Synthesis, Characterization, Modeling and Applications of Functional Porous Materials: Functional Porous Materials I
Sponsored by: ACerS: Engineering Ceramics Division, ACerS: Electronics Divisions
Program Organizers: Lan Li, Boise State University; Winnie Wong-Ng, National Institute of Standards and Technology; Kevin Huang, University of South Carolina
Monday 8:00 AM
November 2, 2020
Room: Virtual Meeting Room 21
Location: MS&T Virtual
Session Chair: Lawrence Cook, The Catholic University of America; Kevin Huang, University of South Carolina
8:00 AM
Introductory Comments: Synthesis, Characterization, Modeling and Applications of Functional Porous Materials: Lan Li1; 1Boise State University
Introductory Comments
8:05 AM Invited
Synchrotron Structure and Sorption Properties of a Metal Organic Framework Compound Ni(3-methyl-4,4’-bipyridine)[Ni(CN)4] for CO2 Mitigation Application: Winnie Wong-Ng1; Jeffrey Culp2; Yu-Sheng Chen3; SuYin Wang3; Daniel Siderius1; Andrew Allen1; Eric Cockayne1; 1National Institute of Standards and Technology; 2LRST/Battelle, National Energy Technology Laboratory; 3University of Chicago
As a major result of fossil fuel burning, CO2 capture and storage (CCS) technology is critical to mitigate global warming. Ni(CN)4-based metal organic framework (MOF) compounds could be effective sorbent materials. The structure of Ni(3-methyl-4,4’-bipyridine)[Ni(CN)4] (Ni-BpyMe) was determined to be different when dimethyl sulfonate (DMSO) and acetone (followed by evacuation) were used as solvent of crystallization. The structure of Ni-BpyMe consists of a 3-D net built from extended 2-D [Ni(CN)4] groups. These layers are connected via the BpyMe ligands at the six-fold Ni2 sites. Ni1 has a four-fold coordination environment. The interesting feature of this structure is that instead of locating the -CH3 group in one position of the pyridine ring, it appears in two positions in both cases due to disorder. Sorption study indicated the compound to be a relatively rigid MOF as no hysteresis loop was observed. A comparison of the two structures will be given.
8:35 AM Invited
Density Functional Theory Study of the Porous Metal-organic Framework Material Ni-Bpy-Me: Eric Cockayne1; Winnie Wong-Ng1; Andrew Allen1; 1National Institute of Standards and Technology
Density functional theory methods are used to study the pillared metal-organic framework material Ni(3-methyl-4,4'-bipyridine)[Ni(CN)4] ("Ni-Bpy-Me" or "PICNIC 21"). The organic ligand in Ni-Bpy-Me has a lower symmetry than that for the related material Ni-Bpene [Allen et al., Nanomaterials, doi: 10.3390/nano9030354], allowing for a greater variety of possible ligand orientation orderings. X-ray powder diffraction results show that the unit cell of Ni-Bpy-Me expands and undergoes a slight change in shape as CO2 is adsorbed. We use density functional theory electronic structure calculations to investigate the unit cell parameters, preferred CO2 adsorption sites, and preferred Bpy-Me orientational ordering patterns as a function of CO2 concentration. The results are compared with experimental measurements on this system.
9:05 AM Invited
Experimental Thermodynamics of Zeolites and Metal-organic Frameworks: Xianghui Zhang1; Cody Cockreham1; Esra Yılmaz1; Baodong Wang2; Hui Sun3; Di Wu1; 1Washington State University; 2National Institute of Clean-and-Low-Carbon Energy; 3East China University of Science and Technology
The development, characterization and applications of porous materials are critical for sustainable conversion and separation of petrochemical compounds, carbon capture and sequestration. Here, I introduce our recent experimental thermodynamic (calorimetric) studies on the synthesis, application and decomposition of two families of porous materials, zeolites and metal-organic frameworks (MOFs), including in situ synthesis of spherical zeolite A and X pellets, energetics of transition metal ion-exchanged zeolites (mordenite, ZSM-5 and SSZ-13), thermal decomposition of bimetallic MOF-74 and the applications of zeolites and MOFs in hydrocarbon separation. The results highlight the crucial role of thermodynamic factors, which govern the material stability and guest – host interactions.
9:35 AM
Luminescent Metal-organic Framework-Based Sensors of Rare Earth Elements in Aqueous Streams: Scott Crawford1; John Baltrus1; Paul Ohodnicki1; 1National Energy Technology Laboratory
Rare earth elements (REEs) are critically important to numerous advanced technologies. Yet factors including monopolistic conditions, expensive separation of co-mined REE ores, and environmental concerns have destabilized the global supply of REEs. Consequently, significant effort has been devoted to increasing REE domestic production, including the extraction of REEs from coal and associated waste streams such as acid mine drainage. Analytical techniques for quantification of REE content in aqueous phases can facilitate REE recovery through rapid identification of high-value waste streams. Here, the porous metal-organic framework BioMOF-100 is evaluated as a fluorescence-based sensor for emissive lanthanides in water, providing rapid (<10 minute) analysis times and sensitive detection (part-per-billion levels) for terbium, dysprosium, samarium, europium, ytterbium, and neodymium in aqueous conditions or following REE extraction into organic solvents. Sensing is also demonstrated using a low-cost, portable, optical fiber-based spectrometer to highlight the potential of the BioMOF-100 sensor for field use.
9:55 AM Invited
Porous Organic Cage Composite Membranes for Post-combustion CO2 Separation: Fangming Xiang1; David Hopkinson1; 1National Energy Technology Laboratory
Porous Organic Cage (POC) is an emerging class of materials that features high surface area (up to 3758 m2/g) and purely organic composition, which makes it likely to be more compatible with polymer composites such as mixed matrix membranes. Despite its great potential, POC has rarely been used in polymer composites. This lack of representation is likely caused by the poor dispersibility of crystalline POC particles. Although it is possible to improve the dispersibility of POC by scrambling its crystal structure to create an amorphous analogue, we will show in this talk that it is possible to uniformly disperse crystalline POC nanoparticles in a polymer matrix using carefully designed fabrication conditions. The addition of 30 wt% POC nanoparticles improved the CO2 permeability and CO2/N2 selectivity of a Matrimid membrane by 763% and 26%, respectively. This result exceeds the performance improvement reported previously for a Matrimid composite membrane with amorphous POC.
10:25 AM
Thermodynamics of Naturally Occurring 2D and 3D Mineral Hosts: Zeolites, Layered Double Hydroxides and Clays: Xianghui Zhang1; Cody Cockreham1; Su Ha1; Di Wu1; 1Washington State University
Zeolites, layered double hydroxides (LDHs) and clays are naturally occurring mineral hosts, which accommodate guest species, such as water, carbon dioxide, ions and organic species in natural environments and industry applications. Here, I present our study on the thermodynamic stability and energetics of guest – host interactions within transition metal ion-exchanged mordenite (TM-MOR), nickel-aluminum bimetallic LDH and a series of clays using various calorimetric techniques, including thermogravimetric analysis – differential scanning calorimetry – mass spectroscopy (TG-DSC-MS) analysis, water adsorption calorimetry and near-room temperature acid solution drop solution calorimetry. Coupled with in situ FTIR and in situ XRD analyses, our results suggest complex interplays among compositional, structural and interfacial factors, which are governed by the overall energetic state of each system, and determine the properties of 2D and 3D mineral hosts in both natural environment and industrial applications.