Structure–activity relationships of simple molecules adsorbed on CPO-27-Ni metal–organic framework: In situ experiments vs. theory

Valenzano, Loredana; Vitillo, Jenny G.; Chavan, Sachin; Civalleri, Bartolomeo; Bonino, Francesca; Bordiga, Silvia; Lamberti, Carlo

doi:10.1016/j.cattod.2011.07.020

Cited by 67 publications

(77 citation statements)

References 190 publications

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“…In the following subsection the deprotonation will be examined in the reaction itself, with explicit consideration of the nature of the acidic donor molecule, and of the presence of one or more adjacent open metal sites. Regarding remarkably larger than those predicted by Valenzano et al [68] The high affinity of Ni 2 dobdc and Co 2 dobdc for CO can be rationalized by considering that the cus in these materials not only can accept an electron pair, but can also provide -backdonation to the CO. [28,61,[69][70][71] Also incorporated in Table 5 are the adsorption energies of acetonitrile on the various M 2 dobdc materials, as we expect a similar adsorption sequence for the donors with nitrile groups, such as MN or ECA. Inspection of Table 5 learns that the correlation between the two series of adsorption energies, for CO and acetonitrile respectively, is rather poor.…”

Section: The Phenolate-metal Active Sitementioning

confidence: 93%

Metal-dioxidoterephthalate MOFs of the MOF-74 type: Microporous basic catalysts with well-defined active sites

Valvekens

Vandichel

Waroquier

et al. 2014

Journal of Catalysis

143

122

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The hybrid frameworks M 2 dobdc (dobdc 4-= 2,5-dioxidoterephthalate, M 2+ = Mg 2+ , Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ ), commonly known as CPO-27 or MOF-74, are shown to be active catalysts in base-catalyzed reactions such as Knoevenagel condensations or Michael additions. Rather than utilizing Nfunctionalized linkers as a source of basicity, the intrinsic basicity of these materials arises from the presence of the phenolate oxygen atoms coordinated to the metal ions. The overall activity is due a complex interplay of the basic properties of these structural phenolates and the reactant binding characteristics of the coordinatively unsaturated sites. The nature of the active site and the order of activity among the different M 2 dobdc materials were rationalized via computational efforts; the most active material, both in theory and experiment, is the Ni-containing variant. The basicity of Ni 2 dobdc was experimentally proven by chemisorption of pyrrole and observation by IR spectroscopy.

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Section: The Phenolate-metal Active Sitementioning

confidence: 93%

Metal-dioxidoterephthalate MOFs of the MOF-74 type: Microporous basic catalysts with well-defined active sites

Valvekens

Vandichel

Waroquier

et al. 2014

Journal of Catalysis

143

122

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“…[ 75 ] It was hypothesized that the lack of agreement was the result of variations in the lattice parameters from the as-prepared samples, highlighting the sensitivity of these calculations to atomic structure. [ 75,103 ] A wide range of in situ spectroscopic methodologies such as IR and Raman, [ 104,105 ] inelastic neutron scattering (INS), [ 106 ] NMR, [ 67 ] and others [107][108][109] are highly sensitive to molecular interactions in porous media, and they have been used to successfully characterize various guest-framework interactions. While many of these techniques directly probe small-molecule dynamics related to rotations, vibrations, and diffusion, the resulting spectra can also be used to extract binding confi gurations, binding enthalpies, and even loading levels.…”

Section: Experimental Approaches Limitations and The Need For Theorymentioning

confidence: 99%

“…While many of these techniques directly probe small-molecule dynamics related to rotations, vibrations, and diffusion, the resulting spectra can also be used to extract binding confi gurations, binding enthalpies, and even loading levels. While we do not intend to review all of these techniques individually, as they have been thoroughly covered elsewhere, [ 104,[109][110][111][112][113] we would like to point out that there are limitations related to data interpretation that can be signifi cantly aided by theoretical investigations. [ 114 ] Information pertaining to small-molecule interactions is often extracted from line shifts, widths, and/ or intensities.…”

Section: Experimental Approaches Limitations and The Need For Theorymentioning

confidence: 99%

Understanding Small‐Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory

et al. 2015

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are intensive scientifi c efforts focused on the development of new physical adsorbents that might enable more energetically favorable gas separation, relative to traditional distillation or absorption processes. This feat is not easy, as the differences in the molecules of interest, such as CO 2 and N 2 -the main components in a postcombustion fl ue gas, are minimal. [ 2,3 ] As such, these separations require tailor-made adsorbent materials with molecule-specifi c chemical interactions on their internal surface. [ 4,5 ] Metal-organic frameworks (MOFs) are a particularly attractive class of porous adsorbents that are under intense investigation for gas separation due to their unmatched structural versatility. Many stable, 3D frameworks that offer unprecedented internal surface areas and the selective adsorption of a wide range of small guest molecules have been discovered. [ 6 ] The molecular nature of the organic ligand in an MOF provides a convenient modular approach to their synthesis and facile chemical tunability, creating a surge towards the directed design of new materials ( Figure 1 ). [7][8][9] Through judicious selection of the ligand and metal, which control pore size/shape and MOF-adsorbate interactions, MOF uptake properties, Metal-organic frameworks (MOFs) have gained much attention as nextgeneration porous media for various applications, especially gas separation/ storage, and catalysis. New MOFs are regularly reported; however, to develop better materials in a timely manner for specifi c applications, the interactions between guest molecules and the internal surface of the framework must fi rst be understood. A combined experimental and theoretical approach is presented, which proves essential for the elucidation of small-molecule interactions in a model MOF system known as M 2 (dobdc) (dobdc 4− = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, or Zn), a material whose adsorption properties can be readily tuned via chemical substitution. It is additionally shown that the study of extensive families like this one can provide a platform to test the effi cacy and accuracy of developing computational methodologies in slightly varying chemical environments, a task that is necessary for their evolution into viable, robust tools for screening large numbers of materials.

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“…[12,13] Adsorption of a guest molecule can reverse this change depending on the strength and mode of interaction with the metal site. These processes are readily observable in the electronic spectra of the material.…”

mentioning

confidence: 99%

“…[5a, 12,13] The UV/Vis spectrum of acetylene adsorbed on CPO-27-Ni shows a partial increase in the coordination number Ni 2 + (details can be found in Figure S3 of the Supporting Information). In this way, both the IR and the UV/Vis spectroscopy results show that acetylene simply interacts with the M 2 + sites via a purely electrostatic interaction, and by hydrogen bonding with metal-ion-neighboring oxygen atoms.…”

mentioning

confidence: 99%

Acetylene Adsorption on CPO‐27‐M Metal–Organic Frameworks (M=Fe, Co and Ni)

et al. 2012

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Structure–activity relationships of simple molecules adsorbed on CPO-27-Ni metal–organic framework: In situ experiments vs. theory

Cited by 67 publications

References 190 publications

Metal-dioxidoterephthalate MOFs of the MOF-74 type: Microporous basic catalysts with well-defined active sites

Metal-dioxidoterephthalate MOFs of the MOF-74 type: Microporous basic catalysts with well-defined active sites

Understanding Small‐Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory

Acetylene Adsorption on CPO‐27‐M Metal–Organic Frameworks (M=Fe, Co and Ni)

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