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Supplementary Table 11: Key clinical data for the CRC cohort showing overall survival (OS)

Supplementary Table 7: Key clinical data for different types of kidney cancer and metastasis

Supplementary Table 2: Clinical-pathological data for colorectal cancer patients used for genomic analysis and validation Supplementary Table 3: Clinical-pathological data for colorectal liver metastasis patients used for genomic analysis and validation Supplementary Table 4: Clinical-pathological data for renal cancer patients used for genomic analysis and validation

Supplementary Table 9: Key clinical data for clear cell RCC cohort 2 showing overall survival (OS)

The structure and molecular signature of tumor-associated vasculature are distinct from those of the host tissue, offering an opportunity to selectively target the tumor blood vessels. To identify tumor-specific endothelial markers, we performed a microarray on tumor-associated and nonmalignant endothelium collected from patients with renal cell carcinoma (RCC), colorectal carcinoma, or colorectal liver metastasis. We identified a panel of genes consistently upregulated by tumor blood vessels, of which melanoma cell adhesion molecule (MCAM) and its extracellular matrix interaction partner laminin alpha 4 (LAMA4) emerged as the most consistently expressed genes. This result was subsequently confirmed by immunohistochemical analysis of MCAM and LAMA4 expression in RCC and colorectal carcinoma blood vessels. Strong MCAM and LAMA4 expression was also shown to predict poor survival in RCC, but not in colorectal carcinoma. Notably, MCAM and LAMA4 were enhanced in locally advanced tumors as well as both the primary tumor and secondary metastases. Expression analysis in 18 different cancers and matched healthy tissues revealed vascular MCAM as highly specific in RCC, where it was induced strongly by VEGF, which is highly abundant in this disease. Lastly, MCAM monoclonal antibodies specifically localized to vessels in a murine model of RCC, offering an opportunity for endothelial-specific targeting of anticancer agents. Overall, our findings highlight MCAM and LAMA4 as prime candidates for RCC prognosis and therapeutic targeting. Cancer Res; 76(8); 2314–26. ©2016 AACR.

Supplementary Table 8: Key clinical data for clear cell RCC cohort 1, showing overall survival (OS)

Supplementary Table 1: Primer sequences for RTqPCR using the Roche Exiqon probe library system. Supplementary Figure 1. Representative images demonstrative of scoring for staining intensity. Images are of MCAM staining in RCC at a weak (i-ii) or strong (iii-iv) level with associated H&E images (v,vi,vii,viii) . Scale bar = 50 μm.

Supplementary Table 5: Matrix metallopeptidase regulation across tissue types (Gene expression comparison shown as Log2 fold change) Supplementary Table 6: Collagen regulation across tissue types (Gene expression comparison shown as Log2 fold change)

The rapid growth, demand, and production of batteries to meet various emerging applications, such as electric vehicles and energy storage systems, will result in waste and disposal problems in the next few years as these batteries reach end-of-life. Battery reuse and recycling are becoming urgent worldwide priorities to protect the environment and address the increasing need for critical metals. As a review article, this paper reveals the current global battery market and global battery waste status from which the main battery chemistry types and their management, including reuse and recycling status, are discussed. This review then presents details of the challenges, opportunities, and arguments on battery second-life and recycling. The recent research and industrial activities in the battery reuse domain are summarized to provide a landscape picture and valuable insight into battery reuse and recycling for industries, scientific research, and waste management.

Redox flow batteries are being utilised as an attractive electrochemical energy storage technology for electricity from renewable generation. At present, the global installed capacity of redox flow battery is 1100 MWh. There are several parameters that significantly govern redox flow battery performance amongst which electrode activation, electrode material, felt compression, electrolyte additive, electrolyte temperature, membrane, and flow field design are notable. This review article presents an overview of the influence of individual components by comparing the performance of a parametrically modified cell with a default cell, which has 0% felt compression, inactivated electrode, zero electrolyte additives, and ambient condition operation. From the reviewed studies, electrode activation (thermal, chemical, laser perforation) and felt compression were identified as the most significant parameters. Electrolyte additive and flow field design were identified to be reasonably significant. Electrolyte temperature and membrane type were identified as the least significant amongst all the parameters. Based on this survey, a parametric matrix has been outlined that will aid researchers to identify appropriate parameters to focus research efforts onto improved redox flow battery performance.

The electrodeposition of lithium metal from room temperature ionic liquid (RTIL) electrolytes consisting of N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (Pyr13[FSI]) with LiFSI, LiTFSI, LiBF4, LiPF6 or LiAsF6 salts onto Pt and Li electrodes was undertaken to identify mechanistic details. Cyclic voltammetry at both Pt and Li electrodes is complicated by the chemical reaction between fresh/electrodeposited Li metal and electrolyte to form a solid-electrolyte interphase (SEI). As such, all electrolyte systems depict quasi-reversible cycling, owing to the concomitant chemical breakdown of the electrolyte and deposition of a passivation product onto the electrode surface. The rate at which the SEI forms can be observed through cyclic voltammetric scan rate studies. Chronoamperometry data supports the cyclic voltammetry studies and indicates that an instantaneous nucleation and growth type mechanism is taking place at all potentials as determined through modelling the current-time transients utilising the Hills-Scharifker theory. We show herein that these RTIL based electrolytes can be cycled effectively in an order of stability of salt inclusion as follows: LiBF4 > LiFSI > LiAsF6 > LiTFSI > LiPF6.

Suppressing dendrite formation at lithium metal anodes during cycling is critical for the implementation of future lithium metal-based battery technology. Here we report that it can be achieved via the facile process of immersing the electrodes in ionic liquid electrolytes for a period of time before battery assembly. This creates a durable and lithium ion-permeable solid–electrolyte interphase that allows safe charge–discharge cycling of commercially applicable Li|electrolyte|LiFePO4 batteries for 1,000 cycles with Coulombic efficiencies >99.5%. The tailored solid–electrolyte interphase is prepared using a variety of electrolytes based on the N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide room temperature ionic liquid containing lithium salts. The formation is both time- and lithium salt-dependant, showing dynamic morphology changes, which when optimized prevent dendrite formation and consumption of electrolyte during cycling. This work illustrates that a simple, effective and industrially applicable lithium metal pretreatment process results in a commercially viable cycle life for a lithium metal battery., Suppressing dendrite formation at lithium anodes during cycling is critical to development of lithium battery technology. Here, the authors show that immersion of lithium electrodes in ionic liquid electrolytes prior to battery assembly produces a durable and lithium ion permeable solid-electrolyte interphase.

Despite the high theoretical capacity of Si anodes, the electrochemical performance of Si anodes is hampered by severe volume changes during lithiation and delithiation, leading to poor cyclability and eventual electrode failure. Nanostructured silicon and its nanocomposite electrodes could overcome this problem holding back the deployment of Si anodes in lithium-ion batteries (LIBs) by providing facile strain relaxation, short lithium diffusion distances, enhanced mass transport, and effective electrical contact. Here, the recent progress in nanostructured Si-based anode materials such as nanoparticles, nanotubes, nanowires, porous Si, and their respective composite materials and fabrication processes in the application of LIBs have been reviewed. The ability of nanostructured Si materials in addressing the above mentioned challenges have been highlighted. Future research directions in the field of nanostructured Si anode materials for LIBs are summarized.

The lithium–sulfur (Li–S) battery in which the ionic liquid (IL) C4mpyr-TFSI is a major component of the electrolyte has attracted much attention by researchers due to the ability of the IL to suppress the polysulfide shuttle effect, combined with advantageous properties of thermal, chemical and electrochemical stability. In a largely parallel stream of research, LiNO3 has come to be known as an additive for improving Li–S battery performance through its influence on protecting the lithium anode and beneficial interaction with the polysulfide shuttle. In this work a deeper understanding is sought of the combined effects of LiNO3 and C4mpyr-TFSI on the factors that impact Li–S cell performance. Specifically, we investigate the formation of the protective surface film on lithium anode and results are compared with those for a typical organic electrolyte for the Li–S battery, DOL:DME. Electrochemical impedance spectroscopy (EIS) confirms that the LiNO3 additive is vital to achieving acceptable levels of performance with the organic electrolyte. Although LiNO3 improves the performance of a battery assembled with IL containing electrolyte, it shows a higher impact in the organic electrolyte based battery. Furthermore X-ray photoelectron spectroscopy (XPS) spectra confirm the participation of C4mpyr-TFSI on the formation of the interphase layer on the anode.

The electrochemical behaviour and electrical performance are investigated for a series of lithium-sulfur (Li-S) cells in which the electrolyte solutions are organic solvent-ionic liquid mixtures that are based on the 1-butyl-1-methylpyrrolidinium (C4mpyr) cation with a range of anions. In each case, performance is compared with cells that are based on a standard mixed-ether organic electrolyte. The capacity of cells assembled with electrolytes containing 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate (C4mpyr-FAP), 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate (C4mpyr-OTf), or 1-butyl-1-methylpyrrolidinium tricyanomethanide (C4mpyr-TCM) decline rapidly due to low conductivity, high polysulfide solubility and side reaction of electrolyte with electrodes, respectively. Our results confirm that polysulfide solubility is strongly controlled by the anion of the ionic liquid and verify that not all ionic liquids decrease polysulfide solubility. In agreement with previous reports, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (C4mpyr-TFSI) shows the best compatibility in Li-S batteries and has a higher coulombic efficiency of greater than 99% over 100 cycles. Furthermore, impedance spectroscopy confirms that electrolyte composition influences the SEI layer formed on the lithium anode and its subsequent impedance.

Demand for portable electronic and electrical devices has led to considerable growth in production of lithium-ion battery cells and the number of manufacturers thereof. However, due to lack of supplied information or independent verification, it is frequently difficult to compare cells based on available data. In this study, we conduct a comparative testing study on five types of 18650-format lithium-ion cells from three different commercial manufacturers, ranging from budget to high-performance cells. Key insights gathered in the comparison were that the tested budget cells frequently offer less than 20% of their rated capacity, that the budget cells degrade at a significantly higher proportional rate than other cells, and that certain high-performance cells exceed the size dimensions of the 18650-format by over 3%. Electrochemical impedance spectroscopy testing showed the budget cells to have internal impedances several times higher than other cells, leading to notably increased heat generation and a significantly reduced cell efficiency. Differential capacity analysis found this high internal resistance to notably impede lithium intercalation processes. The presented methodology is intended as a base framework for conducting subsequent comparative testing studies for Li-ion cells.

The effect of ionic strength on the electrodeposition of silver has been investigated in acetonitrile (MeCN) containing TBAPF6 or in the ionic liquid [EMIm][OTf]. The use of an ionic liquid allows a greater ionic strength to be investigated as the solubility limits of supporting electrolytes in organic solvents can be overcome using neat ionic liquid. The SEM and XRD data show that polycrystalline silver is deposited in a fcc structure and that dendrite formation is retarded at high ionic strength. Electrochemical measurements undertaken in electrolytes of low ionic strength indicate that the deposition and growth of a few nuclei is preferred and leads to dendrite formation. However, at higher ionic strength, the deposition and growth of significantly more nuclei is observed and therefore dendrite growth rates and tip currents are lower leading to the deposition of spherical particulates. Crucially, the data shows that if the ionic strength of the electrolyte is controlled there are no differences between ionic liquids and molecular solvents for the electrodeposition of silver.

Homomorphic encryption is the encryption scheme which means the operations on the encrypted data. Homomorphic encryption can be applied in any system by using various public key algorithms. When the data is transferred to the public area, there are many encryption algorithms to secure the operations and the storage of the data. But to process data located on remote server and to preserve privacy, homomorphic encryption is useful that allows the operations on the cipher text, which can provide the same results after calculations as the working directly on the raw data. In this paper, the main focus is on public key cryptographic algorithms based on homomorphic encryption scheme for preserving security. The case study on various principles and properties of homomorphic encryption is given and then various homomorphic algorithms using asymmetric key systems such as RSA, ElGamal, Paillier algorithms as well as various homomorphic encryption schemes such as BrakerskiGentry-Vaikuntanathan (BGV), Enhanced homomorphic Cryptosystem (EHC), Algebra homomorphic encryption scheme based on updated ElGamal (AHEE), Non-interactive exponential homomorphic encryption scheme (NEHE) are investigated.

At first glance, the combination of the lightest, most electropositive metal (lithium) with a safe, abundant (and reasonably light) non-metal (sulfur) makes good sense as a prospective battery. However, while the lithium–sulfur battery offers a very high theoretical specific energy (∼2600 W h kg−1) the actual performance delivered is proving to be severely limited—in many cases, this is directly related to the role of the electrolyte. The fundamental issue is that the reduction of sulfur proceeds through a series of polysulfide species, which are for the most part soluble in common organic solvents, including those employed in battery electrolyte solutions. So, despite the fact that the ultimate product (Li2S) is essentially insoluble, the intermediate stages of discharge see a migration of redox-active species out of the cathode, from where they can react with the lithium anode, which sets in train a series of equilibria that cause both a loss of charging efficiency and a gradual loss of discharge capacity. In the last decade, a major stream of the research to overcome this complex situation has focused on minimizing the solubility of polysulfides. From this we now have a range of media in which the lithium–sulfur system can operate with much improved charge–discharge characteristics: ionic liquids (and blends with organic media); super-saturated salt-solvent mixtures; polymer-gelled organic media; solid polymers; solid inorganic glasses. Underlining the multi-faceted nature of interactions within the lithium–sulfur cell, though, none of these improved electrolytes has been able to bring the performance of this system up to the levels of reliability and capacity maintenance (without sacrificing high specific energy) that are benchmarks in energy storage applications. Our survey indicates that only by combining particular electrolytes with cathode materials that are designed to actively retain sulfur and its reduction products, have a relatively few studies been able to obtain the desired levels of performance. Ultimately the successful development of the lithium–sulfur battery requires careful coordination of the choice of modified electrolyte with the specific nature of the cathode material, underpinned by the assumption that the resulting electrolyte composition will meet established criteria for compatibility with the lithium anode.

This study reports the synthesis of extremely high aspect ratios (>3000) organic semiconductor nanowires of Ag–tetracyanoquinodimethane (AgTCNQ) on the surface of a flexible Ag fabric for the first time. These one-dimensional (1D) hybrid Ag/AgTCNQ nanostructures are attained by a facile, solution-based spontaneous reaction involving immersion of Ag fabrics in an acetonitrile solution of TCNQ. Further, it is discovered that these AgTCNQ nanowires show outstanding antibacterial performance against both Gram negative and Gram positive bacteria, which outperforms that of pristine Ag. The outcomes of this study also reflect upon a fundamentally important aspect that the antimicrobial performance of Ag-based nanomaterials may not necessarily be solely due to the amount of Ag+ ions leached from these nanomaterials, but that the nanomaterial itself may also play a direct role in the antimicrobial action. Notably, the applications of metal-organic semiconducting charge transfer complexes of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) have been predominantly restricted to electronic applications, except from our recent reports on their (photo)catalytic potential and the current case on antimicrobial prospects. This report on growth of these metal-TCNQ complexes on a fabric not only widens the window of these interesting materials for new biological applications, it also opens the possibilities for developing large-area flexible electronic devices by growing a range of metal-organic semiconducting materials directly on a fabric surface.

The repetitive cycling of lithium metal electrodes in Li metal | ionic liquid electrolytes | Li metal coin cells was investigated. Lithium metal electrodes achieved 800 charge-discharge cycles at current densities of 0.1, 10 and 100 mA cm-2. Voltage-time plots show evidence for instabilities manifesting themselves as voltage spikes. SEM imaging of cycled electrodes crucially shows no evidence for dendrite formation capable of leading to short circuit conditions, under all cycling regimes. SEM study shows evidence for surface corrosion. Based on the SEM study and cycling behavior a corrosion based equivalent circuit is presented and fitted to impedance data. SEM and impedance data are used to describe the changes in the voltage-time plots and ascribe the voltage spikes observed to changes in the lithium metal surface and subsequent corrosion. FTIR spectroscopy was used to analyze lithium electrodes after cycling. Evidence for IL surface coordination and LiOH formation was found.

The effect of extended cycling on lithium metal electrodes has been investigated in an ionic liquid electrolyte. Cycling studies were conducted on lithium metal electrodes in a symmetrical Li|electrolyte|Li coin cell configuration for 5000 charge–discharge cycles at a current density of 0.1 mA cm−2. The voltage–time plots show evidence of some unstable behavior which is attributed to surface reorganization. No evidence for lithium dendrite induced short circuiting was observed. SEM imaging showed morphology changes had occurred but no evidence of needle-like dendrite based growth was found after 5000 charge–discharge cycles. This study suggests that ionic liquid electrolytes can enable next generation battery technologies such as rechargeable lithium-air, in which a safe, reversible lithium electrode is a crucial component. Keywords: Li metal batteries, Ionic liquids, Electrodeposition, Cyclic voltammetry

Chemical reaction studies of N-methyl-N-propyl-pyrrolidinium- bis(fluorosulfonyl)imide-based ionic liquid with the lithium metal surface were performed using ab initio molecular dynamics (aMD) simulations and X-ray Photoelectron Spectroscopy (XPS). The molecular dynamics simulations showed rapid and spontaneous decomposition of the ionic liquid anion, with subsequent formation of long-lived species such as lithium fluoride. The simulations also revealed the cation to retain its structure by generally moving away from the lithium surface. The XPS experiments showed evidence of decomposition of the anion, consistent with the aMD simulations and also of cation decomposition and it is envisaged that this is due to the longer time scale for the XPS experiment compared to the time scale of the aMD simulation. Overall experimental results confirm the majority of species suggested by the simulation. The rapid chemical decomposition of the ionic liquid was shown to form a solid electrolyte interphase composed of the breakdown products of the ionic liquid components in the absence of an applied voltage.

The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4mPyr][TFSI]), and an aqueous KNO3 solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation–growth kinetics. Analysis of chronoamperometric data indicated that the nucleation–growth mechanism is instantaneous at all potentials in the case of [BMIm][BF4] and [C4mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO3. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C4mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL. It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction.

Electrode-dependent potential windows (see picture, GC=glassy carbon) are determined for five dialkylammonium carbamate (dialcarb) room-temperature ionic liquids in a systematic study of their physical and electrochemical properties. The viscosity and conductivity of the dialcarb ionic liquids, which are "distillable" at low temperature, are comparable to those of some conventional room-temperature ionic liquids. The physical and electrochemical properties of five "distillable" room-temperature ionic liquids from the dialcarb family (dialkylammonium carbamates formed from CO(2) and dialkyl amines) are systematically investigated. In particular dimethyl (DIMCARB), diethyl (DIECARB), dipropyl (DIPCARB), methylethyl (MEETCARB), and methylpropyl (MEPRCARB) carbamate ionic liquids are studied. The temperature dependence of the viscosity and conductivity of MEETCARB exhibit an Arrhenius-type relationship. Except for DIPCARB, which has too high a resistance, a reference potential scale is available by using the IUPAC recommended redox system, that is the cobalticenium/cobaltocene (Cc(+)/Cc) process, which exhibits an ideal reversible voltammetric response. Oxidation of decamethylferrocene, but not ferrocene, also is ideal in DIMCARB, DIECARB, MEETCARB, and MEPRCARB. The magnitudes of the potential windows of the electrochemically viable dialcarbs are investigated and follow the order of glassy carbon>Au>Pt>Hg. Diffusion coefficients of Cc(+), DmFc, and double-layer capacitance values are compared in each dialcarb. Despite the considerable viscosity of the dialcarbs, steady-state voltammetric behavior is achieved at a rotating disk electrode for rotation rates of 1000 rpm or higher.

The reduction of Ag + to Ag 0 has been studied electrochemically at glassy carbon electrodes using the tech

The structure and molecular signature of tumor-associated vasculature are distinct from those of the host tissue, offering an opportunity to selectively target the tumor blood vessels. To identify tumor-specific endothelial markers, we performed a microarray on tumor-associated and nonmalignant endothelium collected from patients with renal cell carcinoma (RCC), colorectal carcinoma, or colorectal liver metastasis. We identified a panel of genes consistently upregulated by tumor blood vessels, of which melanoma cell adhesion molecule (MCAM) and its extracellular matrix interaction partner laminin alpha 4 (LAMA4) emerged as the most consistently expressed genes. This result was subsequently confirmed by immunohistochemical analysis of MCAM and LAMA4 expression in RCC and colorectal carcinoma blood vessels. Strong MCAM and LAMA4 expression was also shown to predict poor survival in RCC, but not in colorectal carcinoma. Notably, MCAM and LAMA4 were enhanced in locally advanced tumors as well as both the primary tumor and secondary metastases. Expression analysis in 18 different cancers and matched healthy tissues revealed vascular MCAM as highly specific in RCC, where it was induced strongly by VEGF, which is highly abundant in this disease. Lastly, MCAM monoclonal antibodies specifically localized to vessels in a murine model of RCC, offering an opportunity for endothelial-specific targeting of anticancer agents. Overall, our findings highlight MCAM and LAMA4 as prime candidates for RCC prognosis and therapeutic targeting. Cancer Res; 76(8); 2314–26. ©2016 AACR.

The fabrication of a superhydrophobic nylon textile based on the organic charge-transfer complex CuTCNAQ (TCNAQ=11,11,12,12-tetracyanoanthraquinodimethane) is reported. The nylon fabric, which is metallized with copper, undergoes a spontaneous chemical reaction with TCNAQ dissolved in acetonitrile to form nanorods of CuTCNAQ that are intertwined over the entire surface of the fabric. This creates the necessary micro- and nanoscale roughness that often allows the Cassie-Baxter state to be obtained with high robustness, thereby achieving a superhydrophobic/superoleophilic surface without the need for a fluorinated surface. The material is characterized with SEM, FTIR spectroscopy, and X-ray photoelectron spectroscopy, and investigated for its ability to separate oil and water in two modes, namely through filtration and as an absorbent material. It is found that the fabric can separate dichloromethane, olive oil, and crude oil from water, and reduce the water content of the oil during the separation process. The fabric is reusable, highly durable, and tolerant to conditions such as seawater, hydrochloric acid, and extensive time periods on the shelf. Given that CuTCNAQ is a copper-based semiconductor, there may also be the possibility of other uses in areas such as photocatalysis and antibacterial applications.

The electrochemical reduction of Pb2+ has been studied in the ‘distillable’ ionic liquid DIMCARB (a mixture of adducts of dimethylamine and carbon dioxide, comprising both neutral and ionic moieties). Voltammetric results show that Pb2+ is reduced in a single step to form Pb metal via a nucleation and growth mechanism on a glassy carbon electrode. Ex situ powder X-ray diffraction studies on deposited lead show the presence of both α- and β-PbO2, as well as elemental lead, suggesting the finely deposited lead particles are in an active rather than passive state. Chronamperometric and scanning electron microscope measurements show that the nucleation and growth follows a progressive nucleation mechanism on glassy carbon. Large peak–peak separations for the Pb reduction and oxidation are consistent with this mechanism and do not suggest electrochemical reversibility. However, experiments with co-deposition of Hg show that this irreversibility is a result of deposition onto a solid glassy carbon surface rather than a solvent effect. The diffusion coefficient of Pb2+ in DIMCARB has been calculated to be 1.8±0.4×10−7 cm2 s−1.

A Th(IV) compound, [Th(TFSI)4(HTFSI)].2H2O [where TFSI = N(SO2CF3)2], has been synthesized and characterized using elemental analysis, thermogravimetric analysis, and vibrational spectroscopy. The analysis suggests that the TFSI anion coordinates to the metal center via the sulfonyl oxygens as well as provides evidence for the coordination of HTFSI. The voltammetric behavior of this compound has been studied in the room-temperature ionic liquid [Me3NnBu][TFSI], and results show that Th(IV) is reduced to Th(0) in this ionic liquid in a single reduction step. Analysis of cyclic voltammograms shows that an insoluble product is being formed at the electrode surface, which is attributed to the formation of ThO2 by reaction with water. The E0 value for the reduction of Th(IV) to Th(0) has been determined to be -2.20 V (vs Fc+/Fc; -1.80 V vs SHE). A comparison of this E0 value with those obtained for Th(IV) reduction in a LiCl-KCl eutectic (400 degrees C), water, and nonaqueous solvents shows that the reduction in [Me3NnBu][TFSI] is easier to accomplish than that in these other solvents.

Ionic liquids are frequently advocated as green media for electrochemical studies. However, they are non-volatile and hence difficult to purify or recover. In this paper the electrochemical behaviour of a ‘distillable’ room temperature ionic liquid, DIMCARB, has been investigated. This ionic liquid is unusual because it is readily prepared, in large quantities and at low cost, by mixing of gaseous carbon dioxide with dimethylamine and also easily recovered by decomposition back into its gaseous components followed by reassociation. Almost ideal reversible voltammetry is observed for the Cc+/0 process (Cc = cobalticinium), which therefore is recommended for reference potential calibration. Another IUPAC recommended reference potential process, Fc+/0 (Fc = ferrocene), is only reversible at fast scan rates and occurs near the positive potential limit available. However, decamethylferrocene (DmFc) is reversibly oxidised and behaves ideally as for the reduction of Cc+. The small diffusion coefficients of 1.2 × 10−7 cm2 s−1 (Cc+) and 5.0 × 10−8 cm2 s−1 (DmFc) at 20 °C are attributed to the relatively high viscosity. The potential window of ca. −1.50 V to +0.50 V vs. SHE indicates that DIMCARB is more suitable for electrochemical studies of reductive rather than oxidative processes. Voltammetric studies in DIMCARB reveal a series of reversible reductive processes for the Keggin [α-SiW12O40]4− polyoxometallate. Comparison of reversible potential data reported in other media indicate that the polarity of DIMCARB is intermediate between that of MeCN and the conventional ionic liquid [BMIM][PF6]. The deposition of metallic Pb also has been studied and reveals that Pb(II) is reduced in a single irreversible 2-electron step to the metallic state via a nucleation/growth mechanism. Overall, these studies show that DIMCARB is highly suitable for electrochemical studies, but that it is a potentially reactive medium.

The voltammetry of the polyoxometalate salts [Bu4N]4[SiW12O40] (α, β, γ* isomers), [Bu4N]4[S2W18O62] (α, γ* isomers) and [Bu4N]4[S2Mo18O62] (α isomer) has been studied in the “distillable ionic liquid” DIMCARB (a mixture of adducts, both ionic and neutral, of dimethylamine and carbon dioxide). Dissolution of these salts tended to be slow and the anions, except [α-SiW12O40]4−, reacted with DIMCARB. However, high quality voltammograms were obtained from microparticles of the salts adhered to a glassy carbon electrode in contact with DIMCARB. Rapid dissolution of the reduced forms of each of the polyoxometalate anions provided reversible potential data. The higher basicity of the more highly reduced anions promoted interactions with the acidic solvent component of this medium. Comparison of reversible potentials indicated that the polarity of DIMCARB is similar to CH3CN, but smaller than that of conventional non-volatile ionic liquids and water. Keywords: Voltammetry of adhered microparticles, Distillable ionic liquid, DIMCARB, Polyoxometalates

The modification of platinum electrodes with commercial filtration membranes is used to study the interplay between solution and membrane mass-transport in non-aqueous solution. Two types of commercial membrane, “track-etched” polyethylene terephthalate and γ-Al 2 O 3 , are employed. Voltammetric and amperometric data is obtained under both hydrodynamic (rotating-disc) and stationary conditions, which is interpreted in terms of a pinhole model. Contrasting behaviour is seen for the different membranes, which can be understood by consideration of the membrane thickness relative to the diffusion layer established in solution. In particular, overlapping diffusion behaviour is observed for the much thinner polymer membranes under hydrodynamic conditions.

The structures and interatomic distances of various chloro complexes of uranium in LiCl–BeCl2 eutectic melt at 380 °C have been determined from EXAFS measurements. Dissolution of UCl4 and UO2Cl2 (in the absence of a chlorine atmosphere) generated UCl 6 2 - ions. Similarly, dissolution of UCl3 generated UCl 6 3 - complexes but dissolution of UO2Cl2 under a chlorine atmosphere yielded a mixture of UCl 6 2 - and UO2 Cl 4 2 - , deduced from electronic absorption spectra measurements. Interatomic distances and uranium coordination are compared with earlier data in molten LiCl, both in melts and for quenched samples at room temperature.

The reduction of selected lanthanide cations to the zerovalent state in the room-temperature ionic liquid [Me3NnBu][TFSI] is reported (where TFSI = bistriflimide, [N(SO2CF3)2]-). The lanthanide cations were introduced to the melt as the TFSI hydrate complexes [Ln(TFSI)3(H2O)3] (where Ln = LaIII, SmIII or EuIII). The lanthanum compound [La(TFSI)3(H2O)3] has been crystallographically characterized, revealing the first structurally characterized f-element TFSI complex. The lanthanide in all three complexes was shown to be reducible to the metallic state in [Me3NnBu][TFSI]. For both the Eu and Sm complexes, reduction to the metallic state was achieved via divalent species, and there was an additional observation of the electrodeposition of Eu metal.

The chlorination of uranium metal or uranium oxides in chloride melts offers an acceptable process for the head-end of pyrochemical reprocessing of spent nuclear fuels. The reactions of uranium metal and ceramic uranium dioxide with chlorine and with hydrogen chloride were studied in the alkali metal chloride melts, NaCl-KCl at 973 K, NaCl-CsCl between 873 and 923 K, and LiCl-KCl at 873 K. The uranium species formed therein were characterised from their electronic absorption spectra measured in situ. The kinetic parameters of the reactions depend on melt composition, temperature and chlorinating agent used. The reaction of uranium dioxide with oxygen in the presence of alkali metal chlorides results in the formation of alkali metal uranates. A spectroscopic study, between 723 and 973 K, on their formation and their solutions was undertaken in LiCl, LiCl-KCl eutectic and NaCl-CsCl eutectic melts. The dissolution of uranium dioxide in LiCl-KCl eutectic at 923 K containing added aluminium trichloride in the ...

As an anode material for lithium-ion batteries, titanium dioxide (TiO 2 ) shows good gravimetric performance (336 mAh g -1 for LiTiO 2 ) and excellent cyclability. To address the poor rate behavior, slow lithium-ion (Li + ) diffusion, and high irreversible capacity decay, TiO 2 nanomaterials with tuned phase compositions and morphologies are being investigated. Here, a promising material is prepared that comprises a mesoporous "yolk-shell" spherical morphology in which the core is anatase TiO 2 and the shell is TiO 2 (B). The preparation employs a NaCl-assisted solvothermal process and the electrochemical results indicate that the mesoporous yolk-shell microspheres have high specific reversible capacity at moderate current (330.0 mAh g -1 at C/5), excellent rate performance (181.8 mAh g -1 at 40C), and impressive cyclability (98% capacity retention after 500 cycles). The superior properties are attributed to the TiO 2 (B) nanosheet shell, which provides additional active area to stabilize the pseudocapacity. In addition, the open mesoporous morphology improves diffusion of electrolyte throughout the electrode, thereby contributing directly to greatly improved rate capacity.

Electrochemical cells and systems play a key role in a wide range of industry sectors. These devices are critical enabling technologies for renewable energy; energy management, conservation, and storage; pollution control/monitoring; and greenhouse gas reduction. A large number of electrochemical energy technologies have been developed in the past. These systems continue to be optimized in terms of cost, life time, and performance, leading to their continued expansion into existing and emerging market sectors. The more established technologies such as deep-cycle batteries and sensors are being joined by emerging technologies such as fuel cells, large format lithium-ion batteries, electrochemical reactors; ion transport membranes and supercapacitors. This growing demand (multi billion dollars) for electrochemical energy systems along with the increasing maturity of a number of technologies is having a significant effect on the global research and development effort which is increasing in both in size and depth. A number of new technologies, which will have substantial impact on the environment and the way we produce and utilize energy, are under development. This paper presents an overview of several emerging electrochemical energy technologies along with a discussion some of the key technical challenges.

In situ EXAFS spectroscopic studies of uranium compounds in high temperature alkali chloride melts indicate the presence of oligomeric species. An investigation into UCl(3) and UCl(4) dissolved in LiCl reveals long range ordering of uranium atoms in the molten state which is not maintained on quenching. Studies of uranium dioxide dissolved in LiCl-KCl eutectic with HCl exhibit long range ordering in both molten and quenched states, and the EXAFS data can be modeled using multiple coordination shells.

Ionic liquids show promise as electrolytes for a host of electrochemical processes due to their favourable physical and electrochemical properties. However, use of conventional aqueous or non-aqueous reference electrodes with ionic liquids poses problems due to the existence of large junction potentials and possible contamination of the test solution.