tag:blogger.com,1999:blog-30747611061296121502024-02-07T19:32:22.467-08:00Porous PolymersA professional network for the developments in science and technology of porous polymersCafer T. Yavuzhttp://www.blogger.com/profile/04545909643748475027noreply@blogger.comBlogger5125tag:blogger.com,1999:blog-3074761106129612150.post-88312652444687147792014-05-27T03:35:00.000-07:002018-01-07T19:57:04.257-08:00Disulfide network polymers absorb ether and chloroalkane selectively<div dir="ltr" style="text-align: left;" trbidi="on">
<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgpFXhF7PBICiBiCoEOzG48HremvJ6zn4WYctV2lCXZ2lxtby3Jkk7vZ-P5xdSrpJunw-q_wKIpaDJkIwBFVmAhKyyrWkvyB4BE2LI_lu5NvNL2lSwsKm6VnRJvlSGU8TIQyy26_SNJCwWU/s1600/TOC-disulfides.gif" imageanchor="1" style="clear: right; float: right; margin-bottom: 1em; margin-left: 1em;"><img border="0" height="133" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgpFXhF7PBICiBiCoEOzG48HremvJ6zn4WYctV2lCXZ2lxtby3Jkk7vZ-P5xdSrpJunw-q_wKIpaDJkIwBFVmAhKyyrWkvyB4BE2LI_lu5NvNL2lSwsKm6VnRJvlSGU8TIQyy26_SNJCwWU/s1600/TOC-disulfides.gif" width="320" /></a>Yavuz and team reported that disulfide linked network polymers from aliphatic building blocks show selective uptake by swelling when treated with ethers and chloro-alkanes. Although the polymers are non-porous, the gate opening behavior by certain functional groups could provide effective separations. Since water and alcohols are almost rejected, it could be useful in water treatment or product separation in chemical industry.<br />
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<i>Reference:</i><br />
<b><a href="http://pubs.rsc.org/en/Content/ArticleLanding/2014/RA/c4ra03355h" target="_blank">Exceptional organic solvent uptake by disulfide polymeric networks</a></b><br />
H. A. Patel, M. S. Yavuz, C. T. Yavuz*<br />
<b><i>RSC Adv.</i></b>, 2014, 4, 24320-24323 DOI: <a href="http://dx.doi.org/10.1039/C4RA03355H" target="_blank">10.1039/C4RA03355H</a><br />
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<a name='more'></a><b><i>Abstract:</i></b><br />
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Disulfide-linked covalent organic polymers (COPs) were prepared through catalyst-free oxidative coupling polymerization. Owing to the excellent swelling behavior, low cost, and efficient synthesis, these materials can be promising materials for removal of organics in concentrated streams. COPs show 1,4-dioxane uptake up to 1.8 g g−1.<br />
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<a href="http://www.rsc.org/suppdata/ra/c4/c4ra03355h/c4ra03355h1.pdf">Direct link for the Supporting Information pdf file (Free access)</a></div>
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Cafer T. Yavuzhttp://www.blogger.com/profile/04545909643748475027noreply@blogger.com2tag:blogger.com,1999:blog-3074761106129612150.post-82340793841748850272014-04-30T23:43:00.000-07:002014-07-20T08:11:28.834-07:00Nanoporous covalent organic polymers incorporating Troger's base functionalities for enhanced CO2 capture<div dir="ltr" style="text-align: left;" trbidi="on">
J. Byun, S. H. Je, H. A. Patel, A. Coskun,* C. T. Yavuz*<br />
<b><i>J. Mater. Chem. A</i></b>, 2014, 2, 12507-12512. DOI: <a href="http://dx.doi.org/10.1039/C4TA00698D" target="_blank">10.1039/C4TA00698D</a><br />
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<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEiqMaZmTOsOgz8FdJlmrAhk68_0ll3qasRTxgG6W7sog63v0p5nwYnkLrSTjbpr4_akcKb2QVZ9tlnA9aT2IjSBuBYh89E3vhMgIaMOYYhkBCoE2w_ZR6ZMf2UxhpI2lPBU3Hoj74jEELdy/s1600/TOC-troger.png" imageanchor="1" style="clear: left; float: left; margin-bottom: 1em; margin-right: 1em;"><img border="0" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEiqMaZmTOsOgz8FdJlmrAhk68_0ll3qasRTxgG6W7sog63v0p5nwYnkLrSTjbpr4_akcKb2QVZ9tlnA9aT2IjSBuBYh89E3vhMgIaMOYYhkBCoE2w_ZR6ZMf2UxhpI2lPBU3Hoj74jEELdy/s1600/TOC-troger.png" height="183" width="320" /></a></div>
<b><i>Notes & Highlights:</i></b>
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<li>Among the highest, TB-COP-1 shows CO2 uptake of 5.19 mmol/g at 1 bar 273 K. Qst is 26 kj/mol, physisorptive.</li>
<li>A non-porous TB-COP-2 captures 0.95 mmol/g CO2.</li>
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<i><b></b></i><br />
<a name='more'></a><i><b><br /></b></i>
<i><b>Abstract:</b></i><br />
<i><b><br /></b></i>
The CO2 uptake capacity and CO2/N2 selectivity of Tröger’s base–bridged nanoporous covalent organic polymers (TB-COPs) were investigated. TB-COPs were synthesized by reacting amine terminals of tetrahedral monomers - namely, tetraanilyladamantane and tetraanilylmethane - with dimethoxymethane in a one–pot reaction under relatively mild conditions. Interestingly, these two tetrahedral monomers formed nanoporous polymers with substantially different surface areas. While the trögerization of tetraanilyladamantane monomer (TB-COP-1) exhibit high surface area of 1340 m2 g-1, that of tetraanilylmethane monomer (TB-COP-2) is found to be only 0.094 m2 g-1. This unusual phenomenon can be explained by the proximity of amino moieties to each other within the monomeric unit. Shorter distance between the amino groups enables intramolecular cyclization along with the intermolecular one, thus resulting in much lower porosity. TB-COP-1 exhibits significant CO2 uptakes up to 5.19 and 3.16 mmol g-1 at 273 and 298K under ambient pressure, and CO2/N2 selectivities of 79.2 and 68.9 at 273 and 298K at 1 bar for the gas mixture of CO2:N2 in the ratio of 0.15:0.85. It is noteworthy that TB-COP-1 showed remarkable selectivity retention with rising temperature from 273 to 298 K.
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<a href="http://www.rsc.org/suppdata/ta/c4/c4ta00698d/c4ta00698d1.pdf">Direct link for the Supporting Information pdf file (FREE access)</a></div>
Cafer T. Yavuzhttp://www.blogger.com/profile/04545909643748475027noreply@blogger.com0tag:blogger.com,1999:blog-3074761106129612150.post-78209881232712325902013-09-30T11:23:00.000-07:002018-01-04T18:48:14.828-08:00A perfluorinated covalent triazine-based framework for highly selective and water–tolerant CO2 capture<div dir="ltr" style="text-align: left;" trbidi="on">
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Y. Zhao, K. X. Yao, B. Teng, T. Zhang, Y. Han*<br />
<b><i>Energy Environ. Sc</i></b><b><i>i.</i></b>, 2013, 6, 3684-3692. DOI: <a href="http://dx.doi.org/10.1039/C3EE42548G" target="_blank">10.1039/C3EE42548G</a><br />
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<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgL-9ARKo88VkqH264J3OnQJITIQ5zozYWmBRG82nZK-XkrGE1hErI9VBOW5YR8WP7DlxetVdy5BKuVyTGjLIx90oiKZO22T6RHoiVeIWQXH-Yk0x5W2rV7q8RP8mB1dfILfJs-lB7vBptK/s1600/FCTF-1.gif" imageanchor="1" style="clear: right; float: right; margin-bottom: 1em; margin-left: 1em;"><img border="0" height="132" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgL-9ARKo88VkqH264J3OnQJITIQ5zozYWmBRG82nZK-XkrGE1hErI9VBOW5YR8WP7DlxetVdy5BKuVyTGjLIx90oiKZO22T6RHoiVeIWQXH-Yk0x5W2rV7q8RP8mB1dfILfJs-lB7vBptK/s320/FCTF-1.gif" width="320" /></a></div>
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<b><i>Notes & Highlights:</i></b>
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<ul style="text-align: left;">
<li>FCTF-1 has one of the highest physisorptive (Q<sup>0</sup><sub>st, FCTF-1</sub> = 35 kj/mol) CO<sub>2</sub> capacities ever recorded: 5.53 mmol/g at 273 K and 1 bar (1.76 at 0.1)</li>
<li>CO<sub>2</sub>/N<sub>2</sub> selectivity increased when mixed gas measured compared to pure gas calculations. This verifies <a href="http://porouspolymers.blogspot.kr/2011/04/polymer-nanosieve-membranes-for-co2.html#more">a 2011 observation by Guiver et al.</a></li>
<li>Moisture (0.03 bar, % 100 RH) lowered CO<sub>2</sub> uptake 12 % at 298 K.</li>
</ul>
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<b><i></i></b><br />
<a name='more'></a><b><i><br /></i></b>
<b><i>Abstract:</i></b><br />
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We designed and synthesized a perfluorinated covalent triazine-based framework (FCTF-1) for selective CO2 capture. The incorporation of fluorine (F) groups played multiple roles in improving the framework's CO2 adsorption and separation capabilities. Thermodynamically, the strongly polar C–F bonds promoted CO2 adsorption via electrostatic interactions, especially at low pressures. FCTF-1's CO2 uptake was 1.76 mmol g−1 at 273 K and 0.1 bar through equilibrium adsorption, exceeding the CO2 adsorption capacity of any reported porous organic polymers to date. In addition, incorporating F groups produced a significant amount of ultra-micropores (< 0.5 nm), which offered not only high gas adsorption potential but also kinetic selectivity for CO<span class="s1">2</span>–N<span class="s1">2 </span>separation. In mixed-gas breakthrough
experiments, FCTF-1 exhibited an exceptional CO<span class="s1">2</span>–N<span class="s1">2 </span>selectivity of 77 under kinetic flow conditions,
much higher than the selectivity (31) predicted from single-gas equilibrium adsorption data. Moreover,
FCTF-1 proved to be tolerant to water and its CO<span class="s1">2 </span>capture performance remained excellent when there
was moisture in the gas mixture, due to the hydrophobic nature of the C–F bonds. In addition, the
moderate adsorbate–adsorbent interaction allowed it to be fully regenerated by pressure swing
adsorption processes. These attributes make FCTF-1 a promising sorbent for CO<span class="s1">2 </span>capture from flue gas.</div>
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Cafer T. Yavuzhttp://www.blogger.com/profile/04545909643748475027noreply@blogger.com0tag:blogger.com,1999:blog-3074761106129612150.post-91116537299576022862011-04-03T03:08:00.000-07:002018-01-04T18:46:18.240-08:00Polymer nanosieve membranes for CO2-capture applications<div dir="ltr" style="text-align: left;" trbidi="on">
N. Du, H. B. Park, G. P. Robertson, M. M. Dal-Cin, T. Visser,
L. Scoles, M. D. Guiver*
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<b><i>Nature Mater.</i></b>, 2011, 10, 372-375 DOI: <a href="http://dx.doi.org/10.1038/NMAT2989" target="_blank">10.1038/NMAT2989</a><br />
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<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEiaX49c6W27AJyaDIu5_sCyoJCwP8sLKASeyE-wBOGHcozYoiuKiVJgSLfrzQOLwenuLzurUAPrpbhHo1k9mKM9zxBohwSfTP73uiWSh8BlfLV4zwZvEOj99hPx-zyoq1dmRMaR0b18b6GH/s1600/guiver-toc.png" imageanchor="1" style="clear: right; float: right; margin-bottom: 1em; margin-left: 1em;"><img border="0" height="248" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEiaX49c6W27AJyaDIu5_sCyoJCwP8sLKASeyE-wBOGHcozYoiuKiVJgSLfrzQOLwenuLzurUAPrpbhHo1k9mKM9zxBohwSfTP73uiWSh8BlfLV4zwZvEOj99hPx-zyoq1dmRMaR0b18b6GH/s1600/guiver-toc.png" width="320" /></a><b><i>Notes & Highlights:</i></b><br />
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<ul style="text-align: left;">
<li>TZPIM-1 is one of the few membranes that broke the Robeson plot for CO2/N2 selectivity.</li>
<li>Guiver also proved calculations from single gas isotherms show lesser selectivity than actual mixed gas measurements.</li>
</ul>
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<a name='more'></a><br />
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<b><i>Abstract:</i></b><br />
Microporous organic polymers (MOPs) are of potential
technological significance for gas storage1–3, gas separation4
and low-dielectric applications5. Among many approaches for
obtaining such materials, solution-processable MOPs derived
from rigid and contorted macromolecular structures are
promising because of their excellent mass transport and mass
exchange capability. Here we show a class of amorphous MOP,
prepared by T2 C 3U cycloaddition modification of a polymer
containing an aromatic nitrile group with an azide compound,
showing super-permeable characteristics and outstanding CO2
separation performance, even under polymer plasticization
conditions such as CO2=light gas mixtures. This unprecedented
result arises from the introduction of tetrazole groups into
highly microporous polymeric frameworks, leading to more
favourable CO2 sorption with superior affinity in gas mixtures,
and selective CO2 transport by presorbed CO2 molecules
that limit access by other light gas molecules. This strategy
provides a direction in the design of MOP membrane materials
for economic CO2 capture processes.<br />
<br />
<a href="http://www.nature.com/nmat/journal/v10/n5/extref/nmat2989-s1.pdf">Direct link for the Supporting Information pdf file (FREE access)</a></div>
Cafer T. Yavuzhttp://www.blogger.com/profile/04545909643748475027noreply@blogger.com0tag:blogger.com,1999:blog-3074761106129612150.post-24777187029764864872010-10-14T08:04:00.000-07:002014-07-20T08:08:01.786-07:00Functional Materials: From Hard to Soft Porous Frameworks<div dir="ltr" style="text-align: left;" trbidi="on">
Arne Thomas*<br />
<b><i>Angew. Chem. Int. Ed.</i></b>, 2010, 49, 8328 – 8344 DOI: <a href="http://dx.doi.org/10.1002/anie.201000167">10.1002/anie.201000167</a><br />
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<b><i>Notes & Highlights:</i></b><br />
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<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEh-k2HY9aE7j0WL0dm0l8kJWfOH4bp_OAJo7nsQUgzmTdxdGfmCi0WOUSLmoWFN-EjC_WkrMVdGABXwJIsPK6fa3kT_3vswOyKTyBWh24cml-18erbzfFE1I5yZn8iADGCWXLK8LqHf-mGS/s1600/thomas-review-toc.png" imageanchor="1" style="clear: right; float: right; margin-bottom: 1em; margin-left: 1em;"><img border="0" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEh-k2HY9aE7j0WL0dm0l8kJWfOH4bp_OAJo7nsQUgzmTdxdGfmCi0WOUSLmoWFN-EjC_WkrMVdGABXwJIsPK6fa3kT_3vswOyKTyBWh24cml-18erbzfFE1I5yZn8iADGCWXLK8LqHf-mGS/s1600/thomas-review-toc.png" height="179" width="200" /></a></div>
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<ul style="text-align: left;">
<li>One of the rare reviews that captures the contrast between hard (mostly inorganic) and soft (organic) framework structures.</li>
<li>All materials have function, there is no such thing as "functional" material.</li>
</ul>
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<a name='more'></a><b><i>Abstract:</i></b><br />
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This Review aims to give an overview of recent research in the area of porous, organic–inorganic and purely organic, functional materials. Possibilities for introducing organic groups that exhibit chemical and/or physical functions into porous materials will be described, with a
focus on the incorporation of such functional groups as a supporting
part of the pore walls. The number of organic groups in the network
can be increased such that porous, purely organic materials are
obtained.
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Cafer T. Yavuzhttp://www.blogger.com/profile/04545909643748475027noreply@blogger.com0