Emrah Ozensoy

In-Situ Vibrational Spectroscopic Studies on Model Catalyst Surfaces at Elevated Pressures

Elucidation of complex heterogeneous catalytic mechanisms at the molecular level is a challenging task due to the complex electronic structure and the topology of catalyst surfaces. Heterogeneous catalyst surfaces are often quite dynamic and readily undergo significant alterations under working conditions. Thus, monitoring the surface chemistry of heterogeneous catalysts under industrially relevant conditions such as elevated temperatures and pressures requires dedicated in situ spectroscopy methods. Due to their photons-in, photons-out nature, vibrational spectroscopic techniques offer a very powerful and a versatile experimental tool box, allowing real-time investigation of working catalyst surfaces at elevated pressures. Infrared reflection absorption spectroscopy (IRAS or IRRAS), polarization modulation-IRAS and sum frequency generation techniques reveal valuable surface chemical information at the molecular level, particularly when they are applied to atomically well-defined planar model catalyst surfaces such as single crystals or ultrathin films. In this review article, recent state of the art applications of in situ surface vibrational spectroscopy will be presented with a particular focus on elevated pressure adsorption of probe molecules (e.g. CO, NO, O2, H2, CH3OH) on monometallic and bimetallic transition metal surfaces (e.g. Pt, Pd, Rh, Ru, Au, Co, PdZn, AuPd, CuPt, etc.). Furthermore, case studies involving elevated pressure carbon monoxide oxidation, CO hydrogenation, Fischer–Tropsch, methanol decomposition/partial oxidation and methanol steam reforming reactions on single crystal platinum group metal surfaces will be provided. These examples will be exploited in order to demonstrate the capabilities, opportunities and the existing challenges associated with the in situ vibrational spectroscopic analysis of heterogeneous catalytic reactions on model catalyst surfaces at elevated pressures.

Photocatalytic Activity of Mesoporous Graphitic Carbon Nitride (mpg-C3N4) Towards Organic Chromophores Under UV and VIS Light Illumination

A template-assisted synthetic method including the thermal polycondensation of guanidine hydrochloride (GndCl) was utilized to synthesize highly-organized mesoporous graphitic carbon nitride (mpg-C3N4) photocatalysts. Comprehensive structural analysis of the mpg-C3N4 materials were performed by XPS, XRD, FT-IR, BET and solid-state NMR spectroscopy. Photocatalytic performance of the mpg-C3N4 materials was studied for the photodegradation of several dyes under visible and UV light illumination as a function of catalyst loading and the structure of mpg-C3N4 depending on the polycondensation temperature. Among all of the formerly reported performances in the literature (including the ones for Degussa P25 commercial benchmark), currently synthesized mpg-C3N4 photocatalysts exhibit a significantly superior visible light-induced photocatalytic activity towards rhodamine B (RhB) dye. Enhanced catalytic efficiency could be mainly attributed to the terminated polycondensation process, high specific surface area, and mesoporous structure with a wide pore size distribution.

Enhanced Sulfur Tolerance of Ceria-Promoted NO x Storage Reduction (NSR) Catalysts: Sulfur Uptake, Thermal Regeneration and Reduction with H2(g)

SOx uptake, thermal regeneration and the reduction of SOx via H2(g) over ceria-promoted NSR catalysts were investigated. Sulfur poisoning and desulfation pathways of the complex BaO/Pt/CeO2/Al2O3 NSR system was investigated using a systematic approach where the functional sub-components such as Al2O3, CeO2/Al2O3, BaO/Al2O3, BaO/CeO2/Al2O3, and BaO/Pt/Al2O3 were studied in a comparative fashion. Incorporation of ceria significantly increases the S-uptake of Al2O3 and BaO/Al2O3 under both moderate and extreme S-poisoning conditions. Under moderate S-poisoning conditions, Pt sites seem to be the critical species for SOx oxidation and SOx storage, where BaO/Pt/Al2O3 and BaO/Pt/CeO2/Al2O3 catalysts reveal a comparable extent of sulfation. After extreme S-poisoning due to the deactivation of most of the Pt sites, ceria domains are the main SOx storage sites on the BaO/Pt/CeO2/Al2O3 surface. Thus, under these conditions, BaO/Pt/CeO2/Al2O3 surface stores more sulfur than that of BaO/Pt/Al2O3. BaO/Pt/CeO2/Al2O3 reveals a significantly improved thermal regeneration behavior in vacuum with respect to the conventional BaO/Pt/Al2O3 catalyst. Ceria promotion remarkably enhances the SOx reduction with H2(g).

A versatile bio-inspired material platform for catalytic applications: micron-sized “buckyball-shaped” TiO2 structures

A simple sol–gel synthesis method is presented for the production of micron-sized buckyball-like TiO2 architectures using naturally occurring Lycopodium clavatum (LC) spores as biotemplates. We demonstrate that by simply altering the calcination temperature and titanium(IV) isopropoxide : ethanol volume ratio, the crystal structure and surface composition of the buckyball-like TiO2 overlayer can be readily fine-tuned. After the removal of the biological scaffold, the unique surface morphology and pore structure of the LC biotemplate can be successfully transferred to the inorganic TiO2 overlayer. We also utilize photocatalytic degradation of Rhodamine B dye samples to demonstrate the photocatalytic functionality of these micron-sized buckyball-like TiO2 architectures. Moreover, we show that the photocatalytic activity of TiO2 overlayers can be modified in a controlled manner by varying the relative surface coverages of anatase and rutile domains. These results open a potential gateway for the synthesis of a variety of bio-inspired materials with unique surface properties and shapes comprised of reducible metal oxides, metal sulfides, mixed-metal oxides, and/or perovskites.

AN XPS STUDY OF THE INTERACTION OF MODEL Ba/TiO2 AND Ba/ZrO2 NSR CATALYSTS WITH NO2

X-ray photoelectron spectroscopy is used to study the interaction of model NO2 storage-reduction catalysts (NSR catalysts) Ba/TiO2 and Ba/ZrO2 with NO2. The catalysts are prepared on the surface of ultrathin Al2O3 film substrates obtained by the FeCrAl alloy oxidation. It is shown that at room temperature the model catalysts react with NO2 with the successive formation of surface barium nitrite and nitrate. The NO2 reduction with the formation of barium nitrite at the initial step of the interaction is assumed to be accompanied by the oxidation of residual metallic barium and amorphous carbon impurity. It is found that the formation of barium nitrate proceeds more efficiently on Ba/ZrO2 rather than on Ba/TiO2.

Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111)

Gold-based heterogeneous catalysts have attracted significant attention due to their selective partial oxidation capabilities, providing promising alternatives for the traditional industrial homogeneous catalysts. In the current study, the energetics of adsorption/desorption of alcohols (CH3OH/methanol, CH3CH2OH/ethanol, CH3CH2CH2OH/n-propanol) and esters (HCOOCH3/methyl formate, CH3COOCH3/methyl acetate, and CH3COOCH2CH3/ethyl acetate) on a planar Au(111) surface was investigated in conjunction with oxidative coupling reactions by means of temperature programmed desorption (TPD) and dispersion-corrected density functional theory (DFT) calculations. The results reveal a complex interplay between inter-molecular and surface-molecule interactions, both mediated by weak van der Waals forces, which dictates their relative stability on the gold surface. Both experimental and theoretical adsorption/desorption energies of the investigated esters are lower than those of the alcohols from which they originate through oxidative coupling reactions. This result can be interpreted as an important indication in favor of the selectivity of Au surfaces in alcohol oxidative coupling/partial oxidation reactions, allowing facile removal of partial oxidation products immediately after their generation preventing their complete oxidation to higher oxygenates.