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- ItemLow-Temperature Steam Reforming of Natural Gas after LPG-Enrichment with MFI Membranes(Basel : MDPI, 2018-12-12) Seeburg, Dominik; Liu, Dongjing; Dragomirova, Radostina; Atia, Hanan; Pohl, Marga-Martina; Amani, Hadis; Georgi, Gabriele; Kreft, Stefanie; Wohlrab, SebastianLow-temperature hydrogen production from natural gas via steam reforming requires novel processing concepts as well as stable catalysts. A process using zeolite membranes of the type MFI (Mobile FIve) was used to enrich natural gas with liquefied petroleum gas (LPG) alkanes (in particular, propane and n-butane), in order to improve the hydrogen production from this mixture at a reduced temperature. For this purpose, a catalyst precursor based on Rh single-sites (1 mol% Rh) on alumina was transformed in situ to a Rh1/Al2O3 catalyst possessing better performance capabilities compared with commercial catalysts. A wet raw natural gas (57.6 vol% CH4) was fully reformed at 650 °C, with 1 bar absolute pressure over the Rh1/Al2O3 at a steam to carbon ratio S/C = 4, yielding 74.7% H2. However, at 350 °C only 21 vol% H2 was obtained under these conditions. The second mixture, enriched with LPG, was obtained from the raw gas after the membrane process and contained only 25.2 vol% CH4. From this second mixture, 47 vol% H2 was generated at 350 °C after steam reforming over the Rh1/Al2O3 catalyst at S/C = 4. At S/C = 1 conversion was suppressed for both gas mixtures. Single alkane reforming of C2–C4 showed different sensitivity for side reactions, e.g., methanation between 350 and 650 °C. These results contribute to ongoing research in the field of low-temperature hydrogen release from natural gas alkanes for fuel cell applications as well as for pre-reforming processes.
- ItemVariation of the Chemical Composition of Waste Cooking Oils upon Bentonite Filtration(Basel : MDPI, 2019) Mannu, Alberto; Vlahopoulou, Gina; Urgeghe, Paolo; Ferro, Monica; Del Caro, Alessandra; Taras, Alessandro; Garroni, Sebastiano; Rourke, Jonathan P.; Cabizza, Roberto; Petretto, Giacomo L.The chemical composition and the color of samples of waste cooking oils (WCOs) were determined prior to and after filtration on two different pads of bentonite differing in particle size. The volatile fraction was monitored by headspace solid-phase microextraction (HS-SPME) coupled with gas-chromatography, while the variation of the composition of the main components was analyzed by 1H NMR. Both techniques allowed the detection of some decomposition products, such as polymers, terpenes, and derivatives of the Maillard process. The analysis of the chemical composition prior to and after bentonite treatment revealed a tendency for the clays to retain specific chemical groups (such as carboxylic acids or double bonds), independent of their particle size. A pair comparison test was conducted in order to detect the sensory differences of the intensity of aroma between the WCO treated with the two different bentonites. In addition, characterization of the bentonite by means of powder X-ray diffraction (XRD) and thermogravimetric measurements (TG) was performed. © 2019 by the authors.
- ItemMorphology, Optical Properties and Photocatalytic Activity of Photo- and Plasma-Deposited Au and Au/Ag Core/Shell Nanoparticles on Titania Layers(Basel : MDPI, 2018-7-6) Müller, Alexander; Peglow, Sandra; Karnahl, Michael; Kruth, Angela; Junge, Henrik; Brüser, Volker; Scheu, ChristinaTitania is a promising material for numerous photocatalytic reactions such as water splitting and the degradation of organic compounds (e.g., methanol, phenol). Its catalytic performance can be significantly increased by the addition of co-catalysts. In this study, Au and Au/Ag nanoparticles were deposited onto mesoporous titania thin films using photo-deposition (Au) and magnetron-sputtering (Au and Au/Ag). All samples underwent comprehensive structural characterization by grazing incidence X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Nanoparticle distributions and nanoparticle size distributions were correlated to the deposition methods. Light absorption measurements showed features related to diffuse scattering, the band gap of titania and the local surface plasmon resonance of the noble metal nanoparticles. Further, the photocatalytic activities were measured using methanol as a hole scavenger. All nanoparticle-decorated thin films showed significant performance increases in hydrogen evolution under UV illumination compared to pure titania, with an evolution rate of up to 372 μL H2 h−1 cm−2 representing a promising approximately 12-fold increase compared to pure titania.
- ItemLow-melting manganese(II)-based ionic liquids: Syntheses, structures, properties and influence of trace impurities(Basel : MDPI, 2019) Peppel, Tim; Geppert-Rybczyńska, Monika; Neise, Christin; Kragl, Udo; Köckerling, MartinThe synthesis of more than 10 new magnetic ionic liquids with [MnX4]2− anions, X = Cl, NCS, NCO, is presented. Detailed structural information through single-crystal X-ray diffraction is given for (DMDIm)[Mn(NCS)4], (BnEt3N)2[Mn(NCS)4], and {(Ph3P)2N}2[Mn(NCO4)]·0.6H2O, respectively. All compounds consist of discrete anions and cations with tetrahedrally coordinated Mn(II) atoms. They show paramagnetic behavior as expected for spin-only systems. Melting points are found for several systems below 100 °C classifying them as ionic liquids. Thermal properties are investigated using differential scanning calorimetry (DSC) measurements. The physicochemical properties of density, dynamic viscosity, electrolytic conductivity, and surface tension were measured temperature-dependent of selected samples. These properties are discussed in comparison to similar Co containing systems. An increasing amount of bromide impurity is found to affect the surface tension only up to 3.3%.
- ItemHighly Selective Syngas/H2 Production via Partial Oxidation of CH4 Using (Ni, Co and Ni–Co)/ZrO2–Al2O3 Catalysts: Influence of Calcination Temperature(Basel : MDPI, 2019) Fakeeha, Anis Hamza; Arafat, Yasir; Ibrahim, Ahmed Aidid; Shaikh, Hamid; Atia, Hanan; Abasaeed, Ahmed Elhag; Armbruster, Udo; Al-Fatesh, Ahmed SadeqIn this study, Ni, Co and Ni–Co catalysts supported on binary oxide ZrO2–Al2O3 were synthesized by sol-gel method and characterized by means of various analytical techniques such as XRD, BET, TPR, TPD, TGA, SEM, and TEM. This catalytic system was then tested for syngas respective H2 production via partial oxidation of methane at 700 °C and 800 °C. The influence of calcination temperatures was studied and their impact on catalytic activity and stability was evaluated. It was observed that increasing the calcination temperature from 550 °C to 800 °C and addition of ZrO2 to Al2O3 enhances Ni metal-support interaction. This increases the catalytic activity and sintering resistance. Furthermore, ZrO2 provides higher oxygen storage capacity and stronger Lewis basicity which contributed to coke suppression, eventually leading to a more stable catalyst. It was also observed that, contrary to bimetallic catalysts, monometallic catalysts exhibit higher activity with higher calcination temperature. At the same time, Co and Ni–Co-based catalysts exhibit higher activity than Ni-based catalysts which was not expected. The Co-based catalyst calcined at 800 °C demonstrated excellent stability over 24 h on stream. In general, all catalysts demonstrated high CH4 conversion and exceptionally high selectivity to H2 (~98%) at 700 °C.
- ItemCatalytic Performance of Lanthanum Vanadate Catalysts in Ammoxidation of 2-Methylpyrazine(Basel : MDPI, 2016) Kalevaru, Venkata; Dhachapally, Naresh; Martin, AndreasThe influence of reaction conditions on the catalytic performance of lanthanum vanadate (La0.1V0.9Ox) catalyst in the ammoxidation of 2-methylpyrazine (MP) to 2-cyanopyarazine (CP) has been investigated. This novel catalytic material exhibited remarkably good performance with very high space-time-yields (STY) of CP. The reaction parameters such as the effect of temperature, gas hourly space velocity (GHSV) and all other reaction variables (e.g., NH3, air, and MP feed rates) on the catalytic performance were explored and optimized. For example, an increase in MP feed rate from 2 to >16 mmol/h led to decreased conversion of MP but increased the STY of CP significantly. Optimal performance was achieved when the reaction temperature was 420 °C and the molar ratio of 2-MP, ammonia, air, H2O and N2 in the feed gas was set to 1:7:26:13:22. Under these optimal reaction conditions, the catalyst showed a MP conversion of ~100%, CP selectivity of 86%, and STY of >500 gCP/(kgcat∙h). On the other hand, the formation of pyrazine (Py) as a by-product was found to be high when the NH3:MP ratio was lower at increased contact time. This suggests possible differences in the reaction mechanism pathways with respect to feed composition over La0.1V0.9Ox catalysts.
- ItemActivation, deactivation and reversibility phenomena in homogeneous catalysis : A showcase based on the chemistry of rhodium/phosphine catalysts(Basel : MDPI, 2019) Alberico, Elisabetta; Möller, Saskia; Horstmann, Moritz; Drexler, Hans-Joachim; Heller, DetlefIn the present work, the rich chemistry of rhodium/phosphine complexes, which are applied as homogeneous catalysts to promote a wide range of chemical transformations, has been used to showcase how the in situ generation of precatalysts, the conversion of precatalysts into the actually active species, as well as the reaction of the catalyst itself with other components in the reaction medium (substrates, solvents, additives) can lead to a number of deactivation phenomena and thus impact the efficiency of a catalytic process. Such phenomena may go unnoticed or may be overlooked, thus preventing the full understanding of the catalytic process which is a prerequisite for its optimization. Based on recent findings both from others and the authors’ laboratory concerning the chemistry of rhodium/diphosphine complexes, some guidelines are provided for the optimal generation of the catalytic active species from a suitable rhodium precursor and the diphosphine of interest; for the choice of the best solvent to prevent aggregation of coordinatively unsaturated metal fragments and sequestration of the active metal through too strong metal–solvent interactions; for preventing catalyst poisoning due to irreversible reaction with the product of the catalytic process or impurities present in the substrate. © 2019 by the authors.
- ItemRice husk derived porous silica as support for pd and CeO2 for low temperature catalytic methane combustion(Basel : MDPI, 2019) Liu, Dongjing; Seeburg, Dominik; Kreft, Stefanie; Bindig, René; Hartmann, Ingo; Schneider, Denise; Enke, Dirk; Wohlrab, SebastianThe separation of Pd and CeO2 on the inner surface of controlled porous glass (CPG, obtained from phase-separated borosilicate glass after extraction) yields long-term stable and highly active methane combustion catalysts. However, the limited availability of the CPG makes such catalysts highly expensive and limits their applicability. In this work, porous silica obtained from acid leached rice husks after calcination (RHS) was used as a sustainable, cheap and broadly available substitute for the above mentioned CPG. RHS-supported Pd-CeO2 with separated CeO2 clusters and Pd nanoparticles was fabricated via subsequent impregnation/calcination of molten cerium nitrate and different amounts of palladium nitrate solution. The Pd/CeO2/RHS catalysts were employed for the catalytic methane combustion in the temperature range of 150–500◦C under methane lean conditions (1000 ppm) in a simulated off-gas consisting of 9.0 vol% O2, and 5.5 vol% CO2 balanced with N2. Additionally, tests with 10.5 vol% H2O as co-feed were carried out. The results revealed that the RHS-supported catalysts reached the performance of the cost intensive benchmark catalyst based on CPG. The incorporation of Pd-CeO2 into RHS additionally improved water-resistance compared to solely Pd/CeO2 lowering the required temperature for methane combustion in presence of 10.5 vol% H2O to values significantly below 500◦C (T90 = 425◦C). © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemRelations between Structure, Activity and Stability in C3N4 Based Photocatalysts Used for Solar Hydrogen Production(Basel : MDPI, 2018-1-29) Sivasankaran, Ramesh P.; Rockstroh, Nils; Hollmann, Dirk; Kreyenschulte, Carsten R.; Agostini, Giovanni; Lund, Henrik; Acharjya, Amitava; Rabeah, Jabor; Bentrup, Ursula; Junge, Henrik; Thomas, Arne; Brückner, AngelikaSolar hydrogen production from water could be a sustainable and environmentally friendly alternative to fossil energy carriers, yet so far photocatalysts active and stable enough for large-scale applications are not available, calling for advanced research efforts. In this work, H2 evolution rates of up to 1968 and 5188 μmol h−1 g−1 were obtained from aqueous solutions of triethanolamine (TEOA) and oxalic acid (OA), respectively, by irradiating composites of AgIn5S8 (AIS), mesoporous C3N4 (CN, surface area >150 m2/g) and ≤2 wt.% in-situ photodeposited Pt nanoparticles (NPs) with UV-vis (≥300 nm) and pure visible light (≥420 nm). Structural properties and electron transport in these materials were analyzed by XRD, STEM-HAADF, XPS, UV-vis-DRS, ATR-IR, photoluminescence and in situ-EPR spectroscopy. Initial H2 formation rates were highest for Pt/CN, yet with TEOA this catalyst deactivated by inclusion of Pt NPs in the matrix of CN (most pronounced at λ ≥ 300 nm) while it remained active with OA, since in this case Pt NPs were enriched on the outermost surface of CN. In Pt/AIS-CN catalysts, Pt NPs were preferentially deposited on the surface of the AIS phase which prevents them from inclusion in the CN phase but reduces simultaneously the initial H2 evolution rate. This suggests that AIS hinders transport of separated electrons from the CN conduction band to Pt NPs but retains the latter accessible by protons to produce H2.
- ItemBimetallic Catalysts Containing Gold and Palladium for Environmentally Important Reactions(Basel : MDPI, 2016) Alshammari, Ahmad; Kalevaru, Venkata Narayana; Martin, AndreasSupported bimetallic nanoparticles (SBN) are extensively used as efficient redox catalysts. This kind of catalysis particularly using SBN has attracted immense research interest compared to their parent metals due to their unique physico-chemical properties. The primary objective of this contribution is to provide comprehensive overview about SBN and their application as promising catalysts. The present review contains four sections in total. Section 1 starts with a general introduction, recent progress, and brief summary of the application of SBN as promising catalysts for different applications. Section 2 reviews the preparation and characterization methods of SBN for a wide range of catalytic reactions. Section 3 concentrates on our own results related to the application of SBN in heterogeneous catalysis. In this section, the oxidation of cyclohexane to adipic acid (an eco-friendly and novel approach) will be discussed. In addition, the application of bimetallic Pd catalysts for vapor phase toluene acetoxylation in a fixed bed reactor will also be highlighted. Acetoxylation of toluene to benzyl acetate is another green route to synthesize benzyl acetate in one step. Finally, Section 4 describes the summary of the main points and also presents an outlook on the application of SBN as promising catalysts for the production of valuable products.