skip to main content

Title: Core–shell adsorbents by electrospun MOF‐polymer composites with improved adsorption properties: Theory and experiments
Abstract

A new class of core–shell adsorbents has been created by electrospun metal–organic framework (MOF) particles embedded in polymer nanofibers, which have provided many unique properties compared to the existing MOF coating technologies. For the first time, we demonstrate the improved adsorption selectivity of CO2over N2using electrospun polymer/ZIF‐8 adsorbents in experiments. Furthermore, an analytical model based on the assumption that the diffusivity in core is 10 times higher than that in shell is developed to describe the theory of improved selectivity for core–shell adsorbents that is validated against a more accurate finite element model developed in COMSOL. Our model shows three regimes including exclusive shell uptake, linear core uptake, and asymptotic core uptake. These regimes are related to material properties and uptake times, which could be used as design criteria to balance core stability, maximum selectivity, and maximum uptake. An advanced HAADF STEM tomography (MovieS1) shows that the shell thickness in the case of polymer/ZIF‐8 is on the order of 10 nm, allowing the regime of maximum selectivity to be realized. Kinetically limited adsorption tests at 45°C demonstrate that these composite fibers can perform in a regime of selectivity and uptake for the separation of CO2and N2that is unobtainable more » by either the MOF or fiber independently, showing a great potential for postcombustion CO2capture.

« less
Authors:
 ;  ;  ;  
Award ID(s):
1825594
Publication Date:
NSF-PAR ID:
10455346
Journal Name:
AIChE Journal
Volume:
66
Issue:
2
ISSN:
0001-1541
Publisher:
Wiley Blackwell (John Wiley & Sons)
Sponsoring Org:
National Science Foundation
More Like this
  1. Recently, metal–organic framework (MOF)-based polymeric substrates show promising performance in many engineering and technology fields. However, a commonly known drawback of MOF/polymer composites is MOF crystal encapsulation and reduced surface area. This work reports a facile and gentle strategy to produce self-supported MOF predominant hollow fiber mats. A wide range of hollow MOFs including MIL-53(Al)–NH 2 , Al-PMOF, and ZIF-8 are successfully fabricated by our synthetic method. The synthetic strategy combines atomic layer deposition (ALD) of metal oxides onto polymer fibers and subsequent selective removal of polymer components followed by conversion of remaining hollow metal oxides into freestanding MOF predominant hollow fiber structures. The hollow MOFs show boosted surface area, superb porosity, and excellent pore accessibility, and exhibit a significantly improved performance in CO 2 adsorption (3.30 mmol g −1 ), CO 2 /N 2 separation selectivity (24.9 and 21.2 for 15/85 and 50/50 CO 2 /N 2 mixtures), and catalytic removal of HCHO (complete oxidation of 150 ppm within 60 min).
  2. Metal–organic frameworks (MOFs), along with other novel adsorbents, are frequently proposed as candidate materials to selectively adsorb CO 2 for carbon capture processes. However, adsorbents designed to strongly bind CO 2 nearly always bind H 2 O strongly (sometimes even more so). Given that water is present in significant quantities in the inlet streams of most carbon capture processes, a method that avoids H 2 O competition for the CO 2 binding sites would be technologically valuable. In this paper, we consider a novel core–shell MOF design strategy, where a high-CO 2 -capacity MOF “core” is protected from competitive H 2 O-binding via a MOF “shell” that has very slow water diffusion. We consider a high-frequency adsorption/desorption cycle that regenerates the adsorbents before water can pass through the shell and enter the core. To identify optimal core–shell MOF pairs, we use a combination of experimental measurements, computational modeling, and multiphysics modeling. Our library of MOFs is created from two starting MOFs-UiO-66 and UiO-67-augmented with 30 possible functional group variations, yielding 1740 possible core–shell MOF pairs. After defining a performance score to rank these pairs, we identified 10 core–shell MOF candidates that significantly outperform any of the MOFs functioning alone.
  3. Abstract

    We elucidate the structural evolution of CoN4sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)‐8‐derived carbon host as an ideal model for Co2+ion adsorption. Subsequent in situ X‐ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co−OH and Co−O species into active CoN4sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four‐electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal‐induced compressive strain of Co−N bonds in CoN4active sites formed at 900 °C. Further, we developed a two‐step (i.e., Co ion doping and adsorption) Co‐N‐C catalyst with increased CoN4site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

  4. Abstract

    We elucidate the structural evolution of CoN4sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)‐8‐derived carbon host as an ideal model for Co2+ion adsorption. Subsequent in situ X‐ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co−OH and Co−O species into active CoN4sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four‐electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal‐induced compressive strain of Co−N bonds in CoN4active sites formed at 900 °C. Further, we developed a two‐step (i.e., Co ion doping and adsorption) Co‐N‐C catalyst with increased CoN4site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

  5. Direct air capture (DAC) of CO2is an emerging technology in the battle against climate change. Many sorbent materials and different technologies such as moisture swing sorption have been explored for this application. However, developing efficient scaffolds to adopt promising sorbents with fast kinetics is challenging, and very limited effort has been reported to address this critical issue. In this work, the availability and kinetic uptake of CO2in sorbents embedded in various matrices are studied. Three scaffolds including a commercially available industrial film containing ion‐exchange resin (IER), IER particles embedded in dense electrospun fibers, and IER particles embedded in porous electrospun fibers are compared, in which a solvothermal polymer additive removal technique is used to create porosity in porous fibers. A frequency response technique is developed to measure the uptake capacity, sorbent availability, and kinetic uptake rate. The porous fiber has 90% IER availability, while the dense fibers have 50% particle accessibility. The sorption half time for both electrospun fiber samples is 10 ± 3 min. Our experimental results demonstrate that electrospinning polymer/sorbent composites is a promising technology to facilitate the handleability of sorbent particles and to improve the sorption kinetics, in which the IER embedded in porous electrospun fibers shows the highestmore »cycle capacity with an uptake rate of 1.4 mol CO2per gram‐hour. © 2018 American Institute of Chemical EngineersAIChE J, 65: 214–220, 2019

    « less