title: Systematic Tuning and Multifunctionalization of Covalent Organic Polymers for Enhanced Carbon Capture.
abstract: Porous covalent polymers are attracting increasing interest in the fields of gas adsorption, gas separation, and catalysis due to their fertile synthetic polymer chemistry, large internal surface areas, and ultrahigh hydrothermal stabilities. While precisely manipulating the porosities of porous organic materials for targeted applications remains challenging, we show how a large degree of diversity can be achieved in covalent organic polymers by incorporating multiple functionalities into a single framework, as is done for crystalline porous materials. Here, we synthesized 17 novel porous covalent organic polymers (COPs) with finely tuned porosities, a wide range of Brunauer-Emmett-Teller (BET) specific surface areas of 430-3624 m(2) g(-1), and a broad range of pore volumes of 0.24-3.50 cm(3) g(-1), all achieved by tailoring the length and geometry of building blocks. Furthermore, we are the first to successfully incorporate more than three distinct functional groups into one phase for porous organic materials, which has been previously demonstrated in crystalline metal-organic frameworks (MOFs). COPs decorated with multiple functional groups in one phase can lead to enhanced properties that are not simply linear combinations of the pure component properties. For instance, in the dibromobenzene-lined frameworks, the bi- and multifunctionalized COPs exhibit selectivities for carbon dioxide over nitrogen twice as large as any of the singly functionalized COPs. These multifunctionalized frameworks also exhibit a lower parasitic energy cost for carbon capture at typical flue gas conditions than any of the singly functionalized frameworks. Despite the significant improvement, these frameworks do not yet outperform the current state-of-art technology for carbon capture. Nonetheless, the tuning strategy presented here opens up avenues for the design of novel catalysts, the synthesis of functional sensors from these materials, and the improvement in the performance of existing covalent organic polymers by multifunctionalization.
authors.affiliation: State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology , Beijing 100029, P.R. China.
authors.forename: Zhonghua
authors.initials: Z
authors.lastname: Xiang
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720-1462, United States.
authors.forename: Rocio
authors.initials: R
authors.lastname: Mercado
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley , Berkeley, California 94720-1462, United States.
authors.forename: Johanna M
authors.initials: JM
authors.lastname: Huck
authors.affiliation: State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology , Beijing 100029, P.R. China.
authors.forename: Hui
authors.initials: H
authors.lastname: Wang
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Tennessee , Knoxville, Tennessee 37996, United States.
authors.forename: Zhanhu
authors.initials: Z
authors.lastname: Guo
authors.affiliation: State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology , Beijing 100029, P.R. China.|International Research Center for Soft Matter, Beijing University of Chemical Technology , Beijing 100029, P.R. China.
authors.forename: Wenchuan
authors.initials: W
authors.lastname: Wang
authors.affiliation: State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology , Beijing 100029, P.R. China.
authors.forename: Dapeng
authors.initials: D
authors.lastname: Cao
authors.affiliation: Computational Research Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720-8139, United States.
authors.forename: Maciej
authors.initials: M
authors.lastname: Haranczyk
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720-1462, United States.|Department of Chemical and Biomolecular Engineering, University of California, Berkeley , Berkeley, California 94720-1462, United States.|Institut des Sciences et Ingénierie Chimiques, Valais, Ecole Polytechnique Fédérale de Lausanne (EPFL) , Rue de l'Industrie 17, CH-1951 Sion, Switzerland.
authors.forename: Berend
authors.initials: B
authors.lastname: Smit