Surface Modulation of 3D Porous CoNiP Nanoarrays In Situ Grown on Nickel Foams for Robust Overall Water Splitting.

The careful design of nanostructures and multi-compositions of non-noble metal-based electrocatalysts for highly efficient electrocatalytic hydrogen and oxygen evolution reaction (HER and OER) is of great significance to realize sustainable hydrogen release. Herein, bifunctional electrocatalysts of the three-dimensional (3D) cobalt-nickel phosphide nanoarray in situ grown on nickel foams (CoNiP NA/NF) were synthesized through a facile hydrothermal method followed by phosphorization. Due to the unique self-template nanoarray structure and tunable multicomponent system, the CoNiP NA/NF samples present exceptional activity and durability for HER and OER. The optimized sample of CoNiP NA/NF-2 afforded a current density of 10 mA cm-2 at a low overpotential of 162 mV for HER and 499 mV for OER, corresponding with low Tafel slopes of 114.3 and 79.5 mV dec-1, respectively. Density functional theory (DFT) calculations demonstrate that modulation active sites with appropriate electronic properties facilitate the interaction between the catalyst surface and intermediates, especially for the adsorption of absorbed H* and *OOH intermediates, resulting in an optimized energy barrier for HER and OER. The 3D nanoarray structure, with a large specific surface area and abundant ion channels, can enrich the electroactive sites and enhance mass transmission. This work provides novel strategies and insights for the design of robust non-precious metal catalysts.

Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation.

NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (∼20 m2 g-1) than expected for a flat-surface structure (<15 m2 g-1). Herein, we present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

Long-lived excited states in metal clusters.

Bare metal clusters have properties that make them interesting for applications in photochemistry and photovoltaics. Long-lived excited states are a prerequisite for such applications, because in them the energy of the photon can be stored. Clusters have a low density of states and long-lived excited states should therefore occur frequently. However, in fact, such states are a rarity, as indicated by time-resolved photoelectron data of mass-selected cluster anions. And there is another puzzling observation: only clusters with narrow peaks in their photoelectron spectra exhibit long-lived excited states. Both findings can be explained if internal conversion, i.e. the conversion of electronic excitation energy into vibrational excitations, is the major relaxation mechanism in clusters. It becomes more likely, if a change of the electronic configuration results in a large geometry change, which is probably the case for most clusters. Only clusters with a weak coupling between geometric and electronic structure may have long-lived excited states and narrow peaks.

Facet-controlled anatase TiO2 nanoparticles through various fluorine sources for superior photocatalytic activity.

Reactive surface-exposed anatase TiO2 (a-TiO2) is highly desirable for applications requiring superior photocatalytic activity. In order to obtain a favorable surface, morphology control of the a-TiO2 using capping agents has been widely investigated. Herein, we systematically study the effects of different F sources (HF, TiF4, and NH4F) as the capping agent on the morphology control and photocatalytic activities of a-TiO2 in a hydrothermal process. When either HF or TiF4 was added, large truncated bipyramids formed with the photocatalytically active {001} facet, whereas the NH4F was not effective for facet control, yielding nanospheres similar to the pure a-TiO2. The morphology changes were related to the decomposition behaviors of the F sources in the solvent material: HF and TiF4 decomposed and supplied F(-) ions before a-TiO2 nucleation, which changed the nucleation rate and growth direction, leading to the resultant a-TiO2 morphology. On the other hand, NH4F supplied F(-) ions after a-TiO2 nucleation and could not change the growth behavior. In terms of the photocatalytic effect, the HF- and TiF4-treated a-TiO2 effectively decomposed ∼90% and ∼80% of methylene blue, respectively, in 1 h, while ∼60% was decomposed for the NH4F-treated a-TiO2. Note that pure a-TiO2 photocatalytically decomposed only ∼10% of methylene blue over the same time. These results pave the way to precise control of the facet of TiO2 through using different capping agents.

Excited state nonadiabatic dynamics of bare and hydrated anionic gold clusters Au3(-)[H2O]n (n = 0-2).

We present a joint theoretical and experimental study of excited state dynamics in pure and hydrated anionic gold clusters Au3(-)[H2O]n (n = 0-2). We employ mixed quantum-classical dynamics combined with femtosecond time-resolved photoelectron spectroscopy in order to investigate the influence of hydration on excited state lifetimes and photo-dissociation dynamics. A gradual decrease of the excited state lifetime with the number of adsorbed water molecules as well as gold cluster fragmentation quenching by two or more water molecules are observed both in experiment and in simulations. Non-radiative relaxation and dissociation in excited states are found to be responsible for the excited state population depletion. Time constants of these two processes strongly depend on the number of water molecules leading to the possibility to modulate excited state dynamics and fragmentation of the anionic cluster by adsorption of water molecules.

Oxidation behavior of P3HT layers on bare and TiO2-covered ZnO ripple structures evaluated by photoelectron spectroscopy.

P3HT layers with a thickness of ∼5 nm were deposited on bare and TiO2-covered ZnO ripple structures. The ZnO ripples were prepared wet-chemically and a TiO2 layer with a thickness less than 5 nm was prepared by atomic layer deposition. Under humid air and visible light illumination, the oxidation behaviors of P3HT on these surfaces were studied using photoelectron spectroscopy. It was found that P3HT on TiO2/ZnO oxidizes more easily than that on bare ZnO ripples. Using a model substrate of a flat ZnO surface in combination with angle-resolved photoelectron spectroscopy, we found that oxidation of P3HT occurs at the surface of the topmost layer of P3HT, not at the P3HT/oxide interfaces, even though P3HT oxidation is strongly influenced by the interface structure. It is suggested that the lifetime of electron-hole pairs can be strongly influenced by the interface structure, which can also affect the oxidation behavior of P3HT.

Thin films of size-selected Mo clusters: growth modes and structures.

Thin films of MoO3 were prepared by deposition of size-selected ligand-free Mo clusters under high vacuum conditions and subsequent exposure to air. The growth pattern is highly dependent on the cluster size. At low coverage, small clusters (Mo51) form a continuous monolayer of fused particles. On top of this monolayer, additional clusters survive as individual entities. Medium sized clusters (Mo251 and Mo1253) do not coalesce and form a monolayer of clusters. Close examination using in situ scanning tunneling microscopy reveals a local order of the particles. At higher coverage a new pattern of large 3-dimensional aggregations of clusters (pylons) appears. The pylons are not formed under high vacuum conditions. Their formation is most likely caused by the air exposure. For the largest clusters (Mo3349) studied here, no monolayer is formed. Instead, the clusters are randomly distributed as expected for particles with zero mobility. These results demonstrate the high potential of cluster deposition for the production of new types of nanostructured surfaces, thin films and nanomaterials.

Metal-organic framework@microporous organic network: hydrophobic adsorbents with a crystalline inner porosity.

This work reports the synthesis and application of metal-organic framework (MOF)@microporous organic network (MON) hybrid materials. Coating a MOF, UiO-66-NH2, with MONs forms hybrid microporous materials with hydrophobic surfaces. The original UiO-66-NH2 shows good wettability in water. In comparison, the MOF@MON hybrid materials float on water and show excellent performance for adsorption of a model organic compound, toluene, in water. Chemical etching of the MOF results in the formation of hollow MON materials.

Hydrophobic polydimethylsiloxane (PDMS) coating of mesoporous silica and its use as a preconcentrating agent of gas analytes.

Mesoporous silica with mean pore size of ∼14 nm was coated by polydimethylsiloxane (PDMS) using a thermal deposition method. We showed that the inner walls of pores larger than ∼8 nm can be coated by thin layers of PDMS, and the surfaces consisting of PDMS-coated silica were superhydrophobic, with water contact angles close to 170°. We used the PDMS-coated silica as adsorbents of various gas-phase chemical warfare agent (CWA) simulants. PDMS-coated silica allowed molecular desorption of various CWA simulants even after exposure under highly humid conditions and, therefore, is applicable as an agent for the preconcentration of gas-phase analytes to enhance the sensitivities of various sensors.

The influence of a fibrous carbon envelope on the formation of CoFe nanoparticles for durable electrocatalytic oxygen evolution.

Co oxides are known to be active and stable alternative anode electrocatalysts possessing the potential to replace the best performing but most expensive Ir and Ru oxides in alkaline water electrolysis. Of late, Co oxides loaded on various carbon supports have been reported as a way to outperform Ir or Ru catalysts by improving the utilization efficiency. In this study, we introduce Co and Fe nanoparticles embedded carbon nanofibers (CoFe-CNFs), fabricated through electrospinning and pyrolysis of a polymer mixed with Co and Fe precursors. This method is a facile route for simultaneously making Co and Fe nanoparticles as well as the stable accommodation of the CoFe nanoparticles in the carbon support. We demonstrate the potential of the CoFe-CNFs as active and stable electrocatalysts for the oxygen evolution reaction (OER) in alkaline media. We conducted detailed physico-chemical characterizations to elucidate the effect of the CNFs on the OER activity and stability of the CoFe-CNFs. It is suggested that the CNFs are a medium in which OER-active CoFe alloy nanoparticles are formed homogeneously, and that carbon layers surrounding the nanoparticles are beneficial to the stability of the CoFe-CNFs in the OER.

Parallel deposition of size-selected clusters: a novel technique for studying size-selectivity on the atomic scale.

A new size-selected cluster deposition technique referred to as "parallel-deposition" is presented. An ion beam of multi-sized Aun clusters was spatially separated into individual cluster sizes by utilizing a Wien filter and the clusters spatially separated based on their atomic sizes were simultaneously deposited on a SiO2/Si(100) substrate. Parallel-deposited Aun clusters (n = 6, 7, and 8) on the SiO2/Si(100) substrate showed even-odd oxidation behaviour upon exposure to an atomic oxygen atmosphere, demonstrating the potential of this new technique to study the size-dependent properties of deposited clusters in various research fields.

Size-selected gold clusters on porous titania as the most "gold-efficient" heterogeneous catalysts.

Research on homogeneous and heterogeneous catalysis is indeed convergent and finds subnanometric particles to be at the heart of catalytically active species. Here, monodisperse gold clusters are deposited from the gas phase onto porous titania generating well-defined model systems and the resulting composite materials exhibit a sharp size-dependency on the number of gold atoms per cluster and exceptionally high-turnovers toward the bromination of 1,4-dimethoxybenzene are observed. This indicates that the deliberate generation of active centres is of utmost importance for the creation of the most "gold-efficient" catalysts.

In Situ Spectroscopic Studies of NH3 Oxidation of Fe-Oxide/Al2O3.

Simple temperature-regulated chemical vapor deposition was used to disperse iron oxide nanoparticles on porous Al2O3 to create an Fe-oxide/Al2O3 structure for catalytic NH3 oxidation. The Fe-oxide/Al2O3 achieved nearly 100% removal of NH3, with N2 as a major reaction product at temperatures above 400 °C and negligible NOx emissions at all experimental temperatures. The results of a combination of in situ diffuse reflectance infrared Fourier-transform spectroscopy and near-ambient pressure-near-edge X-ray absorption fine structure spectroscopy suggest a N2H4-mediated oxidation mechanism of NH3 to N2 via the Mars-van Krevelen pathway on the Fe-oxide/Al2O3 surface. As a catalytic adsorbent-an energy-efficient approach to reducing NH3 levels in living environments via adsorption and thermal treatment of NH3-no harmful NOx emissions were produced during the thermal treatment of the NH3-adsorbed Fe-oxide/Al2O3 surface, while NH3 molecularly desorbed from the surface. A system with dual catalytic filters of Fe-oxide/Al2O3 was designed to fully oxidize this desorbed NH3 to N2 in a clean and energy-efficient manner.

Surface Structures of Fe-TiO2 Photocatalysts for NO Oxidation.

Commercial rutile TiO2 particles capped with Al2O3 and ZrO2 layers, which are widely used in white pigments, can serve as a starting material for the fabrication of visible light-responsive photocatalysts toward gas-phase NO oxidation. The as-received TiO2 with iron impurities exhibited reduced photocatalytic activity, and the activity was boosted by the deposition of additional iron comparable in quantity to the intrinsic iron impurity level. Analyses using X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectroscopy, and low-energy ion scattering spectroscopy revealed that the deposited iron and intrinsic impurity iron are dissimilar in terms of location, oxidation states, and interaction with TiO2. This suggests that tracking the structure and impurity levels of photocatalyst elements can be crucial for understanding structure-activity relationships of real catalysts.

Engineering Interface on a 3D CoxNi1-x(OH)2@MoS2 Hollow Heterostructure for Robust Electrocatalytic Hydrogen Evolution.

Clarifying the responsibilities and constructing the synergy of different active phases are of great significance but still an urgent challenge for the heterostructure catalyst to improve the hydrogen evolution reaction (HER) process. Here, three-dimensional (3D) CoxNi(1-x)(OH)2 hollow structure integrating MoS2 nanosheet catalysts [CoxNi(1-x)(OH)2@MoS2] were ingeniously designed and prepared. This unique structure has realized the construction of a dual active phase for the optimized stepwise-synergetic hydrogen evolution process over a universal pH range through interface assembly engineering. Meanwhile, the 3D hollow heterostructure with a high surface-to-volume ratio can effectively avoid the agglomeration of MoS2 and enhance the CoxNi(1-x)(OH)2-MoS2 heterointerfaces. Thus, superior HER activity and stability were obtained over the universal pH range. Density functional theory calculation reveals that CoxNi(1-x)(OH)2 and MoS2 phases provide efficient active sites for rate-determining water dissociation and H* adsorption/H2 generation on CoxNi(1-x)(OH)2-MoS2 heterointerfaces, respectively, resulting in an optimized energy barrier for HER. This work proposes a constructive strategy to design highly efficient electrocatalysts based on the heterointerface with a defined responsible active phase of electrocatalysts.

Effect of Secondary Structures on the Adsorption of Peptides onto Hydrophobic Solid Surfaces Revealed by SALDI-TOF and MD Simulations.

The adsorption of peptides and proteins on hydrophobic solid surfaces has received considerable research attention owing to their wide applications to biocompatible nanomaterials and nanodevices, such as biosensors and cell adhesion materials with reduced nanomaterial toxicity. However, fundamental understandings about physicochemical hydrophobic interactions between peptides and hydrophobic solid surfaces are still unknown. In this study, we investigate the effect of secondary structures on adsorption energies between peptides and hydrophobic solid surfaces via experimental and theoretical analyses using surface-assisted laser desorption/ionization-time-of-flight (SALDI-TOF) and molecular dynamics (MD) simulations. The hydrophobic interactions between peptides and hydrophobic solid surfaces measured via SALDI-TOF and MD simulations indicate that the hydrophobic interaction of peptides with random coil structures increased more than that of peptides with an α-helix structure when polar amino acids are replaced with hydrophobic amino acids. Additionally, our study sheds new light on the fundamental understanding of the hydrophobic interaction between hydrophobic solid surfaces and peptides that have diverse secondary structures.

Surface property change of C doped TiO2 nano-pillars by O2 plasma treatment.

TiO2 surface is led to super-hydrophilic surface by modifying to hydroxyl group. The super-hydrophilic surface can be applied to anti-fogging, because of preventing formation of water droplet on the surface. Super-hydrophilic coatings are made of metal oxides, polymers, or their mixtures. In this study, columnar-structured C doped TiO2 nano-pillars were grown on glass substrates by MOCVD method. For change of surface properties, grown columnar-structured C-TiO2 nano-pillars were treated by oxygen plasma. After oxygen plasma treatment, the surface property of grown columnar structured C-TiO2 nano-pillars changed from hydrophobic surface to super hydrophilic surface. For determination of this mechanism, scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, and contact angle analyzer were employed.

ZnO nanosheets decorated with CdSe and TiO2 for the architecture of dye-sensitized solar cells.

Pure and TiO2- and CdSe-deposited ZnO nanosheets aligned vertically to the surface of ITO (Indium tin oxide) are prepared using electrodeposition, which is used for building blocks of dye sensitized solar cell. A significant improvement in the photovoltaic efficiency can be obtained by depositing TiO2 or CdSe on ZnO. Photoluminescence spectra show that the TiO2 and CdSe nanostructures suppress the recombination of the electron-hole pair of ZnO. We suggest that the interface charge transfer at TiO2-ZnO and CdSe-ZnO should be responsible for the suppression of the electron-hole pair recombination and enhanced solar cell efficiency by TiO2 and CdSe nanostructures.

Enhanced removal efficiency of toluene over activated carbon under visible light.

Toluene removal rates using activated carbon (AC) at various relative humidity (RH) levels (0%, 30%, 60%) were compared under dark and visible-light conditions. Light exposure significantly increased toluene-removal efficiency independent of RH. When AC was pre-treated with an optimal concentration of HNO3, its toluene-removal efficiency was enhanced further with light, an effect that can be attributed to increased surface-area and porosity. Fourier-transform infrared analysis confirmed that exposure of HNO3-modified AC to light induced partial oxidation of toluene. Within visible-light range (380-650 nm), shorter wavelengths were more effective for toluene-removal compared with longer wavelengths. This suggests that hydroxyl groups formed on AC-surface under light strongly interact with aromatic rings of toluene, allowing for greater uptake of toluene. Moreover, AC can sustain its photo-activity when mixed with cement and cured, suggesting its potential applications in air-purifying building materials. An efficient and practical method for regeneration of spent AC is also demonstrated.

Phase-selective active sites on ordered/disordered titanium dioxide enable exceptional photocatalytic ammonia synthesis.

Photocatalytic N2 fixation to NH3 via defect creation on TiO2 to activate ultra-stable N[triple bond, length as m-dash]N has drawn enormous scientific attention, but poor selectivity and low yield rate are the major bottlenecks. Additionally, whether N2 preferentially adsorbs on phase-selective defect sites on TiO2 in correlation with appropriate band alignment has yet to be explored. Herein, theoretical predictions reveal that the defect sites on disordered anatase (Ad) preferentially exhibit higher N2 adsorption ability with a reduced energy barrier for a potential-determining-step (*N2 to NNH*) than the disordered rutile (Rd) phase of TiO2. Motivated by theoretical simulations, we synthesize a phase-selective disordered-anatase/ordered-rutile TiO2 photocatalyst (Na-Ad/Ro) by sodium-amine treatment of P25-TiO2 under ambient conditions, which exhibits an efficient NH3 formation rate of 432 µmol g-1 h-1, which is superior to that of any other defect-rich disordered TiO2 under solar illumination with a high apparent quantum efficiency of 13.6% at 340 nm. The multi-synergistic effects including selective N2 chemisorption on the defect sites of Na-Ad with enhanced visible-light absorption, suitable band alignment, and rapid interfacial charge separation with Ro enable substantially enhanced N2 fixation.