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1.
Chemistry ; 2020 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-32427389

RESUMO

In this work, an MWW-type zeolite with pillars containing silicon and niobium oxide was synthesized to obtain a hierarchical zeolite. The effect of niobium insertion in the pillaring process was determined by combining a controllable acidity and accessibility in the final material. All pillared materials had niobium occupying framework positions in pillars and extra-framework positions. The pillared material, Pil-Nb-4.5 with 4.5 wt % niobium, did not compromise the mesoporosity formed by pillaring, while the increase of niobium in the structure gradually decreased the mesoporosity and ordering of lamellar stacking. The morphology of the pillared zeolites and the niobium content were found to directly affect the catalytic activity. Specifically, we report on the activity of the MWW-type zeolites with niobium catalyzing the gas-phase oxidation of volatile organic compounds (VOCs), which is an important reaction for clean environmental. All produced MWW-type zeolites with niobium were catalytically active, even at low temperatures and low niobium loading, and provided excellent conversion efficiencies.

2.
Materials (Basel) ; 12(12)2019 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-31213003

RESUMO

Different metalorganic lamellar hybrid materials based on associated nanoribbons were synthesized by the use of alkyl-benzyl monocarboxylate spacers, containing alkyl tails with variable lengths, which acted like structural growing inhibitors. These molecular agents were perpendicularly located and coordinated to aluminium nodes in the interlayer space, controlling the separation between individual structure sub-units. The hybrid materials were studied by X-ray diffraction (XRD), chemical and thermogravimetrical analysis (TGA), nuclear magnetic resonance (NMR) and infrared spectroscopy (IR), and field emission scanning electron microscopy (FESEM)/transmission electron microscopy (TEM), showing their physicochemical properties. The specific capacity of the metalorganic materials to be exfoliated through post-synthesis treatments, using several solvents due to the presence of 1D structure sub-units and a marked hydrophobic nature, was also evidenced.

3.
Chem Sci ; 10(7): 2053-2066, 2019 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-30842863

RESUMO

Novel MOF-type materials with different morphologies based on assembled 1D organic-inorganic sub-domains were prepared using specific monodentate benzylcarboxylate spacers with functional substituents in the para-position as structure modulating agents. The combination of electron-withdrawing or electron-donating functions in the organic spacers with suitable solvothermal synthesis conditions allowed modulating the structuration level (2D or 3D), vacancies, physico-chemical properties and Lewis acidity strength of the metal-organic structures. Furthermore, bimetallic (Al/Fe) MOF-type materials were synthesized by a one-pot direct process without modification of the structural framework. The activity of these hybrid materials as Lewis acid catalysts was evaluated to prepare cyanohydrins as precursors for the synthesis of biologically active compounds, and for aerobic oxidation of thiols to disulfides. The catalytic results showed that the derived MOFs exhibited modulatable Lewis acid capacities which are a function of the morphology, functionality of monodentate substituents present in the networks and a cooperative effect between metallic nodes of different nature.

4.
ACS Appl Mater Interfaces ; 10(38): 32885-32894, 2018 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-30160470

RESUMO

The distribution and interactions of organic molecules adsorbed on the surface of materials play important roles in many catalytic and photonic processes. Here, we show that the length and chemical structure of the linker in new Al-ITQ metal-organic frameworks (MOFs) are fundamental for the dynamics of the dye Nile Red (NR) adsorbed on its surface. For the studied composites using Al-ITQ-4-ethylbenzoic acid (EB), Al-ITQ-4-aminobenzoic acid (AB), and Al-ITQ-EB exposed to the aniline (AN) or N, N-dimethylaniline (DMA) atmospheres, we observed a very fast (∼1.2 ps) intramolecular charge-transfer reaction in adsorbed NR molecules. For NR@Al-ITQ-EB, where the linker has a shorter aliphatic chain (two carbons), the dye molecules present a homoenergy-transfer (ET) process, which is faster (∼90 ps) than in the previously reported NR@Al-ITQ-4-heptylbenzoic acid composite with longer aliphatic chain (seven carbons, ∼220 ps). The more polar environment created by the Al-oxide nodes in Al-ITQ-EB surface around the NR populations strongly favors the ET event. When the linker structure contains phenyl amine moieties, the resulting NR@Al-ITQ-AB composites show different and rich photodynamics, in which a fast electron transfer reaction from the MOF aniline moiety to the adsorbed NR occurs in ∼17 ps, inhibiting the ET process between the dye molecules near the MOF surface. This process also was confirmed in Al-ITQ-EB MOF exposed to AN and DMA gas atmospheres, as well as NR in pure aniline. The obtained results demonstrate how modifications in the length and structure of the organic linker in this MOF change the interface interactions and outcome of the photoinduced processes in the composites. Our findings on dye-MOF interface photobehavior are relevant to the design of new materials in which the interface plays a key role in their performance in the fields of catalysis and photonics.

5.
ACS Omega ; 3(6): 6217-6223, 2018 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-29978144

RESUMO

The chemistry between layered MWW zeolite and carbon black pearls (BP 2000) as an inexpensive hard template was investigated to develop a rational one-pot synthesis of MCM-22 microspheres. The characterization results showed that the insertion of BP 2000 in the gel synthesis did not substantially compromise the crystallinity and microporosity, and the microscopic analyses showed that BP 2000 played a key role in controlling the final morphology of the MCM-22 zeolite, creating beautiful dandelion-like microspherical particles. The morphology obtained is due to the tortuous shape of the hard template, the particular MWW particle crystals, the interaction with the external surface of the MWW zeolitic precursor, and the synthesis conditions. The stacking of MWW crystals with edge-to-face orientations generates meso-/macrovoids, allowing access to the interiors of the microspheres. The microspheres were homogeneous with sizes ranging from 6 to 8 µm with an increase of the external surface and a macroporous size distribution centered at 200 nm, which is two times that of the traditional MCM-22 zeolite.

6.
ACS Appl Mater Interfaces ; 10(23): 20159-20169, 2018 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-29779377

RESUMO

In this work, we unravel how the two-dimensional Al-ITQ-4-heptylbenzoic acid (HB) metal-organic framework (MOF) changes the interactions of Nile red (NR) adsorbed on its surface. Time-resolved emission experiments indicate the occurrence of energy transfer between adsorbed NR molecules, in abnormally long time constant of 2-2.5 ns, which gets shorter (∼0.25 ns) when the concentration of the surface-adsorbed NR increases. We identify the emission from local excited state of aggregates and charge transfer and energy transfer between adsorbed molecules. Femtosecond emission studies reveal an ultrafast process (∼425 fs) in the NR@Al-ITQ-HB composites, assigned to an intramolecular charge transfer in NR molecules. A comparison of the observed photobehavior with that of NR/SiO2 and NR/Al2O3 composites suggests that the occurrence of energy transfer in the NR@MOF complexes is a result of specific and nonspecific interactions, reflecting the different surface properties of Al-ITQ-HB that are of relevance to the reported high catalytic activity. Our results provide new knowledge for further researches on other composites with the aim to improve understanding of photocatalytic and photonic processes within MOFs.

7.
Dalton Trans ; 47(15): 5492-5502, 2018 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-29611585

RESUMO

Novel aluminium MOF-type materials structured by 1D subdomains, such as organic-inorganic nanoribbons, were synthesized by modifying the conditions of solvothermal synthesis and the nature of the solvents in the presence of aryl monocarboxylate linkers with long alkyl chains, which acted as growth-modulating agents. Specifically, three different families of materials were prepared with various morphological characteristics: (i) isoreticular MIL-53(Al)-type materials, (ii) mesoscopic metalorganic structures and (iii) lamellar aluminium MOFs. The length of the alkyl chain in the aryl linker and the hydrophobic/hydrophilic nature of the solvothermal synthesis media determined the structuration level that was achieved. The derived Al-MOFs are active and stable catalysts for the synthesis of fine chemicals. This was illustrated by the efficient synthesis of 2,3-dihydro-2,2,4-trimethyl-1H-1,5-benzodiazepine.

8.
Catal Sci Technol ; 8(22): 5835-5847, 2018 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-30713656

RESUMO

A new chiral mesoporous hybrid material was synthesized based on pyrrolidine units included in a siliceous framework, HybPyr, and integrated into the organic-inorganic structure, from a specific bis-silylated precursor. A fluoride sol-gel methodology under soft synthesis conditions and in the absence of sophisticated structural directing agents allowed the generation of a mesoporous architecture with a homogeneous distribution of active chiral moieties along the network. The hybrid material was studied by means of different characterization techniques (TGA, NMR and IR spectroscopy, chemical and elemental analyses, TEM, and textural measurements), verifying the stability and integrity of the asymmetric active sites in the solid. The hybrid material, HybPyr, is an excellent asymmetric heterogeneous and recyclable catalyst for enantioselective Michael addition of linear aldehydes to ß-nitrostyrene derivatives with high stereocontrol of the reaction products.

9.
ACS Omega ; 3(2): 1600-1608, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-31458482

RESUMO

In this work, we unravel the photodynamics of Nile Red (NR) interacting with Al-ITQ-HB nanostructure, a new layer-type metal-organic framework (MOF) with potential catalytic and photonic applications. Steady-state spectroscopy reveals the presence of NR monomers and aggregates when interacting with the MOF structure. Time-resolved experiments provide emission lifetimes of the interacting monomers, H- and J-type aggregates. We observed contributions from two monomer populations having different environments. One monomer species emits from the local-excited state and another from a photoproduced charge-separated state resulting from an ultrafast intramolecular charge transfer (ICT). Femtosecond fluorescence experiments reveal that the ICT process occurs in ∼1 ps. Fluorescence microscopy on single crystals and agglomerates of the composites shows a homogenous distribution of the dye lifetimes within the material. This study shows that the photobehavior of NR in Al-ITQ-HB MOF is dictated by its location within the material. The reported findings using a well-known polarity probe and a new two-dimensional MOF provide information on the microenvironment of this material, which may help for designing smart MOFs with potential applications in photonics and nanocatalysis.

10.
Chemistry ; 24(16): 3944-3958, 2018 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-29194811

RESUMO

The design of new hybrid materials with tailored properties at the nano-, meso-, and macro-scale, with the use of structural functional nanobuilding units, is carried out to obtain specific multi-functional materials. Organization into controlled 1D, 2D, and 3D architectures with selected functionalities is key for developing advanced catalysts, but this is hardly accomplished using conventional synthesis procedures. The use of pre-formed nanostructures, derived either from known materials or made with specific innovative synthetic methodologies, has enormous potential in the generation of multi-site catalytic materials for one-pot processes. The present concept article introduces a new archetype wherein self-assembled nanostructured builder units are the base for the design of multifunctional catalysts, which combine catalytic efficiency with fast reactant and product diffusion. The article addresses a new generation of versatile hybrid organic-inorganic multi-site catalytic materials for their use in the production of (chiral) high-added-value products within the scope of chemicals and fine chemicals production. The use of those multi-reactive solids for more nanotechnological applications, such as sensors, due to the inclusion of electron donor-acceptor structural arrays is also considered, together with the adsorption-desorption capacities due to the combination of hydrophobic and hydrophilic sub-domains. The innovative structured hybrid materials for multipurpose processes here considered, can allow the development of multi-stage one-pot reactions with industrial applications, using the materials as one nanoreactor systems, favoring more sustainable production pathways with economic, environmental and energetic advantages.

11.
13.
Nat Mater ; 16(1): 132-138, 2017 01.
Artigo em Inglês | MEDLINE | ID: mdl-27669051

RESUMO

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

14.
Angew Chem Int Ed Engl ; 55(37): 11026-30, 2016 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-27444798

RESUMO

A new family of stable layered organic-inorganic materials has been prepared, in one-step solvothermal process. They are based on an ordered nickel cluster-type nanoribbons separated from each other by specific alkyl (heptyl- or dodecyl-) arylic mono-carboxylate moieties acting as molecular spacers, perpendicular to the 1D inorganic chains. These organic spacers contain hydrocarbon tails with different length which control the separation level between inorganic 1D sub-units, inhibiting the 3D growth of conventional DUT-8-type metal-organic frameworks (MOFs). The lamellar nature of the materials formed was studied and confirmed by different characterization techniques, showing the structural location of individual organic and inorganic building units. They have been successfully used as a long-lasting biodegradable and water-proof materials for controlled release of chemicals, such as pheromones for sustainable treatment of insect plagues.


Assuntos
Liberação Controlada de Fármacos , Estruturas Metalorgânicas/química , Nanoestruturas/química , Níquel/química , Feromônios/análise , Feromônios/química , Cinética , Estruturas Metalorgânicas/síntese química , Tamanho da Partícula , Difração de Raios X
15.
Nat Commun ; 7: 10835, 2016 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-26912294

RESUMO

Coordination polymers and metal-organic frameworks are appealing as synthetic hosts for mediating chemical reactions. Here we report the preparation of a mesoscopic metal-organic structure based on single-layer assembly of aluminium chains and organic alkylaryl spacers. The material markedly accelerates condensation reactions in water in the absence of acid or base catalyst, as well as organocatalytic Michael-type reactions that also show superior enantioselectivity when comparing with the host-free transformation. The mesoscopic phase of the solid allows for easy diffusion of products and the catalytic solid is recycled and reused. Saturation transfer difference and two-dimensional (1)H nuclear Overhauser effect NOESY NMR spectroscopy show that non-covalent interactions are operative in these host-guest systems that account for substrate activation. The mesoscopic character of the host, its hydrophobicity and chemical stability in water, launch this material as a highly attractive supramolecular catalyst to facilitate (asymmetric) transformations under more environmentally friendly conditions.

16.
Chem Commun (Camb) ; 52(7): 1401-4, 2016 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-26621199

RESUMO

A homochiral vanadium-salen based MOF with the pcu topology is constructed via in situ synthesis under solvothermal conditions. The synthesized MOF exhibits BET surface areas of 574 m(2) g(-1), showing the highest H2 adsorption capacity (1.05 wt% at 77 K, 1 bar) and the highest CO2 uptake (51 cm(3) g(-1) at 273 K, 1 bar) for currently known salen-based MOFs. This framework shows excellent performance as an asymmetric catalyst in solvent-free cyanosilylation.

17.
Dalton Trans ; 43(27): 10292-316, 2014 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-24457617

RESUMO

Relevant layered zeolites have been considered in this perspective article from the point of view of the synthesis methodologies, materials characterization and catalytic implications, considering the unique physico-chemical characteristics of lamellar materials. The potential of layered zeolitic precursors to generate novel lamellar accessible zeolites through swelling, intercalation, pillarization, delamination and/or exfoliation treatments is studied, showing the chemical, functional and structural versatility exhibited by layered zeolites. Recent approaches based on the assembly of zeolitic nanosheets which act as inorganic structural units through the use of dual structural directing agents, the selective modification of germanosilicates and the direct generation of lamellar hybrid organic-inorganic aluminosilicates are also considered to obtain layered solids with well-defined functionalities. The catalytic applications of the layered zeolites are also highlighted, pointing out the high accessibility and reactivity of active sites present in the lamellar framework.

18.
Chem Soc Rev ; 42(9): 4083-97, 2013 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-23288312

RESUMO

Organic-inorganic hybrid materials with different levels of structuration and porous hierarchy and one or several types of active sites in the framework can catalyze multistep chemical processes in a one-pot reactor system following a cascade of reaction events. It will show how the different active sites can act in a synergistic or in a consecutive way following a similar functionality model to biological multisite catalysts. Research on this subject for heterogeneous catalysts is still in the beginning stage and very interesting results can be expected if we are able to successfully combine the properties of organic and inorganic catalysts.


Assuntos
Compostos de Organossilício/química , Catálise , Modelos Moleculares , Estrutura Molecular , Tamanho da Partícula , Porosidade , Propriedades de Superfície
19.
Dalton Trans ; 41(36): 10913-8, 2012 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-22878532

RESUMO

This manuscript describes the synthesis and structural study of new second generation Hoveyda-Grubbs catalysts: 1,3-dimesityl-acenaphthylenyl-4,5-imidazolin-2-ylidene (BIAN-NHC) ruthenium isopropoxybenzylidene dichloride and 1,3-bis(2,6-dimethylphenyl)-2,3-dihydro-1H-imidazole Cl(2)Ru(=CH-o-O-i-PrC(6)H(4)) . The electrochemical and catalytic behavior of these new complexes was compared with the conventional NHC carbene Hoveyda II IMes-type complexes and for ring closing metathesis reactions.

20.
Chemistry ; 18(28): 8659-72, 2012 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-22678926

RESUMO

A family of hybrid mesoporous materials with high temperature stability was obtained by the suitable covalent combination of two types of siloxane precursors. Specifically, cubic T(8) polyhedral oligomeric (POSS) and aryl bridged silsesquioxane monomers (1,4-bis(triethoxysilyl)benzene, BTEB) play the role of nanobuilders. An optimal molar ratio of the two precursors (5-25 mol% of total silicon content from the BTEB disilane) generated a homogenous, highly accessible, and well-defined mesoporous material with hexagonal symmetry and narrow pore-size distribution. Physicochemical, textural, and spectroscopic analysis corroborated the effective integration and preservation of the two different nanoprecursors, thereby confirming the framework of the mesoporous hybrid materials. A post-synthesis amination treatment allowed the effective incorporation of amino groups onto the aryl linkers, thereby obtaining a stable and recyclable basic catalyst for use in C-C bond-formation processes.

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