Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 89
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Nat Mater ; 2020 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-32778813

RESUMO

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.

2.
Chemistry ; 2020 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-32488940

RESUMO

The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine-based COFs (termed P-COFs) with well-defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P-COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine-based COF family, but also demonstrates their application in immobilizing homogeneous metal-based (e.g., Rh-phosphine) catalysts for application in heterogeneous catalysis.

3.
Artigo em Inglês | MEDLINE | ID: mdl-32521078

RESUMO

Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction conditions and fast catalyst deactivation. To improve this process, understanding the mechanism of the initial C-C bond formation is essential. However, consensus about the actual reaction mechanism is still to be achieved. In this work, using advanced magic-angle spinning (MAS) solid-state NMR spectroscopy, we study in detail the early stages of the reaction over a well-dispersed Mo/H-ZSM-5 catalyst. Simultaneous detection of acetylene (i.e., presumably the direct C-C bond-forming product from methane), methylidene, allenes, acetal, and surface-formate species, along with the typical olefinic/aromatic species, allow us to conclude the existence of at least two independent C-H activation pathways. Moreover, this study emphasizes the significance of mobility-dependent host-guest chemistry between an inorganic zeolite and its trapped organic species during heterogeneous catalysis.

4.
Chem Rev ; 2020 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-32223183

RESUMO

More than 95% (in volume) of all of today's chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic research field. In this regard, metal-organic frameworks (MOFs) offer great opportunities for the rational design of new catalytic solids, as highlighted by the unprecedented number of publications appearing over the past decade. In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed. MOFs with intrinsic thermocatalytic activity, as hosts for the incorporation of metal nanoparticles, as precursors for the manufacture of composite catalysts and those active in photo- and electrocatalytic processes are critically reviewed. The review is wrapped up with our personal view on future research directions.

5.
ChemSusChem ; 2020 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-32239790

RESUMO

Since 1887, red mud has been an unavoidable waste derived from the production of alumina in the Bayer process. Because of its high alkalinity and metal loading, red mud disposal and storage constitute a significant environmental risk. With worldwide storage capacity reaching its limits and no alternatives to the Bayer Process, the development of methods for the valorization of red mud is a must. In this study, red mud is converted into an efficient catalyst for the valorization of CO2 . By simple potassium promotion, 45 % conversion of CO2 with a light olefin (C2 -C4 ) selectivity of 36 % is achieved at 375 °C, 30 bar, and 9600 mL g-1 h-1 , matching the performance of some of the best catalysts reported to date.

6.
Artigo em Inglês | MEDLINE | ID: mdl-32315516

RESUMO

The one-step synthesis and characterization of a new and robust titanium-based metal-organic framework, ACM-1, is reported. In this structure, which is based on infinite Ti-O chains and 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge-separation lifetimes. The suitable energies for band gap and conduction band minimum (CBM) offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.

7.
J Am Chem Soc ; 141(47): 18814-18824, 2019 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-31682134

RESUMO

Producing aromatics directly from the smallest hydrocarbon building block, methane, is attractive because it could help satisfy increasing demand for aromatics while filling the gap created by decreased production from naphtha crackers. The system that catalyzes the direct methane dehydroaromatization (MDA) best so far is Mo supported on zeolite. Mo has shown to outperform other transition metals (TMs). Here we attempt to explain the superiority of Mo by directly comparing Fe and Mo supported on HZSM-5 zeolite. To determine the most important parameters responsible for the superior performance of Mo, detailed characterization using X-ray absorption spectroscopy (XAS) techniques combined with catalytic testing and theoretical calculations are performed. The higher abundance of mono- and dimeric sites for the Mo system, their ease of carburization in methane, as well as intrinsically lower activation energy barriers of breaking the methane C-H bond over Mo explain the better catalytic performance. In addition, a pretreatment in CO is presented to more easily carburize Fe and thereby improve its catalytic performance.

8.
ACS Appl Mater Interfaces ; 11(47): 44133-44143, 2019 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-31612697

RESUMO

Shaping and optimal compositional formulation are major challenges in the successful industrial application of heterogeneous catalysts. The choice of components during formulation plays a vital role in endowing the final catalyst's mechanical strength, durability, and lifetime and may even affect activity and selectivity. Herein, we evaluate the application of spray drying to manufacture spherical ZSM-5-based catalysts and their applicability in the methanol-to-olefins process. Several critical parameters of the spray drying process and various aspects related to catalyst formulation (binder, zeolite, and clay) are investigated. Chemical composition and structure of the clay matrix substantially influence the catalytic performance.

9.
J Am Chem Soc ; 141(37): 14823-14842, 2019 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-31464134

RESUMO

A systematic molecular level and spectroscopic investigation is presented to show the cooperative role of Brønsted acid and Lewis acid sites in zeolites for the conversion of methanol. Extra-framework alkaline-earth metal containing species and aluminum species decrease the number of Brønsted acid sites, as protonated metal clusters are formed. A combined experimental and theoretical effort shows that postsynthetically modified ZSM-5 zeolites, by incorporation of extra-framework alkaline-earth metals or by demetalation with dealuminating agents, contain both mononuclear [MOH]+ and double protonated binuclear metal clusters [M(µ-OH)2M]2+ (M = Mg, Ca, Sr, Ba, and HOAl). The metal in the extra-framework clusters has a Lewis acid character, which is confirmed experimentally and theoretically by IR spectra of adsorbed pyridine. The strength of the Lewis acid sites (Mg > Ca > Sr > Ba) was characterized by a blue shift of characteristic IR peaks, thus offering a tool to sample Lewis acidity experimentally. The incorporation of extra-framework Lewis acid sites has a substantial influence on the reactivity of propene and benzene methylations. Alkaline-earth Lewis acid sites yield increased benzene methylation barriers and destabilization of typical aromatic intermediates, whereas propene methylation routes are less affected. The effect on the catalytic function is especially induced by the double protonated binuclear species. Overall, the extra-framework metal clusters have a dual effect on the catalytic function. By reducing the number of Brønsted acid sites and suppressing typical catalytic reactions in which aromatics are involved, an optimal propene selectivity and increased lifetime for methanol conversion over zeolites is obtained. The combined experimental and theoretical approach gives a unique insight into the nature of the supramolecular zeolite catalyst for methanol conversion which can be meticulously tuned by subtle interplay of Brønsted and Lewis acid sites.

10.
Chem Asian J ; 14(20): 3452-3461, 2019 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-31241861

RESUMO

The electrochemical reduction of CO2 holds great promise for lowering the concentration of CO2 in the Earth's atmosphere. However, several challenges have hindered the commercialization of this technology, including energy efficiency, the solubility of CO2 in the aqueous phase, and electrode stability. In this Minireview, we highlight and summarize the main advantages and limitations that metal-organic frameworks (MOFs) may offer in this field of research, either when used directly as electrocatalysts or when used as catalyst precursors.

11.
Nat Mater ; 17(12): 1057-1058, 2018 12.
Artigo em Inglês | MEDLINE | ID: mdl-30397309
12.
Angew Chem Int Ed Engl ; 57(46): 14982-14985, 2018 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-30328242

RESUMO

Ketenes in the limelight: The influential role of ketenes has never been adequately acknowledged in zeolite chemistry and catalysis; unlike other first generation highly reactive intermediates, such as carbocations, carbanions, radicals, and carbenes. In fact, the role that ketenes play during catalysis-whether beneficial or detrimental-is a contentious subject that requires further consideration.

13.
Chem Sci ; 9(33): 6765-6773, 2018 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-30310609

RESUMO

Reaction paths underlying the catalytic oxidation of methane with H2O2 over an Fe containing MIL-53(Al) metal-organic framework were studied by periodic DFT calculations. Not only the activation of methane, but the full reaction network was considered, which includes the formation of the active site, the overoxidation of methane to CO2 and the decomposition of H2O2 to H2O and O2. Calculations indicate that the activation barrier for the initial activation of the Fe sites upon reaction with H2O2 is comparable to that of the subsequent C-H activation and also of the reaction steps involved in the undesirable overoxidation processes. The pronounced selectivity of the oxidation reaction over MIL-53(Al,Fe) towards the target mono-oxygenated CH3OH and CH3OOH products is attributed to the limited coordination freedom of the Fe species encapsulated in the extended octahedral [AlO6] structure-forming chains, which effectively prevents the direct overoxidation paths prior to product desorption from the active sites. Importantly, our computational analysis reveals that the active sites for the desired methane oxidation are able to much more efficiently promote the direct catalytic H2O2 decomposition reaction, rendering thus the current combination of the active site and the reactants undesirable for the prospective methane valorization process.

14.
ACS Appl Mater Interfaces ; 10(39): 33574-33580, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30200764

RESUMO

We demonstrate that b-oriented MFI (Mobil Five) zeolite membranes can be manufactured by in situ crystallization using an intermediate amorphous SiO2 layer. The improved in-plane growth by using a zeolite growth modifier leads to fusion of independent crystals and eliminates boundary gaps, giving good selectivity in the separation of CO2/Xe mixtures. The fast diffusion of CO2 dominates the overall membrane selectivity toward the CO2/Xe mixture. Because of the straight and short [010] channels, the obtained CO2 permeation fluxes are several orders of magnitude higher than those of carbon molecular sieving membranes and polymeric membranes, opening opportunities for Xe recovery from waste anesthetic gas.

15.
ACS Catal ; 8(9): 7961-7972, 2018 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-30221027

RESUMO

Periodic density functional theory (DFT) calculations were carried out to investigate the mechanism of methane oxidation with H2O2 over the defined Fe sites in Fe/ZSM-5 zeolite. The initial Fe site is modeled as a [(H2O)2-Fe(III)-(µO)2-Fe(III)-(H2O)2]2+ extraframework cluster deposited in the zeolite pore and charge-compensated by two anionic lattice sites. The activation of this cluster with H2O2 gives rise to the formation of a variety of Fe(III)-oxo and Fe(IV)-oxo complexes potentially reactive toward methane dissociation. These sites are all able to promote the first C-H bond cleavage in methane by following three possible reaction mechanisms: namely, (a) heterolytic and (b) homolytic methane dissociation as well as (c) Fenton-type reaction involving free OH radicals as the catalytic species. The C-H activation step is followed by formation of MeOH and MeOOH and regeneration of the active site. The Fenton-type path is found to proceed with the lowest activation barrier. Although the barriers for the alternative heterolytic and homolytic pathways are found to be somewhat higher, they are still quite favorable and are expected to be feasible under reaction conditions, resulting ultimately in MeOH and MeOOH products. H2O2 oxidant competes with CH4 substrate for the same sites. Since the oxidation of H2O2 to O2 and two [H+] is energetically more favorable than the C-H oxofunctionalization, the overall efficiency of the latter target process remains low.

16.
Sci Adv ; 4(9): eaau1698, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-30255154

RESUMO

The development of new membranes with high H2 separation performance under industrially relevant conditions (high temperatures and pressures) is of primary importance. For instance, these membranes may facilitate the implementation of energy-efficient precombustion CO2 capture or reduce energy intensity in other industrial processes such as ammonia synthesis. We report a facile synthetic protocol based on interfacial polymerization for the fabrication of supported benzimidazole-linked polymer membranes that display an unprecedented H2/CO2 selectivity (up to 40) at 423 K together with high-pressure resistance and long-term stability (>800 hours in the presence of water vapor).

17.
Nat Chem ; 10(8): 897, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29991809

RESUMO

In the version of this Article originally published, on the right side of Fig. 4b, the 'Aromatic cycle' label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.

18.
Chem Sci ; 9(21): 4801-4807, 2018 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-29910931

RESUMO

The mechanism of methane activation on Mo/HZSM-5 is not yet fully understood, despite the great interest in methane dehydroaromatization (MDA) to replace aromatics production in oil refineries. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide (CO), the MDA active site formation was isolated from coke formation. With this a clear 13C NMR signal solely from the active site and not obscured by coke was obtained, and it revealed two types of likely molecular Mo (oxy-)carbidic species in addition to the ß-Mo2C nanoparticles often mentioned in the literature. Furthermore, separating the active site formation from coking by pre-carburization helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (13CH4). Carbon originating from the pre-formed carbide was incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic behavior of the (oxy-)carbidic active sites.

19.
ACS Appl Mater Interfaces ; 10(25): 21381-21389, 2018 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-29869872

RESUMO

The preparation and the performance of mixed matrix membranes based on metal-organic polyhedra (MOPs) are reported. MOP fillers can be dispersed as discrete molecular units (average 9 nm in diameter) when low filler cargos are used. In spite of the low doping amount (1.6 wt %), a large performance enhancement in permeability, aging resistance, and selectivity can be achieved. We rationalize this effect on the basis of the large surface to volume ratio of the filler, which leads to excellent dispersion at low concentrations and thus alters polymer packing. Although membranes based only on the polymer component age quickly with time, the performance of the resulting MOP-containing membranes meets the commercial target for postcombustion CO2 capture for more than 100 days.

20.
Nat Chem ; 10(8): 804-812, 2018 08.
Artigo em Inglês | MEDLINE | ID: mdl-29941905

RESUMO

The combination of well-defined acid sites, shape-selective properties and outstanding stability places zeolites among the most practically relevant heterogeneous catalysts. The development of structure-performance descriptors for processes that they catalyse has been a matter of intense debate, both in industry and academia, and the direct conversion of methanol to olefins is a prototypical system in which various catalytic functions contribute to the overall performance. Propylene selectivity and resistance to coking are the two most important parameters in developing new methanol-to-olefin catalysts. Here, we present a systematic investigation on the effect of acidity on the performance of the zeolite 'ZSM-5' for the production of propylene. Our results demonstrate that the isolation of Brønsted acid sites is key to the selective formation of propylene. Also, the introduction of Lewis acid sites prevents the formation of coke, hence drastically increasing catalyst lifetime.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA