The development of a comprehensive toolbox based on multi-level,high-throughput screening of MOFs for CO/N2 separations

The separation of CO/N₂ mixtures is a challenging problem in the petrochemical sector due to the very similar physical properties of these two molecules, such as size, molecular weight and boiling point. To solve this and other challenging gas separations, one requires a holistic approach. The complexity of a screening exercise for adsorption-based separations arises from the multitude of existing porous materials, including metal–organic frameworks. Besides, the multivariate nature of the performance criteria that needs to be considered when designing an optimal adsorbent and a separation process – i.e. an optimal material requires fulfillment of several criteria simultaneously – makes the screening challenging. To address this, we have developed a multi-scale approach combining high-throughput molecular simulation screening, data mining and advanced visualization, as well as process system modelling, backed up by experimental validation. We have applied our recent advances in the engineering of porous materials'' morphology to develop advanced monolithic structures. These conformed, shaped monoliths can be used readily in industrial applications, bringing a valuable strategy for the development of advanced materials. This toolbox is flexible enough to be applied to multiple adsorption-based gas separation applications.

The separation of challenging mixtures through adsorption is a multidimensional problem that requires a holistic approach. Our toolbox combines experiments, molecular and process simulations with data visualization to find optimal, porous materials.     

Determination of the Preassembled Nucleating Units That Are Critical for the Crystal Growth of the Metal–Organic Framework CdIF‐4

Identifying the form and role of the chemical species that traverse the stages of crystallization is critical to understanding the formation process of coordination polymers. Herein, we report the combined use of in situ atomic force microscopy and mass spectrometry to identify preformed, complex, cadmium 2‐ethylimidazole containing solution species in the growth solution of the cadmium 2‐ethylimidazolate metal–organic framework CdIF‐4, and show that they are critical in the surface nucleation for the crystal growth of this material. Surface nucleation appears to be instigated by these [Cd_x(CH₃CO₂)_y(C₅H₇N₂/C₅H₈N₂)_z]‐containing solution species and not by sole addition of the ligand molecules. The CH₃CO₂^? or Cd(CH₃CO₂)₂ groups of the former are substituted subsequently as the framework growth proceeds. Our greater understanding of such solution species and their role in crystallization will guide future syntheses of designed functional coordination polymers.     

Large coupled magnetoresponses in EuNbO2N

We have explored a new strategy to discover materials with large resistive or capacitive responses to magnetic fields by synthesizing EuMO2N (M = Nb, Ta) perovskites that combine ferromagnetic order of S = 7/2 Eu2+ spins with possible off-center distortions of the d0 M5+ cations enhanced by covalent bonding to N. EuNbO2N shows colossal magnetoresistances at low temperatures and a giant magnetocapacitance. However, the latter response originates from a microstructural effect rather than an intrinsic multiferroism.     

Combined powder neutron and X-ray diffraction study of charge and orbital order in Bi0.75Sr0.25MnO3

The room temperature structure of Bi_0.75Sr_0.25MnO₃ has been fitted to high-resolution synchrotron X-ray and time-of-flight neutron powder diffraction data. Constrained structural models were refined using a Pn11 supercell (, , , and α=89.894(1)°) of the underlying Pnma perovskite structure. The best-fit model evidences a 3:1 Mn³⁺/Mn⁴⁺charge ordering with only 30% of the ideal separation of bond valence sums. An ordered intergrowth of antiferro-orbitally ordered (LaMnO₃ type) and charge and ferro-orbitally ordered (YBaMn₂O₆ type) blocks is observed. Off-centre Bi/Sr displacements are ferroelectrically ordered in this model.     

Materials Discovery and Crystal Growth of Zeolite A Type Zeolitic–Imidazolate Frameworks Revealed by Atomic Force Microscopy

A new zeolitic–imidazolate framework (ZIF), [Zn(imidazolate)_2?x(benzimidazolate)_x], that has the zeolite A (LTA) framework topology and contains relatively inexpensive organic linkers has been revealed using in situ atomic force microscopy. The new material was grown on the structure‐directing surface of [Zn(imidazolate)_1.5(5‐chlorobenzimidazolate)_0.5] (ZIF‐76) crystals, a metal–organic framework (MOF) that also possesses the LTA framework topology. The crystal growth processes for both [Zn(imidazolate)_2?x(benzimidazolate)_x] and ZIF‐76 were observed using in situ atomic force microscopy; it is the first time the growth process of a nanoporous material with the complex zeolite A (LTA) framework topology has been monitored temporally at the nanoscale. The results reveal the crystal growth mechanisms and possible surface terminations on the {100} and {111} facets of the materials under low supersaturation conditions. Surface growth of these structurally complex materials was found to proceed through both “birth‐and‐spread” and spiral crystal‐growth mechanisms, with the former occurring through the nucleation and spreading of metastable and stable sub‐layers reliant on the presence of non‐framework species to bridge the framework during formation. These results support the notion that the latter process may be a general mechanism of surface crystal growth applicable to numerous crystalline nanoporous materials of differing complexity and demonstrate that the methodology of seeded crystal growth can be used to discover previously unobtainable ZIFs and MOFs with desirable framework compositions.