Structure−Reactivity Relationship for Catalytic Activity of Gallium Oxide and Sulfide Clusters in Zeolite

Pidko, Evgeny A.; Santen, Rutger A. van

doi:10.1021/jp8113607

Cited by 34 publications

(26 citation statements)

References 23 publications

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“…The later parameter has been chosen as the reactivity descriptor because it reflects strength of the associated active Lewis acid-base pairs. The relationship presented points to the optimum composition and structure of the intrazeolite Ga cluster -[H-Ga(O)(OH)Ga] 2+ -for the catalytic dehydrogenation of light alkanes [110]. Similar active species have been previously proposed to account for the enhanced dehydrogenation activity of Ga-modified ZSM-5 zeolite upon water cofeeding [109,111].…”

Section: Structural Properties Of Zeolites: Framework Al Distributionsupporting

confidence: 64%

“…The performance of different cationic oxygenand sulfur-containing Ga clusters in light alkane dehydrogenation has been analyzed by means of periodic DFT calculations [110]. From the results thus obtained a structure-reactivity relationship of a remarkable predictive power has been derived for their catalytic performance.…”

Section: Structural Properties Of Zeolites: Framework Al Distributionmentioning

confidence: 99%

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Theoretical Chemistry of Zeolite Reactivity

Pidko

Santen

2010

Zeolites and Catalysis

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IntroductionNowadays, advances in chemical theory rely to a significant extent on computations. Novel theoretical concepts arising directly from experiments usually require further investigations using computational modeling. This is necessary to develop a conclusive molecular-level picture of the observed phenomenon. As a result, computational methods are nowadays widely and extensively applied in the chemical, physical, biomedical, and engineering sciences. They are used in assisting the interpretation of experimental data and increasingly in predicting the properties and behavior of matter at the atomic level.Computational simulation techniques can be divided into two very broad categories. The first is based on the use of interatomic potentials (force fields). These methods are usually empirical and do not consider explicitly any electron in the system. The system of interest is described with functions (normally analytical), which expresses its energy as a function of nuclear coordinates. These are then used to calculate structures and energies by means of minimization methods, to calculate ensemble averages using Monte Carlo simulations, or to model dynamic processes via molecular dynamics simulations using classical Newton's law of motion. The current capabilities and challenges for the corresponding computational methods have been recently reviewed in excellent papers by Woodley and Catlow [1] and by Smit and Maesen [2, 3].The second category includes quantum chemical methods based on the calculation of the electronic structure of the system. Such methods are particularly important for processes that depend on bond breaking or making, which include, of course, catalytic reactions. Hartree Fock (HF), Density Functional Theory (DFT), and post-HF ab initio approaches have been used in modeling zeolites, although DFT methods have predominated in recent applications.This chapter focuses on illustrating the power and capabilities of modern quantum chemical techniques, and aims at highlighting the key areas and challenges

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Section: Structural Properties Of Zeolites: Framework Al Distributionsupporting

confidence: 64%

Section: Structural Properties Of Zeolites: Framework Al Distributionmentioning

confidence: 99%

Theoretical Chemistry of Zeolite Reactivity

Pidko

Santen

2010

Zeolites and Catalysis

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“…To compensate for the positive charge of the extra-framework cationic Cu complexes, two framework Si 4+ ions in the MOR supercell were substituted by two Al 3+ at the side-pocket position of Al I SP . The other two [AlO 2 ] − units at the side-pocket position of Al II SP were charge compensated by two BASs 48 . The resulting MOR model had a Si/Al ratio of 11.…”

Section: Methodsmentioning

confidence: 99%

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

et al. 2015

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Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.

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“…[138] A similar acid-base synergistic mechanism has been proposed for alkane activation by Ga-modified zeolites. [139] The catalytic performance of these systems was shown to be defined by both the Lewis acidity of the metal center and the basicity of the adjacent base site.…”

Section: Acid-base Synergymentioning

confidence: 99%

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective

Pidko

2018

ChemCatChem

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111

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Zeolites have a broad spectrum of applications as robust microporous catalysts for various chemical transformations. The reactivity of zeolite catalysts can be tailored by introducing heteroatoms either into the framework or at the extraframework positions that gives rise to the formation of versatile Brønsted acid, Lewis acid and redox‐active catalytic sites. Understanding the nature and catalytic role of such sites is crucial for guiding the design of new and improved zeolite‐based catalysts. This work presents an overview of recent computational studies devoted to unravelling the molecular level details of catalytic transformations inside the zeolite pores. The role of modern computational chemistry in addressing the structural problem in zeolite catalysis, understanding reaction mechanisms and establishing structure‐activity relations is discussed. Special attention is devoted to such mechanistic phenomena as active site cooperativity, multifunctional catalysis as well as confinement‐induced and multisite reactivity commonly encountered in zeolite catalysis.

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Structure−Reactivity Relationship for Catalytic Activity of Gallium Oxide and Sulfide Clusters in Zeolite

Cited by 34 publications

References 23 publications

Theoretical Chemistry of Zeolite Reactivity

Theoretical Chemistry of Zeolite Reactivity

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective

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