Browsing by Author "Brückner, Angelika"
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- ItemAvoiding Pitfalls in Comparison of Activity and Selectivity of Solid Catalysts for Electrochemical HMF Oxidation(Weinheim : Wiley-VCH, 2021) Wöllner, Sebastian; Nowak, Timothy; Zhang, Gui-Rong; Rockstroh, Nils; Ghanem, Hanadi; Rosiwal, Stefan; Brückner, Angelika; Etzold, Bastian J. M.Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) offers a renewable approach to produce the value-added platform chemical 2,5-furandicarboxylic acid (FDCA). The key for the economic viability of this approach is to develop active and selective electrocatalysts. Nevertheless, a reliable catalyst evaluation protocol is still missing, leading to elusive conclusions on criteria for a high-performing catalyst. Herein, we demonstrate that besides the catalyst identity, secondary parameters such as materials of conductive substrates for the working electrode, concentration of the supporting electrolyte, and electrolyzer configurations have profound impact on the catalyst performance and thus need to be optimized before assessing the true activity of a catalyst. Moreover, we highlight the importance of those secondary parameters in suppressing side reactions, which has long been overlooked. The protocol is validated by evaluating the performance of free-standing Cu-foam, and CuCoO modified with NaPO2H2 and Ni, which were immobilized on boron-doped diamond (BDD) electrodes. Recommended practices and figure of merits in carefully evaluating the catalyst performance are proposed. © 2021 The Authors. Published by The Chemical Society of Japan & Wiley-VCH GmbH
- ItemCobalt Single-Atom Catalysts with High Stability for Selective Dehydrogenation of Formic Acid(Weinheim : Wiley-VCH, 2020) Li, Xiang; Surkus, Annette-Enrica; Rabeah, Jabor; Anwar, Muhammad; Dastigir, Sarim; Junge, Henrik; Brückner, Angelika; Beller, MatthiasMetal–organic framework (MOF)-derived Co-N-C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co-N-C catalyst achieves superior activity, better acid resistance, and improved long-term stability compared with nanoparticles synthesized by a similar route. High-angle annular dark-field–scanning transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and X-ray absorption fine structure characterizations reveal the formation of CoIINx centers as active sites. The optimal low-cost catalyst is a promising candidate for liquid H2 generation. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemConversion of γ-Valerolactone to Ethyl Valerate over Metal Promoted Ni/ZSM-5 Catalysts : Influence of Ni0/Ni2+ Heterojunctions on Activity and Product Selectivity(Weinheim : Wiley-VCH Verlag, 2019) Velisoju, Vijay Kumar; Jampaiah, Deshetti; Gutta, Naresh; Bentrup, Ursula; Brückner, Angelika; Bhargava, Suresh K.; Akula, VenugopalPromoter (Cr, Mo and W) modified Ni/ZSM-5 catalysts were explored in the vapor phase conversion of γ-valerolactone (GVL) to ethyl valerate (EV; gasoline blender) at atmospheric pressure. Among the three different promoters (Cr, Mo and W) tested the Mo-modified catalyst was found to be the best candidate. In addition, this catalyst was found to be stable up to 50 h reaction time with an insignificant decrease in activity. The good catalytic performance is related to an optimal ratio of acid and hydrogenation functions provided by Ni2+ and Ni0, respectively. In situ FTIR spectroscopic studies revealed a strong adsorption of GVL on all catalysts which quickly reacts with dosed ethanol by formation of EV, most pronounced on the Mo-modified catalyst, while VA was identified as side product. These findings suggest the preferred GVL ring opening by cracking the C−O bond on the methyl side of the GVL molecule on this type of catalysts leading to pentenoic acid as intermediate, which is quickly hydrogenated and esterified. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemDetermining the location of Co2+ in zeolites by UV-Vis diffuse reflection spectroscopy : A critical view(Basel : MDPI, 2020) Bellmann, Andrea; Rautenberg, Christine; Bentrup, Ursula; Brückner, AngelikaUV-Vis spectroscopy as well as in situ FTIR spectroscopy of pyridine and CO adsorption were applied to determine the nature of Co species in microporous, mesoporous, and mixed oxide materials like Co-ZSM-5, Co/Na-ZSM-5, Co/Al-SBA-15, and Co/Al2O3-SiO2. Because all sample types show comparable UV-Vis spectra with a characteristic band triplet, the former described UV-Vis band deconvolution method for determination and quantification of individual cationic sites in the zeolite appears doubtful. This is also confirmed by results of pyridine and CO adsorption revealing that all Co-zeolite samples contain two types of Co2+ species located at exchange positions as well as in oxide-like clusters independent of the Co content, while in Co/Al-SBA-15 and Co/Al2O3-SiO2 only Co2+ species in oxide-like clusters occur. Consequently, the measured UV-Vis spectra represent not exclusively isolated Co2+ species, and the characteristic triplet band is not only related to γ-, β-, and α-type Co2+ sites in the zeolite but also to those dispersed on the surface of different oxide supports. The study demonstrates that for proper characterization of the formed Co species, the use of complementary methods is required. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemDonor-acceptor covalent organic frameworks for visible light induced free radical polymerization(Cambridge : RSC, 2019) Pachfule, Pradip; Acharjya, Amitava; Roeser, Jérôme; Sivasankaran, Ramesh P.; Ye, Meng-Yang; Brückner, Angelika; Schmidt, Johannes; Thomas, ArneCovalent organic frameworks (COFs) are promising materials for applications in photocatalysis, due to their conjugated, porous and chemically stable architectures. Alternating electron donor-acceptor-type structures are known to enhance charge carrier transport mobility and stability in polymers and are therefore also interesting building units for COFs used as photocatalysts but also as photoinitiator. In this work, two donor-acceptor COFs using electron deficient 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno[3,2-b]thiophene-2,5-dicarbaldehyde or [2,2′-bithiophene]-5,5′-dicarbaldehyde linkers are presented. The resulting crystalline and porous COFs have been applied as photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to poly-methyl methacrylate (PMMA). These results pave the way to the development of robust and heterogeneous systems for photochemistry that offers the transfer of radicals induced by visible light. © The Royal Society of Chemistry 2019.
- ItemThe Effect of Iron and Vanadium in VOy/Ce1-xFexO2-δ Catalysts in Low-Temperature Selective Catalytic Reduction of NOx by Ammonia(Weinheim : WileyY-VCH Verlag, 2020) Keller, Sonja; Agostini, Giovanni; Antoni, Hendrik; Kreyenschulte, Carsten R.; Atia, Hanan; Rabeah, Jabor; Bentrup, Ursula; Brückner, AngelikaSupported VOy/Ce1-xFexO2-δ catalysts (x=0, 0.5, 0.1, 0.2) and bare supports were prepared and tested in selective catalytic reduction (SCR) of NOx by NH3 between 150 and 300 °C with a GHSV of 70 000 h−1. Iron was found to be beneficial for the activity of the pristine supports, reaching 80 % conversion at 275 °C. When vanadium was additionally introduced into the system, iron was found to be detrimental for NOx-conversion. To derive structure-reactivity relationships, V-free supports and VOy/Ce1-xFexO2-δ catalysts were characterized by XRD, XPS, Raman spectroscopy and TEM. In situ XANES, as well as operando DRIFTS and EPR measurements were performed to study the behavior of the catalysts under reaction conditions. Up to an iron content of x=0.1, a solid Ce1-xFexO2-δ solution was formed. Higher iron contents led to formation of iron oxide agglomerates. These agglomerates, as well as an increased amount of surface oxygen species were found to be responsible for increased NOx-conversion over of pure supports. For V-containing catalysts, an interaction of Fe and V centers could be found. Under reaction conditions, Fe3+ was preferentially reduced instead of V5+, decreasing the catalytic activity of VOy/Ce1-xFexO2-δ. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemHighly selective visible light-induced Ti–O bond splitting in an ansa-titanocene dihydroxido complex(Cambridge : Soc., 2015) Godemann, Christian; Dura, Laura; Hollmann, Dirk; Grabow, Kathleen; Bentrup, Ursula; Jiao, Haijun; Schulz, Axel; Brückner, Angelika; Beweries, TorstenIrradiation of a substituted ansa-titanocene(IV) dihydroxido complex with visible light induces Ti–O bond dissociation. In contrast to previous studies on structurally similar unbridged complexes, no side reactions are observed and formation of the Ti(III) species is highly selective. The formation of OH radicals was proved using a biradicaloid species.
- ItemImpact of Al Activators on Structure and Catalytic Performance of Cr Catalysts in Homogeneous Ethylene Oligomerization : A Multitechnique in situ/operando Study(Weinheim : Wiley-VCH Verlag, 2019) Grauke, Reni; Schepper, Rahel; Rabeah, Jabor; Schoch, Roland; Bentrup, Ursula; Bauer, Matthias; Brückner, AngelikaThe effect of different AlR3 activators (R=methyl, ethyl, isobutyl, n-octyl) has been studied in comparison to modified methylaluminoxane (MMAO) by operando EPR as well as by in situ UV-vis, ATR-IR and XANES/EXAFS spectroscopy during oligomerization of ethylene at 20 bar and 40 °C with a homogeneous Cr complex catalyst formed in situ upon mixing a Cr(acac)3 precursor, a Ph2PN(iPr)PPh2 ligand (PNP) and the activator. Coordination of PNP to Cr(acac)3 is initiated only in the presence of an activator. Highest 1-octene productivity (detected during operando EPR measurements) was obtained with MMAO which promotes bidentate coordination of the ligand to form an active (PNP)CrII(CH3)2 chelate complex. Rising bulkiness of R in AlR3 leads to only monodentate coordination of PNP to the Cr center by one P atom and increasing reduction to CrI to a maximum extend of around 30 % for AlOct3. This lowers the catalytic performance, which is mainly governed by the mode of PNP coordination rather than by the CrI content. ©2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemNi-In Synergy in CO2Hydrogenation to Methanol(Washington, DC : ACS Publications, 2021) Zhu, Jiadong; Cannizzaro, Francesco; Liu, Liang; Zhang, Hao; Kosinov, Nikolay; Filot, Ivo A.W.; Rabeah, Jabor; Brückner, Angelika; Hensen, Emiel J.M.Indium oxide (In2O3) is a promising catalyst for selective CH3OH synthesis from CO2but displays insufficient activity at low reaction temperatures. By screening a range of promoters (Co, Ni, Cu, and Pd) in combination with In2O3using flame spray pyrolysis (FSP) synthesis, Ni is identified as the most suitable first-row transition-metal promoter with similar performance as Pd-In2O3. NiO-In2O3was optimized by varying the Ni/In ratio using FSP. The resulting catalysts including In2O3and NiO end members have similar high specific surface areas and morphology. The main products of CO2hydrogenation are CH3OH and CO with CH4being only observed at high NiO loading (≥75 wt %). The highest CH3OH rate (∼0.25 gMeOH/(gcath), 250 °C, and 30 bar) is obtained for a NiO loading of 6 wt %. Characterization of the as-prepared catalysts reveals a strong interaction between Ni cations and In2O3at low NiO loading (≤6 wt %). H2-TPR points to a higher surface density of oxygen vacancy (Ov) due to Ni substitution. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and electron paramagnetic resonance analysis of the used catalysts suggest that Ni cations can be reduced to Ni as single atoms and very small clusters during CO2hydrogenation. Supportive density functional theory calculations indicate that Ni promotion of CH3OH synthesis from CO2is mainly due to low-barrier H2dissociation on the reduced Ni surface species, facilitating hydrogenation of adsorbed CO2on Ov © 2021 The Authors. Published by American Chemical Society
- ItemOrigins of high catalyst loading in copper(i)-catalysed Ullmann-Goldberg C-N coupling reactions(Cambridge : RSC, 2017) Sherborne, Grant J.; Adomeit, Sven; Menzel, Robert; Rabeah, Jabor; Brückner, Angelika; Fielding, Mark R.; Willans, Charlotte E.; Nguyen, Bao N.A mechanistic investigation of Ullmann-Goldberg reactions using soluble and partially soluble bases led to the identification of various pathways for catalyst deactivation through (i) product inhibition with amine products, (ii) by-product inhibition with inorganic halide salts, and (iii) ligand exchange by soluble carboxylate bases. The reactions using partially soluble inorganic bases showed variable induction periods, which are responsible for the reproducibility issues in these reactions. Surprisingly, more finely milled Cs2CO3 resulted in a longer induction period due to the higher concentration of the deprotonated amine/amide, leading to suppressed catalytic activity. These results have significant implications on future ligand development for the Ullmann-Goldberg reaction and on the solid form of the inorganic base as an important variable with mechanistic ramifications in many catalytic reactions.
- ItemPromoting Photocatalytic Hydrogen Evolution Activity of Graphitic Carbon Nitride with Hole-Transfer Agents(Weinheim : Wiley-VCH, 2021) Indra, Arindam; Beltrán-Suito, Rodrigo; Müller, Marco; Sivasankaran, Ramesh P.; Schwarze, Michael; Acharjya, Amitava; Pradhan, Bapi; Hofkens, Johan; Brückner, Angelika; Thomas, Arne; Menezes, Prashanth W.; Driess, MatthiasVisible light-driven photocatalytic reduction of protons to H2 is considered a promising way of solar-to-chemical energy conversion. Effective transfer of the photogenerated electrons and holes to the surface of the photocatalyst by minimizing their recombination is essential for achieving a high photocatalytic activity. In general, a sacrificial electron donor is used as a hole scavenger to remove photogenerated holes from the valence band for the continuation of the photocatalytic hydrogen (H2 ) evolution process. Here, for the first time, the hole-transfer dynamics from Pt-loaded sol-gel-prepared graphitic carbon nitride (Pt-sg-CN) photocatalyst were investigated using different adsorbed hole acceptors along with a sacrificial agent (ascorbic acid). A significant increment (4.84 times) in H2 production was achieved by employing phenothiazine (PTZ) as the hole acceptor with continuous H2 production for 3 days. A detailed charge-transfer dynamic of the photocatalytic process in the presence of the hole acceptors was examined by time-resolved photoluminescence and in situ electron paramagnetic resonance studies.
- 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.
- ItemSchlussbericht zum Antrag des LIKAT auf Gewährung einer Zuwendung zur Erweiterung der EPR- Spektrometertechnik für den Wissenschaftscluster „Light2Hydrogen“ im Rahmen des BMBF-Programms „Spitzenforschung und Innovation in den Neuen Ländern“(Hannover : Technische Informationsbibliothek (TIB), 2013) Brückner, Angelika[no abstract available]
- ItemSelektive katalytische Oxidation von Isobutan zu Methacrylsäure (MAA) : Abschlussbericht zum BMBF-Verbundprojekt ; Bearbeitungszeitraum: 01.01.2004 - 31.12.2006(Hannover : Technische Informationsbibliothek (TIB), 2007) Bentrup, Ursula; Brückner, Angelika[no abstract available]
- ItemSupported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines(Weinheim : Wiley-VCH, 2021) Dai, Xingchao; Wang, Xinzhi; Rabeah, Jabor; Kreyenschulte, Carsten; Brückner, Angelika; Shi, FengThe shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and .NHPh radicals, in which the selective formation of .OOH radicals might play a key role. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
- ItemSynergistic Nanostructured MnOx/TiO2 Catalyst for Highly Selective Synthesis of Aromatic Imines(Weinheim : Wiley-VCH, 2021) Sudarsanam, Putla; Köckritz, Angela; Atia, Hanan; Amin, Mohamad Hassan; Brückner, AngelikaThis work reports the development of a synergistic nanostructured MnOx/TiO2 catalyst, with highly dispersed MnOx nanoparticles (4.5±1 nm) on shape-controlled TiO2 nanotubes (8–11 nm width and 120–280 nm length), for selective synthesis of valuable aromatic imines at industrially important conditions. Pristine TiO2 nanotubes exhibited 97 % imine selectivity at a 38.3 % benzylamine conversion, whereas very low imine selectivity was obtained over commercial TiO2 materials, indicating the catalytic significance of shape-controlled TiO2 nanotubes. The MnOx nanoparticle/TiO2 nanotube (10 wt% Mn) catalyst calcined at 400 °C showed the best activity with 95.6 % benzylamine conversion and 99.9 % imine selectivity. This catalyst exhibited good recyclability for four times and is effective for converting numerous benzylamines into higher yields of imines. The high catalytic performance of MnOx/TiO2 nanotubes was attributed to higher number of redox sites (Mn3+), high dispersion of Mn species, and shape-controlled structure of TiO2, indicating that this catalyst could be a promising candidate for selective oxidation reactions. © 2021 The Authors. ChemCatChem published by Wiley-VCH GmbH
- ItemSynthesis of Single Atom Based Heterogeneous Platinum Catalysts: High Selectivity and Activity for Hydrosilylation Reactions(Washington, DC : ACS Publ., 2017) Cui, Xinjiang; Junge, Kathrin; Dai, Xingchao; Kreyenschulte, Carsten; Pohl, Marga-Martina; Wohlrab, Sebastian; Shi, Feng; Brückner, Angelika; Beller, MatthiasCatalytic hydrosilylation represents a straightforward and atom-efficient methodology for the creation of C-Si bonds. In general, the application of homogeneous platinum complexes prevails in industry and academia. Herein, we describe the first heterogeneous single atom catalysts (SACs), which are conveniently prepared by decorating alumina nanorods with platinum atoms. The resulting stable material efficiently catalyzes hydrosilylation of industrially relevant olefins with high TON (≈105). A variety of substrates is selectively hydrosilylated including compounds with sensitive reducible and other functional groups (N, B, F, Cl). The single atom based catalyst shows significantly higher activity compared to related Pt nanoparticles.
- ItemTracing Active Sites in Supported Ni Catalysts during Butene Oligomerization by Operando Spectroscopy under Pressure(Washington, DC : ACS, 2016) Rabeah, Jabor; Radnik, Jörg; Briois, Valérie; Maschmeyer, Dietrich; Stochniol, Guido; Peitz, Stephan; Reeker, Helene; La Fontaine, Camille; Brückner, AngelikaSupported Ni catalysts have been studied during the dimerization of butenes by operando electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) at 353 K and up to 16 bar. Single NiI/NiII shuttles were identified as active sites, whereby the conversion of initial NiI to NiII by oxidative addition of butene is obviously faster than the re-reduction of NiII to NiI by reductive elimination of the C8 product, rendering the equilibrium percentage of NiI small. At p ≤ 2 bar, NiI single sites form inactive Ni0 aggregates, while this is suppressed at higher pressure (∼12 bar). A reaction mechanism is proposed.