Complex anion inclusion compounds: flexible anion-exchange materials

Williams, Edward R.; Leithall, Rebecca M.; Raja, Robert; Weller, Mark T.

doi:10.1039/c2cc36484k

Cited by 17 publications

(15 citation statements)

References 18 publications

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“…21 Employing similar imaging methodologies, the morphology of the platinum chloride and palladium chloride supported phases have been shown to have a homogenous distribution of cubic crystals across 45 Fig. 6 Powder XRD patterns of the calcined platinum catalyst (blue line) and the catalyst post-catalysis (red line).…”

Section: Resultsmentioning

confidence: 99%

“…Whilst there is immense potential for the 40 designed porous framework host to be catalytically active in itself; metal nanoparticle-framework interactions and metal-metal interactions (e.g. multimetallic nanoparticles) can be suitably engineered and investigated for eliciting synergistic enhancements [6][7][8][21][22][23] …”

Section: Prospects and Potentialmentioning

confidence: 99%

“…Catalytic studies for Au nanoparticles have revealed that the activity is inversely proportional to the particle size, especially below 10 nm, 18 thus highlighting the importance of -supported copper chloropyrophosphate with an analogous framework as 25 CU-2 was reported. 20,21 Herein, we adopt a modified approach for the generation of Pt ( Fig. 1) and Pd nanoparticles for the aerobic selective oxidation of benzyl alcohol.…”

Section: Introductionmentioning

confidence: 99%

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Probing the origin of in situ generated nanoparticles as sustainable oxidation catalysts

et al. 2013

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A novel method for the in situ generation of catalytically active small metal nanoparticles, by anion extrusion on a parent porous copper chloropyrophosphate framework, have been developed to generate gold, platinum and palladium 10 nanoparticles for sustainable catalytic oxidations using molecular oxygen as the oxidant. Transmission electron microscopy coupled with detailed structural and physicochemical characterisation, in combination with in-depth kinetic analysis have afforded profound insights into the 15 nature of the active site for facilitating structure-property correlations.

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Section: Resultsmentioning

confidence: 99%

Section: Prospects and Potentialmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Probing the origin of in situ generated nanoparticles as sustainable oxidation catalysts

et al. 2013

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“…In recent years classical solid state synthesis methods employing reactive molten alkali and alkaline-earth metal halide salts at high temperatures have been reported. [1][2][3][4][5][6][7][8][9] Thereby, intriguing insights into the structural richness of the fascinating class of salt-inclusion type of compounds has been gained. These explorative studies indicate that extended halide/oxide lattices present opportunities to controlthe dimensionality of structural features.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures, magnetic properties, and lattice dynamics of Ba2XCu(OH)[V2O7] with X=Cl, Br

Sun

Litvinchuk

Tapp

et al. 2016

Journal of Solid State Chemistry

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We have synthesized Ba 2 XCu(OH)[V 2 O 7 ] with X = Cl, Br by hydrothermal methods. The isotypic structures (Pnma, Z = 4, a ≈ 15.1 Å, b ≈ 6.1 Å, c ≈ 9.6 Å) contain distorted hexagonal layers of Ba and X in a BN-type arrangement. Each halide is further coordinated by one out-of plane Ba atom in an alternate up-down fashion resulting in an overall 2  [Ba 2 X] 3+ structural feature. The planar Ba-X hexagonal rings are centered by divanadate groups in an eclipsed orientation. Edge-sharing chains of 1  [CuO 2/2 (OH) 2/2 O 2/1 ] 5complement the structure. The magnetic properties are associated with the magnetic Cu 2+ ions and can be described as an antiferromagnetic quasi 1D S = 1/2 Heisenberg system. Confirmation is obtained from both magnetic and specific heat measurements. Furthermore, lattice dynamics are studied by DFT methods, IR, and Raman spectroscopy.

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“…Nevertheless,ithas been observed that when the calcination temperature exceeds 500 8C, the selectivity of the catalyst drastically diminishes. In addition, it wasp reviously noted [18] that these materials can undergo thermald egradation at temperatures above 600 8C, and indeed, inconsistencies in the powder X-ray diffraction patterns (PXRD)o ft hese materials are observed at such elevated temperatures ( Figure SI-6). Consequently, in all kinetic work reported herein the Pt/CuClPc atalysts were activated by calcinationa t5 00 8C, and optimizedo xidant to substrate ratios wereu sed for maximizing the reaction selectivity towards benzaldehyde.…”

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confidence: 99%

Utilizing Benign Oxidants for Selective Aerobic Oxidations Using Heterogenized Platinum Nanoparticle Catalysts

et al. 2015

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By using platinum nanoparticle catalysts that are generated in situ by extrusion from a porous copper chlorophosphate framework, the role of oxidants in the selective oxidation of benzyl alcohol to benzaldehyde was evaluated, with a view to establishing structure-property relationships. With a detailed 5 study of the kinetic properties of the oxidation reaction, it has been determined that the aerobic oxidation pathways progress with lower levels of product selectivity and higher activation energies (72.4 kJ/mol) than the peroxide-based ones (23.6 kJ/mol); affording valuable insights in the design of solid catalysts for selective 10 oxidation reactions. Furthermore, through the use of X-ray absorption spectroscopy, the effect of calcination temperature on the degree of extrusion and its influence on nanoparticle formation have been evaluated, leading to the establishment of structure-activity correlations between the observed activation energies and the 15 proportion of nanoparticle species generated .Oxidation reactions are ubiquitous in the pharmaceutical and fine-chemical industries, and are fundamentally important to introducing oxygen rich functional groups to organic molecules. For example, aldehyde and ester containing molecules are 20 heavily employed as flavouring and fragrance agents due to their volatility and distinctly aromatic nature that are often pleasing to smell and taste.[1] Benzaldehyde is a key component for most almond-based flavourings, although it finds other uses as precursors for plastic additives and as a pharmaceutical 25 intermediate toward antibiotic drugs such as chloramphenicol and ampicillin, as well as stimulants like ephedrine.[2] Industrially, it is synthesized by the hydrolysis of benzal chloride, however the dehydrogenative oxidation of benzyl alcohol is a viable, chloride free and environmentally benign alternative. [2] 30 Traditionally, industrial oxidation reactions are based on the use of stoichiometric quantities of inorganic metal-based oxidizing agents such as MnO2 or CrO3, or harsh mineral acids like H2SO4 and HNO3, which result in hazardous, corrosive and toxic operating conditions as well as leading to the generation of 35 large quantities of polluting waste by-products.[3] Due to the heightened socio-economic demand for the chemical and related industries to reduce their negative impact on the environment, there is a significant drive to find alternative economic and sustainable oxidation reagents and synthetic 40 protocols.[3] The abundance of molecular oxygen, its high atomeconomy in oxidation reactions, low costs and mild reaction conditions make it an appealing candidate as an oxidant, [4] although high-pressure and relatively high reaction temperatures are often required, owing to the gaseous nature of the reaction. 45 Similarly, simple peroxides such as H2O2 and tert-butyl hydroperoxide (TBHP), are often considered as alternative green oxidants.[4] Although, this often leads to the generation of larger quantities of by-products in compa...

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Complex anion inclusion compounds: flexible anion-exchange materials

Cited by 17 publications

References 18 publications

Probing the origin of in situ generated nanoparticles as sustainable oxidation catalysts

Probing the origin of in situ generated nanoparticles as sustainable oxidation catalysts

Synthesis, crystal structures, magnetic properties, and lattice dynamics of Ba2XCu(OH)[V2O7] with X=Cl, Br

Utilizing Benign Oxidants for Selective Aerobic Oxidations Using Heterogenized Platinum Nanoparticle Catalysts

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