Michael Hunger

Zusammenfassung

ABSTRACTBiochar is a promising material for environmental amendment. However, the adsorption mechanism of nitrogen-based ionic species, particularly the pH dependence, is still under debate because of its high susceptibility to experimental conditions. In this study, the adsorption of ammonium sulfate by rice-husk biochar produced by low-temperature carbonization as an eco-friendly approach was studied using Fourier-transform infrared (FT-IR) spectroscopy, 13C magic-angle spinning (MAS) nuclear magnetic resonance (NMR), and open-space analysis using positrons coupled with molecular simulations. In the aqueous solution with pH of 5.38, graphenes are isolated exposing fresh surfaces, which physisorb NH4+ via interaction with π electrons rather than surface functional groups. Furthermore, the low-temperature carbonization leads to a lower degree of graphitization with grain boundary defects in graphene, triggering the fracture of graphene during the shaking process in an aqueous solution. SO42− physisorption occurs as an outer-sphere surface complex on the positive charge caused by a charge transfer of ∼2.5\% from the terminal hydrogen at the graphene edge. A decrease in aqueous pH by ∼0.7\% significantly changes the above adsorption properties both on the surfaces and at the edges: diminishment of physisorption and transition to chemisorption by the formation of an inner-sphere surface complex.

Zusammenfassung

Lactic acid and alkyl lactates are widely applied in the production of food, cosmetics, pharmaceuticals, organic synthesis and biodegradable polymers. They can be prepared via one-pot synthesis from renewable trioses, such as dihydroxyacetone (DHA). Brønsted–Lewis bifunctional solid acids (BAS & LAS) can promote the reaction via a two-step cascade reaction mechanism. BAS catalyses the dehydration of DHA, resulting in the formation of pyruvaldehyde (PA) via the rearrangement of the enol form. Upon alcohol addition, PA can be converted to the desired alkyl lactates at LAS or to pyruvaldehyde hemiacetal (PAHA) at strong BAS. The density and strength control of Brønsted acid sites (BAS) and Lewis acid sites (LAS) and the optimization of their cooperation are essential for the efficient conversion of trioses to the target products. Here, we prepared a series of Sn-containing mesoporous MCM-41 catalysts with various BAS/LAS ratios by room temperature techniques. Sn-doped SiMCM-41 having a lower BAS/LAS ratio in this research shows a high initial selectivity to ethyl lactate (EL) and similar EL yield in 6 hours as the reported best Sn catalyst Sn-grafted SiMCM-41/carbon network materials in DHA conversion. A relatively large density of LAS in Sn-doped SiMCM-41 causes a fast conversion of PA to EL, while the overall yield has been limited by the BAS density for the DHA conversion. New H-form SnMCM-41, having a suitable density of LAS and weak BAS and an optimized BAS/LAS ratio, provides a 100% yield of ethyl lactate in the catalytic conversion of DHA in ethanol within 30 min, showing a superior performance hitherto.

Zusammenfassung

Nano-ZSM-5/SBA-15 analog composites (ZSC) were prepared in a two-step process from ZSM-5 precursors with different Si/Al molar ratios (10--50) via high-temperature synthesis in mildly acidic media (200 °C, pH 3.5) aiming to evaluate the influence of the initial Si/Al ratio on their structural, acidic and catalytic properties. The resulting materials were characterized by SAXS, XRD, FTIR, TEM, N2 sorption, 27Al solid state-NMR, NH3-TPD, FTIR spectroscopy of adsorbed pyridine, AAS and ICP-AES. Under the applied synthesis conditions, a ZSC material with controlled distribution of nano-ZSM-5 and SBA-15 analog phases can be prepared from ZSM-5 precursors by adjusting the initial Si/Al ratio in the range of 20--30. Increasing the initial Si/Al ratio to 50, only ZSM-5 nanocrystals were obtained whereas reducing the initial Si/Al ratio to 10 led to the formation of a disordered mesoporous SBA-15 analog. The total acidity increases with the crystallinity of the ZSM-5 phase as varying the Si/Al ratio from 10 to 30 despite the decreased amount of incorporated aluminum. However, the acidity declines slightly when raising the Si/Al ratio to 50 because of the low incorporated aluminum. The catalytic performance of the ZSC materials compared to the reference materials, i.e. purely mesoporous Al-SBA-15 and purely microporous H-ZSM-5 was assessed in the gas phase cracking of cumene and 1,3,5-tri-isopropylbenzene (TIPB) as test reactions. The results show that a balanced ratio of nano-ZSM-5 and SBA-15 analog phases obtained by tuning the initial Si/Al ratio is crucial to achieve superior catalytic performance of the ZSC materials in the cracking of both cumene and TIPB.

Zusammenfassung

Solid-state NMR spectroscopy was utilized for investigating the post-synthetic formation of surface acid sites via AlCl3 modification of dealuminated zeolite Y (DeaY) and siliceous mesoporous SBA-15 and subsequent thermal treatment. Upon calcination at 723 K, aluminum atoms introduced by the AlCl3 modification coordinate at Q2 (Si(2Si,2OH)) and Q3 (Si(3Si,1OH)) sites and form tetrahedrally coordinated (AlIV) framework aluminum species. Most of the spectroscopically observed pentacoordinated (AlV) and octahedrally coordinated (AlVI) aluminum atoms are extra-framework species, partially acting as Lewis acid sites (LAC). The aluminum coordination at the framework is accompanied by the formation of Brønsted acidic SiOH groups with weak acid strength. The weak Brønsted acidity of these SiOH groups is explained by neighboring framework aluminum atoms with strongly disturbed tetrahedral oxygen coordination. For zeolite DeaY, in addition to the aluminum incorporation into silanol nests, also the aluminum incorporation via surface reactions of AlCl3 with the intact SiO2 framework occurs. In the case of mesoporous SBA-15, with a fivefold higher density of SiOH groups of the parent material compared with that of the parent zeolite DeaY, the aluminum incorporation into silanol nests is the dominating mechanism. By solid-state NMR spectroscopy of the dehydrated samples loaded with probe molecules, significantly larger densities (factor of 3--8) of LAC compared with those of Brønsted acid sites were determined for the AlCl3-modified and calcined zeolite DeaY and mesoporous SBA-15.

Zusammenfassung

Radioactive Cs released into a soil environment migrates along with groundwater in a manner dependent on Cs concentration. Data on the variation of Cs adsorption as a function of solution concentration are an essential prerequisite to successful decontamination work in Fukushima. To aid the ongoing decontamination work, the adsorption of Cs in aqueous solution across a wide Cs+ molarity range is studied for the case of saponite clay as adsorbent, an inorganic layered material that is an abundant mineral in the soil environment. The local molecular structures, i.e. nanosheet surfaces, nanosheet edges, and oncoming hexagonal cavities, participating in Cs adsorption are qualitatively highlighted by means of a recently developed analytical method using data from a conventional elution test, 133Cs magic-angle-spinning nuclear magnetic resonance (MAS NMR), and the radiocesium interception potential (RIP) K. Sato, et al., J. Phys. Chem. C, 2016, 120, 1270. The concentrations of nanosheet edges amount to between 100 and 400 mmol kg-1, which are not substantially different from those of the nanosheet surfaces, generally regarded as the main decontamination sites. This unambiguously implies that the nanosheet edges should be targeted as the molecular sites for decontaminating radioactive Cs, in addition to the nanosheet surfaces.

Zusammenfassung

Low-silica AlPO-34 materials with similar crystal sizes but different Brønsted acid site densities were prepared and investigated as catalysts in methanol-to-olefin (MTO) conversion. The effect of Brønsted acid site density on catalyst activity and the dominant reaction mechanism during the MTO conversion was investigated via TGA, GC-MS, solid-state NMR spectroscopy, and in situ UV/vis spectroscopy together with the catalytic performance. For the catalysts with lower Brønsted acid site densities, the olefin-based cycle mechanism is the dominant mechanism during the MTO conversion. Long-chain alkenes, e.g., C5–C6 alkenes, act as intermediates that are cracked to lower olefins, or are converted to dienes via hydride transfer reactions, and can also diffuse out of the cages of low-silica AlPO-34 catalysts as the products. With decreasing Brønsted acid site density or reaction temperature, the methylation route of the olefin-based cycle was found to be much more favored than the cracking route. Therefore, a higher selectivity to C5–C6 alkenes (∼50%) is achieved. Simultaneously, dienes are the predominant deposits occluded in the used catalysts. For catalysts with slightly higher Brønsted acid site densities, the long-chain alkenes are rapidly transformed to aromatics and, subsequently, an aromatic-based cycle mechanism contributes to the MTO conversion. Interestingly, the catalyst with the most suitable Brønsted acid site density can well balance the above-mentioned two reaction cycles accompanied by a low deactivation rate, leading to a long catalyst lifetime of up to 15 h.

Zusammenfassung

Size-confined Pt nanoparticles of about 1.5 nm have been introduced into AlMCM-41 supports with similar acid strength but various population densities of acid sites by means of wet impregnation. The Pt nanoparticles covered preferentially the surface Brønsted acid sites (BAS) of the supports or were located near acid sites rather than on the bigger free space between acid sites even at a very low acid density (6 BAS per 1000 nm2). The free BAS around the Pt particles did not interact with Pt atoms and the electronic properties of the Pt nanoparticles as probed by DRIFTS combined with CO adsorption were similar for Pt/AlMCM-41 with and without nearby free BAS. Ionic effects were generated by the Pt-covered acid sites, whereas the population of BAS did not contribute significantly to the ionic effects induced on the Pt nanoparticles. The coverage of BAS of similar strength by platinum nanoparticles led to similar chemoselectivity and product distribution in acetophenone (Aph) hydrogenation, though the density of BAS on the supports increased by more than 11 times. However, increasing the number of BAS on the supports significantly changed the hydrogenation rate. TOFs continuously increased from 125 h−1 up to 534 h−1, when the population of free BAS increased from 18.2 BAS per 1000 nm2 to 39.9 BAS per 1000 nm2. When the free BAS density was further increased to 70.4 BAS per 1000 nm2, the TOF then dropped to 176 h−1. The hydrogenation pathway is similar for both monofunctional (Pt covering all BAS) and bifunctional catalysts (Pt with free BAS), and the reaction was initiated on the Pt surface. This finding indicates that proper tuning of the population density of acid sites on the support can significantly improve the catalytic performance of the supported metal catalysts while keeping similar product selectivities.

Zusammenfassung

Mesoporous zirconosilicate, stannosilicate, and titanosilicate with the BEA structure framework have been prepared from the commercially available Beta zeolite via acid–alkaline treatments and subsequent dry impregnation of appropriate organometallic precursors. N2 adsorption–desorption isotherms and TEM observations confirm that alkaline treatment can induce desilication to create intra-crystalline mesopores from the partially dealuminated Beta sample. The incorporation of Zr species into the zeolite framework at formed silanol defect sites is monitored by infrared and 1H MAS NMR spectroscopy. Characterization results from UV-vis and XPS reveal that the majority of the incorporated Zr species exist in the form of tetrahedral Zr(iv) in the zeolite framework. The creation of Lewis acid sites with moderate acid strength upon Zr incorporation is confirmed by FTIR spectroscopy with pyridine adsorption. The as-prepared mesoporous Zr-Beta exhibits a remarkable catalytic activity and regio-selectivity to β-amino alcohols in the ring-opening aminolysis of epoxides, and the presence of mesopores can promote the reaction to a great extent through enhanced mass transfer. The impacts of the Lewis acidity of the catalysts, the basicity of amines and adsorption of reactants on the ring-opening aminolysis of epoxides are discussed in detail.

Zusammenfassung

A new technique is introduced allowing simultaneous in situ MAS NMR investigations of hydrocarbon conversions on solids under flow conditions and on-line gas chromatography. For adsorption of methanol on zeolite HBeta, equal amounts of adsorbed molecules were determined by both analytical methods. Studying the synthesis of methyl tertiary-butyl ether (MTBE) on zeolite HBeta using an MAS NMR rotor reactor, a constant yield of MTBE of Ymtbe= 27\% was obtained up to a weight hourly space velocity of 1.4 h-1. The variation of the reaction temperature led to a simultaneous change of the 13C MAS NMR signals of isobutoxy species and of the yield of MTBE determined by on-line gas chromatography which indicates that isobutoxy species act as chemically active compounds. In this first application, the new in situ technique has demonstrated its advantage for a simultaneous investigation of compounds with a long residence time on the catalyst surface and of compounds rapidly leaving the catalyst surface.

Zusammenfassung

The synthesis of the high-silica zeolite NU-87 and its physicochemical characterization are reported. The catalytic properties of zeolite HNU-87 were investigated in the conversion of 1- and 2-methylnaphthalene. Both isomerization to the corresponding methylnaphthalene and transalkylation to naphthalene and dimethylnaphthalenes are observed. The influence of reaction temperature and the modified residence time on the product distributions is reported and discussed in terms of shape selectivity effects in the peculiar pore system of NU-87. For comparison, typical results obained with zeolite HMCM-22, which possesses a similar pore architecture, are also included. The results of methylnaphthalene conversion over HNU-87 are compared to those obtained in the alkylation of naphthalene with methanol on the same zeolite catalyst.