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. In this work, 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 m² g^–1, and a broad range of pore volumes of 0.24–3.50 cm³ 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 overmore » 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.« less

Authors:

Xiang, Zhonghua ^[1]; Mercado, Rocio ^[2]; Huck, Johanna M. ^[2]; Wang, Hui ^[1]; Guo, Zhanhu ^[3]; Wang, Wenchuan ^[1]; Cao, Dapeng ^[1]; Haranczyk, Maciej ^[4]; Smit, Berend ^[5]

---

+ Show Author Affiliations

1. Beijing Univ. of Chemical Technology, Beijing (People's Republic of China)
2. Univ. of California, Berkeley, CA (United States)
3. Univ. of Tennessee, Knoxville, TN (United States)
4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
5. Univ. of California, Berkeley, CA (United States); Ecole Polytechnique Fédérale de Lausanne (EPFL), Sion (Switzerland)

Publication Date:

Sun Sep 27 00:00:00 EDT 2015

Research Org.:

Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations (CGS); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); National 863 Programs; National Natural Science Foundation of China (NSFC); Scientific Research Funding; Beijing University of Chemical Technology; Fundamental Research Funds for the Central Universities

OSTI Identifier:

1386970

Grant/Contract Number:  

SC0001015; AC02-05CH11231

Resource Type:

Accepted Manuscript

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Volume: 137; Journal Issue: 41; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane, carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); functionalization; porosity; functional groups; mathematical methods; materials