Molecular Motions of Adsorbed CO<sub>2</sub> on a Tetrazole-Functionalized PIM Polymer Studied with <sup>13</sup>C NMR

Moore, Julia; Guiver, Michael D.; Du, Naiying; Hayes, Sophia E.; Conradi, Mark S.

doi:10.1021/jp4084234

Cited by 8 publications

(35 citation statements)

References 28 publications

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“…In both PIM samples, the onset of hopping from the weakly adsorbed CO 2 molecules is evident at 80 K and the hopping occurs rapidly at 100 K. This result is demonstrated by the CSA powder pattern being averaged to zero. Because weakly adsorbed CO 2 molecules on both PIM-1 and MTZ-PIM exhibit a comparable hopping mechanism, also shown for TZ-PIM previously, 32 the second adsorption site on each polymer must be similar. When comparing the structure of these polymer samples, as shown in Figure 1, the consistent moiety in each sample is the polymer backbone.…”

Section: ■ Results and Discussionsupporting

confidence: 67%

“…The line narrowing that occurs due to joint translation−reorientation hopping has been studied previously in solid CO 2 , 30 α-CO, 35 The Journal of Physical Chemistry C Article N 2 O, 36 and benzene 37 as well as CO 2 adsorbed on an MOF material 12−14 and TZ-PIM. 32 As the temperature is increased further, the hopping motion becomes rapid on the NMR time scale, which time-averages the CSA interaction essentially to zero. With rapid CO 2 hopping between the orientationally random adsorption sites, the 13 C NMR spectrum is a single, symmetric resonance.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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CO₂ Adsorption on PIMs Studied with ¹³C NMR Spectroscopy

Moore¹,

Marti²,

Guiver³

et al. 2018

J. Phys. Chem. C

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Polymers of intrinsic microporosity (PIMs) can be functionalized with nitrogen-bearing groups, such as a nitrile group for PIM-1 and a methylated tetrazole group for MTZ-PIM, to physisorb CO 2. Static 13 C NMR spectroscopy was used to investigate CO 2 dynamics by analysis of onedimensional spectra and T 2 relaxation times at temperatures ranging from 6 to 295 K. Each polymer had two different loadings of CO 2 to determine the dominating relaxation mechanism at lower temperatures and deduce the identity of the weaker secondary adsorption site on the rigid polymer backbone. Both polymers, with a high loading of CO 2 , experience a narrowing of the 13 C NMR line width as the samples are warmed to 80 K, which is the onset of the weakly adsorbed CO 2 hopping on and off the polymer backbone.

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Section: ■ Results and Discussionsupporting

confidence: 67%

Section: ■ Results and Discussionmentioning

confidence: 99%

CO₂ Adsorption on PIMs Studied with ¹³C NMR Spectroscopy

Moore¹,

Marti²,

Guiver³

et al. 2018

J. Phys. Chem. C

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“…1a), is readily prepared by a double aromatic nucleophilic substitution reaction between two commercially available monomers (5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethyl-1,1 0 -spirobisindane and tetrauoroterephthalonitrile) and has been extensively studied. A variety of chemical modications of PIM-1 have been reported, including conversion of the nitrile groups to carboxylic acid, [17][18][19][20] tetrazole, 21,22 methyl tetrazole, 23 thioamide, 24 amidoxime 25,26 and amine. 27 The sulfonation of PIM-1 has also been attempted, 28 and various approaches have been employed to crosslink PIM-1, including nitrene reactions with diazide crosslinkers, 29,30 as well as thermal treatment of the carboxylated polymer.…”

Section: Introductionmentioning

confidence: 99%

Base-catalysed hydrolysis of PIM-1: amide versus carboxylate formation

2014

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“…The introduced tetrazole groups resulted in more favorable CO 2 sorption with superior affinity. The dynamics of CO 2 adsorption on TZ-PIM-1 was intensively investigated via in situ 13 C nuclear magnetic resonance spectroscopy [220]. The results indicated that the CO 2 molecules interacted with tetrazole sites via physisorption, and two adsorption sites were available when the CO 2 loading approached to one CO 2 molecule per tetrazole unit.…”

Section: Polymers Of Intrinsic Microporosity-based Membranesmentioning

confidence: 99%