 200 nm is still a challenge, because such elongated-ultrafine fibers tend to break into beads before they reach the collector. Here, we exploits the thixotropy of the solution given by the addition of 2,2,6,6-tetramethylpiperidin-1-oxyl-oxidized cellulose nanofibers to recover the solution viscosity for stabilizing the electrostatically elongated nanofibers, whereby the solution is smooth in the syringe needle owing to the shear force but regain its original viscosity after being freed from electrostatic force. Using this method, we successfully fabricated a non-woven ultrafine-long nanofiber made of PVP and PAA with a mean diameter as low as ~ 90 nm with a negligible number of beads.

CO oxidation activity of non-reducible oxide-supported mass-selected few-atom Pt single-clusters.

Platinum nanocatalysts play critical roles in CO oxidation, an important catalytic conversion process. As the catalyst size decreases, the influence of the support material on catalysis increases which can alter the chemical states of Pt atoms in contact with the support. Herein, we demonstrate that under-coordinated Pt atoms at the edges of the first cluster layer are rendered cationic by direct contact with the Al2O3 support, which affects the overall CO oxidation activity. The ratio of neutral to cationic Pt atoms in the Pt nanocluster is strongly correlated with the CO oxidation activity, but no correlation exists with the total surface area of surface-exposed Pt atoms. The low oxygen affinity of cationic Pt atoms explains this counterintuitive result. Using this relationship and our modified bond-additivity method, which only requires the catalyst-support bond energy as input, we successfully predict the CO oxidation activities of various sized Pt clusters on TiO2.

Morphology of size-selected Ptn clusters on CeO2(111).

Supported Pt catalysts and ceria are well known for their application in automotive exhaust catalysts. Size-selected Pt clusters supported on a CeO2(111) surface exhibit distinct physical and chemical properties. We investigated the morphology of the size-selected Ptn (n = 5-13) clusters on a CeO2(111) surface using scanning tunneling microscopy at room temperature. Ptn clusters prefer a two-dimensional morphology for n = 5 and a three-dimensional (3D) morphology for n ≥ 6. We further observed the preference for a 3D tri-layer structure when n ≥ 10. For each cluster size, we quantitatively estimated the relative fraction of the clusters for each type of morphology. Size-dependent morphology of the Ptn clusters on the CeO2(111) surface was attributed to the Pt-Pt interaction in the cluster and the Pt-O interaction between the cluster and CeO2(111) surface. The results obtained herein provide a clear understanding of the size-dependent morphology of the Ptn clusters on a CeO2(111) surface.

Significant Transient Mobility of Platinum Clusters via a Hot Precursor State on the Alumina Surface.

Relaxation dynamics of hot metal clusters on oxide surfaces play a crucial role in a variety of physical and chemical processes. However, their transient mobility has not been investigated as much as other systems such as atoms and molecules on metal surfaces due to experimental difficulties. To study the role of the transient mobility of clusters on the oxide surface, we investigated the initial adsorption process of size-selected Pt clusters on a thin Al2O3 film. Soft-landing the size-selected clusters while suppressing the thermal migration resulted in the transient migration controlling the initial adsorption states as an isolated and aggregated cluster, as revealed using scanning tunneling microscopy. We demonstrate that transient migration significantly contributes to the initial cluster adsorption process; the cross section for aggregation is seven times larger than the expected value from geometrical considerations, indicating that metal clusters are highly mobile during a energy dissipation process on the oxide surface.

Morphology and chemical states of size-selected Pt(n) clusters on an aluminium oxide film on NiAl(110).

The adsorption states of size-selected Ptn clusters (7 ≤ n ≤ 20) soft-landed on an Al2O3/NiAl(110) substrate were investigated using scanning tunneling microscopy, infrared reflection absorption spectroscopy, and temperature programmed desorption. Ptn clusters lay flat on the surface with a planar structure (n ≤ 18), and three-dimensional two-layer clusters start to appear at n ≥ 19. By considering the Pt-Pt and Pt-oxide bonds in the cluster, the morphological transition could be reasonably explained. Using CO probe molecules, the chemical states of the Pt atoms inside the clusters were investigated. Two ontop CO species were observed inside the clusters, and were assigned as adsorbed CO on neutral and slightly cationic Pt atoms. Despite the first layer Pt atoms, the Ptn clusters are composed of two kinds of Pt atoms. The observed size dependence of the Pt atoms inside the clusters may contribute to the size-dependent chemical reactivity of Ptn clusters on the Al2O3 surface.

Epitaxial growth of CeO2(111) film on Ru(0001): scanning tunneling microscopy (STM) and x-ray photoemission spectroscopy (XPS) study.

We formed an epitaxial film of CeO2(111) by sublimating Ce atoms on Ru(0001) surface kept at elevated temperature in an oxygen ambient. X-ray photoemission spectroscopy measurement revealed a decrease of Ce(4+)/Ce(3+) ratio in a small temperature window of the growth temperature between 1070 and 1096 K, which corresponds to the reduction of the CeO2(111). Scanning tunneling microscope image showed that a film with a wide terrace and a sharp step edge was obtained when the film was grown at the temperatures close to the reduction temperature, and the terrace width observed on the sample grown at 1060 K was more than twice of that grown at 1040 K. On the surface grown above the reduction temperature, the surface with a wide terrace and a sharp step was confirmed, but small dots were also seen in the terrace part, which are considerably Ce atoms adsorbed at the oxygen vacancies on the reduced surface. This experiment demonstrated that it is required to use the substrate temperature close to the reduction temperature to obtain CeO2(111) with wide terrace width and sharp step edges.

Dewetting growth of crystalline water ice on a hydrogen saturated Rh(111) surface at 135 K.

We investigated the water (D(2)O) adsorption at 135 K on a hydrogen pre-adsorbed Rh(111) surface using temperature programmed desorption and infrared reflection absorption spectroscopy (IRAS) in ultrahigh vacuum. With increasing the hydrogen coverage, the desorption temperature of water decreases. At the saturation coverage of hydrogen, dewetting growth of water ice was observed: large three-dimensional ice grains are formed. The activation energy of water desorption from the hydrogen-saturated Rh(111) surface is estimated to be 51 kJ/mol. The initial sticking probability of water decreases from 0.46 on the clean surface to 0.35 on the hydrogen-saturated surface. In IRAS measurements, D-down species were not observed on the hydrogen saturated surface. The present experimental results clearly show that a hydrophilic Rh(111) clean surface changes into a hydrophobic surface as a result of hydrogen adsorption.

Adsorption and reaction of NO on the clean and nitrogen modified Rh(111) surfaces.

The adsorption states and thermal reactions of NO on the clean and nitrogen modified Rh(111) surfaces were investigated between 20 and 150 K using infrared reflection adsorption spectroscopy (IRAS) and temperature programmed desorption. On the clean surface, singleton species at atop and hollow sites were observed at 1816 and 1479 cm(-1), respectively. Using time-resolved IRAS, the activation energy and pre-exponential factor of the site change from atop to hollow sites on Rh(111) were estimated to be 117 meV and 1.7x10(10) s(-1), respectively. On the saturated monolayer, physisorbed NO dimers were formed. In the second layer, they were adsorbed with the N-N bond nearly parallel to the surface. In the multilayer formed at 20 K, the NO dimers were randomly oriented. On the nitrogen modified Rh(111) surface, a new adsorption state of chemisorbed monomer was observed as well as atop and hollow species. Physisorbed NO dimers were a precursor to N(2)O formation on the nitrogen modified Rh(111) surface. In the N(2)O formation reaction, three kinds of N(2)O species were identified. The first species desorbed from the surface immediately after the formation reaction, which is a reaction-limited process. The second species was physisorbed on the surface and desorbed at 86 K, which is a desorption-limited process. The third species was chemisorbed on the surface and decomposed above 100 K.

The growth process of first water layer and crystalline ice on the Rh(111) surface.

The adsorption states and growth process of the first layer and multilayer of water (D(2)O) on Rh(111) above 135 K were investigated using infrared reflection absorption spectroscopy (IRAS), temperature programed desorption, spot-profile-analysis low-energy electron diffraction, and scanning tunneling microscopy (STM). At the initial stage, water molecules form commensurate ( radical3x radical3)R30 degrees islands, whose size is limited for several hexagonal units; the average diameter is approximately 2.5 nm. This two-dimensional (2D) island includes D-down species, and free OD species exist at the island edge. With increasing coverage, the D-up species starts to appear in IRAS. At higher coverages, the 2D islands are connected in STM images. By the titration of Xe adsorption we estimated that the D-down domain occupies about 55% on Rh(111) at the saturation coverage. Further adsorption of water molecules forms three-dimensional ice crystallites on the first water layer; thus, the growth mode of crystalline water layers on Rh(111) is a Stranski-Krastanov type. We have found that an ice crystallite starts to grow on D-down domains and the D-down species do not reorient upon the formation of a crystalline ice.

Coverage-dependent sticking probability and desorption kinetics of water molecules on Rh(111).

The adsorption and desorption kinetics of water molecules on Rh(111) were investigated using temperature programed desorption (TPD). Water molecules on Rh(111) show coverage-dependent sticking probability; the initial sticking probability is estimated to be 0.46. In the desorption process, a dilute gaslike phase and two-dimensional islands of water coexist on the surface. Based on the model proposed by Kreuzer and Payne [Surf. Sci.200, L433 (1988)], the apparent fractional-order TPD spectra can be interpreted as first-order desorption from the coexistence of two phases on which the sticking probabilities are different. Based on this, the previous estimation of pre-exponential factors assuming half-order desorption [A. Beniya et al., J. Chem. Phys.125, 054717 (2006)] should be revised.

Transient diffusion and cluster formation of water molecules on Rh(111) at 20 K.

The authors investigated the initial stage of water adsorption on Rh(111) at 20 K, using infrared reflection absorption spectroscopy. In this low coverage region, isolated water molecules and small water clusters are observed. Since thermal diffusion is suppressed at 20 K, the formation of water clusters at low coverage is controlled by both coverage and transient diffusion on the surface. Within a simple random walk model of the transient diffusion and clustering process, the authors estimate the mean lateral displacement from the first impact point to the final adsorption site to be 7.6 A; an incoming water molecule on Rh(111) is trapped with eight postcollision hops on the average.

The first layer of water on Rh(111): microscopic structure and desorption kinetics.

The adsorption states and growth process of the first water (D2O) layer on Rh(111) were investigated using infrared reflection absorption spectroscopy, temperature programed desorption, and spot-profile-analysis low energy electron diffraction. Water molecules wet the Rh(111) surface intact. At the early stage of first layer growth, a (square root 3 x square root 3)R30 degrees commensurate water layer grows where "up" and "down" species coexist; the up and down species represent water molecules which have free OD, pointing to a vacuum and the substrate, respectively. The up domain was a flatter structure than an icelike bilayer. Water desorption from Rh(111) was a half-order process. The activation energy and the preexponential factor of desorption are estimated to be 60 kJ/mol and 4.8 x 10(16) ML(1/2)/s at submonolayer coverage, respectively. With an increase in water coverage, the flat up domain becomes a zigzag layer, like an ice bilayer. At the saturation coverage, the amount of down species is 1.3 times larger than that of the up species. In addition, the activation energy and the preexponential factor of desorption decrease to 51 kJ/mol and 1.3 x 10(14) ML(1/2)/s, respectively.

Water adsorption on Rh(111) at 20 K: from monomer to bulk amorphous ice.

The adsorption of water (D(2)O) molecules on Rh(111) at 20 K was investigated using infrared reflection absorption spectroscopy (IRAS). At the initial stage of adsorption, water molecules exist as monomers on Rh(111). With increasing water coverage, monomers aggregate into dimers, larger clusters (n = 3-6), and two-dimensional (2D) islands. Further exposure of water molecules leads to the formation of three-dimensional (3D) water islands and finally to a bulk amorphous ice layer. Upon heating, the monomer and dimer species thermally migrate on the surface and aggregate to form larger clusters and 2D islands. Based on the temperature dependence of OD stretching peaks, we succeeded in distinguishing water molecules inside 2D islands from those at the edge of 2D islands. From the comparison with the previous vibrational spectra of water clusters on other metal surfaces, we conclude that the number of water molecules at the edge of 2D islands is comparable with that of water molecules inside 2D islands on the Rh(111) surface at 20 K. This indicates that the surface migration of water molecules on Rh(111) is hindered as compared with the cases on Pt(111) and Ni(111) and thus the size of 2D islands on Rh(111) is relatively small.