Diffusion Control in Single-Site Zinc Reticular Amination Catalysts.
Zn-containing metal-organic frameworks have been used for the first time as heterogeneous catalysts in the amination of C-Cl bonds. The use of extended bis(pyrazolate) linkers can generate highly porous architectures, which favor the diffusion of amines to the confined spaces with respect to other imidazolate frameworks with narrower pore windows. The N4Zn nodes of the Zn-reticular framework show comparable activity to state-of-the-art homogeneous Zn amination catalysts, avoiding the use of basic conditions, precious metals, or other additives. This is combined with long-term activity and stability upon several reaction cycles, without contamination of the reaction product. ispartof: INORGA…
Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction
The preparation of novel efficient catalysts-that could be applicable in industrially important chemical processes-has attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag2subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal-organic framework, with the formula [Ag2]@AgNa{Ni[Cu(Mempba)]}·48HO [Mempba= N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalyst-fully characterized with the help of single-c…
Metal-organic frameworks-based catalysts for biomass valorization
Abstract The objective of this chapter is to review the most promising metal-organic framework (MOF) catalysts in biomass valorization processes in the bulk and fine chemical industries. Either bulk metal-organic frameworks, encapsulated catalytic species in MOFs, or MOF-derived catalysts are revised in terms of activity, selectivity, and stability for biomass valorization applications. The work revised here is focused on the transformation of lignocellulose biomass through purely chemical pathways. In the first part of the chapter, the few studies of cellulose hydrolysis into monosaccharides reported are commented, since this crucial first step in the valorization of hemicellulose is expec…
Catalytic activity of a CuGHK peptide-based porous material
The CuGHK peptide-based porous material with a periodic distribution of pockets decorated with lysine side chain active sites was synthesized using a room temperature one-step method and used as a heterogeneous organocatalyst. The pockets are capable of benzaldehyde molecule uptake and show high activity in the Henry reaction with nitromethane. Mechanistic pathways are investigated using an integrative experimental/computational approach.
Organic synthesis of high added value molecules with MOF catalysts
Recent examples of organic synthesis of fine chemicals and pharmaceuticals in confined spaces of MOFs are highlighted and compared with silica-based ordered porous solids, such as zeolites or mesoporous (organo)silica. These heterogeneous catalysts offer the possibility of stabilizing the desired transition states and/or intermediates during organic transformations of functional groups and (C-C/C-N) bond forming steps towards the desired functional high added value molecular scaffolds. A short introduction on zeolites, mesoporous silica and metal-organic frameworks is followed by relevant applications in which confined active sites in the pores promote single or multi-step organic synthesis…
Palladium-Based Metal Organic Frameworks as Heterogeneous Catalysts for C-C Couplings
Among the various cross coupling reactions, C−C cross coupling reaction has attracted many researchers to investigate in the last four decades. The continuous, constant, and consistent progress in this field fetched a Noble prize in 2010, showing the importance of this reaction in diversified fields. Among the various transition metals studied for this reaction, Pd is one of the metals that has exhibited the highest activity due to its unique features and reactivity. Although Pd-based homogeneous catalyst was the preferred choice for many researchers, the field slowly diverted towards the development of Pd-based heterogeneous catalysts for C−C coupling reactions. This is obviously due to th…
MOF-Triggered Synthesis of Subnanometer Ag02 Clusters and Fe3+ Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions
Design of Hierarchical Architectures in Metal–Oganic Frameworks for Catalysis and Adsorption
A key factor to improve the performance of metal–organic frameworks (MOFs) is the design and synthesis of hierarchical interconnected porosity at different length scales. The presence of secondary ...
Supported Single Atom Catalysts for C−H Activation: Selective C−H Oxidations, Dehydrogenations and Oxidative C−H/C−H Couplings
MOF‐derived/zeolite hybrid catalyst for the production of light olefins from CO2
ispartof: ChemCatChem vol:12 issue:22 pages:5750-5758 status: published
CCDC 2155456: Experimental Crystal Structure Determination
Related Article: Estefanía Tiburcio, Yongkun Zheng, Marta Mon, Nuria Martín, Jesús Ferrando−Soria, Donatella Armentano, Antonio Leyva−Pérez, Emilio Pardo|2022|Inorg.Chem.|61|11796|doi:10.1021/acs.inorgchem.2c01508
CCDC 2155455: Experimental Crystal Structure Determination
Related Article: Estefanía Tiburcio, Yongkun Zheng, Marta Mon, Nuria Martín, Jesús Ferrando−Soria, Donatella Armentano, Antonio Leyva−Pérez, Emilio Pardo|2022|Inorg.Chem.|61|11796|doi:10.1021/acs.inorgchem.2c01508