A chemical cosubstitution strategy was implemented to design potential ultraviolet (UV) and deep-UV nonlinear optical (NLO) materials. Taking the classic β-BaB2O4 as a maternal structure, by simultaneously replacing the Ba2+ and [B3O6]3– units with monovalant (K+), divalent (alkaline earth metal), trivalent (rare-earth metal, Bi3+) ions, and the [B5O10]5– clusters through two different practical routes, 12 new mixed-metal noncentrosymmetric borates K7MIIRE2(B5O10)3 (MII = Ca, Sr, Ba, K/RE0.5; RE = Y, Lu, Gd) as well as K7MIIBi2(B5O10)3 (MII = Pb, Sr) were successfully designed and synthesized as high-quality single crystals. The selected K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3 compounds were subjected to experimental and theoretical characterizations. They all exhibit suitable second-harmonic generation (SHG) responses, as large as that of commercial KH2PO4 (KDP), and also exhibit short UV cutoff edges. These results confirm the feasibility of this chemical cosubstitution strategy to design NLO...

Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as Potential Ultraviolet Nonlinear Optical Materials.

Anthropogenic emissions have developed the environmental demands for proficient carbon dioxide (CO2) separation technologies Adsorption and membrane technologies are widely used to separate CO2 from other light gases due to their multiple technological benefits, including but not limited to factors such as energy efficiency and low environmental footprint In this context, zeolites are often used due to their intrinsic molecular sieving capacity This review initially addresses recent technological advances to enhance the gas separation performance of zeolite materials Current trends directed toward improving CO2 adsorption capacity of zeolites include amine, silica, and ion-exchange modifications Other promising efforts to improve the adsorption performance of zeolites involve processing zeolite nanoparticles, nanofibers, and zeolite-based foams The second part of the review deals with pristine and modified zeolites beneficial properties for designing polymer-based mixed matrix membranes (MMMs), which enable to adapt a desirable gas separation performance The gas transport mechanisms and morphological properties of MMMs are essential This review addresses the most current strategies used to improve interfacial adhesions between zeolite particulates and polymer matrices to overcome the trade-off between gas selectivity and permeability faced by pure polymeric membranes Filler shape and size play vital roles in determining the filler and polymer matrix's interfacial adhesions New structures of inorganic fillers have been designed to fabricate MMMs with excellent gas transport properties Hollow zeolite spheres (HZSs) are particularly interesting as they effectively minimize agglomeration and improve filler dispersion in the polymer matrix Furthermore, approaches that employ nanoporous layered fillers, including AMH-3 and Jilin-Davy-Faraday, layered solid No 1 (JDF-L1), have been reviewed to overcome the limitation of incorporating high contents of zeolites, which are required to improve the gas transport properties of MMMs Furthermore, this review explores implementing zeolitic imidazolate frameworks (ZIFs) in MMMs because of their tunable pore structure and remarkably high adsorption capacity and surface area as well as excellent chemical and thermal properties Lastly, we address the prospects and future developments in gas separation applications

A review on recent advances in CO2 separation using zeolite and zeolite-like materials as adsorbents and fillers in mixed matrix membranes (MMMs)

More than 3900 crystalline borates, including borate minerals and synthetic inorganic borates, in addition to a wealth of industrially-important boron-containing glasses, have been discovered and characterized. Of these compounds, 99.9 % contain only the traditional triangular BO3 and tetrahedral BO4 units, which polymerize into superstructural motifs. Herein, a mixed metal K5Ba2(B10O17)2(BO2) with linear BO2 structural units was obtained, pushing the boundaries of structural diversity and providing a direct strategy toward the maximum thresholds of birefringence for optical materials design. 11B solid-state nuclear magnetic resonance (NMR) is a ubiquitous tool in the study of glasses and optical materials; here, density functional theory-based NMR crystallography guided the direct characterization of BO2 structural units. The full anisotropic shift and quadrupolar tensors of linear BO2 were extracted from K5Ba2(B10O17)2(BO2) containing BO2, BO3, and BO4 and serve as guides to the identification of this powerful moiety in future and, potentially, previously-characterized borate minerals, ceramics, and glasses.

/pdf/expanding-the-chemistry-of-borates-with-functional-bo2-4psoh4106x.pdf

Expanding the chemistry of borates with functional [BO2]- anions.

In the early stage of membrane technology development in gas separation, utilization of polymeric membranes has gained attention due to their robustness and ease of fabrication. However, the performance of polymeric membranes is limited by the trade-off between permeability and selectivity. Meanwhile, inorganic membrane is capable to exhibit great enhancement in separation performance but unfortunately its fabrication process is hard and costly. Thus, development of mixed matrix membranes (MMMs) by incorporating inorganic fillers into the polymer matrix has become a potential alternative to overcome the limitations of polymeric and inorganic membranes in gas separation. Nevertheless, fabrication of defect-free MMMs with improved separation performance and without compromising the mechanical and thermal stability is extremely difficult and challenging. In the current review paper, various types of inorganic fillers for MMMs fabrication and recent reported efforts to tailor the underlying problems on MMMs f...

Current Development and Challenges of Mixed Matrix Membranes for CO2/CH4 Separation

A new borate LiBa3 (OH)[B9 O16 ][B(OH)4 ], which combines the uniform porosity of open-frameworks with the extraordinary NLO properties of borates, has been obtained under hydrothermal conditions by using mixed lithium and barium ions as templates. The framework displays an acs-type net with large 21-ring channels. The second harmonic generation (SHG) measurement shows that it is a type I phase-matchable material with a strong SHG signal intensity about 3.1 times that of KDP (KH2 PO4 ). UV/Vis-NIR diffuse reflectance analysis indicates that the compound has a wide transparency range with the short-wavelength absorption edge below 200 nm. These characteristics reveal that the compound is a promising deep-UV nonlinear optical material.

Deep-Ultraviolet Nonlinear Optics in a Borate Framework with 21-Ring Channels

Na2B10O17·H2en: a three-dimensional open-framework layered borate co-templated by inorganic cations and organic amines

Two new cluster open framework borates, NaB3O5·0.5H2O (1) and NH4NaB6O10 (2) have been made under solvothermal conditions and characterized by IR, emission, and diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. The common structural features contain the oxoboron cluster building units, B3O7 and B6O13 cluster units for 1 and 2, in which the B3O7 and B6O13 clusters act as 4- and 6-connected nodes to further link each other, resulting in chiral qtz and achiral pcu nets, respectively.

NaB3O5·0.5H2O and NH4NaB6O10: Two Cluster Open Frameworks with Chiral Quartz and Achiral Primitive Cubic Nets Constructed from Oxo Boron Cluster Building Units

The new compounds (III) and (V) are characterized by single crystal XRD and IR, emission, and UV/VIS diffuse reflectance spectroscopy.

NaB3O5·0.5H2O and NH4NaB6O10: Two Cluster Open Frameworks with Chiral Quartz and Achiral Primitive Cubic Nets Constructed from Oxo Boron Cluster Building Units.

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Na2B10O17·H2en: a three-dimensional open-framework layered borate co-templated by inorganic cations and organic amines

NaB3O5·0.5H2O and NH4NaB6O10: Two Cluster Open Frameworks with Chiral Quartz and Achiral Primitive Cubic Nets Constructed from Oxo Boron Cluster Building Units

NaB3O5·0.5H2O and NH4NaB6O10: Two Cluster Open Frameworks with Chiral Quartz and Achiral Primitive Cubic Nets Constructed from Oxo Boron Cluster Building Units.