Skip to main content
Log in

Impact of tailored chemical and textural properties on the performance of nanoporous borazine-linked polymers in small gas uptake and selective binding

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

Six borazine-linked polymers (BLPs) have been synthesized through the thermolysis reaction of p-phenylenediamine, 1,3,5-tris-(4-aminophenyl)benzene, benzidine, or tetra-(4-aminophenyl)methane with boron tribromide or boron trichloride. Each product exists as an amorphous polymer whose chemical connectivity was confirmed by FT-IR and elemental analysis while thermogravimetric analysis revealed moderate thermal stabilities up to about 200 °C under nitrogen atmosphere. All BLPs possess high surface areas with chlorinated BLPs exhibiting higher values than brominated BLPs (1,174–1,569 vs. 503–849 m2/g, respectively). Gas storage capabilities were investigated as well. BLPs possess good hydrogen uptakes (0.68–1.75 wt% at 77 K) and zero-coverage isosteric heat of adsorption, Q st, (7.06–7.65 kJ/mol) as calculated by the virial method. The uptakes and heat of adsorption for carbon dioxide (51–141 mg/g at 273 K with Q st: 22.2–31.7 kJ/mol) are also attractive. BLPs do not, however, appear to exhibit significant methane storage capacities (1.9–15.2 mg/g at 273 K with Q st: 17.1–21.7 kJ/mol). Accordingly, CO2/CH4 selectivity studies were performed using the ideal adsorbed solution theory and further supported by initial slope calculations. The results indicate that BLP-1(Br) and BLP-2(Br) exhibit very high CO2/CH4 selectivities 23 and 26, respectively, which make them attractive for small gas separation applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • An J, Geib SJ, Rosi NL (2010) High and selective CO2 uptake in a cobalt adeninate metal-organic framework exhibiting pyrimidine- and amino-decorated pores. J Am Chem Soc 132:38–39

    Article  CAS  Google Scholar 

  • Anand B, Nöth H, Schwenk-Kircher H, Troll A (2008) Structural chemistry of borazines. Eur J Inorg Chem 20:3186–3199

    Article  Google Scholar 

  • Bao C, Lu R, Jin M, Xue P, Tan C, Xu T, Liu G, Zhao Y (2006) Helical stacking tuned by alkoxy side chains in π-conjugated triphenylbenzene discotic derivatives. Chem Eur J 12:3287–3294

    Article  CAS  Google Scholar 

  • Belof JL, Stern AC, Eddaoudi M, Space B (2007) On the mechanism of hydrogen storage in a metal-organic framework material. J Am Chem Soc 129:15202–15210

    Article  CAS  Google Scholar 

  • Ben T, Ren H, Ma S, Cao D, Lan J, Jing X, Wang W, Xu J, Deng F, Simmons JM, Qiu S, Zhu G (2009) Targeted synthesis of a porous polybenzene: poly-tetraphenylene methane (C(Ph)4)n with high stability and exceptionally high surface area. Angew Chem Int Ed 48:9457–9460

    Article  CAS  Google Scholar 

  • Budd PM, Msayib KJ, Tattershall CE, Ghanem BS, Reynolds KJ, McKeown NB, Fritsch D (2005) Gas separation membranes from polymers of intrinsic microporosity. J Membr Sci 251:263–269

    Article  CAS  Google Scholar 

  • Caskey SR, Wong-Foy AG, Matzger AJ (2008) Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. J Am Chem Soc 130:10870–10871

    Article  CAS  Google Scholar 

  • Cavenati S, Grande CA, Rodrigues AE (2004) Adsorption equilibrium of methane, carbon dioxide, and nitrogen on zeolite 13X at high pressures. J Chem Eng Data 49:1095–1101

    Article  CAS  Google Scholar 

  • Côté AP, El-Kaderi HM, Furukawa H, Hunt JR, Yaghi OM (2007) Reticular synthesis of microporous and mesoporous 2D covalent organic frameworks. J Am Chem Soc 129:12914–12915

    Article  Google Scholar 

  • Du N, Park HB, Robertson GP, Dal-Cin MM, Visser T, Scoles L, Guiver MD (2011) Polymer nanosieve membranes for CO2-capture applications. Nat Mater 10:372–375

    Article  CAS  Google Scholar 

  • Duperrier S, Bernard S, Calin A, Sigala C, Chiriac R, Miele P, Balan C (2007) Design of a series of preceramic B-tri(methylamino)borazine-based polymers as fiber precursors: shear rheology investigations. Macromolecules 40:1028–1034

    Article  CAS  Google Scholar 

  • El-Kaderi HM, Hunt JR, Mendoza-Cortés JL, Côté AP, Taylor RE, O’Keeffe M, Yaghi OM (2007) Designed synthesis of 3D covalent organic frameworks. Science 316:268–272

    Article  CAS  Google Scholar 

  • Farha OK, Spokoyny AM, Hauser BG, Bae YS, Brown SE, Snurr RQ, Mirkin CA, Hupp JT (2009) Synthesis, properties and gas separation studies of a robust diimide-based microporous organic polymer. Chem Mater 21:3033–3035

    Article  CAS  Google Scholar 

  • Furukawa H, Yaghi OM (2009) Storage of hydrogen, methane, and carbon dioxide in highly porous covalent organic frameworks for clean energy applications. J Am Chem Soc 25:8875–8883

    Article  Google Scholar 

  • Germain J, Svec F, Fréchet JMJ (2009) Nanoporous polymers for hydrogen storage. Small 5:1098–1111

    Article  CAS  Google Scholar 

  • Han SS, Furukawa H, Yaghi OM, Goddard WA (2008) Covalent organic frameworks as exceptional hydrogen storage materials. J Am Chem Soc 130:11580–11581

    Article  CAS  Google Scholar 

  • Herm ZR, Swisher JA, Smit B, Krishna R, Long JR (2011) Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture. J Am Chem Soc 133:5664–5667

    Article  CAS  Google Scholar 

  • Hunt JR, Doonan CJ, LeVangie JD, Côté AP, Yaghi OM (2008) Reticular synthesis of covalent organic borosilicate frameworks. J Am Chem Soc 130:11872–11873

    Article  CAS  Google Scholar 

  • Jackson KT, Rabbani MG, Reich TE, El-Kaderi HM (2011) Synthesis of highly porous borazine-linked polymers and their application to H2, CO2, and CH4 storage. Polym Chem 2:2775–2777

    Article  CAS  Google Scholar 

  • Jäschke T, Jansen M (2006) A new borazine-type single source precursor for Si/B/N/C ceramics. J Mater Chem 16:2792–2799

    Article  Google Scholar 

  • Jiang JX, Su F, Trewin A, Wood CD, Niu H, Jones JTA, Khimyak YZ, Cooper AI (2008) Synthetic control of the pore dimension and surface area in conjugated microporous polymer and copolymer networks. J Am Chem Soc 130:7710–7720

    Article  CAS  Google Scholar 

  • Katsoulidis AP, Kanatzidis MG (2011) Phloroglucinol based microporous polymeric organic frameworks with –OH functional groups and high CO2 capture capacity. Chem Mater 23:1818–1824

    Article  CAS  Google Scholar 

  • Kuhn P, Antonietti M, Thomas A (2008a) Porous, covalent triazine-based frameworks prepared by ionothermal synthesis. Angew Chem Int Ed 47:3450–3453

    Article  CAS  Google Scholar 

  • Kuhn P, Forget A, Su D, Thomas A, Antonietti M (2008b) From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks. J Am Chem Soc 130:13333–13337

    Article  CAS  Google Scholar 

  • Lu W, Yuan D, Zhao D, Schilling CI, Plietzsch O, Muller T, Bräse S, Guenther J, Blümel J, Krishna R, Li Z, Zhou HC (2010) Porous polymer networks: synthesis, porosity, and applications in gas storage/separation. Chem Mater 22:5964–5972

    Article  CAS  Google Scholar 

  • Ma SQ, Zhou HC (2010) Gas storage in porous metal-organic frameworks for clean energy applications. Chem Commun 46:44–53

    Article  CAS  Google Scholar 

  • Ma S, Sun D, Simmons JM, Collier CD, Yuan D, Zhou HC (2008) Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake. J Am Chem Soc 130:1012–1016

    Article  CAS  Google Scholar 

  • McKeown NB, Budd PM (2010) Exploitation of intrinsic microporosity in polymer-based materials. Macromolecules 43:5163–5176

    Article  CAS  Google Scholar 

  • Menon VC, Komarneni S (1998) Porous adsorbents for vehicular natural gas storage: a review. J Porous Mater 5:43–58

    Article  CAS  Google Scholar 

  • Murthi M, Snurr RQ (2004) Effects of molecular siting and adsorbent heterogeneity on the ideality of adsorption equilibria. Langmuir 20:2489–2497

    Article  CAS  Google Scholar 

  • Myers AL, Prausnitz JM (1965) Thermodynamics of mixed-gas adsorption. AIChE J 11:121–127

    Article  CAS  Google Scholar 

  • Nöth H, Wrackmeyer B (1978) Nuclear magnetic resonance spectroscopy of boron compounds. Springer-Verlag, New York

    Book  Google Scholar 

  • Pandey P, Katsoulidis AP, Eryazici I, Wu Y, Kanatzidis MG, Nguyen ST (2010) Imine-linked microporous polymer organic frameworks. Chem Mater 22:4974–4979

    Article  CAS  Google Scholar 

  • Phan A, Doonan CJ, Uriberomo FJ, Knobler CB, O’Keeffe M, Yaghi OM (2010) Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks. Acc Chem Res 43:58–67

    Article  CAS  Google Scholar 

  • Plietzsch O, Schilling CI, Tolev M, Nieger M, Richert C, Muller T, Brase S (2009) Four-fold click reactions: generation of tetrahedral methane- and adamantane-based building blocks for higher molecular assemblies. Org Biomol Chem 7:4734–4743

    Article  CAS  Google Scholar 

  • Rabbani MG, El-Kaderi HM (2011) Template-free synthesis of a highly porous benzimidazole-linked polymer for CO2 capture and H2 storage. Chem Mater 23:1650–1653

    Article  CAS  Google Scholar 

  • Rabbani MG, Reich TE, Kassab R, Jackson KT, El-Kaderi HM (2012) High CO2 uptake and selectivity by triptycene-derived benzimidazole-linked polymers. Chem Commun 48:1141–1143

    Article  CAS  Google Scholar 

  • Reich TE, Jackson KT, Li S, Jena P, El-Kaderi HM (2011) Synthesis and characterization of highly porous borazine-linked polymers and their performance in hydrogen storage application. J Mater Chem 21:10629–10632

    Article  Google Scholar 

  • Reich TE, Behera S, Jackson KT, Jena P, El-Kaderi HM (2012) Highly selective CO2/CH4 gas uptake by a halogen-decorated borazine-linked polymer. J Mater Chem 21:13524–13528

    Article  Google Scholar 

  • Rowsell JLC, Yaghi OM (2006) Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks. J Am Chem Soc 128:1304–1315

    Article  CAS  Google Scholar 

  • Salles V, Bernard S, Li J, Brioude A, Chehaidi S, Foucaud S, Miele P (2009) Design of highly dense boron nitride by the combination of spray-pyrolysis of borazine and additive-free sintering of derived ultrafine powders. Chem Mater 21:2920–2929

    Article  CAS  Google Scholar 

  • Schlapbach L, Zuttel A (2001) Hydrogen-storage materials for mobile applications. Nature 414:353–358

    Article  CAS  Google Scholar 

  • Sham IHT, Kwok CC, Che CM, Zhu N (2005) Borazine materials for organic optoelectronic applications. Chem Commun 28:3547–3549

    Article  Google Scholar 

  • Spitler EL, Dichtel WR (2010) Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks. Nat Chem 2:672–677

    Article  CAS  Google Scholar 

  • Tilford WR, Gemmil WR, zur Loye HC, Lavigne JJ (2006) Facile synthesis of a highly crystalline, covalently linked porous boronate network. Chem Mater 18:5296–5301

    Article  CAS  Google Scholar 

  • Tilford RW, Mugavero SJ, Pellechia PJ, Lavigne J (2008) Tailoring microporosity in covalent organic frameworks. Adv Mater 20:2741–2746

    Article  CAS  Google Scholar 

  • Tozawa T, Jones JTA, Swamy SI, Jiang S, Adams DJ, Shakespeare S, Clowes R, Bradshaw D, Hasell T, Chong SY, Tang C, Thompson S, Parker J, Trewin A, Bacsa J, Slawin AMZ, Steiner A, Cooper AI (2009) Porous organic cages. Nat Mater 8:973–978

    Article  CAS  Google Scholar 

  • Uribe-Romo FJ, Hunt JR, Furukawa H, Klöck C, O’Keeffe M, Yaghi OM (2009) A crystalline imine-linked 3-D porous covalent organic framework. J Am Chem Soc 131:4570–4571

    Article  CAS  Google Scholar 

  • Vaidhyanathan R, Iremonger SS, Dawson KW, Shimizu GKH (2009) An amine-functionalized metal organic framework for preferential CO(2) adsorption at low pressures. Chem Commun 35:5230–5232

    Article  Google Scholar 

  • Vaidhyanathan R, Iremonger SS, Shimizu GHK, Boyd PG, Alavi S, Woo TK (2010) Direct observation and quantification of CO binding within an amine-functionalized nanoporous solid. Science 330:650–653

    Article  CAS  Google Scholar 

  • Wakamiya A, Ide T, Yamaguchi S (2005) Toward p-conjugated molecule bundles; synthesis of a series of B, B′, B″-trianthryl-N, N’, N”-triarylborazines and the bundle effects on their properties. J Am Chem Soc 127:14859–14866

    Article  CAS  Google Scholar 

  • Wan S, Guo J, Kim J, Ihee H, Jiang D (2008) A belt-shaped, blue luminescent, and semiconducting covalent organic framework. Angew Chem Int Ed 47:8826–8830

    Article  CAS  Google Scholar 

  • Wan S, Guo J, Kim J, Ihee H, Jiang D (2009) A photoconductive covalent organic framework: self-condensed arene cubes composed of eclipsed 2D polypyrene sheets for photocurrent generation. Angew Chem Int Ed 48:5439–5442

    Article  CAS  Google Scholar 

  • Weber J, Antonietti M, Thomas A (2008) Microporous networks of high-performance polymers: elastic deformations and gas sorption properties. Macromolecules 41:2880–2885

    Article  CAS  Google Scholar 

  • Yamaguchi S, Wakamiya A (2006) Boron as a key component for new p electron materials. Pure Appl Chem 78:1413–1424

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Research supported by the US Department of Energy, Office of Basic Energy Sciences under award number (DE-SC0002576).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hani M. El-Kaderi.

Additional information

This article is part of the topical collection on nanomaterials in energy, health and environment

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 3192 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Reich, T.E., El-Kaderi, H.M. Impact of tailored chemical and textural properties on the performance of nanoporous borazine-linked polymers in small gas uptake and selective binding. J Nanopart Res 15, 1368 (2013). https://doi.org/10.1007/s11051-012-1368-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-012-1368-5

Keywords

Navigation