ECS‐3: A Crystalline Hybrid Organic–Inorganic Aluminosilicate with Open Porosity

Bellussi, Giuseppe; Montanari, Erica; Paola, Eleonora Di; Millini, Roberto; Carati, Angela; Rizzo, Caterina; Parker, Wallace O.; Gemmi, Mauro; Mugnaioli, Enrico; Kolb, Ute; Zanardi, Stefano

doi:10.1002/anie.201105496

Cited by 65 publications

(69 citation statements)

References 22 publications

(27 reference statements)

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“…These characteristics have allowed obtaining, in some cases, layered hybrid materials with specific surface areas and porous volumes close to 350 m Figure 31, taking ECS-3 material as example, being evidenced the regular and ordered arrangement between inorganic and organic sheets. 210,211 Inside this family, it is remarkable the ECS-14 material that contained a system of Although highly elegant and interesting, these novel layered hybrid materials were only successfully prepared with rigid and non-active arylic fragments, this strongly restricting their catalytic possibilities. Moreover, the elevated concentration of intracrystalline sodium cations, the practically exclusive presence of framework aluminum in the inner and inaccessible part of the inorganic layers and the excessively reduced size of the microporous channels, delimited by 6MR, along the inorganic layers, make necessary further investigations to overcome these important limitations.…”

Section: -Direct Synthesis Of Layered Hybrid Organic-inorganic Matermentioning

confidence: 69%

Layered zeolitic materials: an approach to designing versatile functional solids

2014

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Section: -Direct Synthesis Of Layered Hybrid Organic-inorganic Matermentioning

confidence: 69%

Layered zeolitic materials: an approach to designing versatile functional solids

2014

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“…50 Probably, these types of thin sheets are structured by effective covalent connection between silicon and aluminum tetrahedron, forming intralayer six member rings (6MR) which are along the plane bc of the inorganic layers, such as it was indicated for ECS-type materials. 40 Instracrystalline sodium cations should be located into these intralayer 6MRs, compensating the positive electric charge due to the presence of aluminum framework. Nevertheless, the location of sodium cations at interlayer space, framework defects and end-edges or corners could also be possible (Figure 3).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

One-pot synthesis of hierarchical porous layered hybrid materials based on aluminosilicate sheets and organic functional pillars

et al. 2014

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Layered hybrid materials (LHMs) based on ordered silicoaluminate sheets linked with organic fragments, perpendicularly located and stabilized in the interlayer space, were synthesized by one-pot direct hydrothermal process, in absence of structural directing agents (SDAs), and using bridged silsesquioxanes as organosilicon precursors. By following the synthesis described here, the preliminary preparation of inorganic layered precursors, post-synthesis swelling and/or pillaring treatments can be avoided. The physico-chemical and structural characteristics of the materials were studied by chemical and thermogravimetrical analyses, X-ray diffraction, TEM microscopy, spectroscopic techniques (NMR and FTIR) and textural measurements. The complete exchange of intracrystalline sodium cations by protons, without substantial structural alteration of hybrid materials, facilitated the generation of hybrid materials, which contained acid and base sites located in the inorganic (silicoaluminate layers) and in the organic interlayer linkers, respectively, being the resultant acid-base materials active and selective catalysts.

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“…that occupy substitutional sites in well-defined, three-dimensionally extended, open-structure silicates of the zeolite type. The well-known and most widely used are the 4-or 5-coordinated Ti(IV) ions accommodated within the crystalline phase of silica, silicalite (9)(10)(11)(12)(13)(14).…”

mentioning

confidence: 99%

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

Yoo

Thomas

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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Understanding the dynamical nature of the catalytic active site embedded in complex systems at the atomic level is critical to developing efficient photocatalytic materials. Here, we report, using 4D ultrafast electron microscopy, the spatiotemporal behaviors of titanium and oxygen in a titanosilicate catalytic material. The observed changes in Bragg diffraction intensity with time at the specific lattice planes, and with a tilted geometry, provide the relaxation pathway: the Ti 4+ =O 2− double bond transformation to a Ti 3+ −O 1− single bond via the individual atomic displacements of the titanium and the apical oxygen. The dilation of the double bond is up to 0.8 Å and occurs on the femtosecond time scale. These findings suggest the direct catalytic involvement of the Ti 3+ −O 1− local structure, the significance of nonthermal processes at the reactive site, and the efficient photo-induced electron transfer that plays a pivotal role in many photocatalytic reactions.ultrafast electron microscopy | single-site photocatalysis | titanium based photocatalyst | ulatrafast phenomena | time-resolved microscopy S ingle-site catalysts of both the thermally and photoactivated kind now occupy a prominent place in industrial-and laboratory-scale heterogeneous catalysis (1-8). Among the most versatile of these are the ones consisting of coordinatively unsaturated transition metal ions (Ti, Cr, Fe, Mn. . .) that occupy substitutional sites in well-defined, three-dimensionally extended, open-structure silicates of the zeolite type. The well-known and most widely used are the 4-or 5-coordinated Ti(IV) ions accommodated within the crystalline phase of silica, silicalite (9-14).Titanosilicates, especially, are used extensively both industrially and in the laboratory for a wide range of chemo-, regio-, and shapeselective oxidations of organic compounds (15-18). These single-site heterogeneous photocatalysts are quite distinct from those typified by TiO 2 , SrTiO 3 , and other titaniferous photocatalysts where the Ti(IV) ions are in 6-coordination; and where, in interpreting the processes involved in harnessing solar radiation, electronic band structure considerations hold sway in preference to the localized states (see, e.g., refs. 19, 20). It has been demonstrated (16-18, 21, 22) that single-site, coordinatively unsaturated Ti(IV)-centered photocatalysts are especially useful in the aerial oxidation of environmental pollutants in the photodegradation of NO (to N 2 and O 2 ), of H 2 O (to H 2 and O 2 ), and in the photocatalytic reduction of CO 2 to yield methanol. There is an exigent need to explore the precise nature of the electronic, temporal, and spatial changes accompanying the initial act of photoabsorption that sets in train the ensuing elementary chemical processes that are of vital environmental significance in, for example, the utilization of anthropogenic CO 2 as a chemical feedstock (23).Here, we report the use of 4D ultrafast electron microscopy (UEM) (24-26) to trace the spatiotemporal behavior of the Ti(IV) and O ...

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ECS‐3: A Crystalline Hybrid Organic–Inorganic Aluminosilicate with Open Porosity

Cited by 65 publications

References 22 publications

Layered zeolitic materials: an approach to designing versatile functional solids

Layered zeolitic materials: an approach to designing versatile functional solids

One-pot synthesis of hierarchical porous layered hybrid materials based on aluminosilicate sheets and organic functional pillars

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

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