title: A single-ligand ultra-microporous MOF for precombustion CO2 capture and hydrogen purification.
abstract: Metal organic frameworks (MOFs) built from a single small ligand typically have high stability, are rigid, and have syntheses that are often simple and easily scalable. However, they are normally ultra-microporous and do not have large surface areas amenable to gas separation applications. We report an ultra-microporous (3.5 and 4.8 Å pores) Ni-(4-pyridylcarboxylate)2 with a cubic framework that exhibits exceptionally high CO2/H2 selectivities (285 for 20:80 and 230 for 40:60 mixtures at 10 bar, 40°C) and working capacities (3.95 mmol/g), making it suitable for hydrogen purification under typical precombustion CO2 capture conditions (1- to 10-bar pressure swing). It exhibits facile CO2 adsorption-desorption cycling and has CO2 self-diffusivities of ~3 × 10(-9) m(2)/s, which is two orders higher than that of zeolite 13X and comparable to other top-performing MOFs for this application. Simulations reveal a high density of binding sites that allow for favorable CO2-CO2 interactions and large cooperative binding energies. Ultra-micropores generated by a small ligand ensures hydrolytic, hydrostatic stabilities, shelf life, and stability toward humid gas streams.
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008, India.
authors.forename: Shyamapada
authors.initials: S
authors.lastname: Nandi
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Phil
authors.initials: P
authors.lastname: De Luna
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Thomas D
authors.identifier: 0000-0003-4837-4143
authors.initials: TD
authors.lastname: Daff
authors.affiliation: Institute of Thermo and Fluid Dynamics, Ruhr-University Bochum, Universitätsstraße 150, D-44801 Bochum, Germany.
authors.forename: Jens
authors.identifier: 0000-0002-0052-7158
authors.initials: J
authors.lastname: Rother
authors.affiliation: Department of Nuclear Engineering, North Carolina State University, Raleigh, NC 27695, USA.
authors.forename: Ming
authors.identifier: 0000-0002-4618-9537
authors.initials: M
authors.lastname: Liu
authors.affiliation: Enovex Technology Corporation, Saint John, New Brunswick E2L 2E9, Canada.
authors.forename: William
authors.identifier: 0000-0001-7956-3882
authors.initials: W
authors.lastname: Buchanan
authors.affiliation: Department of Nuclear Engineering, North Carolina State University, Raleigh, NC 27695, USA.
authors.forename: Ayman I
authors.initials: AI
authors.lastname: Hawari
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Tom K
authors.initials: TK
authors.lastname: Woo
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008, India.; Enovex Technology Corporation, Saint John, New Brunswick E2L 2E9, Canada.
authors.forename: Ramanathan
authors.initials: R
authors.lastname: Vaidhyanathan
keywords: CO2 self-diffusivity; Hydrogen purification; Metal Organic Framework; Single-ligand MOF; Ultra-microporous; mixed-gas adsorption simulation; positron annihilation lifetime spectroscopy of MOF; pre-combustion CO2 capture
references.citation: Science. 2013 Aug 30;341(6149):1230444
references.pmid: 23990564
references.citation: Langmuir. 2011 May 17;27(10):6368-73
references.pmid: 21488612
references.citation: Angew Chem Int Ed Engl. 2015 Jan 2;54(1):221-6
references.pmid: 25521699
references.citation: Nat Commun. 2012 Jan 24;3:642
references.pmid: 22273680
references.citation: Nat Commun. 2012 Jul 17;3:954
references.pmid: 22805561
references.citation: Sci Rep. 2013 Oct 10;3:2916
references.pmid: 24107974
references.citation: J Am Chem Soc. 2011 Apr 20;133(15):5664-7
references.pmid: 21438585
references.citation: Adv Mater. 2010 Apr 12;22(14):1598-601
references.pmid: 20496387
references.citation: J Am Chem Soc. 2009 Jul 8;131(26):9186-8
references.pmid: 19530682
references.citation: Angew Chem Int Ed Engl. 2015 Jan 2;54(1):149-54
references.pmid: 25385329
references.citation: Angew Chem Int Ed Engl. 2012 Feb 20;51(8):1826-9
references.pmid: 22213592
references.citation: Angew Chem Int Ed Engl. 2009;48(44):8335-9
references.pmid: 19777524
references.citation: Energy Fuels. 2014 Feb 20;28(2):1028-1040
references.pmid: 24578590
references.citation: J Am Chem Soc. 2009 Dec 9;131(48):17546-7
references.pmid: 19916507
references.citation: Chem Soc Rev. 2014 Aug 21;43(16):5415-8
references.pmid: 25011480
references.citation: Angew Chem Int Ed Engl. 2007;46(5):795-8
references.pmid: 17163558
references.citation: Science. 2010 Oct 29;330(6004):650-3
references.pmid: 21030651
references.citation: J Am Chem Soc. 2008 Oct 22;130(42):13850-1
references.pmid: 18817383
references.citation: Nat Mater. 2012 Jun 03;11(8):710-6
references.pmid: 22660661
references.citation: Angew Chem Int Ed Engl. 2010 Aug 16;49(35):6058-82
references.pmid: 20652916
references.citation: J Am Chem Soc. 2006 Jul 12;128(27):8904-13
references.pmid: 16819886
references.citation: Environ Sci Technol. 2010 Mar 1;44(5):1820-6
references.pmid: 20143826
references.citation: Nat Chem. 2012 Oct;4(10):810-6
references.pmid: 23000994
references.citation: Angew Chem Int Ed Engl. 2013 Sep 23;52(39):10316-20
references.pmid: 23788267
references.citation: Inorg Chem. 2009 Jul 20;48(14):6860-72
references.pmid: 19472992
references.citation: Nature. 2013 Mar 7;495(7439):80-4
references.pmid: 23446349