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1.
Nat Commun ; 11(1): 2409, 2020 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-32415106

RESUMO

In spite of numerous works in the field of chemical valorization of carbon dioxide into methanol, the nature of high activity of Cu/ZnO catalysts, including the reaction mechanism and the structure of the catalyst active site, remains the subject of intensive debate. By using high-pressure operando techniques: steady-state isotope transient kinetic analysis coupled with infrared spectroscopy, together with time-resolved X-ray absorption spectroscopy and X-ray powder diffraction, and supported by electron microscopy and theoretical modeling, we present direct evidence that zinc formate is the principal observable reactive intermediate, which in the presence of hydrogen converts into methanol. Our results indicate that the copper-zinc alloy undergoes oxidation under reaction conditions into zinc formate, zinc oxide and metallic copper. The intimate contact between zinc and copper phases facilitates zinc formate formation and its hydrogenation by hydrogen to methanol.

2.
Inorg Chem ; 2020 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-32407085

RESUMO

We recently discovered that aging a solution of zirconium(IV) tetrachloride (ZrCl4) in N,N-dimethylformamide (DMF) in the presence of water, followed by the addition of a terephthalic acid linker, reduces the crystallite size of the metal-organic framework UiO-66 (Chem. Commun. 2016, 52, 6411-6414). In an effort to shed light on the nature of the aging effect and on its relationship with the crystallite size of UiO-66, we report here the isolation and structural characterization of a microcrystalline zirconium-based compound of the formula [ZrCl(OH)2(DMF)2]Cl, which is formed during the aging process. The Zr(IV) ions are coordinated by hydroxide, DMF, and chloride to produce a one-dimensional polymer. Thanks to the presence of two -OH groups per zirconium atom, [ZrCl(OH)2(DMF)2]Cl is a suitable precursor for the synthesis of UiO-66 in dry DMF, affording a product having a smaller crystallite size than that obtained from a reaction mixture having the same chemical composition but using ZrCl4 as the Zr(IV) source. By starting from ZrCl4 and generating [ZrCl(OH)2(DMF)2]Cl in situ in solution through aging, we obtained smaller crystallites as the aging time increased, proving that [ZrCl(OH)2(DMF)2]Cl plays a role in the aging process. The possible role of [ZrCl(OH)2(DMF)2]Cl in the crystallization mechanism of UiO-66 is also discussed, with emphasis on its relationship with the amount of water in the reaction mixture.

3.
Chimia (Aarau) ; 74(4): 237-240, 2020 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-32331539

RESUMO

The selective partial oxidation of methane to methanol remains a great challenge in the field of catalysis. Cu-exchanged zeolites are promising materials, directly and selectively converting methane to methanol with high yield under cyclic conditions. However, the economic viability of these aluminosilicate materials for potential industrial applications remains a challenge. Exploring copper supported on non-microporous oxide supports and rationalising the structure/reactivity relationships extends the scope of material investigation and opens new possibilities. Recently, copper on alumina was demonstrated to be active and selective for the partial oxidation of methane. This work aims to explore the formation of well-defined Cu(II) oxo species on silica via surface organometallic chemistry and examines their reactivity for the selective transformation of methane to methanol. Isolated Cu(II) sites were generated via grafting of a tailored molecular precursor. Activation under oxidative conditions and subsequent removal of organic moieties from the grafted copper centres led to the formation of small copper (II) oxide clusters, which are active in the partial oxidation of methane under mild conditions, albeit significantly less efficient than the corresponding isolated Cu(II) sites on alumina.

4.
Nat Commun ; 11(1): 1118, 2020 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-32111846

RESUMO

The heterogenization of Wacker catalysts using chloride-free systems can potentially be a good alternative for the commercial homogeneous Wacker oxidation of ethylene, which utilizes excessive aqueous chloride solvents. However, the mechanism of the heterogeneous system has not been clarified, preventing the rational design of better catalysts. Here, we report a transient X-ray absorption spectroscopic (XAS) investigation of the heterogeneous Wacker oxidation over Pd-Cu/zeolite Y coupled with kinetic studies and chemometric analysis. Insight is obtained by operando quickXAS allowing the quantitative determination of rates and thereby revealing a rapid redox reaction involving copper. Our work demonstrates that copper is not only the site of oxygen activation, but is also involved in the formation of undesired carbon dioxide. Without detecting the presence of Cu(0) and Pd(I), our results suggest that two one-electron transfers to two Cu(II) ions to reoxidize Pd(0) is at work in this heterogeneous Wacker catalyst.

5.
Artigo em Inglês | MEDLINE | ID: mdl-32216306

RESUMO

In this study, the synergistic behavior of Ni species and bimodal mesoporous undoped SnO2 is investigated in oxygen evolution reactions (OERs) under alkaline conditions without any other modification of the compositional phases or using noble metals. An efficient and environmentally friendly hydrothermal method to prepare bimodal mesoporous undoped SnO2 with a very high surface area (>130 m2 g-1) and a general deposition-precipitation method for the synthesis of well-dispersed Ni species on undoped SnO2 are reported. The powders were characterized by adsorption-desorption isotherms, TG-DTA, XRD, SEM, TEM, Raman, TPR-H2, and XPS. The best NiSn composite generates, under certain experimental conditions, a very high TOF value of 1.14 s-1 and a mass activity higher than 370 A g-1, which are remarkable results considering the low amount of Ni deposited on the electrode (3.78 ng). Moreover, in 1 M NaOH electrolyte, this material produces more than 24 mA cm-2 at an overpotential value of approximately +0.33 V, with only 5 wt % Ni species. This performance stems from the dual role of undoped SnO2, on the one hand, as a support for active and well-dispersed Ni species and on the other hand as an active player through the oxygen vacancies generated upon Ni deposition.

6.
Chemistry ; 2020 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-32154949

RESUMO

Non-oxidative CH 4 coupling is promoted by silica with incorporated iron sites, but the role of these sites and their speciation under reaction conditions are poorly understood. Here, silica-supported iron(II) single sites, prepared via surface organometallic chemistry and stable at 1020 °C in vacuum, are shown to rapidly initiate CH 4 coupling at 1000 °C, leading to 15-22% hydrocarbons selectivity at 3-4% conversion. During this process, iron reduces and forms carburized iron(0) nanoparticles. This reactivity contrasts with what is observed for (iron-free) partially dehydroxylated silica, that readily converts methane, albeit with low hydrocarbon selectivity and after an induction period. This study supports that iron sites facilitate faster initiation of radical reactions and tame the surface reactivity.

7.
Phys Chem Chem Phys ; 22(13): 6826-6837, 2020 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-32186570

RESUMO

Copper(ii) containing materials are widely studied for a very diverse array of applications from biology, through catalysis, to many other materials chemistry based applications. We show that, for grafted copper compounds at the surface of silica, and for the study of the selective conversion of methane to methanol using copper ion-exchanged zeolites, the application of focused X-ray beams for spectroscopic investigations is subject to significant challenges. We demonstrate how unwanted effects due to the X-rays manifest, which can prevent the study of certain types of reactive systems, and/or lead to the derivation of results that are not at all representative of the behavior of the materials in question. With reference to identical studies conducted at a beamline that does not focus its X-rays, we then delineate how the total photon throughput and the brilliance of the applied X-rays affect the apparent behavior of copper in zeolites during the stepwise, high temperature and aerobic activation approach to the selective conversion of methane to methanol. We show that the use of increasingly brilliant X-ray sources for X-ray spectroscopy can bring with it significant caveats to obtaining valid and quantitative structure-reactivity relationships (QSARS) and kinetics for this class of material. Lastly, through a systematic study of these effects, we suggest ways to ensure that valuable allocations of X-ray beam time result in measurements that reflect the real nature of the chemistry under study and not that due to other, extraneous, factors.

8.
Chem Soc Rev ; 49(5): 1449-1486, 2020 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-32107517

RESUMO

In this critical review we examine the current state of our knowledge in respect of the nature of the active sites in copper containing zeolites for the selective conversion of methane to methanol. We consider the varied experimental evidence arising from the application of X-ray diffraction, and vibrational, electronic, and X-ray spectroscopies that exist, along with the results of theory. We aim to establish both what is known regarding these elusive materials and how they function, and also where gaps in our knowledge still exist, and offer suggestions and strategies as to how these might be closed such that the rational design of more effective and efficient materials of this type for the selective conversion of methane might proceed further.

9.
Chem Commun (Camb) ; 2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31909776

RESUMO

Exchanging low amounts of palladium with excess copper in a heterogeneous zeolite Y catalyst leads to high Wacker activity and mitigates activity loss by reducing the extent of palladium sintering. Employing periodic regenerative treatments in oxygen to remove carbon deposits and reoxidize palladium results in the partial (but reversible) recovery of the high initial activity.

10.
Angew Chem Int Ed Engl ; 59(2): 910-918, 2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31680368

RESUMO

The reaction of methane with copper-exchanged mordenite with two different Si/Al ratios was studied by means of in situ NMR and infrared spectroscopies. The detection of NMR signals was shown to be possible with high sensitivity and resolution, despite the presence of a considerable number of paramagnetic CuII species. Several types of surface-bonded compounds were found after reaction, namely molecular methanol, methoxy species, dimethyl ether, mono- and bidentate formates, CuI monocarbonyl as well as carbon monoxide and dioxide, which were present in the gas phase. The relative fractions of these species are strongly influenced by the reaction temperature and the structure of the copper sites and is governed by the Si/Al ratio. While methoxy species bonded to Brønsted acid sites, dimethyl ether and bidentate formate species are the main products over copper-exchange mordenite with a Si/Al ratio of 6; molecular methanol and monodentate formate species were observed mainly over the material with a Si/Al ratio of 46. These observations are important for understanding the methane partial oxidation mechanism and for the rational design of the active materials for this reaction.

11.
Phys Chem Chem Phys ; 22(2): 734-739, 2020 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-31832632

RESUMO

ZSM-5 zeolites attract considerable attention owing to their wide range of applications in catalysis and separation. The crystals that are synthesized with tetrapropylammonium ions (TPA+) as the template show aluminum-zoning, i.e. aluminum being concentrated in the rim part of the crystal. Here, we study the aluminum distribution within individual crystals as a function of synthesis time and find that the degree of aluminum-zoning evolves. Crystals with inhomogeneous aluminum distribution persist since their emergence from the early stages of hydrothermal treatment. The degree of aluminum-zoning in the crystals increases with the synthesis time, accompanied by an increase in the crystal size and subsequently the formation of a well-defined crystal morphology. This indicates a gradual aluminum migration toward the crystal surface during the course of crystallization. Moreover, the addition of high-aluminum-containing species to the existing crystals preferentially takes place at the late stages of synthesis, which contributes to the inhomogeneous aluminum distribution within a crystal. As a result, the finally formed crystals have not only the largest crystal size but also the highest degree of aluminum-zoning. The insight into the origin of aluminum-zoning that our work provides advances our understanding of the relationship between aluminum distribution in zeolites and the synthesis time to design better catalysts.

12.
Phys Chem Chem Phys ; 22(1): 28-38, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31602438

RESUMO

Through the combination of density functional theory calculations and ab initio atomistic thermodynamics modeling, we demonstrate that atomically dispersed platinum species on ceria can adopt a range of local coordination configurations and oxidation states that depend on the surface structure and environmental conditions. Unsaturated oxygen atoms on ceria surfaces play the leading role in stabilization of PtOx species. Any mono-dispersed Pt0 species are thermodynamically unstable compared to bulk platinum, and oxidation of Pt0 to Pt2+ or Pt4+ is necessary to stabilize mono-dispersed platinum atoms. Reduction to Pt0 leads to sintering. Both Pt2+ and Pt4+ prefer to form the square-planar [PtO4] configuration. The two most stable Pt2+ species on the (223) and (112) surfaces are thermodynamically favorable between 300 and 1200 K. The most stable Pt4+ species on the (100) surface tends to desorb from the surface as gas phase above 950 K. The resulting phase diagrams of the atomically dispersed platinum in PtOx clusters on various ceria surfaces under a range of experimentally relevant conditions can be used to predict dynamic restructuring of atomically dispersed platinum catalysts and design new catalysts with engineered properties.

13.
Chemistry ; 25(69): 15879-15886, 2019 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-31553090

RESUMO

Hollow ZSM-5 zeolites of size below one micrometer can be produced by desilication of crystals with aluminium zoning. The parent crystals have a core-shell structure: the core part has nearly no aluminium, whereas the aluminium content in the shell increases when extending to exterior surface. Transmission electron microscopy confirmed the preservation of the crystalline shell after base leaching, but could not identify its subtle change. An increase of the Si/Al ratio of the surface was detected upon leaching the parent material to form the hollow zeolite by using ambient pressure X-ray photoelectron spectroscopy and infrared spectroscopy of substituted alkylpyridines. 27 Al MAS NMR showed that base leaching results in a reduced percentage of distorted tetrahedrally coordinated aluminium. The reprecipitation of dissolved species occurs and tetrahedrally coordinated tin atoms can thus be introduced to the shell framework. Overall, the formation of hollow ZSM-5 zeolites by desilication involves not only the removal of silicon-rich core, but also a reduced percentage of exterior aluminium-related acid sites, which should be considered while using hollow zeolites in acid-catalyzed reactions.

14.
Chem Commun (Camb) ; 55(78): 11794-11797, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31524890

RESUMO

The isothermal, low-temperature stepwise conversion of methane to methanol over copper-exchanged zeolites eliminates the time-consuming heating and cooling steps of the conventional high temperature activation approach. To better understand differences between the two approaches, a series of zeolites were screened, of which omega zeolite (MAZ) showed superior performance in both the isothermal and conventional approaches.

15.
Chem Commun (Camb) ; 55(79): 11833-11836, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31495847

RESUMO

Au/TiO2 is a much-used catalyst for the conversion of ethanol to acetic acid. The proposed mechanism speaks of two essential reaction steps on the catalytic surface. The first is the ethanol to acetaldehyde and the second the acetaldehyde to acetic acid. When operating in the gas phase, acetic acid is usually absent. This work focuses on determining what triggers the second step by comparing the ethanol with acetaldehyde oxidation and the liquid with gas-phase reaction. We propose an updated reaction mechanism: acetaldehyde autoxidises non-catalytically to acetic acid, likely driven by radicals. The requirement for the autoxidation is the presence of oxygen and water in the liquid-phase. The understanding of the interplay between the catalytic ethanol to acetaldehyde and the following non-catalytic reaction step provides guiding principles for the design of new and more selective alcohol oxidation catalysts.

16.
Chem Commun (Camb) ; 55(72): 10725-10728, 2019 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-31429426

RESUMO

A facile aerosol-based method for the synthesis of pure and stable amorphous calcium carbonate (ACC) is presented. The method relies on the instantaneous carbonation of calcium hydroxide aerosols with carbon dioxide followed by rapid drying of the freshly formed ACC. The ACC display extended stability against humidity induced crystallization.

17.
Nat Commun ; 10(1): 3316, 2019 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-31346178

RESUMO

3D electron crystallography has recently attracted much attention due to its complementarity to X-ray crystallography in determining the structure of compounds from submicrometre sized crystals. A big obstacle lies in obtaining complete data, required for accurate structure determination. Many crystals have a preferred orientation on conventional, flat sample supports. This systematically shades some part of the sample and prevents the collection of complete data, even when several data sets are combined. We introduce two types of three-dimensional sample supports that enable the collection of complete data sets. In the first approach the carbon layer forms coils on the sample support. The second approach is based on chaotic nylon fibres. Both types of grids disrupt the preferred orientation as we demonstrate with a well suited crystal type of MFI-type zeolites. The easy-to-obtain three-dimensional sample supports have different features, ensuring a broad spectrum of applications for these 3D support grids.

18.
Proc Natl Acad Sci U S A ; 116(25): 12212-12219, 2019 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-31160448

RESUMO

A massive reduction in CO2 emissions from fossil fuel burning is required to limit the extent of global warming. However, carbon-based liquid fuels will in the foreseeable future continue to be important energy storage media. We propose a combination of largely existing technologies to use solar energy to recycle atmospheric CO2 into a liquid fuel. Our concept is clusters of marine-based floating islands, on which photovoltaic cells convert sunlight into electrical energy to produce H2 and to extract CO2 from seawater, where it is in equilibrium with the atmosphere. These gases are then reacted to form the energy carrier methanol, which is conveniently shipped to the end consumer. The present work initiates the development of this concept and highlights relevant questions in physics, chemistry, and mechanics.

19.
Angew Chem Int Ed Engl ; 58(29): 9841-9845, 2019 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-31069914

RESUMO

Monomeric CuII sites supported on alumina, prepared using surface organometallic chemistry, convert CH4 to CH3 OH selectively. This reaction takes place by formation of CH3 O surface species with the concomitant reduction of two monomeric CuII sites to CuI , according to mass balance analysis, infrared, solid-state nuclear magnetic resonance, X-ray absorption, and electron paramagnetic resonance spectroscopy studies. This material contains a significant fraction of Cu active sites (22 %) and displays a selectivity for CH3 OH exceeding 83 %, based on the number of electrons involved in the transformation. These alumina-supported CuII sites reveal that C-H bond activation, along with the formation of CH3 O- surface species, can occur on pairs of proximal monomeric CuII sites in a short reaction time.

20.
J Synchrotron Radiat ; 26(Pt 3): 785-792, 2019 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-31074443

RESUMO

The successful design, installation and operation of a high spatial resolution X-ray photoelectron spectrometer at the Swiss Light Source is presented. In this instrument, a Fresnel zone plate is used to focus an X-ray beam onto the sample and an electron analyzer positioned at 45° with respect to the incoming beam direction is used to collect photoelectrons from the backside of the sample. By raster scanning the sample, transmitted current, X-ray absorption and X-ray photoemission maps can be simultaneously acquired. This work demonstrates that chemical information can be extracted with micrometre resolution; the results suggest that a spatial resolution better than 100 nm can be achieved with this approach in future. This kind of photoelectron spectromicroscope will allow in situ measurements with high spatial resolution also under ambient pressure conditions (in the millibar range). Element-specific X-ray photoemission maps can be obtained before and while exposing the sample to gas/gas mixtures to show morphological and chemical changes of the surface.

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