Surface chemistry and kinetics of the hydrolysis of isocyanic acid on anatase

In order to meet the stricter NO_x and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO₂. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 °C the reaction was in the intrinsic kinetic regime (E_A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH₃ and NO₂, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO₂ were most effective in blocking cations and anions of TiO₂. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO₂ forms Ti–NCO and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH₃ and NO₂ retards hydrolysis leading to the appearance of isocyanate species on the surface.     

Energetic and entropic contributions controlling the sorption of benzene in zeolites

The energetic and entropic contributions controlling the sorption of benzene on acidic (H/ZSM-5) and non-acidic (Silicalite-1) MFI type materials were studied using gravimetry, calorimetry and in situ IR spectroscopy to follow the qualitative and quantitative interactions of benzene with the pores and the functional SiOH and SiOHAl groups. The model derived to describe the sorption isotherms indicates the presence of sterically constrained sorption structures for benzene in MFI type materials. The interaction of benzene with the pore walls controls the sorption energetically, while the localized interaction with the bridging hydroxy groups contributes only to a minor degree. If benzene is located close to SiOHAl groups perturbed hydroxy groups are formed. Their wavenumber reflects the local sorption geometry of benzene as well as the acid strength of the hydroxy group and the base strength of benzene. Two perturbed hydroxy groups were observed for benzene adsorbed, which are assigned to two orientations of the molecules inside the pores, i.e., with the ring parallel to the pore wall and with the ring being oriented towards the bridging hydroxy groups. At higher coverage benzene adsorbs at SiOHAl groups additionally in an unconstrained environment, most probably at the pore openings.     

Inelastic Neutron Scattering of Hydrogen and Butyronitrile Adsorbed on Raney-Co Catalysts

Inelastic Neutron Scattering (INS) spectroscopy was used to characterize the catalytic hydrogenation of butyronitrile on the surface of parent and LiOH-modified Raney-Co. At low pressure hydrogen is mainly adsorbed on 3-fold sites. Co-adsorbed butyronitrile and hydrogen react on the unmodified Raney-Co sample to several partially hydrogenated products that contain N-H bonds. The nature of the species suggests that bi-molecular condensation leading to N-Butylidene-1-butanamine is feasible.     

Diffusion pathways of benzene, toluene and p-xylene in MFI

The diffusion of alkyl-substituted aromatic molecules in H-ZSM-5 was investigated by means of the frequency response method decoupling particle size effects and intracrystalline diffusion. For zeolite crystals above 5 μm average diameter, the transport in the zeolite pores exerts a significant effect on the overall transport causing anisotropic diffusion as the aspect ratio of the aromatic molecules increases. Diffusion of benzene is nearly isotropic, while p-xylene shows marked differences between the diffusive processes in the straight and sinusoidal channel system of ZSM-5. The isotropic diffusion of benzene is rationalized on the basis of its ability to reorient between the two channel systems without major hindrances. For p-xylene, switching between the channels is only possible by energetically unfavorable rotational motions leading to a low probability for changing between both channel systems.     

Structure of Co and Co oxide clusters in MCM-41

The structural properties of Co/MCM-41 with pore diameters between 2.9 and 3.6 nm prepared by direct synthesis and impregnation were investigated. For both preparation methods, the size of the metal particles decreased with the pore diameter. For Co/MCM-41 with the same pore diameter we observed that the direct synthesis method led to significantly smaller metal clusters compared to the impregnation method. For all Co/MCM-41 samples constraints of the metal cluster sizes were observed, which are speculated to result from influences of the micro structure during the formation of the catalyst precursor.     

Oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides

The oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides is reported. High yields of olefins and only moderate formation of carbon oxides was observed. Both are primary products that hardly interconvert under the reaction conditions used. Addition of chloride increases the rate of reaction, while slightly decreasing the selectivity to olefins. The addition of carbon dioxide strongly decreases the rate of reaction, the negative order of 0.5 indicating that two active Li⁺sites are blocked by the adsorption of one CO₂molecule. The reaction proceeds at low oxygen pressure primarily via elimination of dihydrogen, while at higher oxygen partial pressure the hydrogen elimination occurs via water formation. It is speculated that dehydrogenation and cracking involve Li⁺and a rather nucleophilic oxygen site.     

On the contribution of X-ray absorption spectroscopy to explore structure and activity relations of Pt/ZrO2 catalysts for CO2/CH4 reforming

X-ray absorption spectroscopy (XAS) has proven to be a very useful technique in characterizing metal-based catalysts exposed to extreme operating conditions. The technique allows in situ evaluation of structural parameters (XAFS) and electronic properties (XANES). The elucidation of the nature and state of Pt-based catalysts in dry reforming of methane with carbon dioxide is presented as case study to show the contribution and potential of XAS to explore property/performance relationships for heterogeneous catalysts. Pt/ZrO₂ is an active and stable catalyst for the reaction between CH₄ and CO₂ to synthesis gas (H₂/CO). The activity and stability of the catalyst is strongly influenced by the catalyst pretreatment (calcination/reduction). The combination of hydrogen chemisorption, IR spectroscopy, XPS and XAS is shown to be suitable to track the changes of the state of the catalyst. In particular, it will be demonstrated, how XAFS helped to correctly attribute variations in the chemisorptive properties of Pt/ZrO₂ after severe temperature treatment to partial and reversible decoration of the small Pt particles with fragments of the oxide support. In situ tracking of the reduction of the catalysts by XANES additionally helped to semiquantitatively assess the partial reduction of the ZrO₂. Finally, XANES helped to demonstrate that CO₂ exposure under these severe conditions did not lead to detectable levels of surface oxidation of Pt. Based on XANES, IR spectroscopy and kinetic measurements it is concluded that in dry reforming activation of methane occurs on Pt, while CO₂ is activated on the support and the two entities react at the metal–support interface. This revised version was published online in June 2006 with corrections to the Cover Date.     

Mechanistic insights into aqueous phase propanol dehydration in H‐ZSM‐5 zeolite

Aqueous phase dehydration of 1‐propanol over H‐ZSM‐5 zeolite was investigated using density functional theory (DFT) calculations. The water molecules in the zeolite pores prefer to aggregate via the hydrogen bonding network and be protonated at the Brønsted acidic sites (BAS). Two typical configurations, i.e., dispersed and clustered, of water molecules were identified by ab initio molecular dynamics simulations of the mimicking aqueous phase H‐ZSM‐5 unit cell with 20 water molecules per unit cell. DFT calculated Gibbs free energies suggest that the dimeric propanol–propanol, the propanol–water, and the trimeric propanol–propanol–water complexes are formed at high propanol concentrations in aqueous phase, which provide a kinetically feasible dehydration reaction channel of 1‐propanol to propene. The calculation results indicate that the propanol dehydration via the unimolecular mechanism becomes kinetically discouraged due to the enhanced stability of the protonated dimeric propanol and the protonated water cluster acting as the BAS site for alcohol dehydration. © 2016 American Institute of Chemical Engineers AIChE J, 63: 172–184, 2017     

Activation mechanism of methane-derived coke (CHx) by CO2 during dry reforming of methane – comparison for Pt/Al2O3 and Pt/ZrO2

The reaction of methane-derived coke (CH_x: intermediate of the reforming reaction and also a source of coke deposition) with CO₂ was studied on supported Pt catalysts in relation with CO₂ reforming of methane. Temperature-programmed hydrogenation (TPH) was performed to investigate the reactivity of coke deposition after the catalyst was exposed to CH₄/He at 1070 K. Coke on Pt/Al₂O₃ could be hydrogenated around 873 K, while for Pt/ZrO₂ this was above 1073 K. The results indicate that the reactivity of coke with hydrogen was higher on Pt/Al₂O₃ than on Pt/ZrO₂, which was different from the reactivity of coke towards CO₂. Thus, the reactivity of CO₂ was studied and compared on these catalysts by several technics. The amount of CO evolution was measured during CO₂ flow at 1070 and 875 K. Rate and amount of converted CO₂ were higher on Pt/ZrO₂ than on Pt/Al₂O₃. Pt/ZrO₂ was proven to react with CO₂ to produce CO and active oxygen (CO₂CO+O) (probably on its oxygen defect site) more easily than Pt/Al₂O₃.