Synthesis, Characterization, Modeling and Applications of Functional Porous Materials: On-Demand Oral Session: Functional Porous Materials
Sponsored by: ACerS Electronics Division, ACerS Engineering Ceramics Division
Program Organizers: Lan Li, Boise State University; Winnie Wong-Ng, National Institute of Standards and Technology; Kevin Huang, University of South Carolina
Friday 8:00 AM
October 22, 2021
Room: On-Demand Room 12
Location: MS&T On Demand
Session Chair: Lan Li, Boise State University
Invited
Probing the Mechanisms of Reactive Capture and Conversion of CO2 into Inorganic Carbonates Using Architected Calcium and Magnesium Silicates: Greeshma Gadikota1; Tianhe Yin1; Xun Gao1; Hassnain Asgar1; 1Cornell University
The urgency in developing scalable and realizable pathways to capture and convert CO2 to inorganic carbonates motivate the advancement of energy efficient approaches. Integrated, single-step reactive capture and conversion pathways of CO2 to produce inorganic carbonates can be developed by harnessing regenerable aqueous solvents to increase the concentration of dissolved inorganic carbon to produce Ca- or Mg-carbonates. Earth abundant Ca- and Mg-silicates have been proposed as a resource for carbon mineralization. However, a calibrated understanding of CO2-aqueous solvents- Ca- and Mg-silicates is limited by the morphological heterogeneity in these naturally occurring minerals. To address this challenge, sol-gel approaches are used to architect Ca- and Mg-silicates with regular pore architectures. We delineate the chemo-morphological mechanisms underlying integrated CO2 capture and conversion to produce inorganic carbonates using regenerable solvents (e.g., sodium glycinate). Mechanistic insights into the transformations of Ca- and Mg-silicates to inorganic carbonates are gleaned from in-operando cross-scale X-ray scattering measurements.
Invited
Hydrogen-bonded Organic Framework Materials for Gas Separation: Wei Zhou1; 1National Institute of Standards and Technology
Hydrogen-bonded organic frameworks (HOFs) are an interesting family of polymeric porous materials that can be easily self-assembled through H-bonding interaction between organic building units. Owing to the reversible and flexible nature of H-bonding connections, HOF materials often exhibit high crystallinity, solution processability, and tunable porosity. These unique features make HOFs highly versatile and multifunctional. One of the promising applications of HOF materials is gas separation. In this talk, I will present our recent work on using computational modeling and various experimental techniques to study the gas adsorption and separation properties of several newly developed HOF materials. I will discuss the gas adsorption energetics and separation mechanisms in these materials. The insights obtained from our studies provide important guidance for further development of new HOFs for gas separation application.
Invited
Layer-by-layer Assembled Polymer/MOF Membrane for H2/CO2 Separation: Fangming Xiang1; David Hopkinson1; 1National Energy Technology Laboratory
Numerous investigators have produced polymer composites containing metal-organic framework (MOF) filler particles in attempts to combine the processability of polymers and the gas selectivity of MOF particles. However, filler particle aggregation and weak filler-matrix interaction have sometimes led to poor gas separation performance. In this study, we combined polyvinylpyrrolidone modified UiO-66-PA particles (PVP + MOF) with poly(acrylic acid) (PAA) through H-bonding assisted layer-by-layer assembly. The resultant PAA/(PVP + MOF) bilayers feature individually dispersed fillers and strong filler-matrix interaction. Of note, this filler-matrix interaction is stronger than the internal strength of fillers, which is a phenomenon previously not seen in polymer/MOF composites. This polymer/MOF membrane is more selective (H2/CO2 = 20.3) than its neat polymer counterpart (H2/CO2 = 12.5) as well as several pure-MOF membranes that were reported previously (H2/CO2 < 10).
Invited
Small Molecules as Guests in Metal-organic Frameworks: Craig Brown1; 1 National Institute of Standards and Technology
Adsorption of molecules in functionalized and high surface area metal-organic frameworks (MOFs) is of emergent technological importance ranging from chemical separations to energy storage. We study the properties of MOFs and other porous materials for storage and separations of industrially important small molecules such as hydrogen, oxygen, carbon dioxide, noble gases, and short chain organics. Besides the geometrical and porosity control available in MOF chemistry, the properties of the frameworks can be tweaked to elevate electrostatic interactions by exposing open metal cation sites or through enhanced van der Waals contacts via functionalizing ligands and introducing flexibility. Here, we discuss the information accessible from neutron and X-ray scattering experiments on a selection of nominally rigid MOFs and those with some flexibility that respond to guests in specific ways dependent upon the exact guest-framework interactions. The results illustrate the governing characteristics of these material properties and the interactions with the guest molecules.
Invited
Thermodynamics of Molybdenum Oxide Clusters Encapsulated in Zeolite Y: Xianghui Zhang1; Vitaliy Goncharov1; Cody Cockreham1; Esra Mertsoy1; Hui Sun2; Su Ha1; Jean-Sabin McEwen1; Xiaofeng Guo1; Di Wu1; 1Washington State University; 2East China University of Science and Technology
Subnanoscale encapsulation of molybdenum (Mo) oxides within zeolites leads to low-cost catalytic materials with comparable performance as precious metal containing zeolite catalysts in important industry scale reactions such as methane conversion and biomass upgrading. Despite extensive exploration in material synthesis, catalytic mechanisms and reaction engineering, the thermodynamics of subnano-encapsulated Mo oxide clusters within the micropores of zeolites are rarely investigated. Here, we present our recent studies on the energetic, structural and catalytic performance evolutions of Mo oxides confined in a family of zeolite Y with faujasite (FAU) topology (Si/Al from 2.9 to 45.6). Using high temperature solution calorimetry, thermal analysis with integrated TG-DSC-MS, in situ XRD, in situ DRIFTS, electron microscopy and a catalyst evaluation system, we successfully measured the formation enthalpies of these MoOx/FAU samples, and elucidated their energetics-structure-performance relationships in methane conversion.
Invited
Structure and CO2 Adsorption Sites in the Flexible Coordination Polymer Ni-Dbm-Bpy from DFT: Eric Cockayne1; Winnie Wong-Ng1; Andrew Allen1; 1National Institute of Standards and Technology
Bis-dibenzoylmethanato 4,4’-dipyridine nickel, or Ni-Dbm-Bpy for short, is a flexible coordination polymer system that accommodates a variety of guest molecules [Soldatov et al., Chem. Mater. 2003, 15, 4810-4818]. Soldatov et al. have refined the structure of the Ni-Dbm-Bpy host with chlorobenzene as a guest, but were unable to obtain sufficiently large single-crystal samples of empty Ni-Dbm-Bpy to determine its structure. Kauffman et al. [Angewandte Chemie 2011, 50, 10888-10892] found selective adsorption of CO2 over other light gases in this system and evidence for a phase transition upon sufficient CO2 adsorption. We use dispersion-corrected density functional theory calculations to model the structure of the empty Ni-Ddm-Bpy, and the favored positions of CO2 at low pressures. The origin of the extreme flexibility and the observed phase transition in this system is discussed in light of our results.
Invited
New Strategies for Defects Formation and Amorphization of Metal-organic Frameworks: Tomce Runcevski1; 1Southern Methodist University
The controlled introduction of defects into MOFs is a powerful strategy to induce new physiochemical properties and improve their performance for target applications. Herein, we present a new strategy for defect formation and amorphization of canonical MOF-74 frameworks based on fine-tuning of adsorbate–framework interactions in the metal congener, hence introducing structural defects. Specifically, we demonstrate that controlled interactions between the MOF and bidentate ligands adsorbed in the pores initiate defect formation and eventual amorphization of the crystal. These structural features unlock properties that are otherwise absent in the ordered framework, such as broad-band fluorescence. The ability to introduce defects by adsorbate–framework interactions, coupled with the inherent tunability and modularity of these structures, provides a new route for the synthesis of diverse heterogeneous and hybrid materials.
Material Characterization Testing of Synthetic Granular Composites Used in Equine Sports Surfaces: John Bridge1; Charles Liu1; Elijah Leonen1; Kris Weisshaupt2; Kaleb Dempsey3; 1University of Washington; 2MAP Laboratories LLC; 3Racing Surfaces Testing Lab
Current material analytical characterization methods for synthetic equine granular composites used in Thoroughbred horse racetracks equine sports arenas are discussed. These synthetic composites are currently becoming popular in North America and other parts of the world as a replacement for traditional dirt surfaces. These synthetic materials are composed of sand, polymer fiber, and rubber particulate components bound together by a wax polymeric binder. Materials testing is performed to analyze material constituent properties and how they change over time due to use, environmental effects, and surface maintenance with the goal of increasing the consistency, and subsequent safety, of the bulk equine sports surfaces. Binder and component tests discussed are Soxhlet extraction, TGA, DSC, GC-FID, FTIR, RI (refractive index), rheology, sand XRD, and microscopy. Correlations to associated new and proposed equine ASTM standards are addressed. Example test results are provided.
Chemical-aided Synthesis of Anorthite-sodalite-afghanite Porous Ceramics from
Granite-clay-plantain Peel Mix
: Odewole Oluwagbenga1; Kashim Bolaji2; Akinbogun Lawrence1; Folorunso Oladayo1; 1Federal University of Technology.; 2.Federal University of Technology.
Utilization of wastes and local raw materials for the synthesis of porous ceramics is a vital path towards achieving environmental sustainability. In this study porous ceramics were developed from a mix of granite powder, ball clay and plantain peel powder with the addition of NaOH and Na2SiO3 as sintering aid. Chemical analysis of the raw materials was carried out using X-ray Fluorescence spectrometry. The mixes obtained were uniaxially pressed at 10MPa and sintered at 8500C. The results of the physical and mechanical properties of the developed porous ceramics revealed water absorption (19.5-41.7%), bulk density (1.39-1.86g/cm3), apparent porosity of (36.4-66.7%) and compressive strength (0.9-18.4MPa). The X-ray Diffraction analysis of the representative sample showed anorthite, sodalite and afghanite crystalline phases. The microstructural analysis of the representative sample revealed inhomogeneous and open-celled morphology. The developed porous ceramics is a promising material for use in separation / filtration application given its unique mineralogical phases.