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Crystal engineering of a family of hybrid ultramicroporous materials based upon interpenetration and dichromate linkers.

ABSTRACT: A new family of 2-fold interpenetrated primitive cubic (pcu) networks of formula [M(L)₂(Cr₂O₇)] _n (M = Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺; L = 4,4'-azopyridine), DICRO-3-M-i, has been synthesised and their structures, permanent porosity and gas sorption properties were comprehensively characterised. Molecular simulations indicate that CO₂ molecules occupy both of the two distinct ultramicropores that run through this isostructural series. The orientation of the Cr₂O₇^2- pillars is thought to contribute to high isosteric enthalpy of adsorption (Q_st) towards CO₂ and temperature programmed desorption experiments reveal that DICRO-3-Ni-i selectively adsorbs CO₂ from gas mixtures that simulate flue gas. Performance in this context is among the highest for physisorbents measured to date and these materials are readily regenerated at 50 °C.

SUBMITTER: Scott HS

PROVIDER: S-EPMC6021753 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

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Crystal engineering of a family of hybrid ultramicroporous materials based upon interpenetration and dichromate linkers.

Scott Hayley S HS Ogiwara Naoki N Chen Kai-Jie KJ Madden David G DG Pham Tony T Forrest Katherine K Space Brian B Horike Satoshi S Perry Iv John J JJ Kitagawa Susumu S Zaworotko Michael J MJ

Chemical science 20160510 8

A new family of 2-fold interpenetrated primitive cubic (pcu) networks of formula [M(L)2(Cr2O7)] n (M = Co2+, Ni2+, Cu2+ and Zn2+; L = 4,4'-azopyridine), DICRO-3-M-i, has been synthesised and their structures, permanent porosity and gas sorption properties were comprehensively characterised. Molecular simulations indicate that CO2 molecules occupy both of the two distinct ultram ...[more]

PMID: 30034686

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Project description:ConspectusIntuitively, chemists see crystals grow atom-by-atom or molecule-by-molecule, very much like a mason builds a wall, brick by brick. It is much more difficult to grasp that small crystals can meet each other in a liquid or at an interface, start to align their crystal lattices and then grow together to form one single crystal. In analogy, that looks more like prefab building. Yet, this is what happens in many occasions and can, with reason, be considered as an alternative mechanism of crystal growth. Oriented attachment is the process in which crystalline colloidal particles align their atomic lattices and grow together into a single crystal. Hence, two aligned crystals become one larger crystal by epitaxy of two specific facets, one of each crystal. If we simply consider the system of two crystals, the unifying attachment reduces the surface energy and results in an overall lower (free) energy of the system. Oriented attachment often occurs with massive numbers of crystals dispersed in a liquid phase, a sol or crystal suspension. In that case, oriented attachment lowers the total free energy of the crystal suspension, predominantly by removal of the nanocrystal/liquid interface area. Accordingly, we should start by considering colloidal suspensions with crystals as the dispersed phase, i.e., "sols", and discuss the reasons for their thermodynamic (meta)stability and how this stability can be lowered such that oriented attachment can occur as a spontaneous thermodynamic process. Oriented attachment is a process observed both for charge-stabilized crystals in polar solvents and for ligand capped nanocrystal suspensions in nonpolar solvents. In this last system different facets can develop a very different reactivity for oriented attachment. Due to this facet selectivity, crystalline structures with very specific geometries can be grown in one, two, or three dimensions; controlled oriented attachment suddenly becomes a tool for material scientists to grow architectures that cannot be reached by any other means. We will review the work performed with PbSe and CdSe nanocrystals. The entire process, i.e., the assembly of nanocrystals, atomic alignment, and unification by attachment, is a very complex and intriguing process. Researchers have succeeded in monitoring these different steps with in situ wave scattering methods and real-space (S)TEM studies. At the same time coarse-grained molecular dynamics simulations have been used to further study the forces involved in self-assembly and attachment at an interface. We will briefly come back to some of these results in the last sections of this review.

Dataset Information

Crystal engineering of a family of hybrid ultramicroporous materials based upon interpenetration and dichromate linkers.

Publications

Crystal engineering of a family of hybrid ultramicroporous materials based upon interpenetration and dichromate linkers.

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