Ghalei B, Sakurai K, Kinoshita Y, , Enhanced selectivity in mixed matrix membranes for CO2 capture through efficient dispersion of amine-functionalised MOF nanoparticles, Nature Energy. 2017, Advance Online publication. Doi: http://dx.doi.org/10.1038/nenergy.2017.86
Shan Jiang, Qilei Song,* Alan Massey, Samantha Y. Chong, Linjiang Chen, Shijing Sun, Tom Hasell,* Rasmita Raval, Easan Sivaniah, Anthony K. Cheetham, Andrew I. Cooper*, Oriented 2D Porous Organic Cage Crystals, Angew. chem. Int. Ed., accepted, 2017. Doi: http://dx.doi.org/10.1002/anie.201704579
Y. Rong, Q. Song, K. Mathwig, E. Madrid, D. He, R. G. Niemann, P. J. Cameron, S. EC Dale, S. Bending, M. Carta, R. Malpass-Evans, N. B. McKeown, F. Marken. pH-induced reversal of ionic diode polarity in 300nm thin membranes based on a polymer of intrinsic microporosity. Electrochemistry Communications, 2016, 69, 41-45.
Maria Jimenez-Solomon+, Qilei Song+, Kim Jelfs, Marta Munoz-Ibanez, Andrew Livingston*. Polymer nanofilms with enhanced microporosity. Nature Materials. 2016. 15, 760-767. Doi:10.1038/nmat4638. (+Contributed equally).
- Press release by Imperial College: Researchers develop "designer" chemical separation membranes
- Media coverage: ScienceDaily | Phys.Org | Materials Today
- Highlight: Polymer Membranes: Contorted Separation by Prof. Neil McKeown at University of Edinburgh.
- Introduction by Prof. Andrew Livingston
- Highlight in IChemE's ChemEngBlog
Q. Song, S. Jiang, T. Hasell, M. Liu, S. Sun, A.K. Cheetham, E. Sivaniah, A.I. Cooper. Porous Organic Cage Thin Films and Molecular-Sieving Membranes. Advanced Materials. 2016, 13, 2629-2637. DOI:10.1002/adma.201505688. Featured on Back Cover.
In collaboration with the group of Prof. Andy Cooper at Liverpool, we fabricate Porous Organic Cages (POCs), a new class of microporous molecular materials, to thin films and selective molecular sieving membranes.
Q. Song, S. Cao, R.H. Pritchard, H. Qiblawey, E.M. Terentjev, A.K. Cheetham, and E. Sivaniah. Nanofiller-tuned microporous polymer molecular sieves for energy and environmental processes. Journal of Materials Chemistry A. 2016,4, 270-279. DOI: 10.1039/C5TA09060A.
Microporous polymers with molecular sieving properties are promising for a wide range of applications in gas storage, molecular separations, catalysis, and energy storage. In this study, we report highly permeable and selective molecular sieves fabricated from crosslinked polymers of intrinsic microporosity (PIMs) incorporated with highly dispersed nanoscale fillers, including nonporous inorganic nanoparticles and microporous metal-organic framework (MOF) nanocrystals.
We demonstrate that the combination of covalent crosslinking of microporous polymers via controlled thermal oxidation and tunable incorporation of nanofillers results in high performance membranes with substantially enhanced permeability and molecular sieving selectivity, as demonstrated in separation of gas molecules, for example, air separation (O2/N2), CO2 separation from natural gas (CH4) or flue gas (CO2/N2), and H2 separation from N2 and CH4.
After ageing over two years, these nanofiller-tuned molecular sieves became more selective and less permeable but maintained permeability levels that are still two orders of magnitude higher than conventional gas separation membranes.
D. Di, K.P. Musselman, G. Li, A. Sadhanala, Y. Ievskaya, Q. Song, Z. Tan, M. L. Lai, J.L. MacManus-Driscoll, N.C. Greenham, R.H. Friend. Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix. The Journal of Physical Chemistry Letters, 2015, 6, 446-450.
D.H.N. Perera, Q. Song, H. Qiblawey, E. Sivaniah. Regulating the aqueous phase monomer balance for flux improvement in polyamide thin film composite membranes. Journal of Membrane Science. 2015, 487, 74-82. Link to the paper
Polyamide thin film composite (PA-TFC) membranes are synthesized from interfacial polymerization via the established polymer chemistry (a) as shown in the figure below. The SEM iamges show the morphology of surface (b) and cross-section (c) of ultrathin polyamide thin films supported on polysulfone membranes. These nanofilm membranes show relatively higher water permeance and high rejection of ions in water desalination applications.
Q. Song, S. Cao, R.H. Pritchard, B. Ghalei, S.A. Al-Muhtaseb, E.M. Terentjev, A.K. Cheetham, and E. Sivaniah. Controlled thermal oxidative crosslinking of polymers of intrinsic microporosity towards tunable molecular sieve membranes. Nature Communications, 2014, 5, 4813. Download PDF | Link to full text | Press release | Phys.org and PDF version | ScienceDaily | News in China Media and 科技日报 | BusinessWeekly
(Note: these media coverages are mainly on CO2 capture applications, but actually these novel microporous polymers have great potential for more broad applications beyond gas separations, and our understandings of the materials science are more important.)
Microporous materials with well-defined micropore (pore dimensions below 2 nm) structure are attractive next-generation materials for gas sorption, storage, catalysis and molecular level separations.
Polymers of intrinsic microporosity (PIMs) contain interconnected regions of micropores with high gas permeability but with a level of heterogeneity that compromises their molecular selectivity.
Here we report controllable thermal oxidative crosslinking of PIMs by heat treatment in the presence of trace amounts of oxygen. The resulting covalently crosslinked networks are thermally and chemically stable, mechanically flexible and have remarkable selectivity at permeability that is three orders of magnitude higher than commercial polymeric membranes.
This study demonstrates that controlled thermochemical reactions can delicately tune the topological structure of channels and pores within microporous polymers and their molecular sieving properties.
A patent (inventors: Q. Song and E. Sivaniah) has been filed based on the work reported in this paper.
Q. Song, S. Cao, P. Zavala-Rivera, L.P. Lu, W. Li, Y. Ji, S.A. Al-Muhtaseb, A.K. Cheetham and E. Sivaniah. Photo-oxidative enhancement of polymeric molecular sieve membranes. Nature Communications, 2013, 4, 1918. Download the PDF | Link to the paper | Press release by University of Cambridge | Phys.org | ScienceDaily | eurekalert
We report photo-oxidation of membranes made of a polymer of intrinsic microporosity (PIMs) and demonstrate how UV light can degrade the polymer while enhancing the selectivity in gas separation. The ultraviolet light field, localized to a near-surface domain, induces reactive ozone that collapses the microporous polymer framework. The rapid, near-surface densification results in asymmetric membranes with a superior selectivity in gas separation while maintaining and apparent permeability that is two orders of magnitude greater than commercially available polymeric membranes. In fact, the gas transport properties need to be considered carefully because the membranes now become heterogeneous composite films. The oxidative chain scission induced by ultraviolet irradiation also indicates the potential application of the polymer in photolithography technology. The key scientific understanding is the oxidative degradation of PIM-1 polymer under irradiation of shortwave-length UV light, which has broad implications on the applications of porous PIM-1 polymers.
A further finding not reported in the paper is that similar oxidative degradation can occur directly by ozone treatment, which induces densification at the surface, depending on the diffusion of ozone in the polymer network. These work were covered in my PhD thesis 'Polymer molecular sieve membranes'.
Story behind the paper....
When we synthesized the PIM-1 polymer in early 2011, we were initially interested in the optoelectronic properties. In collaboration with the optoelectronics group in the Cavendish lab (Prof. R.H. Friend group), we fabricated polymer light emittting diodes (PLED) devices and confirmed the electroluminenscence of PIM-1 polymer. However, the performance is not that great, and the science behind this phenomenon were not well understood.
It was later known that the inventors of PIM-1 polymer did similar research on PLED when they invented the materials 10 years ago! While I was working on polymer films and membranes, we realized that there are a lot of literature on photoprocessing of polymers in polymer science field and membrane field as well. This leads to our work on understanding the science behind the phenomenon and how the UV/ozone treatment of PIM-1 polymer changed the physical properties, including the gas transport properties.
We reported the story in a 3-page conference paper submitted to Euromembrane conference in March 2012, but it took us sometime to understand the mechanism well, therefore the publication of our paper were delayed until 2013. In the end, we have a better understanding of the materials.
Q. Song, W. Liu, C. D. Bohn, R. N. Harper, E. Sivaniah, S. A. Scott and J. S. Dennis. A high performance oxygen storage material for chemical looping processes with CO2 capture, Energy & Environmental Science, 2013, 6, 288-298. Link
We report a method for preparing of oxygen storage materials from layered double hydroxides(LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination.
Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2release capacity (5 wt%), stable oxygen storage capacity (12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu2O-Cu at high temperatures.
We anticipate that the strategy can be extended to manufacture a variety of metal oxidecomposites for applications in novel high temperature looping cycles for clean energy production.
Q. Song, S. K. Nataraj, M. V. Roussenova, J. C. Tan, D. J. Hughes, W. Li, P. Bourgoin, M. A. Alam, A. K. Cheetham, S. A. Al-Muhtaseb and E. Sivaniah. Zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes for gas separation, Energy & Environmental Science, 2012, 5, 8359-8369. Link
As-synthesised zeolitic imidazolate framework (ZIF-8) nanocrystals were dispersed into a polymer matrix forming nanocomposite membranes with enhanced gas permeability.
14. Polymer nanofilms with enhanced microporosity by Interfacial Polymerization. North American Membrane Society Meeting. May, 2016.
13. Thin Film Composite Membranes with Intrinsic Microporosity by Interfacial Polymerization for Molecular Separations. EuroMembrane Conference, September 2015.
12. Nanostructured metal oxides for chemical looping processes. Invited talk at the 250th ACS National Meeting & Exposition, August 2015. Boston, USA.
11. Advanced Molecular Sieve Membranes. Session of Porous Materials for Energy & Sustainability from Discovery to Application. Invited talk at the 250th ACS National Meeting & Exposition, August 2015. Boston, USA.
10. Advanced Microporous Molecular Sieve Membranes. Poster presentation at the 12th International Conference on Materials Chemistry (MC12), York, UK, July 2015.
9. Design and Fabrication of Novel Functional Energy Materials. ChemEngDayUK conference, Sheffield, UK, April 2015.
8. High-performance Molecular Sieve Membranes Derived from Polymers of Intrinsic Microporosity. The 10th International Congress on Membranes and Membrane Processes. Suzhou, China, 2014.
7. Nanoporous polymer membranes for gas separation. Theme Day of BSS group, Cavendish Laboratory, University of Cambridge, December, 2012.
6. High Performance Gas separation membrane from a polymer of intrinsic microporosity by photochemical surface modification. AIChE annual meeting, Pittsburgh, USA, October, 2012.
5. Nanocomposite membrane of a polymer of intrinsic microporosity and zeolitic imidazolate frameworks for gas separation. AIChE annual meeting, Pittsburgh, USA, October, 2012.
4. Nanoporous polymer membranes for gas separation. RSC/SCI Macro Group UK Young Researcers Meeting, Cambridge, September, 2012. Poster
3. High performance gas separation membrane from a polymer of intrinsic microporosity by photochemical surface modification. Euromembrane Conference, London, UK, September, 2012.
2. Nanocomposite membrane of a polymer of intrinsic microporosity and zeolitic imidazolate frameworks for gas separation. Euromembrane Conference, London, UK, September, 2012. (Best Oral Presentation Award)
1. Nanoporous polymer membrane for gas separation. NanoDTC forum, University of Cambridge, 09/2012.
- University of Science and Technology of China (USTC), December 2015.
- Nanjing University of Technology, Nanjing, December 2015
- Southeast University, Nanjing, December 2015
- Design and Fabrication of Functional Nanomaterials for Energy Applications. Newcastle University, Newcastle, UK. 2014.
- Polymer Molecular Sieve Membranes, Dalian Institute of Chemical Physics, Dalian, China. 2014.
- Polymer Molecular Sieve Membranes, National Center for Nanoscience and Technology, Beijing, China. 2014.
- Polymer Molecular Sieve Membranes, Department of Chemistry, Tsinghua University, Beijing, China. 2014.
- Advanced Materials for Energy and Environmental Applications: from Combustion to Membrane Separations. Southeast University, Nanjing, China. 2014.
- Polymer Molecular Sieve Membranes. University of Liverpool, Liverpool, UK. 2013.