Graphene-based membranes

Lead Research Organisation: University of Manchester
Department Name: Chemistry

Abstract

Membranes containing functionalized or pristine graphene offer remarkable potential for selective uptake and transport of molecular or ionic species. For example, research at the University of Manchester (UoM) has shown that graphene oxide (GO) laminate membranes exhibit unimpeded water permeation while being impermeable to organic liquids, vapours and gases. Building on UoM expertise in graphene and novel membrane materials, a range of membranes will be developed for application in the areas of:
(1) Molecular separations. Cost-effective and energy-efficient processes for separation of liquid (e.g. recovery of bioalcohols) or gaseous (e.g. CO2 capture from flue gas) mixtures.
(2) Selective barriers. In defence, protection from toxic agents for personnel and installations. In food packaging, maintaining food quality.
(3) Ionic conductors. Better and more economic membranes for fuel cells and other electrochemical applications.
(4) Sensors. Sensitization layers in photonic sensors for disease detection (e.g., renal disease, diabetes) and biomimetic membranes in electronic sensors for detecting the action of agricultural pests.

The research programme is driven by the engineering requirements for economic processing into membranes on a variety of substrates, including flat-sheet, tubular, hollow-fibre and monolith supports. Filtration, casting, dip-coating and spray-coating methods will be applied and scaled-up for deposition from aqueous or organic dispersions. Chemical vapour deposition will be used where necessary. Polymer/graphene mixed matrix membranes will also be prepared, utilising a range of high performance membrane polymers invented at UoM (polymers of intrinsic microporosity, PIMs). Membranes will be fully characterized using state-of-the-art techniques, including Raman spectroscopy, X-ray photoelectron spectroscopy and high resolution transmission electron microscopy, and relationships will be established between structure at the nano-scale and performance under conditions of use. Computer simulation methods will be established to provide a fundamental insight into the formation, structure and performance of graphene-based membranes, and to guide membrane development for specific applications. Company partners will contribute to the management of the project and will assist in assessing membrane performance in identified application areas. The most promising materials and applications will be selected for intensive development in the final two years of the five year programme. Intellectual property arising from the programme will be exploited as appropriate through UoM's technology transfer company and with suitable partners.

Planned Impact

The most immediate benefits will be to the commercial and public sector partners who have agreed to participate in the proposed programme of research, as they will be first to see the research results and to assess their importance for their own activities. These partners include a membrane manufacturer, and end-user companies in a variety of application areas, as well as the Defence Science and Technology Laboratory and an Institute dedicated to Membrane Research and Development. It is anticipated that additional partners will become involved as results are disseminated more widely. The researchers involved in the programme will themselves benefit from the interactions with these partners, which will enhance their skills, experience and knowledge base.

The primary purpose of the research programme is to take graphene-based membranes from the status of laboratory curiosity as far towards commercialisation as is possible within a five-year project. The research is expected to generate intellectual property (IP), which will be protected and exploited as appropriate.

The application areas that are the specific focus of the research are in areas which affect everybody's daily life: energy, sustainability, defence, food and health. In the long-term, the successful development of a product in any one of these areas will bring significant benefits to the public at large. The programme is seeking to develop processes that will make biofuel production more economically viable and carbon dioxide recovery more energy-efficient; materials that will give cheaper, better fuel cells; ways of keeping defence personnel safe from toxic agents and ways of keeping foodstuffs safe for consumption; and sensors for detecting diseases and agricultural pests.

Publications

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Abraham J (2017) Tunable sieving of ions using graphene oxide membranes. in Nature nanotechnology

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Alberto M (2018) Impeded physical aging in PIM-1 membranes containing graphene-like fillers in Journal of Membrane Science

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Althumayri K (2016) The influence of few-layer graphene on the gas permeability of the high-free-volume polymer PIM-1. in Philosophical transactions. Series A, Mathematical, physical, and engineering sciences

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Balakrishnan P (2017) 2D materials graphene and hBN boost DMFC performance in Fuel Cells Bulletin

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Brent JR (2014) Production of few-layer phosphorene by liquid exfoliation of black phosphorus. in Chemical communications (Cambridge, England)

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Conti S (2016) Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene. in Chemphyschem : a European journal of chemical physics and physical chemistry

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Ghorbanfekr-Kalashami H (2017) Dependence of the shape of graphene nanobubbles on trapped substance. in Nature communications

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Gonciaruk A (2015) PIM-1/graphene composite: A combined experimental and molecular simulation study in Microporous and Mesoporous Materials

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Gonciaruk A (2015) In silico designed microporous carbons in Carbon

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Latychevskaia T (2018) Convergent beam electron holography for analysis of van der Waals heterostructures. in Proceedings of the National Academy of Sciences of the United States of America

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Lewis E (2016) Imaging the Hydrated Microbe-Metal Interface Using Nanoscale Spectrum Imaging in Particle & Particle Systems Characterization

 
Description Graphene oxide membranes in a hydrated state act as molecular sieves, blocking solutes with a hydrodynamic radius larger than 0.45 nm. (Science, 2014, 343, 752-754)

Multilayer graphitic films, made by chemical reduction of graphene oxide laminates, have exceptional barrier properties, being impermeable to gases, liquids, and aggressive chemicals such as HF. (Nature Commun., 2014, 5, 4843)

The polymer of intrinsic microporosity PIM-1 can interact with graphene sheets and facilitate graphene dispersion. (Micropor. Mesopor. Mater., 2014, 209, 126-134)

Graphene prepared by chemical vapour deposition (CVD) has been deposited on racetrack type silicon cavity resonators, and limits established for the cavity length for optical sensing applications. (Optics Express, 2014, 22, 18625-18632)

Few-layer phosphorene nanosheets can be formed by liquid phase exfoliation (LPE) of black phosphorus. (Chem. Commun., 2014, 50, 13338-13341)

In the plasma hydrogenation of graphene, conditions can be tuned to clean graphene, functionalize graphene, or etch it away layer-by-layer. (Appl. Phys. Lett., 2014, 105, 183104)

The first atomic scale resolution scanning transmission electron microscopy images have been obtained of graphene defect structures induced by ion-irradiation. (Nature Scientific Reports, 2014, 4, Article number 6334)

Advanced transmission electron microscopy (TEM) techniques show a change from a flat to a three-dimensional structure on passage of an electric current through graphite. (Nanotechnology, 2014, 25, 465601)

For nanocomposites of few-layer graphene in polypropylene, graphene flakes act as nucleation sites for polymer crystallization; large (20 ?m) flakes are more effective than small (5 ?m) flakes for polymer reinforcement. (Faraday Discuss., 2014, 173, 379-390)

A simple computational approach has been developed to represent the pore structures of carbonaceous materials. (Carbon, 2015, 88, 185-195)

n-Octylbenzene acts as a graphene dispersion stabilizing agent in the liquid phase exfoliation (LPE) of graphite (Nature Scientific Reports, 2015, 5, Article number 16684)

Wastewater from membrane fabrication can be treated utilising an adsorbent such as a polymer of intrinsic microporosity, greatly improving the sustainability of membrane manufacture. (Green Chem., 2015, 17, 5196-5205)

Low loadings (0.05 vol.%) of few-layer graphene in the polymer of intrinsic microporosity PIM-1 can give membranes with enhanced gas permeability that maintain good performance on ageing. (Phil. Trans. R. Soc. A, 2016, 374, 20150031)

Chemical functionalization of coronene by perchloro substitution significantly enhances its propensity to form a self-assembled monolayer on graphene. (Chem. Phys. Chem., 2016, 17, 352-357)

Advanced characterization techniques have been developed to enable graphene to be visualised within an organic polymer. (Carbon, 2016, 102, 357-356)

Smooth, nanometre-sale capillaries can be fabricated utilising two-dimensional crystals as spacers; enhanced water flow is observed in channels that can accommodate only a few layers of water. (Nature, 2016, 538, 222-225)

Superconductivity is observed in Ca-doped graphene laminates. (Sci Rep. 2016, 6, 23254)

The pressure of liquids encapsulated between two graphene sheets can reach 1GPa and induce chemical reactions that would not occur at atmospheric conditions. (Nat. Comm. 2016, 7, 12168)

Graphene oxide membranes could be used for the water treatment of the nuclear industry to selectively separate ions with similar size but different hydration free energies. (Env. Sci. Tech., 2016, 50, 3875)

A novel membrane photo-reactor was made of graphitic carbon nitride (g-C3N4) nanosheets; it was used as both separation layer and catalyst for highly efficient photo-oxidation of organic dyes. (J. Mater. Chem. A, 2016, 4, 11666-11671)

The polymer of intrinsic microporosity PIM-1 shows unusual molecular motions and conductivity at high temperature. (ACS Macro Lett., 2016, 5, 528-532)

The performance of a direct methanol fuel cell at elevated temperature is significantly improved by the addition of a single layer graphene or hexagonal boron nitride layer. (Adv. Energy Mater., 2016, 1601216)

A graphene oxide coating has a beneficial effect in embryonic stem cell differentiation, which opens up possibilities for graphene in biomedical applications. (Scientific Reports, 2016, 6, 25917)

A technique has been developed for the fabrication of pressurized and stable graphene membranes that can hold up to 14 bar and ?2% strain. (Appl. Phys. Lett., 2016, 108, 221907)

MoS2 nanosheets, suitable for applications in catalysis, can be formed on a microporous substrate of diatomaceous earth. (Chem. Mater., 2016, 28, 5582-5586)

Following intravenous administration of graphene oxide sheets to mice there was extensive urinary excretion, with no impairment to kidney function. (ACS Nano, 2016, 10, 10753-10767)

High-resolution imaging techniques offer the potential to visualize the microbe-metal interface during the bioproduction of a range of functional materials. (Part. Part. Syst. Charact., 2016, 33, 833-841)

The addition of graphene-like fillers to the polymer PIM-1 gives membranes with improved separation for biobutanol recovery. (J. Membr. Sci., 2017, 526, 437-449)

Membranes comprising a thin film of PIM-1 on a tailored macroporous PVDF support show excellent performance for biobutanol recovery. (J. Membr. Sci., 2017, 529, 207-214)

The addition of polyhedral oligomeric phenethyl-silsesquioxanes (POSS) to the polymer PIM-1 gives membranes with enhanced performance for gas separation. (J. Membr. Sci., 2017, 529, 274-285)

Ion permeation and selectivity of graphene oxide membranes with sub-nm channels dramatically alters with the change in interlayer distance due to dehydration effects whereas permeation of water molecules remains largely unaffected. (Nature Nanotechnology, 2017, 12, 546-550)

Atomic scale defects in monolayer NbSe2 have been observed. (ACS Nano, 2017, 11, 2894-2904)

A two dimensional form of the mineral franckeite can be produced by mechanical exfoliation. (Nature Communications, 2017, 8, Article No 14410)

In situ analytical transmission electron microscopy has been applied to examine the localised oxidation reactions that occur in a Ni-Cr-Fe alloy. (Ultramicroscopy, 2017, 176, 46-51)

A new experimental platform, which allows real time, nanoscale, elemental and structural changes to be studied at temperatures up to 1000 ?C and pressures up to 1 atm, has been applied to understand complex structural changes occurring during reduction of a bimetallic catalyst. (ChemPhysChem 10.1002/cphc.201700425)

A new model of ion-carbon interaction shows that cations are strongly adsorbed onto a graphene surface with a trend (Li+ < Na+ < K+) opposite to that predicted by previous calculations. (J. Phys. Chem. Lett., 2017, 8, 703-708)

Carbon nanotubes act as cages for organic molecules, enabling them to be optimally positioned for Surface Enhanced Raman Scattering (SERS). (Faraday Discuss., 2017, 205, 85-103)

Excellent ion sieving properties are achieved for laminar MoS2 membranes functionalised with dyes. (ACS Nano 2017, 11, 11082-11090)

Ultrathin graphene oxide membranes show potential for organic solvent nanofiltration. (Nature Mater., 2017, 16, 1198-1202)

The interaction of phospholipid membranes with graphene derivatives has been studied using a quartz crystal microbalance with dissipation monitoring. Lipid monolayers on reduced graphene oxide are of interest for biosensing applications. (Nanoscale, 2018, 10, 2555-2567)

Low-cost, flexible strain gauges can be produced on paper by inkjet printing with a graphene ink. (Carbon, 2018, 129, 462-467)

New methods for analysing Raman data enable the effects of strain and doping in graphene to be evaluated. (2D Mater. 2018, 5, 015016)

Elemental mapping can be performed on liquid samples with high spatial resolution with a new design of graphene-based cell in a scanning transmission electron microscope. (Nano Lett. 2018, 18, 1168-1174)

Atomic resolution imaging in an environmental TEM enables the process of aluminium oxidation to be studied from first oxide nucleation through to complete film formation. (ACS Appl. Mater. Interfaces 2018, 10, 2230-2235)

Inelastic neutron scattering reveals that PIM-1, an ultrapermeable polymer of interest for gas separation membranes, exhibits a Boson peak at lower frequencies than conventional glassy polymers, indicating a higher compressibility at the molecular scale. (Phys. Chem. Chem. Phys., 2018, 20, 1355-1363)

Atomistic simulation gives an insight into the effects of hydration on graphene oxide membranes. (Nanoscale, 2018, 10, 1946-1956)

Design rules have been established for selecting solvents and dispersants for graphene and carbon nanotubes. (ACS Nano, 2018, 12, 1043-1049)

Graphene oxide acts as a performance-enhancing filler in polyethersulfone mixed matrix membranes for ultrafiltration of aqueous solutions. (Chem. Eng. J., 2018, 334, 789-799)

Electrical control of water permeation through a graphene oxide membrane has been demonstrated. (Nature, 2018, 559, 236-240)

Membranes incorporating functionalised graphene oxide show potential for desalination by membrane distillation. (J. Membr. Sci., 2018, 554, 309-323; Desalination, 2019, 452, 196-207)

Graphene laminates form highly effective barriers to acid gases such as CO2 and H2S under extreme conditions (Adv. Mater. Interf., 2018, 5, 1800304)
Exploitation Route Facilities for membrane fabrication, scale-up and testing are being established in Manchester at the Graphene Engineering Innovation Centre and are accessible by industrial partners. Patents have been applied for.
Sectors Chemicals,Energy,Environment,Manufacturing, including Industrial Biotechology

 
Description Public awareness of the potential of graphene-based membranes: worldwide publicity about graphene-based membranes for seawater desalination, see e.g. https://www.epsrc.ac.uk/newsevents/news/graphenesieve/, http://www.bbc.co.uk/news/science-environment-39482342 A partnership with Lifesaver is seeking to develop enhanced water filtration products, see https://www.manchester.ac.uk/discover/news/national-graphene-institute-to-develop-graphene-water-filtration-with-lifesaver/
First Year Of Impact 2017
Impact Types Societal

 
Description Collaborative project with Airbus (R.R. Nair)
Amount £300,000 (GBP)
Funding ID FSIR-AIRBUS-TSB 
Organisation Innova UK 
Sector Private
Country Unknown
Start 04/2014 
End 09/2017
 
Description EPSRC
Amount £1,675,667 (GBP)
Funding ID EP/P009050/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 12/2016 
End 05/2020
 
Description Feasibility project (R.R. Nair)
Amount £68,000 (GBP)
Organisation Neometals Ltd 
Sector Private
Country Australia
Start 02/2016 
End 08/2016
 
Description Marie Curie Fellowship (R.R. Nair - Stable Crosslinked Graphene Membranes for Water and Molecular Separation)
Amount £136,000 (GBP)
Funding ID 707220 
Organisation Marie Sklodowska-Curie Actions 
Sector Academic/University
Country Global
Start 08/2017 
End 07/2019
 
Description Newton Fund UK-Gulf Institutional Link
Amount £391,576 (GBP)
Funding ID 279336045 
Organisation British Council 
Sector Charity/Non Profit
Country United Kingdom
Start 06/2017 
End 05/2019
 
Description Programme Grant
Amount £5,327,896 (GBP)
Funding ID EP/P00119X/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 10/2016 
End 09/2021
 
Description Standard research grant
Amount £489,657 (GBP)
Funding ID EP/N013670/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 03/2016 
End 02/2019
 
Title REDUCED GRAPHENE OXIDE BARRIER MATERIALS 
Description This invention relates to barrier materials comprising reduced graphene oxide, methods of making said materials and their uses. The reduced graphene oxide is preferably formed from the reduction of graphene oxide by HI, HBr or ascorbic acid. 
IP Reference WO2015145155 
Protection Patent application published
Year Protection Granted 2015
Licensed Commercial In Confidence
Impact Engagement with industry
 
Title Separation of water using a membrane 
Description This invention relates to the uses of graphene oxide, and in particular graphene oxide on a porous support, and a membrane composed of these materials. This invention also relates to methods of dehydration, which include vapour phase separation and pervaporation. 
IP Reference US20180071692 
Protection Patent application published
Year Protection Granted 2017
Licensed Commercial In Confidence
Impact Growth of interest in graphene-based membranes for water treatment applications.
 
Title Analysis of coupled membrane deformation and mass transport 
Description Software developed for analysis of coupled membrane deformation and mass transport through membrane - deposited on group web-page https://mapos.manchester.ac.uk 
Type Of Technology Software 
Year Produced 2017 
Impact New capability. 
URL https://mapos.manchester.ac.uk
 
Description Academic guest lecture by Prof. Peter M. Budd: Giant molecules and 2D materials 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact Lecture delivered at Audenshaw School (19/09/16), Buxton Community School (11/11/16), Al-Jimiatul Islamiyah School Bolton (24/01/17), Giggleswick School (13/3/17). South Wirral High School (24/1/18), Deeside sixth form (21/11/18), East Manchester Academy (6/12/18), Preston Muslim Girls High School (13/12/18).
Year(s) Of Engagement Activity 2016,2017,2018
URL http://www.manchester.ac.uk/connect/teachers/students/academic-guest-lecture-series/