Control of Physical Aging in Super Glassy Polymer Membranes Without Permeability Loss MOF Mixed Matrix Membranes
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1 Discover Develop Deploy Virtual screening Chemistry Tuning porosity Material scale-up Commercial design Control of Physical Aging in Super Glassy Polymer Membranes Without Permeability Loss MOF Mixed Matrix Membranes Cher Hon (Sam) LAU Research Scientist 25 March 2015 MANUFACTURING FLAGSHIP/ ADAPTIVE POROUS MATERIALS TEAM
2 Presentation Outline Adaptive Porous Materials Team Porous Frameworks CSIRO s Approach Conclusion Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 1
3 Adaptive Porous Materials Team in CSIRO Triggered Release Materials Energy/Gas Storage Nanoporous Materials MOFs PAFs MOPs COFs Cages Electrochemical storage Membrane Separations Drug Delivery Water Quality Agriculture Catalysis Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 2
4 Porous Frameworks Metal Organic Frameworks (MOFs) Metal Salt + = Organic Linker Sites for functionalisation Void space for storage Porous Aromatic Frameworks (PAFs) Thermally and chemically very stable Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 3
5 Virtual screening of MOF candidates Elements Building Blocks MOF Candidates Properties Applications Carbon Zinc Oxygen Hydroge n Nitrogen + Zn +2 Cu +2 BTB BDC DOBDC + PAFs ZIFs COFs POCs SNUs + Surface area Porosity Gas adsorption Gas permeation Water permeation + Separation Storage Catalysis Sensors Barriers + Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 4
6 Triggered Release Materials UV-triggered release of CO 2 R. Lyndon, K. Konstas, M. R. Hill; Angew. Chem. Int. Ed., 2013, 52, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 5
7 Triggered Release Materials R. Lyndon, K. Konstas, M. R. Hill; Angew. Chem. Int. Ed., 2013, 52, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 6
8 Intelligent Fertilizers H 2 O Plant demand Requirements: High pore volume Water stable Low cost Eco-friendly Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 7
9 Intelligent Fertilizers Retained fraction of fertilizer after initial leaching Leached fraction of fertilizer Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 8
10 Carbon Capture UiO-66(Ti 56 ) 81 % UiO-66(Zr 100 ) Lau, C. H.; Babarao, R.; Hill, M. R., Chem. Commun. 2013, 49 (35), 3634 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 9
11 Energy & Gas Storage CO 2 adsorption at 273K CO ml/g CO 2 78 ml/g UiO-66 Zr-MOF K. Konstas, M. R. Hill; Angew. Chem. Int. Ed., 2012, 51, Highest MOFs Current MOF H 2 adsorption at 77K CH 4 adsorption at 273K Mixed 11 Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 10
12 Energy & Gas Storage Babarao, R. et al. Chem. Commun., 2014, 50, Point of interest (0.15 bar ) Predicted selectivity for CO 2 /N 2 (15/85 wt %) mixture) of 590 at 293 K and 1 atm Flue gas composition CO 2 (15%), N 2 (75%), O 2 (4-5 %), H 2 O (5-8 %) and SOx and Nox Predict mixed gas isotherms (difficult to obtain experimentally) Witold, MB; Babarao, R; Hill, MR; Doonan, CJ; Sumby, CJ, J. Am. Chem. Soc., 135, 2013 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 11
13 Porous Frameworks As adsorbents for CO 2 capture MOF CO 2 Capacity b 146 tonne MOF = $2.9 billion (based on BASF prices) 600 MW coal-fired power plant Flue gas 13 % CO 2 (460 tonnes/hr) a MOF Mixed Matrix Membrane a, b 0.17 million m million m tonne MOF a) T. C. Merkel, H. Lin, X. Wei, R. Baker; J. Membr. Sci., 359 (2010) b) J. Liu, P. K. Thallapally, B. P. McGrail, D. R. Brown, J. Liu; Chem. Soc. Rev, 2012,41, c) L. M. Robeson, J. Membr. Sci., 2008, 320, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 12
14 Permeability (P gas A ) Selectivity (P gas A / P gas B ) Permeability (P gas A ) What we aim to achieve with CSIRO s MOF Membranes? Trade-off relationship between permeability and selectivity Plasticization Lose selectivity Permeability (P gas A ) Physical Aging Lose permeability Pressure Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 13 Time
15 Example: Screening for membrane materials Application: CO 2 capture and H 2 generation Industrial Feasibility Criteria Intergovernmental Panel on Climate Change (IPCC) Candidate Materials: Zeolitic Imidazolate Frameworks a) ZIF-7 c) ZIF-11 Zn(bIm) 2 b) ZIF-8 Zn(mIm) 2 d) ZIF-69 Zn(bIm) 2 Zn(cbIm)(nIm) Thornton et al. Feasibility of Zeolitic Imidazolate Framework membranes for clean energy applications Energy & Environmental Science Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 14
16 CSIRO s Approach Mixed Matrix Membranes with Porous Frameworks Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 15
17 CSIRO s Membranes Slow Aging Membranes Carbon Capture Additive: UiO-66 MOF, Ti-UiO-66 Polymer: PIM-1 Smith, S. J. D.; Ladewig, B. P.; Hill, A. J.; Lau, C. H.; Hill, M. R., Sci. Rep. 2015, 5, 7823 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 16
18 CSIRO s Membranes Slow Aging Membranes Carbon Capture Additive: UiO-66 MOF Smith, S. J. D.; Ladewig, B. P.; Hill, A. J.; Lau, C. H.; Hill, M. R., Sci. Rep. 2015, 5, 7823 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 17
19 CSIRO s Membranes Slow Aging Membranes Organic Solvent Nanofiltration Additive: PAF-1 Water-Hydrocarbon Separations Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 18
20 CSIRO s Membranes Slow Aging Membranes Organic Solvent Nanofiltration Additive: PAF-1 Hydrocarbon-Dye Separations (a) (a) (a) Li, X.; De Feyter, S.; Chen, D.; Aldea, S.; Vandezande, P.; Du Prez, F.; Vankelecom, I. F. J. Chem. Mater. 2008, 20, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 19
21 CSIRO s Membranes Selective Aging Membranes Hydrogen Purification Additive: PAF-1 Polymer: PIM-1 C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F. Kennedy, S. C. Howard, A. J. Hill, M. R. Hill, Angew. Chem. Int. Ed. 2015, 54, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 20
22 CSIRO s Membranes Selective Aging Membranes Hydrogen Purification David et al.; J. Am. Chem. Soc. 2014, 136, C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F. Kennedy, S. C. Howard, A. J. Hill, M. R. Hill, Angew. Chem. Int. Ed. 2015, 54, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 21
23 CSIRO s Membranes Selective Aging Membranes Hydrogen Purification C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F. Kennedy, S. C. Howard, A. J. Hill, M. R. Hill, Angew. Chem. Int. Ed. 2015, 54, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 22
24 CSIRO s Membranes Anti-Aging Membranes Carbon Capture Additive: PAF-1 Polymer: PTMSP, PMP, PIM-1 C. H. Lau, M. R. Hill et al. Angew. Chem. 2014, 53, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 23
25 CSIRO s Membranes Anti-Aging Membranes Carbon Capture Additive: PAF-1 Polymer: PTMSP, PMP, PIM-1 C. H. Lau, M. R. Hill et al. Angew. Chem. 2014, 53, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 24
26 CSIRO s Membranes Anti-Aging Membranes Carbon Capture C. H. Lau, M. R. Hill et al. Angew. Chem. 2014, 53, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 25
27 CSIRO s Membranes How does it work? 1. Intimate interaction between porous additives and polymers C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F. Kennedy, S. C. Howard, A. J. Hill, M. R. Hill, Angew. Chem. Int. Ed. 2015, 54, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 26
28 CSIRO s Membranes How does it work? 2. Freezing mobility in carbon atoms of bulky groups in polymer C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F. Kennedy, S. C. Howard, A. J. Hill, M. R. Hill, Angew. Chem. Int. Ed. 2015, 54, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 27
29 CSIRO s Membranes How does it work? 3. Unchanged pore sizes over time Anti-aging membranes Selective-aging membranes C. H. Lau, M. R. Hill et al. Angew. Chem. 2014, 53, Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 28
30 Scale-Up Production Membranes & MOFs Membranes Material scale-up Hollow Fiber Spinning Line Deploy MOFs Commercial design Flow Chemistry M. Rubio-Martinez, M. P. Batten, A. Polyzos, K.-C. Carey, J. I. Mardel, K.-S. Lim, M. R. Hill, Sci. Rep. 2014, 4: 5443 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 29
31 Scale Up Production MOFs Proof-of-concept HKUST-1 UiO-66 NOTT-400 Proof-of-scalability Al fumarate M. Rubio-Martinez, M. P. Batten, A. Polyzos, K.-C. Carey, J. I. Mardel, K.-S. Lim, M. R. Hill, Sci. Rep. 2014, 4: 5443 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 30
32 Scale-Up Production MOFs Al fumarate Proof-of-concept: 40 g/h Proof-of-scalability: 400 g/h Scale-up: 10 kg/h Reactor: 2,5,10mL T: 0-150C Diameter tube: 1mm Flow rate: ml/min (up to 10 bar) Reactor: 100mL T: 0-150C Diameter tube: 6mm Flow rate: 1-45mL/min Reactor: 2000mL T: 0-150C Diameter tube: 12mm Flow rate: 1000mL/min Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 31
33 Conclusions Capable of scale up productions of porous additives required to: 1) Enhance gas permeability by up to 300 % 2) Maintain enhanced gas permeability beyond 1 year 3) Tailor aging mechanism in membranes according to application 4) Fabricate multi-functional membranes for carbon capture, solvent purification, and dye sequestration. Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page 32
34 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page
35 Thank you Manufacturing Flagship/Adaptive Porous Materials Team Cher Hon (Sam) Lau Research Scientist t e cherhon.lau@csiro.au MANUFACTURING FLAGSHIP/ADAPTIVE POROUS MATERIALS
36 CSIRO s Membranes Slow Aging Membranes Carbon Capture Additive: UiO-66 MOF Enthalpy of Adsorption Pore Size Lau, C. H.; Babarao, R.; Hill, M. R., Chem. Commun. 2013, 49 (35), 3634 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page
37 CSIRO s Membranes Slow Aging Membranes Carbon Capture Additive: UiO-66 MOF Smith, S. J. D.; Ladewig, B. P.; Hill, A. J.; Lau, C. H.; Hill, M. R., Sci. Rep. 2015, 5, 7823 Mixed Matrix Membranes with Porous Frameworks Cher Hon (Sam) Lau Page
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