Manipulating Catalytic Pathways: Deoxygenation of Palmitic Acid on Multifunctional Catalysts

The mechanism of the catalytic reduction of palmitic acid to n‐pentadecane at 260 °C in the presence of hydrogen over catalysts combining multiple functions has been explored. The reaction involves rate‐determining reduction of the carboxylic group of palmitic acid to give hexadecanal, which is catalyzed either solely by Ni or synergistically by Ni and the ZrO₂ support. The latter route involves adsorption of the carboxylic acid group at an oxygen vacancy of ZrO₂ and abstraction of the α‐H with elimination of O to produce the ketene, which is in turn hydrogenated to the aldehyde over Ni sites. The aldehyde is subsequently decarbonylated to n‐pentadecane on Ni. The rate of deoxygenation of palmitic acid is higher on Ni/ZrO₂ than that on Ni/SiO₂ or Ni/Al₂O₃, but is slower than that on H‐zeolite‐supported Ni. As the partial pressure of H₂ is decreased, the overall deoxygenation rate decreases. In the absence of H₂, ketonization catalyzed by ZrO₂ is the dominant reaction. Pd/C favors direct decarboxylation (?CO₂), while Pt/C and Raney Ni catalyze the direct decarbonylation pathway (?CO). The rate of deoxygenation of palmitic acid (in units of mmol mol_{total metal}^?1 h^?1) decreases in the sequence r_{(Pt black)}≈r_{(Pd black)}>r_{(Raney Ni)} in the absence of H₂. In situ IR spectroscopy unequivocally shows the presence of adsorbed ketene (C?C?O) on the surface of ZrO₂ during the reaction with palmitic acid at 260 °C in the presence or absence of H₂.     

Electrochemically Tunable Proton-Coupled Electron Transfer in Pd-Catalyzed Benzaldehyde Hydrogenation

Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted-acid sites. In contrast, the hydrogenation rate is not affected when H₂ is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H₂-induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support-generated hydronium ions in the proximity of the metal particles.     

Soft-computing base analyses of the relationship between annoyance and coping with noise and odor

The majority of research on annoyance as an important impact of noise, odor, and other stressors on man, has regarded the person as a passive receptor. It was however recognized that this person is an active participant trying to alter a troubled person-environment relationship or to sustain a desirable one. Coping has to be incorporated. This is of particular importance in changing exposure situations. For large populations a lot of insight can be gained by looking at average effects only. To investigate changes in annoyance and effects of coping, the individual or small group has to be studied. Then it becomes imperative to recognize the inherent vagueness in perception and human behavior. Fortunately, tools have been developed over the past decades that allow doing this in a mathematically precise way. These tools are sometimes referred to by the common label: soft-computing, hence the title of this paper. This work revealed different styles of coping both by blind clustering and by (fuzzy) logical aggregation of different actions reported in a survey. The relationship between annoyance and the intensity of coping it generates was quantified after it was recognized that the possibility for coping is created by the presence of the stressor rather than the actual fact of coping. It was further proven that refinement of this relationship is possible if a person can be identified as a coper. This personal factor can be extracted from a known reaction to one stressor and be used for predicting coping intensity and style in another situation. The effect of coping on a perceived change in annoyance is quantified by a set of fuzzy linguistic rules. This closes the loop that is responsible for at least some of the dynamics of the response to a stressor. This work thus provides all essential building blocks for designing models for annoyance in changing environments.     

Characterization of alkali exchanged ZSM5 by IR spectrosopy

The use of time resolved FTIR spectroscopy for characterizing time dependent adsorbate concentrations has been demonstrated with the examples of adsorption/desorption of ammonia and of adsorption and reactions of propan-2-ol. Adsorption sites and adsorbate structures are discussed.