Tip-enhanced Raman spectroscopy reveals rich nanoscale adsorption chemistry of 2-mercaptopyridine on Ag

Adsorption of 2-mercatopyridine (2MPy) on Ag surfaces was studied by tip-enhanced Raman spectroscopy (TERS), which allows the measurement of Raman spectra with nanometer scale spatial resolution on flat surfaces that themselves do not show any surface-enhancement Raman scattering (SERS) activity. We found that the adsorption behavior of 2MPy was affected by the parameters of the preparation for the adsorbate layers, i.e., solution concentration, solution volume, and the exposure time. Besides that, variation of the TERS spectra at randomly chosen sample positions was observed. Only some of the bands appearing in SERS experiments showed up in each TERS measurement. We propose that this is caused by different local adsorption behavior of 2MPy on the Ag surfaces. This observation perfectly demonstrates the advantage of TERS over SERS, i.e., TERS can give localized chemical information on the nanometer scale, whereas SERS can only afford average spectra with micrometer scale resolution. Finally, TERS mapping with a spatial resolution of 24 nm was demonstrated.     

Synthesis and characterization of coaxial silver/silica/polypyrrole nanocables

Double‐shelled coaxial nanocables of silver nanocables with SiO₂ and polypyrrole (PPy; Ag/SiO₂/PPy) were synthesized by a simple method. The thickness of the outer PPy shell could be controlled by the amount of pyrrole monomer. The silver nanocables encapsulated in the interior of the hollow PPy nanotubes were obtained by the removal of the midlayer SiO₂. By the silver‐mirror reaction, flowerlike Ag nanostructures could be formed on the surface of the Ag/SiO₂/PPy multilayer nanocable. The application of the as‐prepared Ag/SiO₂/PPy–Ag composites in surface‐enhanced Raman scattering (SERS) was studied with Rhodamine B (Rh B) as a probe molecule. We found that the composites could be used as SERS substrates and that they exhibited excellent enhancement ability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanistic aspects of N2O and N2 formation in NO reduction by NH3 over Ag/Al2O3: The effect of O2 and H2

A mechanistic scheme of N₂O and N₂ formation in the selective catalytic reduction of NO with NH₃ over a Ag/Al₂O₃ catalyst in the presence and absence of H₂ and O₂ was developed by applying a combination of different techniques: transient experiments with isotopic tracers in the temporal analysis of products reactor, HRTEM, in situ UV/vis and in situ FTIR spectroscopy. Based on the results of transient isotopic analysis and in situ IR experiments, it is suggested that N₂ and N₂O are formed via direct or oxygen-induced decomposition of surface NH₂NO species. These intermediates originate from NO and surface NH₂ fragments. The latter NH₂ species are formed upon stripping of hydrogen from ammonia by adsorbed oxygen species, which are produced over reduced silver species from NO, N₂O and O₂. The latter is the dominant supplier of active oxygen species. Lattice oxygen in oxidized AgO_x particles is less active than adsorbed oxygen species particularly below 623 K. The previously reported significant diminishing of N₂O production in the presence of H₂ is ascribed to hydrogen-induced generation of metallic silver sites, which are responsible for N₂O decomposition.     

Preparation and characterization of electrospun Ag/polyacrylonitrile composite nanofibers

Novel composite nanofibers consisting of Ag nanoparticles and polyacrylonitrile (PAN) were fabricated successfully. The Raman properties of these Ag/PAN nanofibers were studied at low temperatures, which showed good Raman characteristics. In the process, a PAN solution containing Ag ions was directly electrospun to obtain nanofiber films containing Ag ions, and the Ag ions of resulting composite nanofibers were reduced to Ag nanoparticles in N₂H₅OH aqueous solution. Then, we treated Ag/PAN composite nanofibers at 100 °C, 200 °C, 400 and 600 °C, respectively. The Ag/PAN nanocomposite film was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) patterns and surface-enhanced Raman scattering (SERS) spectroscopy.     

Partial oxidation of methane to synthesis gas over a Pt/10% Rh gauze

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag₂O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag₂O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag₂O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin-holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of subsurface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

A convenient approach to synthesize stable silver nanoparticles and silver/polystyrene nanocomposite particles

In this study, silver nanoparticles were prepared by the reduction of silver nitrate in SDS+ isopentanol/styrene/H₂O reverse microemulsion system using sodium citrate as reducing agent. The Ag/PS nanocomposite particles were prepared by in situ emulsion polymerization of the styrene system containing silver nanoparticles that did not separate from the reaction solution. The polymerization dynamic characteristic was studied, at the same time, silver nanparticles and the encapsulation of composite particles were characterized by Fourier‐transform‐infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X‐ray diffraction (XRD) measurement, UV–vis diffuse reflectance spectroscopy, and X‐ray photoelectron spectroscopy (XPS). The results of TEM and UV–vis absorption spectra showed that well‐dispersed silver nanoparticles have a narrow size distribution. XRD showed that Ag and Ag/PS nanocomposite particles were less than 10 and 20 nm in size, which is similar to those observed by TEM. The results of XPS spectra revealed that the microemulsion system can stabilize the silver nanoparticles from aggregation and provided supporting evidence for the polystyrene encapsulated silver nanoparticle structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Role of organic nitro compounds in selective reduction of NOx with ethanol over different supported silver catalysts

The adsorption of organic nitro compounds such as nitromethane and nitroethane on different supported silver catalysts (Ag/Al₂O₃, Ag/TiO₂, Ag/SiO₂) has been studied using infrared spectroscopy. The adsorbed NCO species formation was strongly influenced by the catalyst support and therefore clearly detected on Ag/Al₂O₃ and Ag/TiO₂ catalysts by thermal decomposition of nitromethane and nitroethane at temperatures higher than 150°C. With the Ag/SiO₂ catalyst, very little NCO formation was observed at 350°C. On the other hand, the catalyst support was found to affect the N₂ formation in the selective reduction of NO_x on supported silver catalysts. On the basis of these findings, the role of adsorbed nitromethane, nitroethane and isocyanate species in the selective reduction of NO_x is discussed with respect to the catalyst support effect and the catalytic activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation and Migration of NCO Species on Ag/SiO2 Catalyst

The adsorption of HNCO has been investigated on Ag/SiO₂ catalyst by means of FTIR spectroscopy. Adsorption of HNCO on the reduced sample at 190 K produced an absorption band at 2,170 cm⁻¹ attributed to NCO bonded to Ag. Annealing the adsorbed layer under continuous degassing, the 2,170 cm⁻¹ band gradually attenuated and at the same time a spectral feature at 2,300 cm⁻¹ due to Si–NCO developed. From these spectral changes it was inferred that NCO bonded to Ag spilt over onto silica.     

Adsorption of CH3 and its reactions with CO2 over TiO2

The adsorption, decomposition of CH₃ and its reactions with CO₂ were followed by means of Fourier transform infrared spectroscopy combined with mass spectrometry. Methyl radicals were produced by the pyrolysis of azomethane. Absorption bands, observed at room temperature adsorption, were attributed to adsorbed CH₃ and CH₃O species. The decomposition of adsorbed CH₃ in vacuum started above 400 K and was accelerated by CO₂. In the study of the interaction of methane with titania, activated in different ways, we found no convincing spectroscopic evidence for the activation of methane at 300 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

In situ FTIR study of photocatalytic NO reaction on photocatalysts under UV irradiation

The photocatalytic reaction of nitric oxide (NO) on TiO₂ and transition metal-loaded M (Cu, V, and Cr)/TiO₂ catalysts was studied using in situ FTIR spectroscopy under UV irradiation. TiO₂ and M/TiO₂ catalysts were prepared by the sol–gel method via controlled hydrolysis of titanium (IV) butoxide. Copper, vanadium, or chromium was loaded onto TiO₂ during the sol–gel procedure. After treatment at 500 °C under air flow, a large amount of surface peroxo species and OH groups were detected on the TiO₂ and M/TiO₂ catalysts. Nitric oxide was adsorbed on TiO₂ and M/TiO₂ in the form of bidentate nitrites and nitrates by reacting with OH groups, peroxo, or MO species. In addition, NO can also be adsorbed on Mⁿ⁺ in the form of nitrosyls. Under UV irradiation, bidentate nitrite was oxidized to either monodentate or bidentate nitrate. Such oxidation was suggested to be induced by superoxo species generated by oxidizing peroxo species via photogenerated holes. The existence of nitrosyls deferred the oxidation of nitrites to nitrates due to the prior oxidation of nitrosyls by superoxo. The XRD and UV–vis spectra showed that the structures and the abilities of absorbing UV light of all catalysts were not influenced by the photocatalytic NO reaction. Possible mechanisms were proposed for the photocatalytic NO oxidation on TiO₂ and M/TiO₂ based on the intermediates found from the in situ FTIR study.     

Sorption studies of microporous sol-gel modified ceramic membranes

Sorption experiments with H₂, CO₂, CH₄ and iso-C₄H₁₀ were performed on microporous SiO₂ and SiO₂/TiO₂ (30 mol% TiO₂) non-supported membrane top-layers using volumetric and gravimetric techniques. For silica, the sorption capacity decreases in the order CO₂>iso-C₄H₁₀>CH₄>H₂ at temperatures <373 K. The isosteric heat of adsorption q ^st is 23, 24, 10 and 6 kJ·mol^–1 for respectively CO₂, iso-C₄H₁₀, CH₄ and H₂. The sub-atmospheric adsorption isotherms are of Henry-type for temperatures equal and higher than 348 K for CO₂, temperatures higher than 373 K for iso-C₄H₁₀, temperatures equal and higher than 194 K for H₂ and for temperatures equal and higher than 273 K for CH₄.The sorption capacity for the SiO ₂/TiO ₂ sample was only slightly lower than for silica, as may be expected due to the lower porosity.     

Enhancement of the photocatalytic performance of Ag-modified TiO2 photocatalyst under visible light

A highly visible-light photocatalytic active Ag-modified TiO₂ (Ag–TiO₂) was prepared by a simple sol–gel process using TiOSO₄ as the starting material, AgNO₃ as a silver doping source, and hydrazine as a reducing agent. The prepared Ag–TiO₂ samples were characterized by several techniques such as X-ray powder diffraction (XRD), BET surface area measurement, scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), energy dispersive X-ray spectrometry (EDX), X-ray absorption spectroscopy (XAS) and UV–vis diffuse reflectance spectroscopy (DRS). The Ag–TiO₂ photocatalyst, a mixture of amorphous and anatase phases, has a high surface area. The silver contents in the Ag–TiO₂ samples were determined by ICP measurements. The diffused reflectance UV–vis spectra indicated that the Ag–TiO₂ samples exhibited higher red shifts compared with the undoped TiO₂ sample. Indigo carmine degradation under visible irradiation indicated that the Ag–TiO₂ catalyst gave higher photocatalytic efficiency than those of commercial P25-TiO₂ and undoped-TiO₂ samples. The Ag–TiO₂ catalyst can be reused many times without any additional treatment.     

Laser Raman spectroscopy – a powerful tool for in situ studies of catalytic materials

Advantages and limitations of laser Raman spectroscopy (LRS) as an in situ vibrational spectroscopy for the study of catalytic materials and surfaces under working conditions are discussed. Measurements can be carried out at temperatures as high as 1200 K in controlled atmospheres. Modern instrumentation permits time resolutions in the sub‐second regime for materials with high Raman cross sections. Transient studies are thus possible. Several examples are presented of in situ LRS studies including the phase analysis of bismuth molybdate and VPO oxidation catalysts, synergy effects and oxygen exchange in Sb₂O₃/MoO₃ oxide mixtures, intermediates in oxidative coupling of methane, NO decomposition on Ba/MgO catalysts, and transient SERS studies of partial oxidation of methanol on Ag single crystal surfaces and of the reduction of oxide overlayers on electrodeposited Rh layers. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of Ag, Cu, and Au Incorporation on the Diesel Soot Oxidation Behavior of SiO2: Role of Metallic Ag

The catalytic behaviors of Ag, Cu, and Au loaded fumed SiO₂ have been investigated for diesel soot oxidation. The diesel soot generated by burning pure Mexican diesel in laboratory was oxidized under air flow in presence of catalyst inside a tubular quartz reactor in between 25 and 600 °C. UV–Vis optical spectroscopy was utilized to study the electronic states of Ag, Cu, and Au(M) in M/SiO₂ catalysts. The soot oxidation was seen to be strongly enhanced by the presence of metallic silver on 3 % Ag/SiO₂ surface, probably due to the formation of atomic oxygen species during the soot oxidation process. The catalyst is very stable due to the stability of Ag⁰ species on the catalyst surface and high thermal stability of SiO₂. Obtained results reveal that though the freshly prepared 3 % Cu/SiO₂ is active for soot oxidation, it gets deactivated at high temperatures in oxidizing conditions. On the other hand, 3 % Au/SiO₂ catalyst does not present activity for diesel soot oxidation in the conventional soot oxidation temperature range. The catalytic behaviors of the supported catalyst samples have been explained considering the electron donating ability of the metals to generate atomic oxygen species at their surface.     

One-pot synthesis of Ag-TiO2/reduced graphene oxide nanocomposite for high performance of adsorption and photocatalysis

The Ag-TiO₂/r-GO nanocomposite was synthesized via a facile one-pot solvothermal method. X-ray diffraction (XRD), Transmission electron microscopy (TEM),High resolution transmission electron microscopy(HRTEM), UV–vis diffuse reflectance spectroscopy (DRS), Fourier transformed infrared spectroscopy (FT-IR), Photoluminescence (PL) and N₂ adsorption-desorption were used for the characterization of prepared samples. The adsorbent and photocatalytic performance of prepared samples were evaluated by remove of Rh B dyes and reduction of CO₂. Both the adsorbent and photocatalytic ability of all the Ag-TiO₂/r-GO samples were much higher than pure hollow TiO₂. The excellent adsorbent capacity can be attributed to the large BET surface area and the enhanced photocatalytic activity can be assigned to the predominant properties of graphene and the localized surface plasmon(LSPR) effect of Ag nanoparticles.     

Catalyst Structure-Performance Relationship Identified by High-Throughput Operando Method: New Insight for Silica-Supported Vanadium Oxide for Methanol Oxidation

The reaction mechanism of methanol oxidation catalyzed by vanadium oxides on a silica support (V₂O₅/SiO₂) was investigated in a high-throughput operando reactor coupled with a Fourier transform-infrared (FT-IR) imaging system for rapid product analysis and six parallel, in situ Raman spectroscopy probes for catalyst characterization. Up to six V₂O₅/SiO₂ catalysts with different vanadium loadings (i.e., from 0 to 7%) were simultaneously monitored under identical experimental conditions. The specific Raman bands of the different catalysts in the six parallel reaction channels are quantitatively determined in this work. Under steady-state reaction conditions, the Raman intensities of C–H stretch in Si–O–CH₃ and V–O–CH₃ were extensively studied at different reaction temperatures and different vanadium loadings. For the first time, we observed enhanced Si–O–CH₃ formation on V₂O₅/SiO₂ catalysts with low vanadium loadings. We attribute this phenomenon to surface cluster edge activation. Careful comparison of the in situ Raman intensity of V–O–CH₃ on V₂O₅/SiO₂ catalysts revealed different methoxy formation mechanisms in different reaction temperature regimes.     

Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2

The effect of zirconia promotion on Cu/SiO₂ for the hydrogenation of CO and CO₂ at 0.65 MPa has been investigated at temperatures between 473 and 573 K. With increasing zirconia loading, the rate of methanol synthesis is greatly enhanced for both CO and CO₂ hydrogenation, but more significantly for CO hydrogenation. For example, at 533 K the methanol synthesis activity of 30.5 wt% zirconia-promoted Cu/SiO₂ is 84 and 25 times that of unpromoted Cu/SiO₂ for CO and CO₂ hydrogenation, respectively. For all catalysts, the rate of methanol synthesis from CO₂/H₂ is higher than that from CO/H₂. The apparent activation energy for methanol synthesis from CO decreases from 22.5 to 17.5 kcal/mol with zirconia addition, suggesting that zirconia alters the reaction pathway. For CO₂ hydrogenation, the apparent activation energies (~12 kcal/mol) for methanol synthesis and the reverse water-gas shift (RWGS) reaction are not significantly affected by zirconia addition. While zirconia addition greatly increases the methanol synthesis rate for CO₂ hydrogenation, the effect on the RWGS reaction activity is comparatively small. The observed effects of zirconia are interpreted in terms of a mechanism which zirconia serves to adsorb either CO or CO₂, whereas Cu serves to adsorb H₂. It is proposed that methanol is formed by the hydrogenation of the species adsorbed on zirconia.     

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.     

Photoactive behavior of polyacrylonitrile fibers based on silver and zirconium co‐doped titania nanocomposites: Synthesis,characterization, and comparative study of solid‐phase photocatalytic self‐cleaning

Silver and zirconium co‐doped and mono‐doped titania nanocomposites were synthesized and deposited onto polyacrylonitrile fibers via sol–gel dip‐coating method. The resulted coated‐fibers were characterized by X‐ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, thermogravimetric analysis, and BET surface area measurement. Photocatalytic activity of the TiO₂‐coated and TiO₂‐doped coated fibers were determined by photomineralization of methylene blue and Eosin Y under UV–vis light. The progress of photodegradation of dyes was monitored by diffuse reflectance spectroscopy. The XRD results of samples indicate that the TiO₂, Ag‐TiO₂, Zr‐TiO₂, and Ag‐Zr‐TiO₂ consist of anatase phase. All samples demonstrated photo‐assisted self‐cleaning properties when exposed to UV–vis irradiation. Evaluated by decomposing dyes, photocatalytic activity of Ag–Zr co‐doped TiO₂ coated fiber was obviously higher than that of pure TiO₂ and mono‐doped TiO₂. Our results showed that the synergistic action between the silver and zirconium species in the Ag‐Zr TiO₂ nanocomposite is due to both the structural and electronic properties of the photoactive anatase phase. These results clearly indicate that modification of semiconductor photocatalyst by co‐doping process is an effective method for increasing the photocatalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Catalytic oxidation of benzene with ozone over Mn ion-exchanged zeolites

Catalytic oxidation of benzene with ozone was carried out over Mn ion-exchanged zeolites at 343 K. Benzene was oxidized on Mn-Y to form CO_x without the release of organic byproducts, whereas formic acid was formed with supported manganese oxide catalysts, Mn/SiO₂ and Mn/SiO₂–Al₂O₃. Mn-Y showed higher activity and selectivity to CO₂ than other zeolite catalysts, Mn-β, Mn-MOR, and Mn-ZSM-5. Linear relationship was observed between benzene consumption, CO_x formation and ozone consumption. Formic acid adsorbed on Mn-Y catalyst was completely oxidized to CO₂ with ozone at around 343 K.