Promoting Aromatic C-H Activation through Reactive Brønsted Acid-Base Pairs on Penta-Coordinated Al-Enriched Amorphous Silica-Alumina.

The surface acidity and local coordination environment of zeolites and amorphous silica-aluminas (ASAs) can promote acid-catalyzed C-H activation in many important hydrocarbon conversion reactions. Acid sites generated by penta-coordinated Al species (AlV) can lead to enhanced acidity and changes in the surface coordination. We evaluated the potential of flame-derived ASAs with enriched AlV for C-H activation using hydrogen/deuterium (H/D) exchange with benzene-d6. With increasing Al content of ASAs, the exchange rate increased, whereas the activation energy (Ea) slightly decreased due to the enhanced Brønsted acidity. The ASAs exhibited significantly higher exchange rates and lower Ea values than the sol-gel-derived ASAs and zeolite H-ZSM-5. The superior activity is attributed to the fact that more oxygen coordinated with AlV species on flame-made ASAs, which can act as acceptors for D+, enhancing the deuterium displacement. These findings could offer a valuable alternative strategy for tailoring high-performance solid acids to promote hydrocarbon conversion reactions.

Engineering the Distinct Structure Interface of Subnano-alumina Domains on Silica for Acidic Amorphous Silica-Alumina toward Biorefining.

Amorphous silica-aluminas (ASAs) are important solid catalysts and supports for many industrially essential and sustainable processes, such as hydrocarbon transformation and biorefining. However, the wide distribution of acid strength on ASAs often results in undesired side reactions, lowering the product selectivity. Here we developed a strategy for the synthesis of a unique class of ASAs with unvarying strength of Brønsted acid sites (BAS) and Lewis acid sites (LAS) using double-flame-spray pyrolysis. Structural characterization using high-resolution transmission electron microscopy (TEM) and solid-state nuclear magnetic resonance (NMR) spectroscopy showed that the uniform acidity is due to a distinct nanostructure, characterized by a uniform interface of silica-alumina and homogeneously dispersed alumina domains. The BAS population density of as-prepared ASAs is up to 6 times higher than that obtained by classical methods. The BAS/LAS ratio, as well as the population densities of BAS and LAS of these ASAs, could be tuned in a broad range. In cyclohexanol dehydration, the uniform Brønsted acid strength provides a high selectivity to cyclohexene and a nearly linear correlation between acid site densities and cyclohexanol conversion. Moreover, the concerted action of these BAS and LAS leads to an excellent bifunctional Brønsted-Lewis acid catalyst for glucose dehydration, affording a superior 5-hydroxymethylfurfural yield.

Experimental and Theoretical Evidence for the Promotional Effect of Acid Sites on the Diffusion of Alkenes through Small-Pore Zeolites.

The diffusion of saturated and unsaturated hydrocarbons is of fundamental importance for many zeolite-catalyzed processes. Transport of small alkenes in the confined zeolite pores can become hindered, resulting in a significant impact on the ultimate product selectivity and separation. Herein, intracrystalline light olefin/paraffin diffusion through the 8-ring windows of zeolite SAPO-34 is characterized by a complementary set of first-principle molecular dynamics simulations, PFG-NMR experiments, and pulse-response temporal analysis of products measurements, yielding information at different length and time scales. Our results clearly show a promotional effect of the presence of Brønsted acid sites on the diffusion rate of ethene and propene, whereas transport of alkanes is found to be insensitive to the presence of acid sites. The enhanced diffusivity of unsaturated hydrocarbons is ascribed to the formation of favorable π-H interactions with acid protons, as confirmed by IR spectroscopy measurements. The acid site distribution is proven to be an important design parameter for optimizing product distributions and separations.

Carbon dioxide adsorption in open nanospaces formed by overlap of saponite clay nanosheets.

Nanoscale open spaces formed by partial overlap of two-dimensional nanosheets in clays, abundantly and ubiquitously available, possess reactive molecular sites such as nanosheet edges in their interior. Here, the capture and storage of CO2 molecules in open spaces within saponite clay are explored by solid-state nuclear magnetic resonance coupled with open space analysis using positronium. CO2 physisorption occurs on the nanosheet surfaces inside the open spaces under ambient conditions. Thereby, CO2 molecules are activated by picking off weakly-bound oxygen from octahedral sites at the nanosheet edges and carbonate species are stabilized on the nanosheet surfaces. This instantaneous mineral carbonation and CO2 physisorption occurs in the absence of an energy-consumption process or chemical solution enhancement. This finding is of potential significance for CO2 capture and storage and presents an approach of environmentally friendly recycling of low contaminated soil in Fukushima.

High population and dispersion of pentacoordinated AlV species on the surface of flame-made amorphous silica-alumina.

Pentacoordinated Al (AlV) species in silica-alumina are promising to promote the formation of acid sites or act as surface defects for tailoring single-atom catalysts. However, pentahedral coordination (AlV) is rarely observed in conventionally prepared silica-alumina. Here, we show that high population and dispersion of AlV species on the surface of amorphous silica-alumina (ASA) can be achieved by means of flame spray pyrolysis. High resolution TEM/EDX, high magnetic-field NMR and DFT calculations are employed to characterize the structure of as-prepared ASAs. Solid-state 27Al multi-quantum MAS NMR experiments show that most of the AlV species are formed independently from the alumina phase and are accessible for guest molecules on the surface. Upon water adsorption, these AlV species are transformed to AlVI species, structurally similar to surface AlIV species, as confirmed by DFT calculations. The outstanding catalytic activity of as-synthesized ASA is demonstrated using the in situ H/D exchange reaction with deuterated benzene as an example. The AlV-rich ASA provides a much lower activation energy (∼30 kJ/mol) than that reported for zeolite H-ZSM-5 (∼60 kJ/mol). The superior catalytic performance is attributed to the high AlV content promoting the surface active sites in ASA. The knowledge gained on the synthesis of AlV-rich ASAs and the nature of aluminum coordination in these materials could pave the way to more efficient silica-alumina based catalysts.

Molecular studies of Cs adsorption sites in inorganic layered materials: the influence of solution concentration.

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.

Separation of Anti-Phase Signals Due to Parahydrogen Induced Polarization via 2D Nutation NMR Spectroscopy.

The present work introduces a novel method for the selective detection of 1 H NMR anti-phase signals caused by the pairwise incorporation of parahydrogen into olefins on noble-metal-containing catalysts. Via a two-dimensional (2D) nutation NMR experiment, the anti-phase signals of hyperpolarized 1 H nuclei are separated due to their double nutation frequency compared to that of thermally polarized 1 H nuclei. For demonstrating this approach, parahydrogen induced polarization (PHIP) was achieved via the hydrogenation of propene with parahydrogen on platinum-containing silica and investigated by in situ 1 H MAS NMR spectroscopy under continuous-flow conditions, that is, the hydrogenation reaction was performed inside the magnet of the NMR spectrometer. The 2D nutation NMR experiment described in the present work is useful for the separation of overlapping anti-phase and in-phase signals due to hyperpolarized and thermally polarized 1 H nuclei, respectively, which is important for research in the field of heterogeneous catalysis.

Evidence of rutile-to-anatase photo-induced electron transfer in mixed-phase TiO2 by solid-state NMR spectroscopy.

With ethanol as a probe molecule, the surface sites of anatase and rutile can be distinguished using (13)C CP/MAS NMR spectroscopy, which offers an opportunity to investigate the transfer of photo-induced electrons from rutile to anatase in the mixed-phase TiO2.

Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica.

The synthesis and single-crystal X-ray structures of the novel molybdenum imido alkylidene N-heterocyclic carbene complexes [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf)2] (3), [Mo(N-2,6-Me2C6H3)(IMes)(CHCMe2Ph)(OTf)2] (4), [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf){OCH(CF3)2}] (5), [Mo(N-2,6-Me2C6H3)(CH3CN)(IMesH2)(CHCMe2Ph)(OTf)](+)BArF(-) (6), [Mo(N-2,6-Cl2C6H3)(IMesH2)(CHCMe3)(OTf)2] (7) and [Mo(N-2,6-Cl2C6H3)(IMes)(CHCMe3)(OTf)2] (8) are reported (IMesH2=1,3-dimesitylimidazolidin-2-ylidene, IMes=1,3-dimesitylimidazolin-2-ylidene, BArF(-)=tetrakis-[3,5-bis(trifluoromethyl)phenyl] borate, OTf=CF3SO3(-)). Also, silica-immobilized versions I1 and I2 were prepared. Catalysts 3-8, I1 and I2 were used in homo-, cross-, and ring-closing metathesis (RCM) reactions and in the cyclopolymerization of α,ω-diynes. In the RCM of α,ω-dienes, in the homometathesis of 1-alkenes, and in the ethenolysis of cyclooctene, turnover numbers (TONs) up to 100,000, 210,000 and 30,000, respectively, were achieved. With I1 and I2, virtually Mo-free products were obtained (<3 ppm Mo). With 1,6-hepta- and 1,7-octadiynes, catalysts 3, 4, and 5 allowed for the regioselective cyclopolymerization of 4,4-bis(ethoxycarbonyl)-1,6-heptadiyne, 4,4-bis(hydroxymethyl)-1,6-heptadiyne, 4,4-bis[(3,5-diethoxybenzoyloxy)methyl]-1,6-heptadiyne, 4,4,5,5-tetrakis(ethoxycarbonyl)-1,7-octadiyne, and 1,6-heptadiyne-4-carboxylic acid, underlining the high functional-group tolerance of these novel Group 6 metal alkylidenes.

Identification of tert-Butyl Cations in Zeolite H-ZSM-5: Evidence from NMR Spectroscopy and DFT Calculations.

Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia.

Long-term self-assembly of inorganic layered materials influenced by the local states of the interlayer cations.

A wide variety of parameters as, e.g., temperature, humidity, particle size, and cation state are known to influence the agglomeration process of two-dimensional (2D) nanosheets, called self-assembly, in inorganic layered materials. The detailed studies on which parameters are decisive and how they influence the self-assembly, however, have not been performed yet. Here, the long-term self-assembly was studied for layered stevensite and hectorite, and compared with our previous data of saponite for elucidating an influence of local states of the interlayer cations. The results were analyzed with respect to a recently established rheological model, in which 2D nanosheets migrate parallel to the layer direction aided by water molecules as lubricants [K. Sato et al., J. Phys. Chem. C, 2012, 116, 22954]. With decreasing the strength of the local electric fields facing to the interlayer spaces, cation positions split into two or three, which makes the distribution of water molecules more uniformly. These water molecules enhance the rheological motion of the 2D nanosheets parallel to the layer direction, thus accelerating the self-assembly process.

Anomalous diamagnetic susceptibility in 13-atom platinum nanocluster superatoms.

We are used to being able to predict diamagnetic susceptibilities χD to a good approximation in atomic increments since there is normally little dependence on the chemical environment. Surprisingly, we find from SQUID magnetization measurements that the χD per Pt atom of zeolite-supported Pt13 nanoclusters exceeds that of Pt(2+) ions by a factor of 37-50. The observation verifies an earlier theoretical prediction. The phenomenon can be understood nearly quantitatively on the basis of a simple expression for diamagnetic susceptibility and the superatom nature of the 13-atom near-spherical cluster. The two main contributions come from ring currents in the delocalized hydride shell and from cluster molecular orbitals hosting the Pt 5d and Pt 6s electrons.

Solid-state nuclear magnetic resonance investigations of the nature, property, and activity of acid sites on solid catalysts.

Further progress in the field of heterogeneous catalysis depends on our knowledge of the nature and behavior of surface sites on solid catalysts and of the mechanisms of chemical reactions catalyzed by these materials. In the past decades, solid-state NMR spectroscopy has been developed to an important tool for routine characterization of solid catalysts. The present work gives a review on experimental approaches and applications of solid-state NMR spectroscopy for investigating Brønsted and Lewis sites on solid acids. Studies focusing on the generation of surface sites via post-synthesis modification routes of microporous and mesoporous materials support the development of new and the improvement of existing catalyst systems. High-temperature and flow techniques of in situ solid-state NMR spectroscopy allow a deeper insight into the mechanisms of heterogeneously catalyzed reactions and open the way for studying the activity of acidic surface sites. They help to clarify the activation of reactants on Brønsted and Lewis acid sites and improve our understanding of mechanisms affecting the selectivity of acid-catalyzed reactions.

Vanadium phosphates on mesoporous supports: model catalysts for solid-state NMR studies of the selective oxidation of n-butane.

SBA-15 was utilized as mesoporous support for the dispersion of vanadium phosphate (VPO) compounds. Loading of SBA-15 with VPO compounds was found to be accompanied by decreasing (29)Si MAS NMR signals of Q(2) (Si(2Si,2OH)) and Q(3) (Si(3Si,1OH)) silicon species, which indicates coverage of the mesoporous support by the guest compounds. The (51)V MAS NNR spectra of the activated VPO/SBA-15 catalysts consist of patterns typical for the alpha(II)- and beta-phases of vanadyl orthophosphate. In the (31)P MAS NMR spectra of the activated VPO/SBA-15 catalysts, signals of beta-, delta-, and alpha(II)-VOPO(4) phases could be identified. Upon conversion of n-butane-(13)C(4), a strong decrease of the (31)P MAS NMR signals characteristic for the delta-VOPO(4) phase occurred, while by (13)C MAS NMR spectroscopy the formation of maleic anhydride, carbon monoxide, and carbon dioxide was observed. This finding supports the active role of the delta-VOPO(4) phase in the selective oxidation of n-butane on VPO/SBA-15 catalysts.

Adsorption-desorption induced structural changes of Cu-MOF evidenced by solid state NMR and EPR spectroscopy.

Adsorption-desorption induced structural changes of Cu(bpy)(H(2)O)(2)(BF(4)),(bpy) (bpy = 4,4'-bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF's structure as indicated by a high-field shift of the (11)B MAS NMR. After desorption, both EPR and (11)B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption-desorption steps are involved such as gas storage, separation, and catalysis.

Insight into the mechanisms of the ethylbenzene disproportionation: transition state shape selectivity on zeolites.

The direct experimental evidence shows that ethylbenzene disproportionation is a transition state shape selective reaction on zeolites: a bimolecular reaction mechanism via diphenylethane-mediated pathway on large-pore zeolites X and Y (ca. 0.74 nm) and a monomolecular reaction mechanism on medium-pore zeolites ZSM-5 (ca. 0.56 nm) via the ethoxy-mediated intermolecular ethyl group transfer. The lifetime of bulky diphenylethane species was prolonged by a fine-tune of FAU-zeolites, which makes this transition state detectable by 13C MAS NMR spectroscopy. Due to tunable catalytic properties and pore shapes, zeolites are promising catalysts toward emulating the efficiency and selectivity in desired reactions.

Reactivity of surface alkoxy species on acidic zeolite catalysts.

[Reaction: see text]. A solid understanding of the mechanisms involved in heterogeneously catalyzed reactions is of fundamental interest for modern chemistry. This information can help to refine modern theories of catalysis and, in a very practical way, can help researchers to optimize existing industrial processes and develop new ones. To understand the mechanisms of heterogeneous catalysis, we need to observe and identify reaction intermediates on a working catalyst. Motivated by this goal, we have monitored the catalytic events in heterogeneous systems using in situ magic-angle-spinning (MAS) NMR under flow conditions. In this Account, we describe the reactivity and possible intermediate role of surface alkoxy species in a variety of zeolite-catalyzed reactions. First, we isolate the surface alkoxy species on a working zeolite catalyst and then investigate the chemical reactivity with different probe molecules under reaction conditions. Finally, we investigate reaction mechanisms facilitated by these intermediate surface alkoxy species. We examined the reactivity of surface methoxy species (SMS) in terms of C-O bond and C-H bond activation. SMS on acidic zeolite catalysts act as an effective methylating agent when reacted with different probe molecules (including methanol, water, ammonia, alkyl halides, hydrochlorides, aromatics, carbon monoxide, and acetonitrile) through C-O bond activation. At higher reaction temperatures (ca. 523 K and above), the C-H bond activation of SMS may occur. Under these conditions, intermediates such as surface-stabilized carbenes or ylides are probably formed. This C-H bond activation is directly related to the initiation mechanism of the methanol-to-olefin (MTO) process and invites further investigation. Based on our experimental results, we also discuss the reactivity and the carbenium-ion-like nature of surface alkoxy species and recent theoretical investigations in this area.