A Platinum Nanowire Sensor for Ethylene in Air.

A single platinum nanowire (PtNW) chemiresistive sensor for ethylene gas is reported. In this application, the PtNW performs three functions: (1) Joule self-heating to a specified temperature, (2) in situ resistance-based temperature measurement, and (3) detection of ethylene in air as a resistance change. Ethylene gas in air is detected as a reduction in nanowire resistance by up to 4.5% for concentrations ranging from 1 to 30 ppm in an optimum NW temperature range from 630 to 660 K. This response is rapid (30-100 s), reversible, and reproducible for repetitive ethylene pulses. A threefold increase in signal amplitude is observed as the NW thickness is reduced from 60 to 20 nm, commensurate with a signal transduction mechanism involving surface electron scattering.

High-Resolution X-ray Photoelectron Spectroscopy of Organometallic (C5H4SiMe3)3LnIII and [(C5H4SiMe3)3LnII]1- Complexes (Ln = Sm, Eu, Gd, Tb).

The capacity of X-ray photoelectron spectroscopy (XPS) to provide information on the electronic structure of molecular organometallic complexes of Ln(II) ions (Ln = lanthanide) has been examined for the first time. XPS spectra were obtained on the air-sensitive molecular trivalent 4fn Cp'3LnIII complexes (Ln = Sm, Eu, Gd, Tb; Cp' = C5H4SiMe3) and compared to those of the highly reactive divalent complexes, [K(crypt)][Cp'3LnII] (crypt = 2.2.2-cryptand), which have either 4fn+1 (Sm, Eu) or 4fn5d1 electron configurations (Gd, Tb). The Ln 4d, Si 2p, and C 1s regions of the Ln(III) and Ln(II) complexes were identified and compared. The metal 4d peaks of these molecular lanthanide complexes were used diagnostically to compare oxidation states. The valence region of the Gd(III) and Gd(II) complexes was also examined with XPS and density function theory/random phase approximation (DFT/RPA) calculations, and this led to the tentative assignment of a signal from the 5d1 electron consistent with a 4f75d1 electron configuration for Gd(II).

Exploring the Solvation of Acetic Acid in Water Using Liquid Jet X-ray Photoelectron Spectroscopy and Core Level Electron Binding Energy Calculations.

Liquid jet X-ray photoelectron spectroscopy was used to investigate changes in the local electronic structure of acetic acid in the bulk of aqueous solutions induced by solvation effects. These effects manifest themselves as shifts in the difference in the carbon 1s binding energy (ΔBE) between the methyl and carboxyl carbons of acetic acid. Furthermore, molecular dynamics simulations, coupled with correlated electronic structure calculations of the first solvation sphere, provide insight into the number of water molecules directly interacting with the carboxyl group that are required to match the ΔBE from the photoelectron spectroscopy experiments. This comparison shows that a single water molecule in the first solvation shell describes the photoelectron ΔBE of acetic acid while at least 20 water molecules are required for the conjugate base, acetate, in aqueous solutions.

Effective one-particle energies from generalized Kohn-Sham random phase approximation: A direct approach for computing and analyzing core ionization energies.

Generalized-Kohn-Sham (GKS) orbital energies obtained self-consistently from the random phase approximation energy functional with a semicanonical projection (spRPA) were recently shown to rival the accuracy of GW quasiparticle energies for valence ionization potentials. Here, we extend the scope of GKS-spRPA correlated one-particle energies from frontier-orbital ionization to core orbital ionization energies, which are notoriously difficult for GW and other response methods due to strong orbital relaxation effects. For a benchmark consisting of 23 1s core electron binding energies (CEBEs) of second-row elements, chemical shifts estimated from GKS-spRPA one-particle energies yield mean absolute deviations from experiment of 0.2 eV, which are significantly more accurate than the standard GW and comparable to Δ self-consistent field theory without semiempirical adjustment of the energy functional. For small ammonia clusters and cytosine tautomers, GKS-spRPA based chemical shifts capture subtle variations in covalent and noncovalent bonding environments; GKS-spRPA 1s CEBEs for these systems agree with equation-of-motion coupled cluster singles and doubles and ADC(4) results within 0.2-0.3 eV. Two perturbative approximations to GKS-spRPA orbital energies, which reduce the scaling from O(N6) to O(N5) and O(N4), are introduced and tested. We illustrate the application of GKS-spRPA orbital energies to larger systems by using oxygen 1s CEBEs to probe solvation and packing effects in condensed phases of water. GKS-spRPA predicts a lowering of the oxygen 1s CEBE of approximately 1.6-1.7 eV in solid and liquid phases, consistent with liquid-jet X-ray photoelectron spectroscopy and gas phase cluster experiments. The results are rationalized by partitioning GKS-spRPA electron binding energies into static, relaxation, and correlation parts.

Characterization of Fe2+ Aqueous Solutions with Liquid Jet X-ray Photoelectron Spectroscopy: Chloride Depletion at the Liquid/Vapor Interface Due to Complexation with Fe2.

Liquid jet X-ray photoelectron spectroscopy is used under near ambient pressure conditions to characterize Fe2+ aqueous solutions. Counter ions, such as Cl- and Br- ions, added to the solution lead to changes in the first solvation sphere of the Fe-aqua complex in solution. Binding energy shifts of 0.4 eV to lower binding energy are observed in the Cl 2p spectra, 2 eV to higher binding energy in the Fe 2p spectra and no shifts are observed in the Br 3d spectra. Depletion of the Cl- species is observed at the interface, caused by coordination with Fe2+. Depletion of Cl- at the liquid/vapor interface may have significant impacts on oxidative chemistry at the interface of atmospheric aerosols that contain both chloride and iron. The Cl- complexation with the Fe2+ ions will also affect the Fenton chemistry that is dependent on this metal ion.

Specific cation effects at aqueous solution-vapor interfaces: Surfactant-like behavior of Li+ revealed by experiments and simulations.

It is now well established by numerous experimental and computational studies that the adsorption propensities of inorganic anions conform to the Hofmeister series. The adsorption propensities of inorganic cations, such as the alkali metal cations, have received relatively little attention. Here we use a combination of liquid-jet X-ray photoelectron experiments and molecular dynamics simulations to investigate the behavior of K+ and Li+ ions near the interfaces of their aqueous solutions with halide ions. Both the experiments and the simulations show that Li+ adsorbs to the aqueous solution-vapor interface, while K+ does not. Thus, we provide experimental validation of the "surfactant-like" behavior of Li+ predicted by previous simulation studies. Furthermore, we use our simulations to trace the difference in the adsorption of K+ and Li+ ions to a difference in the resilience of their hydration shells.

Liquid-Jet X-ray Photoelectron Spectra of TiO(2) Nanoparticles in an Aqueous Electrolyte Solution.

Titania has attracted significant interest due to its broad catalytic applications, many of which involve titania nanoparticles in contact with aqueous electrolyte solutions. Understanding the titania nanoparticle/electrolyte interface is critical for the rational development of such systems. Here, we have employed liquid-jet ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to investigate the solid/electrolyte interface of 20 nm diameter TiO2 nanoparticles in 0.1 M aqueous nitric acid solution. The Ti 2p line shape and absolute binding energy reflect a fully oxidized stoichiometric titania lattice. Further, by increasing the X-ray excitation energy, the difference in O 1s binding energies between that of liquid water (O 1sliq) and the titania lattice (O 1slat) oxygen was measured as a function of probe depth into the particles. The titania lattice, O 1slat, binding energy decreases by 250 meV when probing from the particle surface into the bulk. This is interpreted as downward band bending at the interface.

Catalytically activated palladium@platinum nanowires for accelerated hydrogen gas detection.

Platinum (Pt)-modified palladium (Pd) nanowires (or Pd@Pt nanowires) are prepared with controlled Pt coverage. These Pd@Pt nanowires are used as resistive gas sensors for the detection of hydrogen gas in air, and the influence of the Pt surface layer is assessed. Pd nanowires with dimensions of 40 nm (h) × 100 nm (w) × 50 µm (l) are first prepared using lithographically patterned nanowire electrodeposition. A thin Pt surface layer is electrodeposited conformally onto a Pd nanowire at coverages, θPt, of 0.10 monolayer (ML), 1.0 ML, and 10 ML. X-ray photoelectron spectroscopy coupled with scanning electron microscopy and electrochemical measurements is consistent with a layer-by-layer deposition mode for Pt on the Pd nanowire surface. The resistance of a single Pd@Pt nanowire is measured during the exposure of these nanowires to pulses of hydrogen gas in air at concentrations ranging from 0.05 to 5.0 vol %. Both Pd nanowires and Pd@Pt nanowires show a prompt and reversible increase in resistance upon exposure to H2 in air, caused by the conversion of Pd to more resistive PdHx. Relative to a pure Pd nanowire, the addition of 1.0 ML of Pt to the Pd surface alters the H2 detection properties of Pd@Pt nanowires in two ways. First, the amplitude of the relative resistance change, ΔR/R0, measured at each H2 concentration is reduced at low temperatures (T = 294 and 303 K) and is unaffected at higher temperatures (T = 316, 344, and 376 K). Second, response and recovery rates are both faster at all temperatures in this range and for all H2 concentrations. For higher θPt = 10 ML, sensitivity to H2 is dramatically reduced. For lower θPt = 0.1 ML, no significant influence on sensitivity or the speed of response/recovery is observed.

Photoelectron angular distributions from liquid water: effects of electron scattering.

Photoelectron angular distributions (PADs) from the liquid-water surface and from bulk liquid water are reported for water oxygen-1s ionization. Although less so than for the gas phase, the measured PADs from the liquid are remarkably anisotropic, even at electron kinetic energies lower than 100 eV, when elastic scattering cross sections for the outgoing electrons with other water molecules are large. The PADs reveal that theoretical estimates of the inelastic mean free path are likely too long at low kinetic energies, and hence the electron probing depth in water, near threshold ionization, appears to be considerably smaller than so far assumed.

Water oxidation using a cobalt monolayer prepared by underpotential deposition.

Development of electrocatalysts for the conversion of water to dioxygen is important in a variety of chemical applications. Despite much research in this field, there are still several fundamental issues about the electrocatalysts that need to be resolved. Two such problems are that the catalyst mass loading on the electrode is subject to large uncertainties and the wetted surface area of the catalyst is often unknown and difficult to determine. To address these topics, a cobalt monolayer was prepared on a gold electrode by underpotential deposition and used to probe its efficiency for the oxidation of water. This electrocatalyst was characterized by atomic force microscopy, grazing-incidence X-ray diffraction, and X-ray photoelectron spectroscopy at various potentials to determine if changes occur on the surface during catalysis. An enhancement of current was observed upon addition of PO4(3-) ions, suggesting an effect from surface-bound ligands on the efficiency of water oxidation. At 500 mV overpotential, current densities of 0.20, 0.74, and 2.4 mA/cm(2) for gold, cobalt, and cobalt in PO4(3-) were observed. This approach thus provided electrocatalysts whose surface areas and activity can be accurately determined.

PbSe quantum dot field-effect transistors with air-stable electron mobilities above 7 cm2 V(-1) s(-1).

PbSe quantum dot (QD) field effect transistors (FETs) with air-stable electron mobilities above 7 cm(2) V(-1) s(-1) are made by infilling sulfide-capped QD films with amorphous alumina using low-temperature atomic layer deposition (ALD). This high mobility is achieved by combining strong electronic coupling (from the ultrasmall sulfide ligands) with passivation of surface states by the ALD coating. A series of control experiments rule out alternative explanations. Partial infilling tunes the electrical characteristics of the FETs.

Iron pyrite thin films synthesized from an Fe(acac)3 ink.

Iron pyrite (cubic FeS2) is a promising candidate absorber material for earth-abundant thin-film solar cells. Here, we report on phase-pure, large-grain, and uniform polycrystalline pyrite films that are fabricated by solution-phase deposition of an iron(III) acetylacetonate molecular ink followed by sequential annealing in air, H2S, and sulfur gas at temperatures up to 550 °C. Phase and elemental compositions of the films are characterized by conventional and synchrotron X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, and X-ray photoelectron spectroscopy (XPS). These solution-deposited films have more oxygen and alkalis, less carbon and hydrogen, and smaller optical band gaps (E(g) = 0.87 ± 0.05 eV) than similar films made by chemical vapor deposition. XPS is used to assess the chemical composition of the film surface before and after exposure to air and immersion in water to remove surface contaminants. Optical measurements of films rich in marcasite (orthorhombic FeS2) show that marcasite has a band gap at least as large as pyrite and that the two polymorphs share similar absorptivity spectra, in excellent agreement with density functional theory models. Regardless of the marcasite and elemental impurity contents, all films show p-type, weakly activated transport with curved Arrhenius plots, a room-temperature resistivity of ~1 Ω cm, and a hole mobility that is too small to measure by Hall effect. This universal electrical behavior strongly suggests that a common defect or a hole-rich surface layer governs the electrical properties of most FeS2 thin films.

Mesoporous manganese oxide nanowires for high-capacity, high-rate, hybrid electrical energy storage.

Arrays of mesoporous manganese dioxide, mp-MnO(2), nanowires were electrodeposited on glass and silicon surfaces using the lithographically patterned nanowire electrodeposition (LPNE) method. The electrodeposition procedure involved the application, in a Mn(ClO(4))(2)-containing aqueous electrolyte, of a sequence of 0.60 V (vs MSE) voltage pulses delineated by 25 s rest intervals. This "multipulse" deposition program produced mp-MnO(2) nanowires with a total porosity of 43-56%. Transmission electron microscopy revealed the presence within these nanowires of a network of 3-5 nm diameter fibrils that were X-ray and electron amorphous, consistent with the measured porosity values. mp-MnO(2) nanowires were rectangular in cross-section with adjustable height, ranging from 21 to 63 nm, and adjustable width ranging from 200 to 600 nm. Arrays of 20 nm × 400 nm mp-MnO(2) nanowires were characterized by a specific capacitance, C(sp), of 923 ± 24 F/g at 5 mV/s and 484 ± 15 F/g at 100 mV/s. These C(sp) values reflected true hybrid electrical energy storage with significant contributions from double-layer capacitance and noninsertion pseudocapacitance (38% for 20 nm × 400 nm nanowires at 5 mV/s) coupled with a Faradaic insertion capacity (62%). These two contributions to the total C(sp) were deconvoluted as a function of the potential scan rate.

Tunable photoconduction sensitivity and bandwidth for lithographically patterned nanocrystalline cadmium selenide nanowires.

Nanocrystalline cadmium selenide (nc-CdSe) nanowires were prepared using the lithographically patterned nanowire electrodeposition method. Arrays of 350 linear nc-CdSe nanowires with lateral dimensions of 60 nm (h) × 200 nm (w) were patterned at 5 µm pitch on glass. nc-CdSe nanowires electrodeposited from aqueous solutions at 25 °C had a mean grain diameter, d(ave), of 5 nm. A combination of three methods was used to increase d(ave) to 10, 20, and 100 nm: (1) The deposition bath was heated to 75 °C, (2) nanowires were thermally annealed at 300 °C, and (3) nanowires were exposed to methanolic CdCl(2) followed by thermal annealing at 300 °C. The morphology, chemical composition, grain diameter, and photoconductivity of the resulting nanowires were studied as a function of d(ave). As d(ave) was increased from 10 to 100 nm, the photoconductivity response of the nanowires was modified in two ways: First, the measured photoconductive gain, G, was elevated from G = 0.017 (d(ave) = 5 nm) to ∼4.9 (100 nm), a factor of 290. Second, the photocurrent rise time was increased from 8 µs for d(ave) = 10 nm to 8 s for 100 nm, corresponding to a decrease by a factor of 1 million of the photoconduction bandwidth from 44 kHz to 44 mHz.

Photodeposition of Ag or Pt onto TiO2 nanoparticles decorated on step edges of HOPG.

Ordered linear arrays of titanium dioxide nanoparticles were fabricated on highly oriented pyrolytic graphite utilizing a step edge decoration method. Ag- or Pt-based nanoparticles were then photodeposited onto the titanium dioxide nanoparticles (∼18 nm) to simultaneously verify photocatalytic activity and to demonstrate a viable route to load the titanium dioxide nanoparticles with metals. Scanning electron microscopy and atomic force microscopy determined the morphology, size, and distribution of the particles. X-ray photoelectron spectroscopy confirmed the identity of the titanium dioxide nanoparticles, and transmission electron microscopy showed that some of the particles were rutile single crystals. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy determined the chemical composition of the metal-based nanoparticles selectively loaded on the linear arrays of titanium dioxide nanoparticles.

Electronic structure of sub-10 nm colloidal silica nanoparticles measured by in situ photoelectron spectroscopy at the aqueous-solid interface.

X-Ray photoelectron spectroscopy has been extended to colloidal nanoparticles in aqueous solution using a liquid microjet in combination with synchrotron radiation, which allowed for depth-dependent measurements. Two distinct electronic structures are evident in the Si 2p photoelectron spectrum of 7 nm SiO(2)-nanoparticles at pH 10. A core-shell model is proposed where only the outermost layer of SiO(2) nanoparticles, which is mainly composed of deprotonated silanol groups, >Si-O(-), interacts with the solution. The core of the nanoparticles is not affected by the solvation process and retains the same electronic structure as measured in vacuum. Future opportunities of this new experiment are also highlighted.

Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water.

Molecular-level insight into the dissociation of nitric acid in water is obtained from X-ray photoelectron spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from shifts of the N1s binding energy of HNO(3)(aq) as a function of concentration and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO(3)(aq) and dissociated NO(3)(-)(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO(3) interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO(3) and water. We suggest that the driving force behind the more structured solvent configuration of HNO(3) is the overlap of nitric acid solvent shells that sets in around 4 M concentration.

Single-molecule imaging of platinum ligand exchange reaction reveals reactivity distribution.

Single-molecule fluorescence microscopy provided information about the real-time distribution of chemical reactivity on silicon oxide supports at the solution-surface interface, at a level of detail which would be unavailable from a traditional ensemble technique or from a technique that imaged the static physical properties of the surface. Chemical reactions on the surface were found to be uncorrelated; that is, the chemical reaction of one metal complex did not influence the location of a future chemical reaction of another metal complex.