Utilizing a Photocatalysis Process to Achieve a Cathode with Low Charging Overpotential and High Cycling Durability for a Li-O2 Battery

The practical applications of non-aqueous lithium-oxygen batteries are impeded by large overpotentials and unsatisfactory cycling durability. Reported here is that commonly encountered fatal problems can be efficiently solved by using a carbon- and binder-free electrode of titanium coated with TiO₂ nanotube arrays (TNAs) and gold nanoparticles (AuNPs). Ultraviolet irradiation of the TNAs generates positively charged holes, which efficiently decompose Li₂O₂ and Li₂CO₃ during recharging, thereby reducing the overpotential to one that is near the equilibrium potential for Li₂O₂ formation. The AuNPs promote Li₂O₂ formation, resulting in a large discharge capacity. The electrode exhibits excellent stability with about 100 % coulombic efficiency during continuous cycling of up to 200 cycles, which is due to the carbon- and binder-free composition. This work reveals a new strategy towards the development of highly efficient oxygen electrode materials for lithium-oxygen batteries.     

Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ(-) monoanion. In the presence of M(x+)(MeCN), reaction with TCNQ(-)(MeCN) leads to deposition of M(x+)[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 mum in length and with diameters of less than 180 nm, and Co[TCNQ](2)(H(2)O)(2) as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal-TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.     

Precise mass measurement of a double-stranded 500 base-pair (309 kDa) polymerase chain reaction product by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd.     

A study of the galvanic replacement reaction at surfaces and the role of lateral charge propagation

The galvanic replacement of isolated nanostructures of copper and silver on conducting supports as well as continuous films of copper with gold is reported. The surface morphology was characterized by scanning electron microscopy and the replacement with gold was confirmed by EDX analysis. It was found that lateral charge propagation during the replacement reaction had a significant effect in all cases. For the isolated nanostructures the deposition of gold was observed not only at the sacrificial template but also at the surrounding unmodified areas of the conducting substrate. In the case of copper films the role of lateral charge propagation was also confirmed by connecting it to an ITO electrode through an external circuit upon which gold deposition was also observed to occur. Interestingly, by inhibiting the rate of charge propagation, through the introduction of a series resistor, the morphology of gold on the copper substrate could be changed from discrete surface decoration with cube like nanoparticles to a more porous rough surface.     

PHOTOCONDUCTIVITY AND PHOTOVOLTAIC EFFECTS IN LANGMUIR-BLODGETT FILMS OF CHLOROPHYLL-a

The DC photoconductivity and photovoltaic effect in Langmuir films of Chlorophyll- a (Chi a ) of precisely controlled thickness formed between Al and Au electrodes have been extensively investigated. The dark conductivity and dark voltage are almost abolished in a N₂ atmosphere. The action spectrum of the photocurrent closely resembles the monolayer absorption spectrum of Chl indicating that the primary event in photoconduction is the generation of singlet excited states. Thicknessdependence studies on the photoconductivity indicate that carrier generation is a surface process and that the mean diffusion length of the excited state is approximately 20 nm. In short (˜1 s) light exposures the photocurrent always increases linearly with both the applied voltage and the light intensity. In continuous light the current-voltage characteristics are highly non-linear and the photocurrent shows a square-root intensity dependence at high intensities and small applied potentials. These results are interpreted in terms of second-order recombination and charge-trapping processes at high carrier densities. The photovoltage usually shows a logarithmic intensity dependence at high intensities and its maximum value in thick films is 800 mV with the Al electrode acquiring a negative polarity. This behaviour, together with some observations on the asymmetry of photocurrent-voltage characteristics and the effect of substituting an aqueous top electrode for Au, further suggest that the photoactive surface is a p-n junction between the Chl and Al₂O₃ layers.     

Electrocrystallization of Phase I, CuTCNQ (TCNQ = 7,7,8,8-Tetracyanoquinodimethane), on indium tin oxide and boron-doped diamond electrodes

The electrochemical reduction of TCNQ to TCNQ*- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to -0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation.     

Voltammetric monitoring of gold nanoparticle formation facilitated by glycyl-L-tyrosine: relation to electronic spectra and transmission electron microscopy images

Voltammetric techniques have been introduced to monitor the formation of gold nanoparticles produced via the reaction of the amino acid glycyl-L-tyrosine with Au(III) (bromoaurate) in 0.05 M KOH conditions. The alkaline conditions facilitate amino acid binding to Au(III), inhibit the rate of reduction to Au(0), and provide an excellent supporting electrolyte for voltammetric studies. Data obtained revealed that a range of time-dependent gold solution species are involved in gold nanoparticle formation and that the order in which reagents are mixed is critical to the outcome. Concomitantly with voltammetric measurements, the properties of gold nanoparticles formed are probed by examination of electronic spectra in order to understand how the solution environment present during nanoparticle growth affects the final distribution of the nanoparticles. Images obtained by the ex situ transmission electron microscopy (TEM) technique enable the physical properties of the nanoparticles isolated in the solid state to be assessed. Use of this combination of in situ and ex situ techniques provides a versatile framework for elucidating the details of nanoparticle formation.     

Tuning the electrocrystallization parameters of semiconducting Co[TCNQ]2-based materials to yield either single nanowires or crystalline thin films

Electrocrystallization of single nanowires and/or crystalline thin films of the semiconducting and magnetic Co[TCNQ]2(H2O)2 (TCNQ=tetracyanoquinodimethane) charge-transfer complex onto glassy carbon, indium tin oxide, or metallic electrodes occurs when TCNQ is reduced in acetonitrile (0.1 M [NBu4][ClO4]) in the presence of hydrated cobalt(II) salts. The morphology of the deposited solid is potential dependent. Other factors influencing the electrocrystallization process include deposition time, concentration, and identity of the Co2+(MeCN) counteranion. Mechanistic details have been elucidated by use of cyclic voltammetry, chronoamperometry, electrochemical quartz crystal microbalance, and galvanostatic methods together with spectroscopic and microscopic techniques. The results provide direct evidence that electrocrystallization takes place through two distinctly different, potential-dependent mechanisms, with progressive nucleation and 3-D growth being controlled by the generation of [TCNQ]*- at the electrode and the diffusion of Co2+(MeCN) from the bulk solution. Images obtained by scanning electron microscopy reveal that electrocrystallization of Co[TCNQ]2(H2O)2 at potentials in the range of 0.1-0 V vs Ag/AgCl, corresponding to the [TCNQ]0/*- diffusion-controlled regime, gives rise to arrays of well-separated, needle-shaped nanowires via the overall reaction 2[TCNQ]*-(MeCN)+Co2+(MeCN)+2H2O right harpoon over left harpoon {Co[TCNQ]2(H2O)2}(s). In this potential region, nucleation and growth occur at randomly separated defect sites on the electrode surface. In contrast, at more negative potentials, a compact film of densely packed, uniformly oriented, hexagonal-shaped nanorods is formed. This is achieved at a substantially increased number of nucleation sites created by direct reduction of a thin film of what is proposed to be cobalt-stabilized {(Co2+)([TCNQ2]*-)2} dimeric anion. Despite the potential-dependent morphology of the electrocrystallized Co[TCNQ]2(H2O)2 and the markedly different nucleation-growth mechanisms, IR, Raman, elemental, and thermogravimetric analyses, together with X-ray diffraction, all confirmed the formation of a highly pure and crystalline phase of Co[TCNQ]2(H2O)2 on the electrode surface. Thus, differences in the electrodeposited material are confined to morphology and not to phase or composition differences. This study highlights the importance of the electrocrystallization approach in constructing and precisely controlling the morphology and stoichiometry of Co[TCNQ]2-based materials.