Catalytic Strategies for Sustainable Oxidations in Water

Carraro, Mauro; Sartorel, Andrea; Scorrano, Gianfranco; Carofiglio, Tommaso; Bonchio, Marcella

doi:10.1055/s-2008-1067086

Cited by 25 publications

(12 citation statements)

References 54 publications

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“…The use of polyoxometalate clusters as catalysts continues to be the most popular application area for POMs, and in particular by industry, with hundreds of papers and many patents published every year covering this topic. Many reviews cover the progress of POM chemistry in this aspect, including recent reviews on the development of green H 2 O 2 ‐based epoxidation systems,128 catalytic oxidation of organic substrates by molecular oxygen and hydrogen peroxide by multi‐step electron‐transfer, a biomimetic approach,129 progress and challenges in POM‐based catalysis and catalytic materials chemistry,130 and catalytic strategies for sustainable oxidations in water 131. For the purposes of this review, we will only focus on important results published during the last two years (Figure 25 and Table 3).…”

Section: Catalytic Applications In Green Chemistry and Energy Systemsmentioning

confidence: 99%

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

2010

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Polyoxometalates (POMs) are a subset of metal oxides that represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form dynamic structures that can range in size from the nano- to the micrometer scale. Herein we present the very latest developments from synthesis to structure and function of POMs. We discuss the possibilities of creating highly sophisticated functional hierarchical systems with multiple, interdependent, functionalities along with a critical analysis that allows the non-specialist to learn the salient features. We propose and present a "periodic table of polyoxometalate building blocks". We also highlight some of the current issues and challenges that need to be addressed to work towards the design of functional systems based upon POM building blocks and look ahead to possible emerging application areas.

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Section: Catalytic Applications In Green Chemistry and Energy Systemsmentioning

confidence: 99%

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

2010

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“…The present protocol represents a further advancement with respect to on-water catalysis and environmentally sustainable oxidations. [33,34] Moreover, by virtue of the POM robustness and fast kinetics, the catalytic set-up can be readily implemented in a flow-mode within microfluidic devices in which the H 2 O 2 feeding can be properly tuned to match the addition/consumption rates and optimize the steady-state concentration of the competent peroxidic intermediate. [30b] The impact of the geometry/structure of the peroxide bridge on the oxygen-transfer catalysis has been further addressed by DFT computations, including relativistic and solvent effects.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Reactive Zr^IV and Hf^IV Butterfly Peroxides on Polyoxometalate Surfaces: Bridging the Gap between Homogeneous and Heterogeneous Catalysis

Carraro

Nsouli

Oelrich

et al. 2011

Chemistry A European J

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At variance with previously known coordination compounds, the polyoxometalate (POM)-embedded Zr(IV) and Hf(IV) peroxides with formula: [M(2)(O(2))(2)(α-XW(11)O(39))(2)](12-) (M=Zr(IV), X=Si (1), Ge (2); M=Hf(IV), X=Si (3)) and [M(6)(O(2))(6)(OH)(6)(γ-SiW(10)O(36))(3)](18-) (M=Zr(IV) (4) or Hf(IV) (5)) are capable of oxygen transfer to suitable acceptors including sulfides and sulfoxides in water. Combined (1)H NMR and electrochemical studies allow monitoring of the reaction under both stoichiometric and catalytic conditions. The reactivity of peroxo-POMs 1-5 is compared on the basis of substrate conversion and kinetic. The results show that the reactivity of POMs 1-3 outperforms that of the trimeric derivatives 4 and 5 by two orders of magnitude. Reversible peroxidation of 1-3 occurs by H(2)O(2) addition to the spent catalysts, restoring oxidation rates and performance of the pristine system. The stability of 1-3 under catalytic regime has been confirmed by FT-IR, UV/Vis, and resonance Raman spectroscopy. The reaction scope has been extended to alcohols, leading to the corresponding carbonyl compounds with yields up to 99% under microwave (MW) irradiation. DFT calculations revealed that polyanions 1-3 have high-energy peroxo HOMOs, and a remarkable electron density localized on the peroxo sites as indicated by the calculated map of the electrostatic potential (MEP). This evidence suggests that the overall description of the oxygen-transfer mechanism should include possible protonation equilibria in water, favored for peroxo-POMs 1-3.

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“…Aktuelle Über-sichten sind zu folgenden Themen erschienen: Entwicklung von umweltverträglichen Epoxidierungssystemen mit H 2 O 2 , [128] biomimetische katalytische Oxidation von organischen Substraten durch molekularen Sauerstoff und Wasserstoffperoxid über mehrstufigen Elektronentransfer, [129] Fortschritte der POM-Katalyse [130] und Strategien für die umweltverträgliche katalytische Oxidation in Wasser. [131] Hier konzentrieren wir uns auf wichtige Ergebnisse aus den letzten beiden Jahren (Abbildung 25 und Tabelle 3).…”

Section: Selbstorganisation Von Pom-nanostrukturenunclassified

Polyoxometallate als Bausteine für funktionelle Nanosysteme

2010

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Die Polyoxometallate (POM), eine Untergruppe der Metalloxide, bilden vielfältige Molekülcluster, die nicht nur außerordentlich vielfältige physikalische Eigenschaften zeigen, sondern auch dynamische Strukturen mit Abmessungen vom Nanometer‐ bis zum Mikrometermaßstab bilden können. Hier beschreiben wir die neuesten Entwicklungen von der Synthese bis zur Struktur und Funktion von Polyoxometallaten. Wir diskutieren Wege zur Herstellung höchst differenzierter hierarchischer Systeme mit mehreren voneinander unabhängigen Funktionalitäten und geben eine kritische Analyse, aus der auch nichtspezialisierte Leser die wichtigsten Eigenschaften ersehen können. In diesem Zusammenhang schlagen wir auch ein “Periodensystem der Polyoxometallat‐Baueinheiten” vor. Schließlich beleuchten wir einige aktuelle Herausforderungen beim Design funktioneller Systeme auf der Basis von POM‐Baueinheiten und geben einen Ausblick auf mögliche Anwendungen.

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Catalytic Strategies for Sustainable Oxidations in Water

Cited by 25 publications

References 54 publications

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

Reactive Zr^IV and Hf^IV Butterfly Peroxides on Polyoxometalate Surfaces: Bridging the Gap between Homogeneous and Heterogeneous Catalysis

Polyoxometallate als Bausteine für funktionelle Nanosysteme

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Catalytic Strategies for Sustainable Oxidations in Water

Cited by 25 publications

References 54 publications

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

Reactive ZrIV and HfIV Butterfly Peroxides on Polyoxometalate Surfaces: Bridging the Gap between Homogeneous and Heterogeneous Catalysis

Polyoxometallate als Bausteine für funktionelle Nanosysteme

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Reactive Zr^IV and Hf^IV Butterfly Peroxides on Polyoxometalate Surfaces: Bridging the Gap between Homogeneous and Heterogeneous Catalysis