Pulse and Continuous Radiolyses of the Europium and Neodymium Decatungstate Anions in Aqueous Solution

We have studied the behavior of aqueous solutions of the [M⁽³⁺⁾(W₅-O₁₈^(6-))₂]⁹⁻ complexes (M = Eu or Nd) under pulse and continuous radiolysis conditions. Both complexes react with e⁻_aq at a diffusion controlled rate. For the Nd³⁺ complex in solution containing 1% 2-propanol, the decay of the e⁻_aq absorption was accompanied by the formation of a broad absorption band in the visible (λ_max 600–650 nm), with a further increase in absorption up to 2 ms. For the Eu³⁺ complex under the same conditions, the decay of the e⁻_aq absorption was accompanied by the formation of an absorption maximum at ∼370 nm, which is characteristic of Eu²⁺ species. On a longer time scale, a relatively intense absorption arose in the visible (λ_max 600–650 nm) according to a complicated kinetic behavior. The two complexes exhibited a quite similar behavior in continuous radiolysis experiments. Blue products (λ_max 600–650 nm) were formed and, for the Eu³⁺ complex, the disappearance of the Eu³⁺ emission was observed. Even after high irradiation doses, the absorption (and, for Eu³⁺, emission) spectra of the solutions were quantitatively regenerated by air oxidation. The behavior of the Nd³⁺ complex is interpreted on the basis of the reduction of a W₅ O₁₈⁶⁻ ligand by e⁻_aq and alcohol radicals, followed by protonation. For the Eu³⁺ complex, the reduction by e⁻_aq causes mainly the formation of a Eu²⁺ complex. On a longer time scale, protonation and/or reaction with alcohol radicals drive back the electron from Eu²⁺ to the W₅O₁₈⁶⁻ ligands, with formation of stable blue products.     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.     

Surface-Enhanced Raman Scattering on Silver Nanoparticles in Different Aggregation Stages

Enhancement factors of surface-enhanced Raman scattering (SERS) are compared for crystal violet attached to 15–60-nm-sized colloidal silver particles in various aggregation stages using 830 nm and 407 nm laser excitation. Enhancement factors on the order of 10⁶–10⁷ have been measured at 407 nm excitation for molecules adsorbed on spatially-isolated silver spheres exhibiting strong, sharp, single-sphere plasmon resonance at 395 nm. Extremely large SERS enhancement factors on the order of 10¹⁴ are obtained at near infrared excitation for molecules on clusters built from colloidal particles. The SERS enhancement factor is demonstrated to be independent of the size of the clusters. The increase of SERS enhancement factors by 7–8 orders of magnitude by the formation of aggregates, as well as the extremely small density of “hot sites” exhibiting this high level of enhancement, provide further strong arguments for the electromagnetic origin of the hot spots and for strongly enhanced local optical fields as a key effect in SERS at an extremely high enhancement level.     

Naturally inspired SERS substrates fabricated by photocatalytically depositing silver nanoparticles on cicada wings

Densely stacked Ag nanoparticles with an average diameter of 199 nm were effectively deposited on TiO₂-coated cicada wings (Ag/TiO₂-coated wings) from a water-ethanol solution of AgNO₃ using ultraviolet light irradiation at room temperature. It was seen that the surfaces of bare cicada wings contained nanopillar array structures. In the optical absorption spectra of the Ag/TiO₂-coated wings, the absorption peak due to the localized surface plasmon resonance (LSPR) of Ag nanoparticles was observed at 440 nm. Strong Surface-enhanced Raman scattering (SERS) signals of Rhodamine 6G adsorbed on the Ag/TiO₂-coated wings were clearly observed using the 514.5-nm line of an Ar⁺ laser. The Ag/TiO₂-coated wings can be a promising candidate for naturally inspired SERS substrates.     

CO adsorption on supported and promoted Ag epoxidation catalysts

CO was used to probe the nature of adsorption sites on Ag/α-Al₂O₃ epoxidation catalysts and to investigate the effect of Cs and Cl promoters by employing diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and chemisorption measurements. In contrast to previous studies, IR absorption bands for CO chemisorbed on reduced, supported Ag crystallites were observed; however, CO adsorption occurred on only 3–7% of the total Ag surface at 300 K and coverage depended on both the pretreatment and CO pressure utilized. No irreversible CO adsorption occurred on the alumina, whereas linearly bonded CO was the dominant species on the metallic Ag sites. After a 30-min purge, the bands due to these chemisorbed forms of CO decreased in intensity while a band due to bridge-bonded CO increased in intensity, which implies that CO reoriented as the surface concentration of CO decreased. In the presence of Cs, similar behavior was observed and the band intensity of the bridge-bonded CO increased. After reduction at 673 K, cesium suboxides appeared to be formed based on the formation of carbonyl complexes at 2028, 1950, and 1869 cm⁻¹. On reduced Ag catalysts, electronic effects of Cs and Cl were observed and adsorbed CO gave a lower frequency, i.e., 2018 and 2009 cm⁻¹ for Cs-promoted samples reduced at 473 and 673 K, respectively, due to an increase in the electron density on surface Ag atoms, while this band occurred at a higher frequency of 2129 cm⁻¹ with a CsCl-promoted Ag catalyst due to a net decrease in the electron density on surface Ag atoms. After CO adsorption on O-covered Cs-promoted and CsCl-promoted catalysts, a band between 1520 and 1491 cm⁻¹ existed which was assigned to a COO⁻ stretching mode in a carbonate species formed on composite AgCs_xO_y sites. These studies with CO provide evidence that reduction at 673 K following a calcination step can lead to redistribution of Cs atoms.     

The Surface Chemistry of 1-Iodopropane Adsorbed on Pt(111)

On Pt(111) at 110 K, 1-iodopropane, C₃H₇I, adsorbs molecularly, but for doses below 1.7 × 10¹⁴ molecules cm⁻², only H₂ and I appear in thermal desorption. C–I bond cleavage occurs between 160 and 220 K, forming adsorbed n-propyl, C_(a)H₂CH₂CH₃, and atomic iodine, based on temperature-programmed desorption (TPD), high-resolution electron energy loss spectroscopy (HREELS), and X-ray photoelectron spectroscopy (XPS). n-Propyl undergoes β-hydride elimination forming propylene, with desorption peaks at 185 and 240 K. At 240 K, hydrogenation to propane also occurs. Some di-σ bonded propylene, C_(a)H₂C_(a)HCH₃, remains at 240 K and it rearranges to propylidyne near 300 K. Atomic H, bound to Pt, recombines and desorbs at ca. 260 K. Further desorption of H₂ is limited by C–H bond breaking and occurs over a broad temperature range with local maxima at ca. 280, 320, and 420 K, typical of propylidyne fragments on Pt. Atomic iodine desorbs in a broad feature at 825 K.     

Effect of boric acid and heat treatment for the formation of poly(vinyl alcohol)/iodine complex films iodinated at solution before casting

This study examined the role of boric acid and the effect of heat treatment on PVA‐iodine polarizing films prepared in the solution state before casting (IBC) of PVA/iodine/boric acid films. The films were prepared by casting aqueous solutions of 10 wt % poly(vinyl alcohol) (PVA) containing boric acid with 0, 0.1, 0.3, and 0.5 mol/l of I₂/KI aqueous solution, and I₂/KI(1 : 2) with 5 wt % of PVA. The effect of boric acid and heat treatment on the durability of the IBC PVA polarizing sheet films was investigated by UV–vis absorption spectroscopy. Boric acid was found to be essential for the complex formation in PVA/iodine solutions at relatively low I₂/KI concentrations and high temperatures. The strength of the complex peak at ∼ 600 nm in UV–vis absorption spectra increased with increasing boric acid concentration. With increasing heating temperature over 90°C the intensity of the peak at 600 nm corresponding to the complex decreased due to the evaporation of I₂ decomposed from I₅⁻, but the peak at 355 nm corresponding to free I₂·I₃⁻ was remained unchanged. From heat treatment at 150°C, the intensity of the peak at 600 nm decreased but the intensity of the complex peak (600 nm) of the sample with 0.5 mol/l boric acid was unaffected. The transmittance and degree of polarization for the films increased and decreased with increasing heat treatment time under heat and a humid atmosphere, respectively. However, this tendency decreased with increasing boric acid concentration and heat treatment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods: Part 1. ATR-FTIRAS spectra of CO adsorbed on highly dispersed Pt catalyst on carbon black and carbon un-supported Pt black

Elecrochemical ATR-FTIRAS measurements were conducted for the first time to investigate nature of CO adsorbed under potential control on a highly dispersed Pt catalyst with average particle size of 2.6 nm supported on carbon black (Pt/C) and carbon un-supported Pt black catalyst (Pt-B). Each catalyst was uniformly dispersed by 10 μg Pt/cm² and fixed by Nafion^® film of 0.05 μm thick on a gold film chemically deposited on a Si ATR prism window. Adsorption of CO was conducted at 0.05 V on the catalysts in 1 and 100% CO atmospheres, for which CO coverage, θ_CO, was 0.69 and 1, respectively. Two well-defined ν(CO) bands free from band anomalies assigned to atop CO (CO(L)) and symmetrically bridge bonded CO (CO(B)_sym.) were observed. It was newly found that the CO(L) band was spitted into two well-defined peaks, particularly in 1% CO, from very early stage of adsorption, which was interpreted in terms of simultaneous occupation of terrace and step-edge sites, denoted as CO(L)_terrace and CO(L)_edge, respectively. This simultaneous occupation was commonly observed in our work both on Pt/C and Pt-B. A new band was also observed around 1950 cm⁻¹ in addition to the bands of CO(L) and CO(B)_sym., which was assigned to asymmetric bridge CO, CO(B)_asym., adsorbed on (1 0 0) terraces, based on our previous ECSTM observation of CO adsorption structures on (1 0 0) facet. The CO(B)_asym. on the Pt/C, particularly in 100% CO atmosphere, results in growth of a sharp band at 3650 cm⁻¹ accompanied by a concomitant development of a band around 3500 cm⁻¹. The former and the latter are assigned to ν(OH) vibrations of non-hydrogen bonded and hydrogen bonded water molecules adsorbed on Pt, respectively, interpreted in term of results from a bond scission of the existing hydrogen bonded networks by CO(L)s and from a promotion of new hydrogen bonding among water molecules presumably by CO(B)_asym..It was found that the frequency ν(CO) of CO(L) both on Pt/C and Pt-B is lower than that on bulky polycrystalline electrode Pt(poly) or different crystal planes of Pt single-crystal electrodes by 30-40 cm⁻¹ at corresponding potentials, which implies a stronger electronic interaction between CO and Pt nano-particles and/or an increased contribution of step-edge sites on the particles. Determination of the band intensities of CO(L), CO(B)_asym. and CO(B)_sym. has led us to conclude a much higher bridged occupation of sites at Pt nano-particles than Pt(poly) electrodes.     

Membrane Electrode Assembly with Ultra Low Platinum Loading for Cathode Electrode of PEM Fuel Cell by Using Sputter Deposition

Cathode electrodes of proton exchange membrane fuel cells were fabricated by using Pt sputter deposition to increase the gravimetric power density (W mg_Pt⁻¹) with reduced Pt loading. Ultra low Pt‐based electrodes having Pt loading in between 0.0011 and 0.06 mg_Pt cm⁻² were prepared by a radio frequency (RF) sputter deposition method on the surface of a non‐catalyzed gas diffusion layer (GDL) substrate by changing the sputtering time (20, 90, 180, 1050 s). The effect of cathode Pt loading on the performance of membrane electrode assembly were investigated using polarization curve, impedance, H₂ crossover and cyclic voltammetry techniques. The effect of backpressure on PEMFC performance was also investigated. Sputter1050 (0.06 mg_Pt cm⁻²) exhibited the best power density at 80 °C cell temperature and without backpressure for H₂/O₂, 100 %RH (297 mW cm⁻² and 5 W mg_Pt⁻¹ at 0.6 V). On the other hand sputter90 (0.005 mg_Pt cm⁻²) showed the peak gravimetric power density (15 W mg_Pt⁻¹ and 75 mW cm⁻² at 0.6 V). The Pt utilization efficiency increased as the Pt loading decreased. Sputter20 and sputter90 electrodes yielded insufficient electrochemical surface area (ECSA), higher charge transfer and ohmic resistance, but sputter180 and sputter1050 yielded sufficient ECSA and lower charge transfer and ohmic resistance.     

Structural and optical properties of diamond and nano-diamond films grown by microwave plasma chemical vapor deposition

We compare structural and optical properties of microcrystalline and nanocrystalline diamond (MCD and NCD, respectively) films grown on mirror polished Si(100) substrates by microwave plasma chemical vapor deposition. The films were characterized by SEM, Raman spectroscopy, XRD, and AFM. Optical properties were obtained from transmittance and reflectance measurements of the samples in the wavelength range of 200–2000 nm. Raman spectrum of the MCD film exhibits a strong and sharp peak near 1335 cm⁻¹, an unambiguous signature of cubic crystalline diamond with weak non-diamond carbon bands. Along with broad non-diamond carbon bands, Raman spectra of NCD films show features near 1140 cm⁻¹, the intensity of which is significantly higher in the film grown at 600°C compared to the NCD film grown at higher temperature. The Raman feature near 1140 cm⁻¹ is related to the calculated phonon density of states of diamond and has been assigned to nanocrystalline or amorphous phase of diamond. XRD patterns of the MCD film show sharp peaks and NCD films show broad features, corresponding to cubic diamond. The rms surface roughness of the films was observed to be approximately 60 nm for MCD film that reduced substantially to 17 and 34 nm in the NCD films grown at 600 and 700°C, respectively. Tauc's optical gap for the diamond film is found to be approximately 5.5 eV. NCD grown at 700°C has a high optical absorption coefficient in the whole spectral region and the NCD film grown at 600°C shows very high transmittance (∼78%) in the near IR region, which is close to that of diamond. This indicates that the NCD film grown at 600°C has the potential for applications as optical windows since its surface roughness is significantly low as compared to the MCD film.     

Quantitative analysis of hydrogen adsorbed on Pt particles on SiO2 in the presence of coadsorbed CO by means of L3-edge X-ray absorption near-edge structure spectroscopy

X-ray absorption near-edge structure (XANES) spectra at the Pt L₃-edge for Pt particles supported on SiO₂ under CO adsorption and CO+H₂ coadsorption were recorded to analyze the amount of adsorbed hydrogen in the coadsorbed state on the Pt particles. Adsorbed CO on the Pt particles revealed a new peak at 6 eV above the Pt L₃-edge in the difference spectra before and after CO adsorption in the coverage range 0.10-0.51. Subsequent adsorption of hydrogen at various coverages on the CO-preadsorbed Pt particles broadened and shifted the peak to the higher energy side. The peak was deconvoluted to two components due to adsorbed hydrogen and CO by a linear least-squares fitting technique. It was found that the fitting coefficient with respect to adsorbed hydrogen was proportional to the amount of adsorbed hydrogen. The XANES difference spectra provide a quantitative analysis method for adsorbed hydrogen on supported Pt particles in the presence of coadsorbates like CO. This revised version was published online in July 2006 with corrections to the Cover Date.     

Infrared Study of Benzene Hydrogenation on Pt/SiO2 Catalyst by Co-adsorption of CO and Benzene

FT-IR spectra of the co-adsorption of benzene and CO have been performed to identify the preferred adsorption sites of hydrogen and benzene on a Pt/SiO₂ catalyst for hydrogenation of benzene. Results of CO adsorbed on atop sites on Pt/SiO₂ includes: an α peak at 2091 cm⁻¹, a β peak at 2080 cm⁻¹ and a γ peak at 2067 cm⁻¹ indicating three kinds of adsorption sites for dissociative hydrogen on Pt/SiO₂. The site of lowest CO stretching frequency offers stronger adsorbates–metal interaction for benzene and hydrogen. Hydrogen binding on the site of lowest CO stretching frequency before benzene adsorption significantly enhances the reaction rate of benzene hydrogenation.     

Reversed micelle Synthesis of Ag/polyaniline nanocomposites via an in situ ultraviolet photo‐redox mechanism

Silver/polyaniline nanocomposites were synthesized in reversed micellar solution, and the reaction was performed via in situ reduction of silver nitrate in aniline by photolysis. The nanocomposites were characterized by ultraviolet‐visible spectroscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, thermo‐gravimetric analysis, differential scanning calorimetric analysis, and electrochemical methods. The results showed that the Ag/polyaniline nanocomposites are composed of nano‐sized particles of 15–30 nm that contain Ag domains of 10–15 nm. The electrical conductivity of an Ag/polyaniline pellet is 95.89 S cm⁻¹, whereas a polyaniline pellet is found to be 3.1 × 10⁻² S cm⁻¹. Ag/polyaniline composites also have a higher degradation temperature and specific capacitance, when compared with pure polyaniline. Potentiodynamic polarization showed the anodic shifting of the zero current potential and a lower exchange current density for the Ag/polyaniline composite. Compared with polyaniline, the Ag/polyaniline nanocomposite is a promising candidate for coatings with improved anticorrosion performance. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.     

Electrochemical deposition of fine Pt particles on n-Si electrodes for efficient photoelectrochemical solar cells

Fine platinum (Pt) particles were deposited electrochemically on n-type silicon (n-Si) electrodes from an aqueous hexachloroplatinic acid(IV) solution by the single potential step (SPS) and double potential step (DPS) methods. The distribution density of the Pt particles on n-Si was 10⁸ cm⁻² for the SPS method, whereas it increased from 10⁹ to 10¹⁰ cm⁻² by a shift of the pulse potential at the initial step of the DPS method from −1.0 to −4.0 V versus SCE and remained nearly constant at more negative potentials. The size of the Pt particles enlarged with the charge density passing across the electrode surface at a potential of −0.70 V versus SCE, which was applied throughout for the SPS method and at the second step for the DPS method. Photoelectrochemical (PEC) solar cells equipped with Pt-electrodeposited n-Si electrodes generated open-circuit photovoltages (V_OC) of 0.51–0.61 V, much higher than those for n-Si electrodes coated with continuous Pt layers (ca. 0.2–0.3 V). Solar cell characteristics changed with the pulsed potential and charge density passing across the electrode surface which changed the size and distribution density of the Pt particles. The characteristics were explained well by our previous theory on metal-dot coated n-Si electrodes.     

Preparation of hydrazine‐modified polyacrylonitrile nanofibers for the extraction of metal ions from aqueous media

Polyacrylonitrile (PAN) nanofibers (prepared by an electrospinning technique) were chemically modified with hydrazine. The Fourier transform infrared spectrum of the hydrazine‐modified polyacrylonitrile (HM–PAN) showed that the intensity of the nitrile peak (2250 cm⁻¹) of the PAN nanofibers decreased significantly after treatment with hydrazine. New peaks at about 3400–3100 cm⁻¹ (N H stretching vibration) also appeared, which showed that the hydrazine was chemically attached to the PAN nanofibers. HM–PAN had a smooth surface (as confirmed by a scanning electron microscopy) and was a suitable material for the adsorption of metal ions from aqueous solutions. The adsorption capacity of HM–PAN increased as the adsorption time increased and became constant at 114 and 217 mg/g for Cu(II) and Pb(II) ions, respectively, after 24 h. In addition, more than 90% of the adsorbed Cu(II) and Pb(II) ions were recovered in a 1M HNO₃ solution after 1 h. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure of the silver containing diamond like carbon films: Study by multiwavelength Raman spectroscopy and XRD

In the present study structure of silver containing diamond like carbon (DLC:Ag) films deposited by reactive magnetron sputtering was investigated by X-ray diffractometry (XRD) and multiwavelength Raman spectroscopy. In the case of the DLC:Ag films containing low amount of silver, crystalline silver oxide prevails over silver. While at higher Ag atomic concentrations formation of the silver crystallites of the different orientations was observed. Surface enhanced Raman scattering (SERS) effect was detected for high Ag content in the films. For UV excited Raman spectra sp³ bonded carbon related Raman scattering T peak at ~ 1060 cm^− 1 was detected only for the films with the highest amount of silver (34.3 at.%). The dependence of the Raman scattering spectra parameters such as position of the G peak, G peak full width at half maximum (FWHM(G)), D/G peak area ratio on Ag atomic concentration in DLC:Ag film as well as Raman scattering spectra excitation wavelength were studied. The dependence on Ag amount in film was more pronounced in the case of the Raman scattering spectra excited by higher wavelength laser beam, while in the case of the spectra excited by 325 nm and 442 nm laser beams only weak dependence (or no dependence) was observed. Overall tendency of the decrease of the dispersion of the G peak with the increase of Ag atomic concentration was found. Thus sp³/sp² bond ratio in DLC:Ag film decreased with the increase of Ag atomic concentration in the films.     

XPS investigation of surface oxidation layers on a platinum electrode in alkaline solution

A thick oxidation layer on a platinum electrode has been grown in 1 N NaOH at 3 V vs Ag/AgCl reference electrode. After transferring the Pt electrode into an ultrahigh vacuum chamber the surface layer was analysed by X-ray photoelectron spectroscopy. Pt4f_5/2 amd O1s electron binding energies of 74.3, 77.6 and 530.9 eV respectively, as well as the broad peak shape of the O1s signal and the oxygen-to-platinum intensity ratio of 3.08 point towards a platinum—oxyhydroxide PtO(OH)₂. This formula is in good agreement with cyclic voltammetry curves, measured for the same electrode, that revealed two cathodic reduction peaks for oxygen surface coverages equivalent to more than two hydrogen monolayers. These two peaks were assigned to PtOH and PtO. XPS analysis at elevated temperatures showed that the thick (5 nm) oxidation layer decomposes at 400 K to a mixture of several oxides and hydroxides of Pt⁴⁺ and Pt²⁺ and Pt metal with a ratio of O-to-Pt of 1. This mixture further gradually decomposes to only a monolayer of oxygen at 770–870 K. Sodium cations were found to be present in trace amounts in the adlayer and to strongly shift the O1s binding energy to lower values.     

A multifunctional Ag/TiO2/reduced graphene oxide with optimal surface-enhanced Raman scattering and photocatalysis

A multifunctional Ag/TiO₂/reduced graphene oxide (rGO) ternary nanocomposite was prepared by a one-step photochemical reaction with TiO₂ and Ag nanoparticles successively deposited on reduced graphene oxide. The structure, morphology, composition, optical, and photoelectrochemical properties of Ag/TiO₂/rGO were investigated in detail. Meanwhile, the ternary nanocomposite possessed much higher adsorption capacity to organic dyes compared with bare TiO₂ and binary Ag/TiO₂, which would help to its use for surface-enhanced Raman scattering detection and photocatalytic degradation. Due to the charge transfer between rGO and organic dyes and enhanced electromagnetic mechanism of Ag, Ag/TiO₂/rGO nanocomposites as surface-enhanced Raman scattering substrates demonstrated dramatically improved sensitivity and good uniformity. The detection limit of rhodamine 6G (R6G) was as low as 10⁻⁹ mol/L, and the relative standard deviation values of the intensities remained below 5%. Most importantly, the synergistic coupling effect of three components extended the photoresponse range and accelerated separation of the electron-hole pairs, leading to greatly improved photocatalytic activity under simulated sunlight. The maximum rate constant (k, 0.06243 min⁻¹) of Ag/TiO₂/rGO was 50 and four times higher than that of TiO₂ and Ag/TiO₂, respectively.     

Improving the Performance of Platinum Nanocrystal Catalysts by Square‐wave Potential Electrochemical Pretreatment

Cube‐shaped Pt nanocrystals (with the size of about 160 nm) are prepared by a square‐wave potential electrochemical pretreatment at the expense of Pt nanospheres. A cyclic voltammogram of Pt nanospheres in sulphuric acid shows two pairs of hydrogen adsorption/desorption peaks, which corresponds to the characteristics of a Pt polyoriented surface. However, a cyclic voltammogram of cubic Pt nanocrystals in sulphuric acid shows another pair of hydrogen adsorption/desorption peak at 0.22 V (vs. NHE), which corresponds to the characteristics of Pt (100) surface orientation. Cubic Pt nanocrystals show enhanced electrocatalytic activity over Pt nanospheres for methanol oxidation. The peak current density of cubic Pt nanocrystals is 1.39 mA cm^–2_Pt, which is 1.48 times that of Pt nanospheres. The poison resistant and oxygen reduction reaction (ORR) activity of cubic Pt nanocrystals are also enhanced compared with those of Pt nanospheres.