Valorisation of 2,5-dimethylfuran over zeolite catalysts studied by on-line FTIR-MS gas phase analysis

The valorisation of 2,5-dimethylfuran (2,5-dmf) by catalytic fast pyrolysis (CFP) was studied by on-line FTIR-MS gas phase analysis. Zeolite beta, H-ZSM-5 and Cu-ZSM-5 were characterised and used as catalysts. The on-line analysis enables sufficient time resolution to follow subminute transient phenomena, e.g., the impact of catalyst pretreatment and time on stream (TOS) on the reaction selectivity. The results show, that the initial selectivity towards benzene, toluene and xylene (BTX) aromatics is high but decreases with TOS while the isomerisation rates of 2,5-dmf towards 2,4-dimethylfuran and cyclic ketones increase. This indicates the involvement of specific active sites for the different conversion processes. The formation of BTX compounds is linked to the availability of specific olefins, as supported by temperature programmed desorption experiments, which is indicative of aromatisation stemming directly from the olefin pool rather than via Diels-Alder reactions

A transient in situ infrared spectroscopy study on methane oxidation over supported Pt catalysts

Catalysts with platinum dispersed on alumina, ceria and mixed alumina-ceria have been prepared by incipient wetness impreg- nation, characterized with transmission electron microscopy and X-ray diffraction, and evaluated for total oxidation of methane under both stationary and transient gas compositions (oxygen pulsing). Further, in situ diffuse reflectance Fourier transformed infrared spectroscopy has been used to monitor the evolution of surface species during precise transient gas composition changes using high-speed gas switching valves. The results show that platinum interacts sufficiently strong with all the supports so as to form small platinum particles. The smallest sizes are observed for the Pt/Ce sample. The alumina con- taining samples show, in contrast to the Pt/Ce sample, a decreased methane conversion with the increasing oxygen concentration and a clear kinetic bistability between increasing and decreasing oxygen concentrations. The bistable kinetics is likely connected to oxidation and reduction of platinum occurring at different stoichiometric gas mixtures depending on the history of the system, for which an oxidation of the platinum particles effectively inhibits the dissociative adsorption of methane leading to low reaction rate. It is shown for the alumina containing samples that the adverse effects of oxygen excess can be circumvented by the use of periodic operation so that the the average methane conversion is improved. Further, Pt/Ce seems to exhibit additional active sites at the platinum-ceria interface explaining the generally higher conversion of methane for this sample

On-Line Composition Analysis of Complex Hydrocarbon Streams by Time-Resolved Fourier Transform Infrared Spectroscopy and Ion− Molecule Reaction Mass Spectrometry

On-line composition analysis of complex hydrocarbon\ua0mixtures is highly desirable to determine the composition of process streams\ua0and to study chemical reactions in heterogeneous catalysis. Here, we show\ua0how the combination of time-resolved Fourier transform infrared spectroscopy and ion−molecule-reaction mass spectrometry (IMR-MS) can be used\ua0for compositional analysis of processed plant biomass streams. The method is\ua0based on the biomass-derived model compound 2,5-dimethylfuran and its\ua0potential catalytic conversion to valuable green aromatics, for example,\ua0benzene, toluene, and ylenes (BTX) over zeolite β. Numerous conversion\ua0products can be determined and quantified simultaneously in a temporal\ua0resolution of 4 min−1 without separation of individual compounds. The\ua0realization of this method enables us to study activity, selectivity, and changes in composition under transient reaction conditions. For example, increasing isomerization of 2,5-dimethylfuran to 2,4-dimethylfuran, 2-methyl-2-cyclopenten-1-one, and 2-methyl-2-cyclopenten-1-one is observed as the catalyst is exposed to the reactant, while BTX and olefin formation is decreasing

Desorption products during linear heating of copper zeolites with pre-adsorbed methanol

Desorption products from zeolites with medium (MFI) and small (CHA) pores and with and without ion-exchanged copper were studied during linear heating after the pre-adsorption of methanol using a chemical flow reactor with a gas phase Fourier transform infrared spectrometer. The methanol desorption profiles were deconvoluted and compared with those predicted from first-principles calculations. In situ diffuse reflectance infrared Fourier transform spectroscopy was used to study the samples during methanol desorption following a step-wise increase of the sample temperature. It is shown that well-dispersed copper species in the Cu-zeolite samples interact more strongly with methanol and its derivatives as compared to the bare zeolites, resulting in methanol desorption at higher temperatures. Moreover, the introduction of Cu leads to CO formation and desorption in larger amounts at lower temperatures compared to the bare zeolites. The formation and desorption of dimethyl ether (DME) from pre-adsorbed methanol takes place at different temperatures depending on both the influence of Cu and the zeolite topology. The Cu sites in zeolites lead to higher DME formation/desorption temperatures, while a small shift of DME desorption towards higher temperatures is observed for the CHA framework structure compared to the MFI framework structure

CO2 Methanation over Rh/CeO2 Studied with Infrared Modulation Excitation Spectroscopy and Phase Sensitive Detection

Methane is a well-established fuel molecule whose production from CO2 through methanation garners increasing interest as an energy storage solution. While often produced with Ni based catalysts, other metals are of interest thanks to higher robustness and activity-selectivity numbers. The Rh/CeO2 catalyst has shown appreciable properties for CO2 methanation and its structural dynamics has been studied in situ. However, the reaction pathway is unknown. Here, we present infrared modulation excitation spectroscopy measurements with phase sensitive detection of a Rh/CeO2 catalyst adsorbate composition during H2 pulsing (0–2 vol.%) to a constant CO2 (0.5 vol.%) feed. Various carbonyl (CO) and carbonate (b-CO3 /p-CO3 ) ad-species clearly respond to the hydrogen stimulus, making them potential reaction intermediates. The different CO ad-species are likely intermediates for product CO and CH4 but their individual contributions to the respective formations are not unambiguously ascertained. As for the carbonate dynamics, it might be linked to the reduction/oxidation of the CeO2 surface upon H2 pulsing. Formate (HCOO) ad-species are clearly visible but appear to be, if not spectators, linked to slow side reactions possibly also affected by CeO2 redox processes

Isomorphous Substitution of Gallium into MFI-Framework Zeolite Increases 2,5-Dimethylfuran to Aromatics Selectivity and Suppresses Catalyst Deactivation

The valorization of biomass-derived molecules into commodity chemicals is important for the transition to renewable feedstocks. The model platform molecule 2,5-dimethylfuran (2,5-dmf) can be converted into value-added aromatics such as benzene, toluene, and xylenes (BTX) over zeolite catalysts. To explore the role of the zeolite acid site(s) in BTX selectivity, gallium has been isomorphously substituted into the framework, resulting in a Ga-silicate. Compared to the ZSM-5 counterpart, this modification shows enhanced benzene selectivity as well as resistance to deactivation by coke in continuous catalytic performance tests.Guido J. L. de Reijer and Christopher Sauer have contributed equally to this work

WRINKLED1 Is Subject to Evolutionary Conserved Negative Autoregulation

High accumulation of storage compounds such as oil and starch are economically important traits of most agricultural crops. The genetic network determining storage compounds composition in crops has been the target of many biotechnological endeavors. Especially WRINKLED1 (WRI1), a well-known key transcription factor involved in the allocation of carbon into oil, has attracted much interest. Here we investigate the presence of an autoregulatory system involving WRI1 through transient expression in Nicotiana benthamiana leaves. Different lengths of the Arabidopsis WRI1 promotor region were coupled to a GUS reporter gene and the activity was measured when combined with constitutive expression of different WRI1 homologs from Arabidopsis thaliana, oat (Avena sativa L.), yellow nutsedge (Cyperus esculentus L.), and potato (Solanum tuberosum L.). We could show that increasing levels of each WRI1 homolog reduced the transcriptional activity of the Arabidopsis WRI1 upstream region. Through structural analysis and domain swapping between oat and Arabidopsis WRI1, we were able to determine that the negative autoregulation was clearly dependent on the DNA-binding AP2-domains. A DNA/protein interaction assay showed that AtWRI1 is unable to bind to its corresponding upstream region indicating non-direct interaction in vivo. Taken together, our results demonstrate a negative feedback loop of WRI1 expression and that it is an indirect interaction most likely caused by downstream targets of WRI1. We also show that it is possible to release WRI1 expression from this autoregulation by creating semi-synthetic WRI1 homologs increasing the potential use of WRI1 in biotechnological applications

Local anisotropy in single crystals of zeotypes with the MFI framework structure evidenced by polarised Raman spectroscopy

Polarised Raman spectroscopy is used to characterise the local structure in single crystals of zeotypes, namely silicalite-1 and ZSM-5, which share the MFI framework structure. Attributes favourable for applying polarised Raman spectroscopy are the orthogonal axes of these single crystals and their size, i.e. 10 to 30 micrometers in all three directions. We show that the intensity of certain vibrational modes in silicalite-1 depends on the polarisation of the incident light, reflecting the anisotropic character of the molecular bonds contributing to these vibrations. Using these observations, and by estimating the depolarisation ratio (rho) and the pseudo-order factor (f), we propose a more accurate assignment of the Raman active modes. More precisely, Raman intensities peaked at 294, 360, 383 and 472 cm(-1) are attributed to bending modes in 10-, 6-, 5- and 4-membered rings, respectively. In the region of stretching modes, the vibration at 832 cm(-1) is assigned to Si-O-Si bonds shared between 5-membered rings, which have an orientation parallel to the a-axis of the crystal. By virtue of having a strongly polarised character, the modes at 472 and 832 cm(-1) can be used as orientational indicators. The proposed assignment is supported by the good agreement between experimental and simulated polar plots, where Raman intensities are plotted as a function of the polarisation angle of the incident light. Finally, upon partial substitution of Si atoms by Al, the crystalline structure is maintained and almost no spectroscopic changes are observed. The only significant difference is the increased width of most vibrational modes, which is consistent with the local lower symmetry. This is also seen in the angular dependence of selected vibrational modes that compared to the case of pure silicalite-1 appear less polarised. In the Raman spectrum of ZSM-5 a new feature at 974 cm(-1) is observed, which we attribute to Al-OH stretching. In the high frequency range, the O-H stretching modes are observed which arise from the Si-O(H)-Al Bronsted acid sites. The intensity of the characteristic mode at 3611 cm(-1) reveals an anisotropic character as well, which is in line with previous findings from solid state NMR that Al atoms distribute nonrandomly within the MFI framework structure

Acidity as Descriptor for Methanol Desorption in B-, Ga- and Ti-MFI Zeotypes

The isomorphous substitution of Si with metals other than Al in zeotype frameworks allows for tuning the acidity of the zeotype and, therefore, to tailor the catalyst\u27s properties as a function of the desired catalytic reaction. In this study, B, Ga, and Ti are incorporated in the MFI framework of silicalite samples and the following series of increasing acidity is observed: Ti-silicalite < B-silicalite < Ga-silicalite. It is also observed that the lower the acidity of the sample, the easier the methanol desorption from the zeotype surface. In the target reaction, namely the direct conversion of methane to methanol, methanol extraction is affected by the zeotype acidity. Therefore, the results shown in this study contribute to a more enriched knowledge of this reaction