Imperial College London

Prof Milo Shaffer

Faculty of Natural SciencesDepartment of Chemistry

Professor of Materials Chemistry



+44 (0)20 7594 5825m.shaffer Website




Mr John Murrell +44 (0)20 7594 2845




M221Royal College of ScienceSouth Kensington Campus





Publication Type

264 results found

Leung AHM, Pike SD, Clancy AJ, Yau HC, Lee WJ, Orchard KL, Shaffer MSP, Williams CKet al., 2018, Layered zinc hydroxide monolayers by hydrolysis of organozincs, CHEMICAL SCIENCE, Vol: 9, Pages: 2135-2146, ISSN: 2041-6520

2D inorganic materials and their exfoliated counterparts are both of fundamental interest and relevant for applications including catalysis, electronics and sensing. Here, a new bottom-up synthesis route is used to prepare functionalised nanoplatelets, in apolar organic solvents, via the hydrolysis of organometallic reagents; the products can be prepared in high yield, at room temperature. In particular, a series of layered zinc hydroxides, coordinated by aliphatic carboxylate ligands, were produced by the hydrolysis of diethyl zinc and zinc carboxylate mixtures, optimally at a molar ratio of [COOR]/[Zn] = 0.6. Layered zinc hydroxides coordinated by oleate ligands form high concentration solutions of isolated monolayers (3 nm thick x ∼ 26 nm) in apolar organic solvents (up to 23 mg mL−1 in toluene), as confirmed by both atomic force and transmission electron microscopies of deposited species. The high solubility of the product allows the synthetic pathway to be monitored directly in situ through 1H NMR spectroscopy. The high solubility also provides a route to solution deposition of active functional materials, as illustrated by the formation of nanoporous films of optically transparent porous zinc oxide (1 μm thickness) after annealing at 500 °C. This new organometallic route to 2D materials obviates common complications of top-down exfoliation syntheses, including sonochemical-degradation and low yields of aggregated polydispersed layers, and may potentially be extended to a wide range of systems.

Journal article

Au H, Rubio N, Shaffer MSP, 2018, Brominated graphene as a versatile precursor for multifunctional grafting, Chemical Science, Vol: 9, Pages: 209-217, ISSN: 2041-6520

A non-destructive and versatile chemical reduction method was used to dissolve and subsequently brominate few-layer graphene sheets (FLGs); the direct covalent attachment of bromine to the graphene framework was demonstrated by X-ray photoelectron spectroscopy (XPS). The brominated few-layer graphenes (FLG-Br) provide a convenient, stable, liquid-phase precursor, suitable for the synthesis of a variety of directly functionalised graphenes. As an example, the FLG-Br species was used to initiate atom transfer radical polymerisation (ATRP), to obtain poly(methyl methacrylate) (PMMA)-grafted graphene (FLG-PMMA), which was six times more dispersible in acetone than controls. In addition, the FLG-Br is active for nucleophilic substitution reactions, as illustrated by the preparation of methoxypolyethylene glycol (mPEG)- and OH-substituted derivatives. The products were characterised by thermogravimetric analysis coupled with mass spectrometry (TGA-MS), XPS and Raman spectroscopy. Grafting ratios (GR) for these polymer-grafted materials varied between 6 and 25%; even at these GRs, all graphene derivatives showed increased solubility in organic solvents.

Journal article

Woodward RT, Markoulidis F, De Luca F, Anthony D, Malko D, McDonald T, Shaffer M, Bismarck Aet al., 2018, Carbon foams from emulsion-templated reduced graphene oxide polymer composites: electrodes for supercapacitor devices, Journal of Materials Chemistry A, Vol: 6, Pages: 1840-1849, ISSN: 2050-7496

Amphiphilic reduced graphene oxide (rGO) is an efficient emulsifier for water-in-divinylbenzene (DVB) high internal phase emulsions. The polymerisation of the continuous DVB phase of the emulsion template and removal of water results in macroporous poly(divinylbenzene) (polyDVB). Subsequent pyrolysis of the poly(DVB) macroporous polymers yields ‘all-carbon’ foams containing micropores alongside emulsion templated-macropores, resulting in hierarchical porosity. The synthesis of carbon foams, or ‘carboHIPEs’, from poly(DVB) produced by polymerisation of rGO stabilised HIPEs provides both exceptionally high surface areas (up to 1820 m2/g) and excellent electrical conductivities (up to 285 S/m), competing with the highest figures reported for carboHIPEs. The use of a 2D carbon emulsifier results in the elimination of post-carbonisation treatments to remove standard inorganic particulate emulsifiers, such as silica particles. It is demonstrated that rGO containing carboHIPEs are good candidates for supercapacitor electrodes where carboHIPEs derived from more conventional polymerised silica-stabilised HIPEs perform poorly. Supercapacitor devices featured a room-temperature ionic liquid electrolyte and electrodes derived from either rGO- or silica-containing poly(DVB)HIPEs and demonstrated a maximum specific capacitance of 26 F g-1, an energy density of 5.2 Wh kg-1 and a power density of 280 W kg-1.

Journal article

Garcia-Trenco A, Regoutz A, White ER, Payne DJ, Shaffer MSP, Williams CKet al., 2018, PdIn intermetallic nanoparticles for the hydrogenation of CO2 to methanol, Applied Catalysis B: Environmental, Vol: 220, Pages: 9-18, ISSN: 0926-3373

Direct hydrogenation of CO2 to methanol could offer significant environmental benefits, if efficient catalysts can be developed. Here, bimetallic Pd-In nanoparticles show good performance as catalysts for this reaction. Unsupported nanoparticles are synthesised by the thermal decomposition of Pd(acetate)2 and In(acetate)3 precursors in a high boiling point solvent (squalane), followed by reduction using dilute H2 gas (210 °C). Adjusting the ratio of the two metallic precursors allow access to 5–10 nm nanoparticles with different phase compositions, including metallic Pd(0), In2O3 and intermetallic PdIn. Liquid phase methanol synthesis experiments (50 bar, 210 °C, H2:CO2 = 3:1) identify the intermetallic PdIn nanoparticles as the most efficient. The catalysts exhibit around 70% higher methanol rates (normalised to the overall molar metal content) compared to the conventional heterogeneous Cu/ZnO/Al2O3 catalyst (900 and 540 μmol mmolPdInorCuZnAl−1 h−1, respectively). In addition, the optimum Pd/In catalyst shows an improved methanol selectivity over the whole temperature range studied (190–270 °C), reaching >80% selectivity at 270 °C, compared to only 45% for the reference Cu/ZnO/Al2O3 catalyst. Experiments showed an improvement in stability; the methanol production rate declined by 20% after 120 h run for the optimum PdIn-based compared with 30% for the Cu/ZnO/Al2O3 catalyst (after 25 h). The optimum catalyst consists of ∼8 nm nanoparticles comprising a surface In-enriched PdIn intermetallic phase as characterised by XRD, HR-TEM, STEM-EDX and XPS. Post-catalysis analysis of the optimum catalyst shows that the same PdIn bimetallic phase is retained with only a slight increase in the nanoparticle size.

Journal article

Finley JM, Yu H, Longana ML, Pimenta S, Shaffer MSP, Potter KDet al., 2017, Exploring the pseudo-ductility of aligned hybrid discontinuous composites using controlled fibre-type arrangements, Composites Part A: Applied Science and Manufacturing, Vol: 107, Pages: 592-606, ISSN: 1359-835X

Pseudo-ductility presents a potential means for preventing catastrophic failure in composite materials; large deformations will prevent brittle fracture and provide warning before final failure. This work explores how the pseudo-ductility and strength of aligned hybrid discontinuous composites can be controlled by manipulating the arrangement of different fibre types. Aligned carbon/glass hybrid specimens with different fibre arrangements are manufactured and tested using a modification to the High Performance Discontinuous Fibre (HiPerDiF) method. Experimental results are complemented by an improved virtual testing framework, which accurately captures the fracture behaviour of a range of hybrid discontinuous composite microstructures. With a randomly intermingled fibre arrangement as a baseline, a 27% increase in strength and a 44% increase in pseudo-ductility can be achieved when low elongation fibres are completely isolated from one-another. Results demonstrate that the HiPerDiF method is the current state-of-the-art for maximising the degree of intermingling and hence the pseudo-ductility of hybrid composites.

Journal article

Rocha VG, Garcia-Tunon E, Botas C, Markoulidis F, Feilden E, D'Elia E, Ni N, Shaffer M, Saiz E, Rocha VG, García-Tuñón E, Botas C, Markoulidis F, Feilden E, D'Elia E, Ni N, Shaffer M, Saiz Eet al., 2017, Multimaterial 3D Printing of Graphene-Based Electrodes for Electrochemical Energy Storage Using Thermoresponsive Inks, ACS APPLIED MATERIALS & INTERFACES, Vol: 9, Pages: 37136-37145, ISSN: 1944-8244

The current lifestyles, increasing population, and limited resources result in energy research being at the forefront of worldwide grand challenges, increasing the demand for sustainable and more efficient energy devices. In this context, additive manufacturing brings the possibility of making electrodes and electrical energy storage devices in any desired three-dimensional (3D) shape and dimensions, while preserving the multifunctional properties of the active materials in terms of surface area and conductivity. This paves the way to optimized and more efficient designs for energy devices. Here, we describe how three-dimensional (3D) printing will allow the fabrication of bespoke devices, with complex geometries, tailored to fit specific requirements and applications, by designing water-based thermoresponsive inks to 3D-print different materials in one step, for example, printing the active material precursor (reduced chemically modified graphene (rCMG)) and the current collector (copper) for supercapacitors or anodes for lithium-ion batteries. The formulation of thermoresponsive inks using Pluronic F127 provides an aqueous-based, robust, flexible, and easily upscalable approach. The devices are designed to provide low resistance interface, enhanced electrical properties, mechanical performance, packing of rCMG, and low active material density while facilitating the postprocessing of the multicomponent 3D-printed structures. The electrode materials are selected to match postprocessing conditions. The reduction of the active material (rCMG) and sintering of the current collector (Cu) take place simultaneously. The electrochemical performance of the rCMG-based self-standing binder-free electrode and the two materials coupled rCMG/Cu printed electrode prove the potential of multimaterial printing in energy applications.

Journal article

Clancy AJ, Serginson JM, Greenfield JL, Shaffer MSPet al., 2017, Systematic Comparison of Single-Walled Carbon Nanotube/ Poly(vinyl Acetate) Graft-to Reactions, Polymer, Vol: 133, Pages: 263-271, ISSN: 0032-3861

The covalent grafting of polymers to single-walled carbon nanotubes (SWCNTs) is widely used to improve solvent compatibility, as well as composite and functional performance. Here, three different graft-to strategies are directly compared, using azide, diazonium, and bromide terminated polymers, over four different molecular weights (oligomeric to 10 kDa) using specifically synthesized low polydispersity, end-group controlled poly(vinyl acetate) (PVAc) prepared by polymerisation using a bespoke protected-amine RAFT agent. Coupling of the bromo-polymer to reduced SWCNTs led to higher degrees of functionalisation (grafting ratios up to 68.9%) than the azide and diazonium grafting reactions, attributed to better initial dispersion of the pre-grafted SWCNTs. The use of higher molecular weight polymers led to a decrease in the total weight of polymer grafted, as the increase in per-polymer weight is more than offset by steric occlusion on the SWCNT surface. For these graft-to reactions, the dispersibility of grafted SWCNTs was found to depend most strongly on the polymer molecular weight, not total weight of grafted polymer or grafting chemistry, with an intermediate Mn∼5757 PVAc giving the best dispersibilities, at up to 118 mg L−1.

Journal article

Miller TS, Suter TM, Telford AM, Picco L, Payton OD, Russell-Pavier F, Cullen PL, Sella A, Shaffer MSP, Nelson J, Tileli V, McMillan PF, Howard CAet al., 2017, Single crystal, luminescent carbon nitride nanosheets formed by spontaneous dissolution, Nano Letters, Vol: 17, Pages: 5891-5896, ISSN: 1530-6984

A primary method for the production of 2D nanosheets is liquid-phase delamination from their 3D layered bulk analogues. Most strategies currently achieve this objective by significant mechanical energy input or chemical modification but these processes are detrimental to the structure and properties of the resulting 2D nanomaterials. Bulk poly(triazine imide) (PTI)-based carbon nitrides are layered materials with a high degree of crystalline order. Here, we demonstrate that these semiconductors are spontaneously soluble in select polar aprotic solvents, that is, without any chemical or physical intervention. In contrast to more aggressive exfoliation strategies, this thermodynamically driven dissolution process perfectly maintains the crystallographic form of the starting material, yielding solutions of defect-free, hexagonal 2D nanosheets with a well-defined size distribution. This pristine nanosheet structure results in narrow, excitation-wavelength-independent photoluminescence emission spectra. Furthermore, by controlling the aggregation state of the nanosheets, we demonstrate that the emission wavelengths can be tuned from narrow UV to broad-band white. This has potential applicability to a range of optoelectronic devices.

Journal article

Rubio Carrero N, Au H, Leese HS, Hu S, Clancy AJ, Shaffer MSPet al., 2017, Grafting from versus grafting to approaches for the functionalisation of graphene nanoplatelets with poly(methyl methacrylate), Macromolecules, Vol: 50, Pages: 7070-7079, ISSN: 0024-9297

Graphene nanoplatelets (GNP) were exfoliated using a nondestructive chemical reduction method and subsequently decorated with polymers using two different approaches: grafting from and grafting to. Poly(methyl methacrylate) (PMMA) with varying molecular weights was covalently attached to the GNP layers using both methods. The grafting ratios were higher (44.6% to 126.5%) for the grafting from approach compared to the grafting to approach (12.6% to 20.3%). The products were characterized using thermogravimetric analysis–mass spectrometry (TGA-MS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The grafting from products showed an increase in the grafting ratio and dispersibility in acetone with increasing monomer supply; on the other hand, due to steric effects, the grafting to products showed lower absolute grafting ratios and a decreasing trend with increasing polymer molecular weight. The excellent dispersibility of the grafting from functionalized graphene, 900 μg/mL in acetone, indicates an increased compatibility with the solvent and the potential to increase graphene reinforcement performance in nanocomposite applications.

Journal article

Buckley DJ, Hodge SA, De Marco M, Hu S, Anthony DB, Linden Cullen P, Skipper NT, Shaffer MSP, Howard CAet al., 2017, Trajectory of the Selective Dissolution of Charged Single-Walled Carbon Nanotubes, Journal of Physical Chemistry C, Vol: 121, Pages: 21703-21712, ISSN: 1932-7447

Single-Walled Carbon Nanotubes (SWCNTs) are materials with an array of remarkable physical properties determined by their geometries, however, SWCNTs are typically produced as a mixture of different lengths and electronic types. Consequently, many methods have been developed to sort the as-produced SWCNT samples by their physical cha-racteristics, often requiring aggressive and unscalable techniques to overcome the strong bundling forces between the nanotubes. Previously, it has been shown that negatively charging SWCNTs can lead to their thermodynamically-driven dissolution in polar solvents, and moreover that this process can selectively dissolve different SWNCT species, albeit with contrasting claims of selectivity. Here we carefully investigate dissolution as a function of charge added to the SWCNT starting material, using a range of complementary techniques. We uncover a far richer dependence on charge of SWCNT dissolution than previously reported. At low charge added, amorphous carbons preferentially dissolve, followed sequentially by metallic, larger diameter semiconducting SWCNTs, and finally smaller diameter semiconducting SWCNTs. At an optimal value, the dissolution yield is maximized across all species, however at higher charge than this we find the larger diameter and metallic SWCNTs are so charged they are no longer soluble, leaving smaller diameter SWCNTs in solution. Our results therefore clearly demonstrate two interconnected mechanisms for dissolution: on one hand charging of the SWNCTs based on their respective electron affinities on the other the solution thermodynamics. This work reconciles contrasting reports in the literature, provides a blueprint for scalable SWCNT separation and more generally demonstrates the..

Journal article

Pike SD, Garcia-Trenco A, White ER, Leung AHM, Weiner J, Shaffer MSP, Williams CKet al., 2017, Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects, Catalysis Science and Technology, Vol: 7, Pages: 3842-3850, ISSN: 2044-4753

The production of methanol from CO2 hydrogenation is a promising potential route to a renewable liquid fuel and renewable energy vector. Herein, three distinct routes to make colloidal catalysts based on mixtures of Cu(0) and ZnO nanoparticles (NPs) and using low-temperature organometallic procedures are reported. The colloids are surface coordinated by a phosphinate ligand: dioctylphosphinate ([DOPA]−), which delivers a high solubility in organic solvents. Further, the synthetic routes allow fine control of the ZnO:Cu and ligand loadings. The catalysts are prepared by mixing small NPs (2 nm) of either Cu(0) or air-stable Cu2O NPs with ZnO NPs (3 nm), or by the synthesis of Cu(0) in presence of ZnO NPs (ZnO: 2 nm, Cu: 6 nm). The resulting colloidal catalysts are applied in the liquid phase hydrogenation of CO2 to methanol (210 °C, 50 bar, 3 : 1 molar ratio of CO2 : H2). The catalysts typically exhibit 3 times higher rates when compared to a heterogeneous Cu–ZnO–Al2O3 commercial catalyst (21 vs. 7 mmolMeOH gCuZnO−1 h−1). The characterisation of the post-catalysis colloids show clear Cu/ZnO interfaces (HR-TEM), which are formed under reducing conditions, as well as differences in the Cu(0) NP size (from 3 to 7 nm) and nanoscale restructuring of the catalysts. The combination of characterisation and catalytic results indicate that the activity is mostly dictated by the Cu(0) particle size and ligand loading. Smaller Cu(0) NPs exhibited lower turnover frequency (TOF) values, whereas higher ligand loadings ([DOPA]−:(Cu + Zn) of 0.2–1.1) lead to smaller Cu(0) NPs and reduce the formation of Cu/ZnO interfaces. UV-vis spectroscopy reveals that the Cu(0) NPs are more stable to oxidation under air after catalysis than beforehand, potentially due to migration of ZnO onto the Cu surface whilst under catalytic conditions.

Journal article

De Marco M, Menzel R, Bawaked SM, Mokhtar M, Obaid AY, Basahel SN, Shaffer Met al., 2017, Hybrid Effects in Graphene Oxide/Carbon Nanotube-Supported Layered Double Hydroxides: Enhancing the CO2 Sorption Properties, Carbon, Vol: 123, Pages: 616-627, ISSN: 0008-6223

Graphene oxide (GO) and multi-walled carbon nanotubes (MWCNT) have been previously used independently as active supports for layered double hydroxides (LDH), and found to enhance the intrinsic CO2 sorption capacity. However, the long-term stability of the materials subjected to temperature-swing adsorption (TSA) cycles still requires improvement. In this contribution, GO and MWCNT are hybridized to produce mixed substrates with improved surface area, and compatibility for the subsequent deposition of LDH platelets, compared to either phase alone. The incorporation of a robust and thoroughly hybridized carbon network considerably enhances the thermal stability of activated, promoted LDH over twenty cycles of gas adsorption-desorption (96% of retention of the initial sorption capacity at the 20th cycle), dramatically reducing the sintering previously observed when either GO or MWCNT were added separately. Detailed characterization of the morphology of the supported LDH, at several stages of the multicycle adsorption process, shows that the initial morphology of the adsorbents is more strongly retained when supported on the robust hybrid GO/MWCNT network; the CO2 adsorption performance correlates closely with the specific surface area of the adsorbents, with both maximized at small loadings of a 1:1 ratio GO:MWCNT substrate.

Journal article

Clancy AJ, anthony D, Fisher S, Leese H, Roberts C, Shaffer Met al., 2017, Reductive dissolution of supergrowth carbon nanotubes for tougher nanocomposites by reactive coagulation spinning, Nanoscale, Vol: 9, Pages: 8764-8773, ISSN: 2040-3372

Long single-walled carbon nanotubes, with lengths >10 μm, can be spontaneously dissolved by stirring in a sodium naphthalide N,N-dimethylacetamide solution, yielding solutions of individualised nanotubide ions at concentrations up to 0.74 mg mL−1. This process was directly compared to ultrasonication and found to be less damaging while maintaining greater intrinsic length, with increased individualisation, yield, and concentration. Nanotubide solutions were spun into fibres using a new reactive coagulation process, which covalently grafts a poly(vinyl chloride) matrix to the nanotubes directly at the point of fibre formation. The grafting process insulated the nanotubes electrically, significantly enhancing the dielectric constant to 340% of the bulk polymer. For comparison, samples were prepared using both Supergrowth nanotubes and conventional shorter commercial single-walled carbon nanotubes. The resulting nanocomposites showed similar, high loadings (ca. 20 wt%), but the fibres formed with Supergrowth nanotubes showed significantly greater failure strain (up to ∼25%), and hence more than double the toughness (30.8 MJ m−3), compared to composites containing typical ∼1 μm SWCNTs.

Journal article

Anthony DB, Qian H, Clancy AJ, Bismarck A, Greenhalgh ES, Shaffer MSPet al., 2017, Applying a potential difference to minimise damage to carbon fibres during carbon nanotube grafting by chemical vapour deposition, Nanotechnology, Vol: 28, ISSN: 1361-6528

The application of an in-situ potential difference between carbon fibres and a graphite foil counter electrode (300 V, generating an electric field ca. 0.3 V μm-1 to 0.7 V μm-1) during the chemical vapour deposition synthesis of carbon nanotube (CNT) grafted carbon fibres, significantly improves the uniformity of growth without reducing the tensile properties of the underlying carbon fibres. Grafted carbon nanotubes with diameters around 55 nm and lengths around 10 μm were well attached to the carbon fibre surface, and were grown without the requirement for protective barrier coatings. The grafted CNTs increased the surface area to 185 m2 g-1 compared to the as-received sized carbon fibre 0.24 m2 g-1. The approach is not restricted to batch systems and has the potential to improve carbon nanotube grafted carbon fibre production for continuous processing.

Journal article

Hu S, Laker ZPL, Leese HS, Rubio N, De Marco M, Au H, Skilbeck MS, Wilson NR, Shaffer MSPet al., 2017, Thermochemical functionalisation of graphenes with minimal framework damage, Chemical Science, Vol: 8, Pages: 6149-6154, ISSN: 2041-6520

Graphene and graphene nanoplatelets can be functionalised via a gas-phase thermochemical method; the approach is versatile, readily scalable, and avoids the introduction of additional defects by exploiting existing sites. Direct TEM imaging confirmed covalent modification of single layer graphene, without damaging the connectivity of the lattice, as supported by Raman spectrometry and AFM nano-indentation measurements of mechanical stiffness. The grafting methodology can also be applied to commercially-available bulk graphene nanoplatelets, as illustrated by the preparation of anionic, cationic, and non-ionic derivatives. Successful bulk functionalisation is evidenced by TGA, Raman, and XPS, as well as in dramatic changes in aqueous dispersability. Thermochemical functionalisation thus provides a facile approach to modify both graphene monolayers, and a wide range of graphene-related nanocarbons, using variants of simple CVD equipment.

Journal article

Hart M, White ER, Chen J, McGilvery CM, Pickard CJ, Michaelides A, Sella A, Shaffer MSP, Salzmann CGet al., 2017, Encapsulation and polymerization of white phosphorus inside single-wall carbon nanotubes, Angewandte Chemie International Edition, Vol: 56, Pages: 8144-8148, ISSN: 1521-3757

Elemental phosphorus displays an impressive number of allotropes with highly diverse chemical and physical properties. White phosphorus has now been filled into single-wall carbon nanotubes (SWCNTs) from the liquid and thereby stabilized against the highly exothermic reaction with atmospheric oxygen. The encapsulated tetraphosphorus molecules were visualized with transmission electron microscopy, but found to convert readily into chain structures inside the SWCNT “nanoreactors”. The energies of the possible chain structures were determined computationally, highlighting a delicate balance between the extent of polymerization and the SWCNT diameter. Experimentally, a single-stranded zig-zag chain of phosphorus atoms was observed, which is the lowest energy structure at small confinement diameters. These one-dimensional chains provide a glimpse into the very first steps of the transformation from white to red phosphorus.

Journal article

Thong AZ, Shaffer MS, Horsfield AP, 2017, HOMO-LUMO coupling: the fourth rule for highly effective molecular rectifiers, Nanoscale, Vol: 9, Pages: 8119-8125, ISSN: 2040-3372

Three rules for creating highly effective unimolecular rectifiers that utilize asymmetric anchoring groups have been proposed by Van Dyck and Ratner [Ratner et al., Nano Lett., 2015, 15, 1577–1584]. This study investigates their proposed rectification mechanism in a functionalised azafullerene system (4TPA–C60) and identifies a fourth rule. NEGF-DFT shows that 4TPA–C60 fulfills the three design rules and finds that a saturated bridge is not required to fulfil the third rule, contrary to previous belief. Instead a twisted-π bridge decouples the donor and acceptor states whilst still providing a high conductance pathway. The molecular junction has a calculated rectification ratio of 145 at a bias of ±1 V and the U-type rectification mechanism is driven by the pinning of the HOMO to the LUMO when the device is forward biased, but not when reverse biased. The switching behaviour is a result of a charge dipole forming at different interfaces for different bias directions. An additional design rule is thus proposed: charge transport should allow bias dependent coupling of filled to unfilled states. The findings in this work not only help in understanding charge transport in molecular rectifiers, but also have wider implications for the design of molecular resonant tunneling devices.

Journal article

Robinson RK, Birrell MA, Adcock JJ, Wortley MA, Dubuis ED, Chen S, McGilvery CM, Hu S, Shaffer MSP, Bonvini SJ, Maher SA, Mudway IS, Porter AE, Carlsten C, Tetley TD, Belvisi MGet al., 2017, Mechanistic link between diesel exhaust particles and respiratory reflexes, Journal of Allergy and Clinical Immunology, Vol: 141, Pages: 1074-1084.e9, ISSN: 1097-6825

BackgroundDiesel exhaust particles (DEPs) are a major component of particulate matter in Europe's largest cities, and epidemiologic evidence links exposure with respiratory symptoms and asthma exacerbations. Respiratory reflexes are responsible for symptoms and are regulated by vagal afferent nerves, which innervate the airway. It is not known how DEP exposure activates airway afferents to elicit symptoms, such as cough and bronchospasm.ObjectiveWe sought to identify the mechanisms involved in activation of airway sensory afferents by DEPs.MethodsIn this study we use in vitro and in vivo electrophysiologic techniques, including a unique model that assesses depolarization (a marker of sensory nerve activation) of human vagus.ResultsWe demonstrate a direct interaction between DEP and airway C-fiber afferents. In anesthetized guinea pigs intratracheal administration of DEPs activated airway C-fibers. The organic extract (DEP-OE) and not the cleaned particles evoked depolarization of guinea pig and human vagus, and this was inhibited by a transient receptor potential ankyrin-1 antagonist and the antioxidant N-acetyl cysteine. Polycyclic aromatic hydrocarbons, major constituents of DEPs, were implicated in this process through activation of the aryl hydrocarbon receptor and subsequent mitochondrial reactive oxygen species production, which is known to activate transient receptor potential ankyrin-1 on nociceptive C-fibers.ConclusionsThis study provides the first mechanistic insights into how exposure to urban air pollution leads to activation of guinea pig and human sensory nerves, which are responsible for respiratory symptoms. Mechanistic information will enable the development of appropriate therapeutic interventions and mitigation strategies for those susceptible subjects who are most at risk.

Journal article

Pike SD, White ER, Regoutz A, Sammy N, Payne DJ, Williams CK, Shaffer MSPet al., 2017, Reversible Redox Cycling of Well-Defined, Ultrasmall Cu/Cu2O Nanoparticles, ACS Nano, Vol: 11, Pages: 2714-2723, ISSN: 1936-0851

Exceptionally small and well-defined copper (Cu) and cuprite (Cu2O) nanoparticles (NPs) are synthesized by the reaction of mesitylcopper(I) with either H2 or air, respectively. In the presence of substoichiometric quantities of ligands, namely, stearic or di(octyl)phosphinic acid (0.1–0.2 equiv vs Cu), ultrasmall nanoparticles are prepared with diameters as low as ∼2 nm, soluble in a range of solvents. The solutions of Cu NPs undergo quantitative oxidation, on exposure to air, to form Cu2O NPs. The Cu2O NPs can be reduced back to Cu(0) NPs using accessible temperatures and low pressures of hydrogen (135 °C, 3 bar H2). This striking reversible redox cycling of the discrete, solubilized Cu/Cu(I) colloids was successfully repeated over 10 cycles, representing 19 separate reactions. The ligands influence the evolution of both composition and size of the nanoparticles, during synthesis and redox cycling, as explored in detail using vacuum-transfer aberration-corrected transmission electron microscopy, X-ray photoelectron spectroscopy, and visible spectroscopy.

Journal article

Gonzalez Carter DA, Leo BF, Ruenraroengsak P, Chen S, Goode A, Theodorou I, Chung KF, Carzaniga R, Shaffer M, Dexter D, Ryan M, Porter Aet al., 2017, Silver nanoparticles reduce brain inflammation and related neurotoxicity through induction of H2S-synthesizing enzymes, Scientific Reports, Vol: 7, ISSN: 2045-2322

Silver nanoparticles (AgNP) are known to penetrate into the brain and cause neuronal death. However, there is a paucity in studies examining the effect of AgNP on the resident immune cells of the brain, microglia. Given microglia are implicated in neurodegenerative disorders such as Parkinson’s disease (PD), it is important to examine how AgNPs affect microglial inflammation to fully assess AgNP neurotoxicity. In addition, understanding AgNP processing by microglia will allow better prediction of their long term bioreactivity. In the present study, the in vitro uptake and intracellular transformation of citrate-capped AgNPs by microglia, as well as their effects on microglial inflammation and related neurotoxicity were examined. Analytical microscopy demonstrated internalization and dissolution of AgNPs within microglia and formation of non-reactive silver sulphide (Ag2S) on the surface of AgNPs. Furthermore, AgNP-treatment up-regulated microglial expression of the hydrogen sulphide (H2S)-synthesizing enzyme cystathionine-γ-lyase (CSE). In addition, AgNPs showed significant anti-inflammatory effects, reducing lipopolysaccharide (LPS)-stimulated ROS, nitric oxide and TNFα production, which translated into reduced microglial toxicity towards dopaminergic neurons. Hence, the present results indicate that intracellular Ag2S formation, resulting from CSE-mediated H2S production in microglia, sequesters Ag+ ions released from AgNPs, significantly limiting their toxicity, concomitantly reducing microglial inflammation and related neurotoxicity.

Journal article

Hodge SA, Buckley D, Yau HC, Skipper N, Howard C, Shaffer MSPet al., 2017, Chemical routes to discharging graphenides, Nanoscale, Vol: 9, Pages: 3150-3158, ISSN: 2040-3372

Chemical and electrochemical reduction methods allow the dispersion, processing, and/or functionalization of discrete sp2-hybridised nanocarbons, including fullerenes, nanotubes and graphenes. Electron transfer to the nanocarbon raises the Fermi energy creating nanocarbon anions, thereby activating an array of possible covalent reactions. The Fermi level may then be partially or fully lowered by intended functionalization reactions, but in general, techniques are required to removeexcess charge without inadvertent covalent reactions that potentially degrade the nanocarbon properties of interest. Here, simple and effective chemical discharging routes are demonstrated for graphenide polyelectrolytes and are expected to apply to other systems, particularly nanotubides. Thedischarging process is inherently linked to the reduction potentials of such chemical discharging agents and the unusual fundamental chemistry of charged nanocarbons.

Journal article

Garcia-Trenco A, White ER, Regoutz A, Payne DJ, Shaffer MSP, Williams CKet al., 2017, Pd2Ga-Based Colloids as Highly Active Catalysts for the Hydrogenation of CO2 to Methanol, ACS Catalysis, Vol: 7, Pages: 1186-1196, ISSN: 2155-5435

Colloidal Pd2Ga-based catalysts are shown to catalyze efficiently the hydrogenation of CO2 to methanol. The catalysts are produced by the simple thermal decomposition of Pd(II) acetate in the presence of Ga(III) stearate, which leads to Pd0 nanoparticles (ca. 3 nm), and the subsequent Pd-mediated reduction of Ga(III) species at temperatures ranging from 210 to 290 °C. The resulting colloidal Pd2Ga-based catalysts are applied in the liquid-phase hydrogenation of carbon dioxide to methanol at high pressure (50 bar). The intrinsic activity is around 2-fold higher than that obtained for the commercial Cu-ZnO-Al2O3 (60.3 and 37.2 × 10–9 molMeOH m–2 s–1), respectively, and 4-fold higher on a Cu or Pd molar basis (3330 and 910 μmol mmolPd or Cu–1 h–1). Detailed characterization data (HR-TEM, STEM/EDX, XPS, and XRD) indicate that the catalyst contains Pd2Ga nanoparticles, of average diameters 5–6 nm, associated with a network of amorphous Ga2O3 species. The proportion of this Ga2O3 phase can be easily tuned by adjusting the molar ratio of the Pd:Ga precursors. A good correlation was found between the intrinsic activity and the content of Ga2O3 surrounding the Pd2Ga nanoparticles (XPS), suggesting that methanol is formed by a bifunctional mechanism involving both phases. The increase in the reaction temperature (190–240 °C) leads to a gradual decrease in methanol selectivity from 60 to 40%, while an optimum methanol production rate was found at 210 °C. Interestingly, unlike the conventional Cu-ZnO-Al2O3, which experienced approximately 50% activity loss over 25 h time on stream, the Pd2Ga-based catalysts maintain activity over this time frame. Indeed, characterization of the Pd/Ga mixture postcatalysis revealed no ripening of the nanoparticles or changes in the phases initially present.

Journal article

Lee W, CLANCY A, KONTTURI E, BISMARCK A, SHAFFER Met al., 2016, Strong and Stiff: High-Performance Cellulose Nanocrystal/Poly(vinyl alcohol) Composite Fibers, ACS Applied Materials & Interfaces, Vol: 8, Pages: 31500-31504, ISSN: 1944-8244

Mechanical properties of rod7like cellulose nanocrystals (CNCs) offer great potential as bioderived reinforcement in (nano)composites. Polyvinyl alcohol (PVOH) is a useful industrial material and very compatible with CNC chemistry. High performance CNC/PVOH composite fibers were produced coaxial coagulation spinning, followed by hot7drawing. DSC and WAXS showed that CNCs increase the alignment and crystallinity of PVOH, as well as providing direct reinforcement, leading to enhanced fiber strength and stiffness. At 40 wt.% CNC loading, the strength and stiffness reached 880 MPa and 29.9 GPa, exceeding the properties of most other nanocellulose based composite fibers previously reported.

Journal article

Mattevi C, 2016, Graphitic carbon nitride as a catalyst support in fuel cells and electrolyzers, Electrochimica Acta, Vol: 222, Pages: 44-57, ISSN: 1873-3859

Electrochemical power sources, such as polymer electrolyte membrane fuel cells (PEMFCs), require the use of precious metal catalysts which are deposited as nanoparticles onto supports in order to minimize their mass loading and therefore cost. State-of-the-art/commercial supports are based on forms of carbon black. However, carbon supports present disadvantages including corrosion in the operating fuel cell environment and loss of catalyst activity. Here we review recent work examining the potential of different varieties of graphitic carbon nitride (gCN) as catalyst supports, highlighting their likely benefits, as well as the challenges associated with their implementation. The performance of gCN and hybrid gCN-carbon materials as PEMFC electrodes is discussed, as well as their potential for use in alkaline systems and water electrolyzers. We illustrate the discussion with examples taken from our own recent studies.

Journal article

Beesley DJ, Price BK, Hunter S, Shaffer MSP, de Mello JCet al., 2016, Direct dispersion of SWNTs in highly conductive solvent-enhanced PEDOT:PSS films, Nanocomposites, Vol: 2, Pages: 135-140, ISSN: 2055-0332

Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) is shown to be an effective dispersant for single-wall carbon nanotubes (SWNTs), enabling uniform aqueous suspensions to be obtained at weight loadings of up to 0.23 mg/ml (>1% by weight relative to PEDOT:PSS) without recourse to additional surfactants. Thin films spin-coated from PEDOT:PSS/SWNT suspensions exhibited sheet resistances of 90 Ω/sq. at 80 % transmittance, slightly higher than equivalent films of pure PEDOT:PSS which exhibited sheet resistances of 70 Ω/sq. at the same transmittance.

Journal article

Pike S, White E, Shaffer M, Williams CKet al., 2016, Simple Phosphinate Ligands Access New Zinc Clusters Identified in the Synthesis of Zinc Oxide Nanoparticles, Nature Communications, Vol: 7, ISSN: 2041-1723

The bottom-up synthesis of ligand-stabilised functional nanoparticles from molecular precursors is widely applied but difficult to study mechanistically. Here, we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of new ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly, and self-assemble in solution based on thermodynamic equilibria, rather than nucleation kinetics. These clusters are also identified, in situ, during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. As well as a versatile and accessible route to new (optionally doped) zinc clusters, the findings provide a new understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.

Journal article

De Marco M, 2016, Hierarchical carbon nanotube and graphene oxide networks for multifunctional applications

Assembling carbon nanomaterials (CNs) into networks and macrostructures is a potentially effective approach for the development of a wide array of technologies, including energy storage and production devices. CNs, such as carbon nanotubes (CNTs) and graphene (G), are characterised by impressive mechanical and electrical properties, however, these features are related to the high quality, individualised single carbon species.1, 2 Producing two/three-dimensional CN architectures presents several hurdles, mainly concerning the need to disassemble the pristine CN aggregates, the damages inflicted on the carbon framework during processing, and the consequent lack of mechanical strength and/or reduced electrical conductivity of the final material. Suitable methods for preparing CN (macro)structures retaining the extraordinary properties of the fundamental CN units, have yet to be fully developed. This Thesis addresses these issues by suggesting two different methodologies for the synthesis of CN networks, which are tailored to specific applications of the final structures. A novel cross-linking strategy of single-walled carbon nanotubes (SWCNTs) is developed, yielding highly connected, high surface area (> 750 m2 g-1) and electrically conductive (> 15 S m-1) cryogels. The cryogels are demonstrated to be effective electrodes within fully working electrochemical devices. In contrast to cross-linking strategies already explored in literature, the SWCNTs are individualised at high concentrations (up to 0.25 M), and cross-linked with p-diiodobenzene without shortening or damaging the carbon framework via a “reductive chemistry” route.3 Careful control of the absolute charge concentration in the system is found to be crucial for maximising the extent of debundling and grafting, with a suggested optimum at 15 mM. Optimised synthesis parameters in turn determine the accessible surface area and the conductive properties of the final freeze-dried cryogels. Multi-

Thesis dissertation

Sweeney S, Hu S, Ruenraroengsak P, Chen S, Gow A, Schwander S, Zhang JJ, Chung KF, Ryan MP, Porter AE, Shaffer MS, Tetley TDet al., 2016, Carboxylation of multiwalled carbon nanotubes reduces their toxicity in primary human alveolar macrophages, Environmental Science: Nano, Vol: 3, Pages: 1340-1350, ISSN: 2051-8153

Surface functionalisation of multiwalled carbon nanotubes (MWCNT) is commonly used to facilitate their various and diverse applications. Inhaled nanomaterials, such as MWCNTs, have a high deposition rate in the alveolar units of the deep lung, where alveolar macrophages (AM) provide the front line of cellular immune defence by removing foreign matter (microbes, particles etc.). The toxicity of MWCNTs (with or without functionalisation) towards primary human AMs is not known. We investigated the physicochemical characteristics and toxicity of two MWCNT materials: acid purified ‘Purified-MWCNT’ and concentrated acid functionalised ‘COOH-MWCNT’. We hypothesised that the bioreactivity with primary human AM would differ between the materials. Full characterisation of the MWCNTs revealed that –COOH functionalisation yielded shorter MWCNTs, accompanied by a greater occurrence of framework defects, in comparison to Purified-MWCNT. In agreement with our hypothesis that the bioreactivity would differ, Purified-MWCNT were significantly more toxic as measured by reduced cell viability and increased inflammatory mediator release. For example, IL-1β and IL-8 release by AMs significantly increased 3.5- and 2.4-fold, respectively (P < 0.05), 24 hours after treatment with Purified-MWCNT. In contrast, IL-1β and IL-8 release by AMs did not significantly change 24 hours after treatment with COOH-MWCNT. We determined that the mechanism of this toxicity is likely due to activation of the inflammasome, as lipopolysaccharide priming of primary human AMs was necessary to see the inflammatory response and this was accompanied by lysosomal disruption and increased generation of reactive oxygen species. This study contributes further to our understanding of the effects of MWCNTs and surface modification on highly relevant human lung AMs; the findings have important implications for the manufacture, application and use of MWCNTs. In particular, this is

Journal article

Mansor N, Jia J, Miller TS, Suter T, Jorge AB, Gibbs C, Shearing P, McMillan PF, Mattevi C, Shaffer M, Brett DJLet al., 2016, Graphitic carbon nitride-graphene hybrid nanostructure as a catalyst support for polymer electrolyte membrane fuel cells, ECS Transactions, Vol: 75, Pages: 885-897, ISSN: 1938-5862

Graphitic carbon nitrides form a class of semiconducting graphene-like polymeric materials with visible light absorption and photocatalytic properties. In addition to high nitrogen content and tunable structure, it was shown that graphitic carbon nitride based on polytrazine imide (PTI) sheets exhibit excellent anti-corrosion ability in ex-situ fuel cell environments. However, in bulk form, their low surface area and poor conductivity limits their applications in fuel cells. In this work, PTI was exfoliated to form an ink made from single to few-layer nanosheets. The ink was then processed to produce 3D networks of carbon nitride nanosheets/reduced graphene oxide (PTI-rGO) hybrid aerogel with large interconnecting pores for fast mass transport of reactants and high surface area. The material was decorated with platinum nanoparticles, and then investigated for its electrochemical properties and applications as a catalyst support for polymer electrolyte membrane (PEM) fuel cells. Initial results show that the cathode catalytic activity of Pt/rGO-PTI hybrid is significantly improved in comparison to Pt/PTI or Pt/rGO. In addition, the in-situ fuel cell performance of Pt/PTI as anode catalyst is comparable to commercial Pt/C especially at low densities, making it attractive as an alternative, durable anode catalyst support material to conventional carbon black.

Journal article

Zhang JJ, Lee KB, He L, Seiffert J, Subramaniam P, Yang L, Chen S, Maguire P, Mainelis G, Schwander S, Tetley T, Porter A, Ryan M, Shaffer M, Hu S, Gong J, Chung KFet al., 2016, Effects of a nanoceria fuel additive on the physicochemical properties of diesel exhaust particles., Environmental Science: Processes & Impacts, Vol: 18, Pages: 1333-1342, ISSN: 2050-7887

Nanoceria (i.e., CeO2 nanoparticles) fuel additives have been used in Europe and elsewhere to improve fuel efficiency. Previously we have shown that the use of a commercial fuel additive Envirox™ in a diesel-powered electricity generator reduced emissions of diesel exhaust particle (DEP) mass and other pollutants. However, such additives are currently not permitted for use in on-road vehicles in North America, largely due to limited data on the potential health impact. In this study, we characterized a variety of physicochemical properties of DEPs emitted from the same engine. Our methods include novel techniques such as Raman spectrometry for analyzing particle surface structure and an assay for DEP oxidative potential. Results show that with increasing Envirox™ concentrations in the fuel (0×, 0.1×, 1×, and 10× of manufacturer recommended 0.5 mL Envirox™ per liter fuel), DEP sizes decreased from 194.6 ± 20.1 to 116.3 ± 14.8 nm; the zeta potential changed from -28.4 mV to -22.65 mV; DEP carbon content decreased from 91.8% to 79.4%; cerium and nitrogen contents increased from 0.3% to 6.5% and 0.2% to 0.6%, respectively; the ratio of organic carbon (OC) to elemental carbon (EC) increased from 22.9% to 38.7%; and the ratio of the disordered carbon structure to the ordered carbon structure (graphitized carbon) in DEPs decreased. Compared to DEPs emitted from 0×, 0.1×, and 1× fuels, DEPs from the 10× fuel had a lower oxidative potential likely due to the increased ceria content because pure ceria nanoparticles exhibited the lowest oxidative potential compared to all the DEPs. Since the physicochemical parameters tested here are among the determinants of particle toxicity, our findings imply that adding ceria nanoparticles into diesel may alter the toxicity of DEPs. The findings from the present study, hence, can help future studies that will examine the impact of nanoceria additives on DEP to

Journal article

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