Targeted Synthesis of a Porous Aromatic Framework with High Stability and Exceptionally High Surface Area

Ben, Teng; Ren, Hao; Ma, Shengqian; Cao, Dapeng; Lan, Jian‐Hui; Jing, Xiaofei; Wang, Wenchuan; Xu, Jun; Deng, Feng; Simmons, Jason M.; Qiu, Shilun; Zhu, Guangshan

doi:10.1002/ange.200904637

Cited by 319 publications

(203 citation statements)

References 30 publications

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“…In addition, the presence of bands in the range of 3,600-3,000 cm À 1 indicates that there are terminal amino groups present in the structure. The presence of chemical shifts in CP/MAS 13 C NMR spectra of azo-COPs, namely, azo-COP-1, azo-COP-2 and azo-COP-3 (also named as COP-68, -69, -70), (www.porouspolymers.com) located at 150.2, 144.7, 129.5, 123.4 and 54.9 ppm confirmed the formation of the azo-linked aromatic polymers 19,34 . Azobenzene moieties have a characteristic ultraviolet-visible spectra where an intense absorption band at 360 nm indicates the presence of transazobenzene unit 35 .…”

Section: Synthesismentioning

confidence: 93%

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Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

et al. 2013

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Post-combustion CO 2 capture and air separation are integral parts of the energy industry, although the available technologies remain inefficient, resulting in costly energy penalties. Here we report azo-bridged, nitrogen-rich, aromatic, water stable, nanoporous covalent organic polymers, which can be synthesized by catalyst-free direct coupling of aromatic nitro and amine moieties under basic conditions. Unlike other porous materials, azo-covalent organic polymers exhibit an unprecedented increase in CO 2 /N 2 selectivity with increasing temperature, reaching the highest value (288 at 323 K) reported to date. Here we observe that azo groups reject N 2 , thus making the framework N 2 -phobic. Monte Carlo simulations suggest that the origin of the N 2 phobicity of the azo-group is the entropic loss of N 2 gas molecules upon binding, although the adsorption is enthalpically favourable. Any gas separations that require the efficient exclusion of N 2 gas would do well to employ azo units in the sorbent chemistry.

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Section: Synthesismentioning

confidence: 93%

“…These mostly organic polymers can easily be designed and constructed via facile synthetic protocols. To date, several crystalline and amorphous nanoporous organic materials with tunable functionality have been developed-namely, COF 14 , PIM 15 , HCP and CMP 16,17 , CTF 18 , PAF 19 , PPN 20 , POF 21 , BILP 22 , EOF 23 , PECONF 24 and COP 25 .…”

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confidence: 99%

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

et al. 2013

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“…DAB acts as the electron-rich aromatic building block [25][26][27] due to its four amino groups while hexachlorocyclotriphosphazene has the role of the nitridic building unit. These building blocks are significantly less expensive than those used for covalent organic frameworks and polymers typically used so far [21][22][23][24] . The materials were obtained as monoliths, which could be solventexchanged and dried without cracking or disintegration ( Supplementary Fig.…”

Section: Synthesismentioning

confidence: 99%

Porous covalent electron-rich organonitridic frameworks as highly selective sorbents for methane and carbon dioxide

2011

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Carbon dioxide capture from point sources like coal-fired power plants is considered to be a solution for stabilizing the Co 2 level in the atmosphere to avoid global warming. methane is an important energy source that is often highly diluted by nitrogen in natural gas. For the separation of Co 2 and CH 4 from n 2 in flue gas and natural gas, respectively, sorbents with high and reversible gas uptake, high gas selectivity, good chemical and thermal stability, and low cost are desired. Here we report the synthesis and Co 2 , CH 4 , and n 2 adsorption properties of hierarchically porous electron-rich covalent organonitridic frameworks (PEConFs). These were prepared by simple condensation reactions between inexpensive, commercially available nitridic and electron-rich aromatic building units. The PEConF materials exhibit high and reversible Co 2 and CH 4 uptake and exceptional selectivities of these gases over n 2 . The materials do not oxidize in air up to temperature of 400 °C.

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“…For PAF-1, tetrakis(4-bromophenyl)-methane ( Figure 1 A (1)) is self-condensed by a Yamamoto coupling reaction to form a carbon-based microporous array ( Figure 1 A (2)). [22] Brunauer-Emmett-Teller (BET) surface areas in PAFs are as high as 5200 m 2 g À1 , which with functionalization can lead to ultrahigh affinities for adsorption of carbon dioxide and other gases. [23] The regular nanopores of around 1.2 nm diameter ( Figure S9 in the Supporting Information) are attractive for the intercalation of polyacetylene side-chain or bulky chemical moieties in PIMs, thereby freezing the as-cast lower-density polymer structure in place and tuning the aging process.…”

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confidence: 99%

Ending Aging in Super Glassy Polymer Membranes

et al. 2014

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Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4‐methyl‐2‐pentyne) (PMP), and polymers with intrinsic microporosity (PIM‐1) reduces gas permeabilities and limits their application as gas‐separation membranes. While super glassy polymers are initially very porous, and ultra‐permeable, they quickly pack into a denser phase becoming less porous and permeable. This age‐old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.

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Targeted Synthesis of a Porous Aromatic Framework with High Stability and Exceptionally High Surface Area

Cited by 319 publications

References 30 publications

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

Porous covalent electron-rich organonitridic frameworks as highly selective sorbents for methane and carbon dioxide

Ending Aging in Super Glassy Polymer Membranes

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