Directed Assembly of High Aspect Ratio Nanoparticles for Hierarchical Materials
Lead Research Organisation:
Imperial College London
Department Name: Chemistry
Abstract
High aspect ratio nanoparticles (HARNs), such as nanorods and nanotubes, span both the micron and the nano domains, and are especially critical for hierarchical materials. The extra degrees of freedom associated with orientation create appealing opportunities but additional challenges. The implicit anisotropy of HARNs is reflected both in their intrinsic properties and in the rich structural variety of assemblies containing them. For example, while transverse quantum confinement can generate unique transport properties along the long axis of an individual nanowire, it is also possible to introduce internal structural or compositional variation, creating complex functionality within a single HARN . On the other hand, in order to use its inherent functionalities, the HARN must be integrated into a wider structure. From this perspective, high aspect ratio allows the formation of open networks or scaffolding with adjustable density, orientation, connectivity, and length scale. If the assembly process can be controlled, there is scope for complicated specific architectures, with ordered branches or junctions in the scaffolding, optimised for given applications. One way to envision the opportunity is to imagine the richness of metal organic frameworks (MOFs) multiplied by the structural and functional diversity that could be introduced by using HARNs as linking struts at a range of lengthscales. Note that although the term 'HARNS' could be taken to include oblate particles, such as nanoclay platelets, the focus here is on prolate rods, tubes, and fibres.At a conceptual level, the assembly of hierarchical materials represents the next challenge in materials science; mastering methods to control matter fully, across the lengthscales, will open up new vistas of science and application. On the other hand, the simplest networks of HARNs are already extremely relevant to a wide range of applications; existing examples include aligned CNT arrays for capacitor electrodes, aerospace epoxy nanocomposites with ultra-low electrical percolation thresholds, and efficient electron collection in titania nanorod photovoltaics. These current networks are almost all randomly designed, or at best, uniaxially oriented. The rational design of HARN architectures across different lengthscales will yield radical improvements in structural and functional performance.
Organisations
- Imperial College London (Lead Research Organisation)
- University College London (Collaboration)
- LG Corporation (South Korea) (Collaboration)
- Thomas Swan and Co Ltd (Collaboration)
- Linde Group (Collaboration)
- Tyco Safety Products (Project Partner)
- Alstom (United Kingdom) (Project Partner)
- Thomas Swan (United Kingdom) (Project Partner)
- Touchstone Innovations (Project Partner)
People |
ORCID iD |
| Milo Shaffer (Principal Investigator) |
Publications
Au H
(2018)
Brominated graphene as a versatile precursor for multifunctional grafting.
in Chemical science
Bayazit MK
(2016)
Carbon nanotube anions for the preparation of gold nanoparticle-nanocarbon hybrids.
in Chemical communications (Cambridge, England)
Bayazit MK
(2017)
Gram-scale production of nitrogen doped graphene using a 1,3-dipolar organic precursor and its utilisation as a stable, metal free oxygen evolution reaction catalyst.
in Chemical communications (Cambridge, England)
Buckley D
(2017)
Trajectory of the Selective Dissolution of Charged Single-Walled Carbon Nanotubes
in The Journal of Physical Chemistry C
Chavez-Valdez A
(2013)
Applications of graphene electrophoretic deposition. A review.
in The journal of physical chemistry. B
Cho J
(2009)
Characterisation of carbon nanotube films deposited by electrophoretic deposition
in Carbon
Clancy A
(2016)
Systematic comparison of conventional and reductive single-walled carbon nanotube purifications
in Carbon
Clancy AJ
(2018)
Charged Carbon Nanomaterials: Redox Chemistries of Fullerenes, Carbon Nanotubes, and Graphenes.
in Chemical reviews
Clancy AJ
(2015)
A one-step route to solubilised, purified or functionalised single-walled carbon nanotubes.
in Journal of materials chemistry. A
De Marco M
(2016)
Cross-linked single-walled carbon nanotube aerogel electrodes via reductive coupling chemistry
in Journal of Materials Chemistry A
Diba M
(2014)
Quantitative evaluation of electrophoretic deposition kinetics of graphene oxide
in Carbon
Fogden S
(2012)
Scalable method for the reductive dissolution, purification, and separation of single-walled carbon nanotubes.
in ACS nano
Garcia-Gallastegui A
(2012)
Graphene Oxide as Support for Layered Double Hydroxides: Enhancing the CO 2 Adsorption Capacity
in Chemistry of Materials
Goode AE
(2014)
Mapping functional groups on oxidised multi-walled carbon nanotubes at the nanometre scale.
in Chemical communications (Cambridge, England)
Hodge S
(2013)
Electrochemical Processing of Discrete Single-Walled Carbon Nanotube Anions
in ACS Nano
Hodge SA
(2017)
Chemical routes to discharging graphenides.
in Nanoscale
Hodge SA
(2012)
Unweaving the rainbow: a review of the relationship between single-walled carbon nanotube molecular structures and their chemical reactivity.
in Chemical Society reviews
Hodge SA
(2013)
Giant cationic polyelectrolytes generated via electrochemical oxidation of single-walled carbon nanotubes.
in Nature communications
Hodge SA
(2014)
Probing the charging mechanisms of carbon nanomaterial polyelectrolytes.
in Faraday discussions
Hu S
(2014)
Aqueous dispersions of oligomer-grafted carbon nanomaterials with controlled surface charge and minimal framework damage.
in Faraday discussions
Hu S
(2017)
Thermochemical functionalisation of graphenes with minimal framework damage.
in Chemical science
Iruretagoyena D
(2013)
Adsorption of carbon dioxide on graphene oxide supported layered double oxides
in Adsorption
Leese HS
(2016)
Reductively PEGylated carbon nanomaterials and their use to nucleate 3D protein crystals: a comparison of dimensionality.
in Chemical science
Liberti E
(2016)
Probing the size dependence on the optical modes of anatase nanoplatelets using STEM-EELS.
in Nanoscale
| Description | The goal was to develop highly-ordered, hierarchical materials, using high aspect ratio nanoparticles (HARNs) as fundamental building blocks to create functional structures designed across different lengthscales. Three work packages addressed the preparation of new, well-defined high aspect ratio nanoparticles, their modification with selective or supramolecular chemistry, and their assembly into high order structures. Carbon nanotubes and titania were selected as the key materials due to their impressive properties and range of potential applications. In both materials systems, significant progress was made. Individual nanotubes were solubilised, purified, and functionalised using chemical reductions in ammonia (developed with Skipper/Howard at UCL) and a new electrochemical charging route. The synthesis of titania nanorods has been refined, and extended to the formation of 2d platelets with detailed mapping of reaction conditions and advanced TEM analysis of structure and electronic properties. The original ambitious supramolecular linking scheme has been demonstrated and used to purify nanotube fractions by endohedral affinity and to assembly defined junctions, as protected by a patent filing. Methods to generate more general multiscale networks of carbon nanomaterials have been developed and subsequently applied to the preparation of catalyst supports and electrochemical electrodes for energy generation and storage. |
| Exploitation Route | General methods for the fabrication of improved nanomaterials are of wide relevance. For example, the titania nanorods and especially nanoplatelets are photocatalytically active, and potentially relevant to a range of solar cells, self-cleaning, and environmental clean-up applications. True solutions of undamaged carbon nanotubes are immediately useful for transparent conductors to replace ITO, as well as other thin film electronics applications, electrochemical electrodes (fuel cells, supercapacitors, etc), catalyst supports, and composites. Hierarchical assemblies are particularly efficient in many contexts. Directed assembly to form specific junctions has long term potential to advance nanoelectronics. |
| Sectors | Aerospace, Defence and Marine,Chemicals,Construction,Electronics,Energy,Environment |
| Description | The production of reductively charged nanocarbons, partly developed during this grant, was patented and licensed, leading to the launch of a commercial product targeted at the electronics industry in 2013. Further developments of the technology are anticipated. Work on supramolecular assembly is under discussion with a major international electronics company. The chemistry developed and extended in this grant has been widely adopted by others, including for making solar cells and high strength fibres. |
| First Year Of Impact | 2013 |
| Sector | Aerospace, Defence and Marine,Chemicals,Electronics |
| Impact Types | Economic |
| Description | Leverhulme Trust |
| Amount | £238,749 (GBP) |
| Funding ID | F/07 058/BT |
| Organisation | The Leverhulme Trust |
| Sector | Charity/Non Profit |
| Country | United Kingdom |
| Start | 10/2011 |
| End | 09/2014 |
| Description | NIEHS |
| Amount | £268,500 (GBP) |
| Funding ID | 1U19ES019536-01 |
| Organisation | National Institutes of Health (NIH) |
| Department | National Institute of Environmental Health Sciences |
| Sector | Public |
| Country | United States |
| Start | 05/2010 |
| End | 05/2015 |
| Description | LG |
| Organisation | LG Electronics |
| Country | Korea, Republic of |
| Sector | Private |
| PI Contribution | Building on the initial work and filing in the group, an industrial research project has been awarded (stc) to develop the technology towards applications. |
| Collaborator Contribution | Financial support |
| Impact | Collaborative research due to start shortly |
| Start Year | 2019 |
| Description | Linde |
| Organisation | Linde Group |
| Country | Global |
| Sector | Private |
| PI Contribution | Developed a technology in partnership and licensed to the company |
| Collaborator Contribution | Technical discussion, hiring a group member, supplying samples and information |
| Impact | Licensed technology and product release. |
| Description | Thomas Swan and Co Ltd |
| Organisation | Thomas Swan and Co Ltd |
| Country | United Kingdom |
| Sector | Private |
| PI Contribution | Long standing partnership developing technology and licensing it |
| Collaborator Contribution | Development of synthesis and processing routes relevant to new company products. Advice and discussion. CASE studentships (3) |
| Impact | New nanomaterials products. |
| Description | University College London |
| Organisation | University College London |
| Country | United Kingdom |
| Sector | Academic/University |
| Start Year | 2005 |
| Title | CROSS-LINKED GRAPHENE NETWORKS |
| Description | The present invention relates to a method for the production of cross-linked graphene and graphene oxide networks, which are selected from aerogels and xerogels with improved performance and characteristics thereof. The invention is also concerned with graphene and graphene oxide networks, which are selected from aerogels and xerogels produced by such processes and uses thereof. |
| IP Reference | US2015122800 |
| Protection | Patent granted |
| Year Protection Granted | 2015 |
| Licensed | No |
| Impact | . |
| Title | Carbon nanotube aerogels and xerogels and xerogels for CO² capture |
| Description | The present invention relates to carbon nanotube networks which are selected from aerogels and xerogels comprising layered double hydroxides (LDHs). The invention is also concerned with the method of preparing such carbon nanotube networks which are selected from aerogels and xerogels and use of such carbon nanotube networks which are selected from aerogels and xerogels for sorption and gas storage. |
| IP Reference | GB2516565 |
| Protection | Patent granted |
| Year Protection Granted | 2015 |
| Licensed | No |
| Impact | . |
| Title | Cross-Linked Carbon Nanotube Networks |
| Description | The present invention relates to a method for the production of cross-linked carbon nanotube networks which are selected from aerogels and xerogels with improved performance and characteristics thereof. The invention is also concerned with carbon nanotube networks which are selected from aerogels and xerogels produced by such processes and uses thereof. |
| IP Reference | US2014012034 |
| Protection | Patent granted |
| Year Protection Granted | 2014 |
| Licensed | No |
| Impact | . |
| Title | Dispersion method |
| Description | Dispersion of graphene platelets by charging methods |
| IP Reference | GB20110010937 |
| Protection | Patent granted |
| Year Protection Granted | 2011 |
| Licensed | No |
| Impact | . |
| Title | Graphene and graphene oxide aerogels/xerogels for CO² capture |
| Description | The present invention relates to graphene materials, particularly to aerogels and xerogels which comprise graphene or graphene oxide, and also contain layered double hydroxides (LDHs). The invention is also concerned with the method of preparing such graphene or graphene oxide aerogels and xerogels and use of such materials for sorption and gas storage. |
| IP Reference | GB2515425 |
| Protection | Patent granted |
| Year Protection Granted | 2014 |
| Licensed | No |
| Impact | . |
| Title | METHOD FOR DISPERSING AND SEPARATING NANOTUBES |
| Description | A method for dispersing nanotubes, comprising contacting the nanotubes with an electronic liquid comprising a metal and an amine solvent, a solution of dispersed nanotuhes, comprising individual nanotuhes at a concentration of greater than about 0.01 mgml-1 and a solvent and a nanotube crystal comprising a close packed array of nanotubes, wherein the crystal has a thickness of 100 nm or more are described. |
| IP Reference | US2011287258 |
| Protection | Patent granted |
| Year Protection Granted | 2011 |
| Licensed | Yes |
| Impact | . |
| Title | METHOD FOR SEPARATING NANOMATERIALS |
| Description | A method for dispersing nanomaterial comprising an electrochemical process, a solution of dispersed nanomaterial, comprising individual charged nanomaterial at a concentration of about O.1 mgm-1 or more and a solvent and an electrochemical cell are described. |
| IP Reference | WO2010001125 |
| Protection | Patent granted |
| Year Protection Granted | 2010 |
| Licensed | Yes |
| Impact | . |
| Title | PURIFICATION METHOD |
| Description | A method for removing impurities from a sample of carbon nanotubes wherein the sample is contacted with an electronic liquid comprising a metal and an amine solvent is described. |
| IP Reference | WO2012131294 |
| Protection | Patent granted |
| Year Protection Granted | 2012 |
| Licensed | Yes |
| Impact | . |
| Title | SELF-ASSEMBLY OF NANOTUBES |
| Description | The present invention relates to a nanostructure comprising a first hollow nanotube having at least one open end and a first anchor structure comprising a first anchor portion configured to anchor within the open end of the first nanotube, the first anchor structure further comprising a tether portion arranged to allow at least a part of said tether portion to extend outside of the end of the nanotube. |
| IP Reference | WO2015063341 |
| Protection | Patent application published |
| Year Protection Granted | 2015 |
| Licensed | No |
| Impact | . |