52 research outputs found
Catalytic Methanol Oxidation over Copper: Observation of Reaction-Induced Nanoscale Restructuring by Means of In Situ Time-Resolved X-ray Absorption Spectroscopy
Towards Experimental Handbooks in Catalysis
The “Seven Pillars” of oxidation catalysis proposed by Robert K. Grasselli represent an early example of phenomenological descriptors in the field of heterogeneous catalysis. Major advances in the theoretical description of catalytic reactions have been achieved in recent years and new catalysts are predicted today by using computational methods. To tackle the immense complexity of high-performance systems in reactions where selectivity is a major issue, analysis of scientific data by artificial intelligence and data science provides new opportunities for achieving improved understanding. Modern data analytics require data of highest quality and sufficient diversity. Existing data, however, frequently do not comply with these constraints. Therefore, new concepts of data generation and management are needed. Herein we present a basic approach in defining best practice procedures of measuring consistent data sets in heterogeneous catalysis using “handbooks”. Selective oxidation of short-chain alkanes over mixed metal oxide catalysts was selected as an example.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat
In Situ Investigations of Structure – Activity Relationships in Heteropolyoxomolybdates as Partial Oxidation Catalysts
Spectrophotometric determination of mercury with iodide and rhodamine B (Penentuan spektrofotometri untuk merkuri dengan menggunakan Rhodamine B dan Iodida)
Spectrophotometric methods for the trace amount determination of Hg(II) via extraction and polyvinylalcohol (PVAl) water stabilization was explored. The methods are based on the formation of ion-association complex of Hg(II) with Rhodamine B, [(HgI4)2-][(Rhodamine B)+]2 in highly acidic solution. Extraction using benzene showed the Beer’s law was obeyed for mercury(II) in the range of 5 to 27 μg Hg(II) / 20 mL of sample and molar absorptivity, ε = 17.68 × 104 L mole-1cm-1. For polyvinylalcohol (PVAl) stabilization method, Beer’s law showed the validity range of 10 to 120 μg Hg(II) / 10 mL of sample and molar absorptivity, ε = 16.84 × 103 L mole-1cm-1. The benzene-extraction method has been applied in assessing the performance of copper sulfide ion-exchanger in removing Hg(II). The result was comparable to the result obtained using cold vapor atomic absorption spectrometry (CVAAS)
Tribochemical activation of iron oxide for the reduction of NO with CO: how lattice defects can influence the catalytic activity
In situ XAS Study on the Evolution of Keggin Anions during Thermal Treatment in different Atmospheres
Tribochemische Aktivierung von Eisenoxid für die Reduktion von NO mit CO: Wie Gitterbaufehler die katalytische Aktivität beeinflussen können
Activation and deactivation behavior of heteropoly acids as catalyst precursors
Activation and deactivation behavior of heteropoly acids as catalyst precursors O.Timpe, H. Noack, und G. Mestl§ Fitz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin Heteropoly acids (HPA) are important catalysts for selective partial oxidations due to their acid and redox active properties. Thee Keggin-type phosphorus molybdo acid H4[PMo12O40] is the basis for an industrially used catalyst in the methacrylic acid synthesis which contains vanadium too. The protons of the free HPA are partially exchanged by Cs+ ions. The insufficient stability of this class of substances does not allow their optimum use as catalysts. A continuous degradation of their catalytic properties and thus of the possible yields is observed under stationary reaction conditions. Due to their characteristic instability, it is unlikely that intact HPA´s are the active catalysts, although frequently stated in the literature. This correlates with the fact that the HPA has to be activated in the industrial application prior to the actual catalysis. The structural and chemical properties of the precursor-HPA are well characterized, correlate however only indirectly with the catalytic data. The oxides of the constituting transition metals are the final state of the HPA-decomposition, whose stoichiometry or degree of oxidation is determined by the surrounding atmosphere. The reaction pathway to these final decomposition products can be understood as a condensation process followed by complete structural reorganization. The loss of water occurs in two steps. The irreversible loss of structural water at elevated temperatures follows after the reversible loss of crystal water at temperatures below 400K. Oxygen defects are introduced into the Keggin anions with the loss of structural water. These defects are presumably the reason for the low reaction barriers of the subsequent structural reorganization of the defective Keggin anions. It could be shown by comparing thermogravimetric measurements of different molybdenum HPA, containing P as well as Si as the hetero atom, in different atmospheres that the reduction of the HPA occurs only after the loss of structural water. This reduction is the consequence of the loss of structural water because these HPA systems do not have a stability plateau after this step of water removal. Under oxidative conditions, the formation of MoO3 is observed after this step of loss of water. The comparison of HPA´s reveals a continuous mass loss of the P-containing samples after the loss of structural water under isothermal conditions in hydrogen atmosphere, which is qualitatively identified as the loss of P in form of reduced P-compounds, e.g. PH3. Directly after this mass loss, the TG curves show a step which is attributed to the reduction of the transition metal ions. The incorporation of V into the Keggin leads to an enhanced destabilizing effect in case of Si-HPA as compared to P-HPA. Investigations of the catalytic activity (TPRS) can be correlated with the TG data. After the loss of structural water, all investigated HPA are active for the partial oxidation reactions. This catalytic activity decreases with time on stream. Under catalytic conditions, the active fragments are not stable which were formed from the Keggin anions after loss of structural water. Total oxidation increases with the reactor temperature. In case of the Si-HPA, the total oxidation is the major reaction path already after the loss of structural water. It can be concluded from a comparison of the catalytic activities and selectivities of the different HPA that P stabilizes the fragments of the decomposed Keggins, which are characterized by a high degree of partial oxidation, in contrary to Si containing catalysts. Olefins react already at room temperature with the crystal water of the acidic HPA under water addition to alcohols. In this way the loss of water of the HPA samples is considerably increased and occurs already at room temperature. In contrast, HPA are not reduced by hydrogen at room temperature. The loss of structural water is shifted to lower temperatures in a similar way in presence of olefins. HPA preparations in which all protons of the HPA were exchanged by Cs+ ions exhibited an considerably enhanced stability toward reduction. These salts cannot desorb structural water. The decomposition and condensation of the Keggin anion fragments therefore is suppressed. Hence, these Cs salts are catalytically inactive for the partial oxidation. In contrast, more unstable tetraalkyl ammionum salts are catalytically active already at much lower temperatures which correlate with the redox potentials of the cations. It can be concluded that structural intact Keggin anions are catalytically inactive and have to be considered as the precursors of the actual active compounds
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