SO2 Capture Using Porous Organic Cages Martínez‐Ahumada, Eva; He, Donglin; Berryman, Victoria ...
Angewandte Chemie (International ed.),
August 2, 2021, Letnik:
60, Številka:
32
Journal Article
Recenzirano
Odprti dostop
We report the first experimental investigation of porous organic cages (POCs) for the demanding challenge of SO2 capture. Three structurally related N‐containing cage molecular materials were ...studied. An imine‐functionalized POC (CC3) showed modest and reversible SO2 capture, while a secondary‐amine POC (RCC3) exhibited high but irreversible SO2 capture. A tertiary amine POC (6FT‐RCC3) demonstrated very high SO2 capture (13.78 mmol g−1; 16.4 SO2 molecules per cage) combined with excellent reversibility for at least 50 adsorption–desorption cycles. The adsorption behavior was investigated by FTIR spectroscopy, 13C CP‐MAS NMR experiments, and computational calculations.
Porous organic cages (POCs) were investigated for the first time for the capture of SO2. A tertiary amine cage (6FT‐RCC3) demonstrated remarkably high SO2 capture that was perfectly reversible for at least 50 adsorption–desorption cycles.
Metal–organic frameworks (MOFs) are some of the most interesting and promising candidates to sequester toxic H2S and SO2 gases. MOFs show interesting advantages over classic porous materials due to ...their chemical composition, ligand functionality, cavity dimensions, ease of preparation, and relatively low cost reactivation. The optimization of the physical–chemical interactions between MOFs and H2S and SO2 molecules is the key to further amplification of their capture. Reversibility after the adsorption of H2S and SO2 can be modulated through noncovalent bonding between functionalized ligands (within MOF structures) and H2S and SO2. This review aims to summarize recent advances in the development of MOF-based systems for the capture and removal of H2S and SO2. We anticipate that this review article can offer very useful information on the significant and rapid progress of the enhancement of H2S and SO2 capture by MOFs.
The first bioinspired microporous metal–organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi2O(H2O)2(C14H2O8)·nH2O ...(SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bioinspired MOF (pH = 2–14, hydrothermal conditions, heated organic solvents, biological media, SO2 and H2S), attributed to the strongly chelating phenolates. A total H2S uptake of 15.95 mmol g–1 was recorded, representing one of the highest H2S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery.
MOFs are promising candidates for the capture of toxic gases since their adsorption properties can be tuned as a function of the topology and chemical composition of the pores. Although the main ...drawback of MOFs is their vulnerability to these highly corrosive gases which can compromise their chemical stability, remarkable examples have demonstrated high chemical stability to SO2, H2S, NH3 and NOx. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases. Thus, the interactions of such functional groups (coordinatively unsaturated metal sites, μ-OH groups, defective sites and halogen groups) with these toxic molecules, not only determines the capture properties of MOFs, but also can provide a guideline for the desigh of new multi-functionalised MOF materials. Thus, this perspective aims to provide valuable information on the significant progress on this environmental-remediation field, which could inspire more investigators to provide more and novel research on such challenging task.
Metal–organic frameworks MIL-53(Al)-TDC and MIL-53(Al)-BDC were explored in the SO2 adsorption process. MIL-53(Al)-TDC was shown to behave as a rigid-like material upon SO2 adsorption. On the ...other hand, MIL-53(Al)-BDC exhibits guest-induced flexibility of the framework with the presence of multiple steps in the SO2 adsorption isotherm that was related through molecular simulations to the existence of three different pore opening phases narrow pore, intermediate pore, and large pore. Both materials proved to be exceptional candidates for SO2 capture, even under wet conditions, with excellent SO2 adsorption, good cycling, chemical stability, and easy regeneration. Further, we propose MIL-53(Al)-TDC and MIL-53(A)-BDC of potential interest for SO2 sensing and SO2 storage/transportation, respectively.
An unprecedented reversible guest-induced metal-linker bond rearrangement in metal–organic framework (MOFs) was revealed by quantum-calculations and DRIFT experiments. As a showcase, the prototypical ...MOF-type MFM-300(Sc) was demonstrated to undergo a substantial Sc-carboxylate bond dynamics upon ammonia adsorption to enable a strong metal–guest binding mode, a key feature to ensure a highly efficient capture of this toxic molecule. Decisively, we evidenced this adsorption mechanism to be fully reversible, preserving the ammonia capture performance and structure integrity over multiple cycles. Such an unconventional mechanism in MOFs can open up new avenues to design novel materials for an efficient capture of highly corrosive molecules.
SO2 Capture and Oxidation in a Pd6L8 Metal–Organic Cage Valencia-Loza, Sergio de Jesús; López-Olvera, Alfredo; Martínez-Ahumada, Eva ...
ACS applied materials & interfaces,
04/2021, Letnik:
13, Številka:
16
Journal Article
Recenzirano
The facile and green preparation of novel materials that capture sulfur dioxide (SO2) with significant uptake at room temperature remains challenging, but it is crucial for public health and the ...environment. Herein, we explored for the first time the SO2 adsorption within microporous metal–organic cages using the palladium(II)-based Pd6L8 ( NO 3 ) 36 tetragonal prism 1, assembled in water under mild conditions. Notably and despite the low BET surface area of 1 (111 m2 g–1), sulfur dioxide was found to be irreversibly and strongly adsorbed within the activated cage at 298 K (up to 6.07 mmol g–1). The measured values for the molar enthalpy of adsorption (ΔH ads) coupled to the FTIR analyses imply a chemisorption process that involves the direct interaction of SO2 with Pd(II) sites and the subsequent oxidation of this toxic chemical by the action of the nitrate anions in 1. To the best of our knowledge, this is the first reported metal–organic cage that proves useful for SO2 adsorption. Metallosupramolecular adsorbents such as 1 could enable new detection applications and suggest that the integration of soft metal ions and self-assembly of molecular cages are a potential means for the easy tuning of SO2 adsorption capabilities and behavior.
Capture, storage and subsequent controlled release or transformation of sulfur dioxide (SO2) in mild conditions is still a challenge in the material science field. Recent advances in the use of ...porous materials have demonstrated good SO2 capture, particularly in metal‐organic frameworks (MOFs), metal‐organic cages (MOCs), and porous organic cages (POCs). The striking feature of these porous materials is the high SO2 uptake capacity in reversible settings. A partially fluorinated MIL‐101(Cr) is stand‐alone material with the highest SO2 uptake in chemically stable MOFs. Likewise, metal‐free adsorbents like POCs exhibits a reversible SO2 uptake behavior. The SO2 adsorption characteristics of these three structurally and functionally unique adsorbent systems are highly dependent on the binding sites and mode of binding of SO2 molecules. This Review has highlighted the preferential binding sites in these materials to give a full perspective on the field. We anticipate that it will offer valuable information on the progress made towards improving SO2 capture by hybrid systems.
Among the porous materials used for SO2 adsorption, the hybrid materials, MOFs and MOCs, as well as purely organic materials POCs are reviewed below. These porous frameworks have proven to be good SO2 adsorbents and, depending on their functionalization, can avoid structure collapse and even reach as high as 18.4 mmol g−1 in MOFs.
MUF-16 is a porous metal–organic framework comprising cobalt(II) ions and 5-aminoisophthalate ligands. Here, we measured its reversible SO2 adsorption–desorption isotherm around room temperature and ...up to 1 bar and observed a high capacity for SO2 (2.2 mmol g–1 at 298 K and 1 bar). The uptake of SO2 was characterized by Fourier transform infrared (FT-IR) spectroscopy, which indicated hydrogen bonding between the SO2 guest molecules and amino functional groups of the framework. The location and packing of the SO2 molecules were confirmed by computational studies, namely, density functional theory (DFT) calculations of the strongest adsorption site and grand canonical Monte Carlo (GCMC) simulations of the adsorption isotherm. Furthermore, MUF-16 showed a remarkable selective fluorescence response to SO2 compared to other gases (CO2, NO2, N2, O2, CH4, and water vapor). The possible fluorescence mechanism was determined by using time-resolved photoluminescence. Also, the limit of detection (LOD) was calculated to be 1.26 mM (∼80.72 ppm) in a tetrahydrofuran (THF) solution of SO2.
Understanding the Mechanism of Amorphization for Co‐URJC‐5 López‐Olvera, Alfredo; Montes‐Andrés, Helena; Martínez‐Ahumada, Eva ...
European journal of inorganic chemistry,
November 22, 2021, Letnik:
2021, Številka:
43
Journal Article
Recenzirano
Irreversible transition from monocrystalline to amorphous phase accompanied by a change in coordination geometry (octahedral to tetrahedral) was first observed in a Co(II)‐based MOF material, named ...Co‐URJC‐5, via SO2 uptake. This structural change is associated with the total loss of the pyridine ligand from the axial positions. These results are corroborated using PXRD and FT‐IR spectroscopy. A plausible amorphization mechanism is proposed using crystal field theory.
Irreversible single crystal‐to‐amorphous‐phase transition accompanied by a coordination geometry change (octahedral to tetrahedral) was first observed in a Co(II)‐based MOF material, namely as Co‐URJC‐5 via SO2 uptake.
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