Browsing by Subject "Ammonia"

Now showing 1 - 6 of 6

Open Access
Doping of 2-Cl-PANI/PVC films by exposure to UV, γ-rays and e-beams
(Elsevier Sequoia SA, Lausanne, Switzerland, 2000) Sevil, U. A.; Güven, O.; Birer, Ö.; Süzer, Ş.
2-Chloro-polyaniline (2-Cl-PANI) is chemically prepared in its non-conducting (Emeraldine Base, EB) form and dissolved together with polyvinylchloride (PVC) in THF for casting into thin (10-50 μm) composite films. The electrical conductivity of these films increases by more than four orders of magnitude (from 10-6 to 10-2 S/cm) when they are exposed to UV, γ-rays and e-beams. This is attributed to the dehydrochlorination (loss of HCl) of PVC by exposure to energetic particles and subsequent doping of the 2-Cl-PANI (i.e., conversion to Emeraldine Salt, ES) by the in-situ-created HCl. The doped films can also be returned to their undoped form by further exposure to NH3 vapours. The UV (or other particles)-induced doping/NH3 undoping cycles can be repeated several times until almost total dehydrochlorination of the PVC matrix. UV-Vis-NIR, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopic (XPS) techniques are employed to follow the changes in the composite films upon doping by exposure to these energetic particles.
Open Access
Enhancement of formic acid dehydrogenation selectivity of Pd(111) single crystal model catalyst surface via Brønsted bases
(American Chemical Society, 2019) Karakurt, Bartu; Koçak, Yusuf; Özensoy, Emrah
The influence of ammonia (NH3) on the doubly deuterated formic acid (DCOOD, FA) dehydrogenation selectivity for a Pd(111) single crystal model catalyst surface was investigated under ultrahigh vacuum conditions using temperature-programmed desorption and temperature-programmed reaction spectroscopy techniques. NH3 adsorption on Pd(111) revealed reversible, molecular desorption without any significant decomposition products, while DCOOD adsorption on Pd(111) yielded D2, D2O, CO, and CO2 as a result of dehydration and dehydrogenation pathways. Functionalizing the Pd(111) surface with ammonia suppressed the FA dehydration and enhanced the dehydrogenation pathway. The boost in the FA dehydrogenation of Pd(111) in the presence of NH3 can be linked to the ease of FA deprotonation as well as the stabilization of the decomposition intermediate (i.e., formate) due to the presence of ammonium counterions on the surface. In addition, the presence of a H-bonded ammonia network on the Pd(111) surface increased the hydrogen atom mobility and decreased the activation energy for molecular hydrogen desorption. In the presence of NH3, catalytic FA decomposition on Pd(111) also yielded amidation reactions, which further suppressed CO liberation and prevented poisoning of the Pd(111) active sites due to strongly bound CO species.
Open Access
Facile Synthesis of Three-Dimensional Pt-TiO2Nano-networks: A Highly Active Catalyst for the Hydrolytic Dehydrogenation of Ammonia–Borane
(Wiley, 2016) Khalily, M. A.; Eren, H.; Akbayrak, S.; Susapto, H. H.; Bıyıklı, Necmi; Özkar, S.; Güler, Mustafa O.
Three‐dimensional (3D) porous metal and metal oxide nanostructures have received considerable interest because organization of inorganic materials into 3D nanomaterials holds extraordinary properties such as low density, high porosity, and high surface area. Supramolecular self‐assembled peptide nanostructures were exploited as an organic template for catalytic 3D Pt‐TiO2 nano‐network fabrication. A 3D peptide nanofiber aerogel was conformally coated with TiO2 by atomic layer deposition (ALD) with angstrom‐level thickness precision. The 3D peptide‐TiO2 nano‐network was further decorated with highly monodisperse Pt nanoparticles by using ozone‐assisted ALD. The 3D TiO2 nano‐network decorated with Pt nanoparticles shows superior catalytic activity in hydrolysis of ammonia–borane, generating three equivalents of H2.
Open Access
Selective catalytic ammonia oxidation to nitrogen by atomic oxygen species on Ag (111)
(American Chemical Society, 2017) Karatok, M.; Vovk, E. I.; Koc, A. V.; Ozensoy, E.
Ammonia-selective catalytic oxidation was studied on the planar Ag(111) single-crystal model catalyst surface under ultra-high-vacuum (UHV) conditions. A variety of oxygen species were prepared via ozone decomposition on pristine Ag(111). Surface coverages of oxygen species were quantified by temperature-programmed desorption (TPD) and X-ray photoemission spectroscopy techniques. Exposure of ozone on Ag(111) at 140 K led to a surface atomic oxygen (Oa) overlayer. Low-energy electron diffraction experiments revealed that annealing of this atomic oxygen-covered Ag(111) surface at 473 K in UHV resulted in the formation of ordered oxide surfaces (Oox) with p(5×1) or c(4×8) surface structures. Ammonia interactions with O/Ag(111) surfaces monitored by temperature-programmed reaction spectroscopy indicated that disordered surface atomic oxygen selectively catalyzed N-H bond cleavage, yielding mostly N2 along with minor amounts of NO and N2O. Higher coverage O/Ag(111) surfaces, whose structure was tentatively assigned to a bulklike amorphous silver oxide (Obulk), showed high selectivity toward N2O formation (rather than N2) due to its augmented oxygen density. In contrast, ordered surface oxide overlayers on Ag(111) (where the order was achieved by annealing the oxygen adlayer to 473 K) showed only very limited reactivity toward ammonia. The nature of the adsorbed NH3 species on a clean Ag(111) surface and its desorption characteristics were also investigated via infrared reflection absorption spectroscopy and TPD techniques. Current findings demonstrate that the Ag(111) surface can selectively oxidize NH3 to N2 under well-defined experimental conditions without generating significant quantities of environmentally toxic species such as NO2, NO, or N2O.
Open Access
Spectroscopic investigation of onset and enhancement of electrical conductivity in PVC/PANI composites and blends by γ-ray or UV irradiation
(American Chemical Society, 1998) Sevil, U. A.; Güven, O.; Süzer, S.
Electrical conductivity of blends and composites of poly(vinyl chloride) (PVC) with nonconducting polyaniline (PANI) increases when they are subjected to γ-rays or UV radiation. This is attributed to a radiation-induced dehydrochlorination (loss of HCl) of PVC, which in turn oxidizes (dopes) PANI within the PVC matrix causing the increase in electrical conductivity of these films. XPS, UV - vis - NIR and FTIR spectroscopic methods are used to characterize and verify this novel process. After the films are subjected to γ-rays (or UV radiation) the intensities in the XPS spectra of both -N+- and Cl- peaks increase, confirming the increase in charged species within the PVC matrix. Similar observations attributable to radiation-induced electrical conductivity are also observed in both the UV - vis - NIR and FTIR spectra. This radiation-induced conductivity can also be reversed to some extent by further exposing the films to NH3 vapors, where the oxidized centers are partially reduced (undoped). Several UV/NH3/UV cycles can be performed without much loss in conductivity- and/or conductivity-related spectroscopic features. The onset of the photoinduced conductivity both in PVC-only and PVC/PANI composite films is determined to be 300 nm (4.1 eV), which coincides with the first UV absorption band of PVC.
Open Access
Visible photoluminescence from low temperature deposited hydrogenated amorphous silicon nitride
(Pergamon Press, 1996) Aydınlı, A.; Serpengüzel, A.; Vardar, D.
Hydrogenated amorphous silicon nitride (a-SiNx:H) samples have been prepared by plasma enhanced chemical vapor deposition (PECVD) using a mixture of silane (SiH4), nitrogen and ammonia (NH3). Most films exhibit visible photoluminescence (PL) and some emit strong PL after annealing. While films grown without NH3 exhibit PL in the deep red, those grown with NH3 show PL in the green. The PL properties of these films with no oxygen (O) content are similar to those of silicon oxide (SiOx) films and porous Si. Using infrared and X-ray Photoelectron Spectroscopy, we suggest that PL from a-SiNx:H films originate from Si clusters which form during PECVD and crystallize upon annealing. We propose that the presence of O is not necessary for efficient PL.