{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T23:58:51Z","timestamp":1788998331253,"version":"build-2803163510"},"reference-count":92,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2013,12,11]],"date-time":"2013-12-11T00:00:00Z","timestamp":1386720000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2014,1,13]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A family of azo\u2010bridged covalent organic polymers (azo\u2010COPs) was synthesized through a catalyst\u2010free direct coupling of aromatic nitro and amine compounds under basic conditions. The azo\u2010COPs formed 3D nanoporous networks and exhibited surface areas up to 729.6\u2005m<jats:sup>2<\/jats:sup>\u2009g<jats:sup>\u22121<\/jats:sup>, with a CO<jats:sub>2<\/jats:sub>\u2010uptake capacity as high as 2.55\u2005mmol\u2009g<jats:sup>\u22121<\/jats:sup> at 273\u2005K and 1\u2005bar. Azo\u2010COPs showed remarkable CO<jats:sub>2<\/jats:sub>\/N<jats:sub>2<\/jats:sub> selectivities (95.6\u2013165.2) at 298\u2005K and 1\u2005bar. Unlike any other porous material, CO<jats:sub>2<\/jats:sub>\/N<jats:sub>2<\/jats:sub> selectivities of azo\u2010COPs increase with rising temperature. It was found that azo\u2010COPs show less than expected affinity towards N<jats:sub>2<\/jats:sub> gas, thus making the framework \u201cN<jats:sub>2<\/jats:sub>\u2010phobic\u201d, in relative terms. Our theoretical simulations indicate that the origin of this unusual behavior is associated with the larger entropic loss of N<jats:sub>2<\/jats:sub> gas molecules upon their interaction with azo\u2010groups. The effect of fused aromatic rings on the CO<jats:sub>2<\/jats:sub>\/N<jats:sub>2<\/jats:sub> selectivity in azo\u2010COPs is also demonstrated. Increasing the \u03c0\u2010surface area resulted in an increase in the CO<jats:sub>2<\/jats:sub>\u2010philic nature of the framework, thus allowing us to reach a CO<jats:sub>2<\/jats:sub>\/N<jats:sub>2<\/jats:sub> selectivity value of 307.7 at 323\u2005K and 1\u2005bar, which is the highest value reported to date. Hence, it is possible to combine the concepts of \u201cCO<jats:sub>2<\/jats:sub>\u2010philicity\u201d and \u201cN<jats:sub>2<\/jats:sub>\u2010phobicity\u201d for efficient CO<jats:sub>2<\/jats:sub> capture and separation. Isosteric heats of CO<jats:sub>2<\/jats:sub> adsorption for azo\u2010COPs range from 24.8\u201332.1\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup> at ambient pressure. Azo\u2010COPs are stable up to 350\u2009\u00b0C in air and boiling water for a week. A promising <jats:italic>cis<\/jats:italic>\/<jats:italic>trans<\/jats:italic> isomerization of azo\u2010COPs for switchable porosity is also demonstrated, making way for a gated CO<jats:sub>2<\/jats:sub> uptake.<\/jats:p>","DOI":"10.1002\/chem.201303493","type":"journal-article","created":{"date-parts":[[2013,12,11]],"date-time":"2013-12-11T08:53:35Z","timestamp":1386752015000},"page":"772-780","source":"Crossref","is-referenced-by-count":150,"title":["Directing the Structural Features of N<sub>2<\/sub>\u2010Phobic Nanoporous Covalent Organic Polymers for CO<sub>2<\/sub> Capture and Separation"],"prefix":"10.1002","volume":"20","author":[{"given":"Hasmukh A.","family":"Patel","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sang 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