A Simple, Low-cost, and Robust System to Measure the Volume of Hydrogen Evolved by Chemical Reactions with Aqueous Solutions.

There is a growing research interest in the development of portable systems which can deliver hydrogen on-demand to proton exchange membrane (PEM) hydrogen fuel cells. Researchers seeking to develop such systems require a method of measuring the generated hydrogen. Herein, we describe a simple, low-cost, and robust method to measure the hydrogen generated from the reaction of solids with aqueous solutions. The reactions are conducted in a conventional one-necked round-bottomed flask placed in a temperature controlled water bath. The hydrogen generated from the reaction in the flask is channeled through tubing into a water-filled inverted measuring cylinder. The water displaced from the measuring cylinder by the incoming gas is diverted into a beaker on a balance. The balance is connected to a computer, and the change in the mass reading of the balance over time is recorded using data collection and spreadsheet software programs. The data can then be approximately corrected for water vapor using the method described herein, and parameters such as the total hydrogen yield, the hydrogen generation rate, and the induction period can also be deduced. The size of the measuring cylinder and the resolution of the balance can be changed to adapt the setup to different hydrogen volumes and flow rates.

Anodized Steel Electrodes for Supercapacitors.

Steel was anodized in 10 M NaOH to enhance its surface texture and internal surface area for application as an electrode in supercapacitors. A mechanism was proposed for the anodization process. Field-emission gun scanning electron microscopy (FEGSEM) studies of anodized steel revealed that it contains a highly porous sponge like structure ideal for supercapacitor electrodes. X-ray photoelectron spectroscopy (XPS) measurements showed that the surface of the anodized steel was Fe2O3, whereas X-ray diffraction (XRD) measurements indicated that the bulk remained as metallic Fe. The supercapacitor performance of the anodized steel was tested in 1 M NaOH and a capacitance of 18 mF cm(-2) was obtained. Cyclic voltammetry measurements showed that there was a large psueudocapacitive contribution which was due to oxidation of Fe to Fe(OH)2 and then further oxidation to FeOOH, and the respective reduction of these species back to metallic Fe. These redox processes were found to be remarkably reversible as the electrode showed no loss in capacitance after 10000 cycles. The results demonstrate that anodization of steel is a suitable method to produce high-surface-area electrodes for supercapacitors with excellent cycling lifetime.

Selective Formation of Trimethylene Carbonate (TMC): Atmospheric Pressure Carbon Dioxide Utilization.

Carbon dioxide utilisation (CDU) is currently gaining increased interest due to the abundance of CO2 and its possible application as a C1 building block. We herein report the first example of atmospheric pressure carbon dioxide incorporation into oxetane to selectively form trimethylene carbonate (TMC), which is a significant challenge as TMC is thermodynamically less favoured than its corresponding co-polymer.

Electrochemical determination of the density of states of nanostructured NiO films.

Mesoporous p-type NiO films were prepared by aerosol-assisted chemical vapor deposition (AACVD) and characterized by X-ray diffraction (XRD). The nanostructure of the films was investigated by field emission gun scanning electron microscopy (FEG-SEM). The density of states (DOS) in these nanostructured films has been determined by means of electrochemical impedance spectroscopy and cyclic voltammetry. The analysis reveals an exponential distribution of band gap states above the valence band that extends around 1.5 eV. In addition, monoenergetic states were also identified which overlap with the exponential distribution. This distribution of states has an enormous influence in the electronic processes of the devices in which NiO electrodes are employed (electrochromism, water splitting or energy storage). Especially, in p-type dye-sensitized solar cells (p-DSCs), it is thought that intra-band-gap states are responsible for the fast observed recombination processes, whose existence and distribution has not been clearly determined yet and are now confirmed and quantified by our analysis. This provides a better comprehension of the recombination events which represent one of the main losses in p-DSCs.

Insights into mechanical compression and the enhancement in performance by Mg(OH)2 coating in flexible dye sensitized solar cells.

The engineering of flexible dye sensitized solar cells (DSCs) by mechanical compression is one of the methods that allow low temperature processing of these devices. However, suppressing the high temperature sintering process also significantly reduces the performance of the cells. In our previous work [J. Phys. Chem. C, 2012, 116, 1211], we have attempted to improve flexible DSC performance by coating the porous TiO2 photoanode with an electrodeposited Mg(OH)2 layer. In that work, we have obtained one of the highest photovoltages reported to date in flexible DSCs (847 mV). In order to gain more insights into the reasons for both poorer performance of compressed cells and the origin of the voltage enhancement achieved by the Mg(OH)2 coating, here we present an in-depth study by means of electrochemical impedance spectroscopy, Mott-Schottky plots analysis and open-circuit voltage decays. The existence of a shunt resistance in the mechanically compressed cells is revealed, causing an additional drawback to the poor inter-particle necking. By introducing the Mg(OH)2 coating the recombination in the cell becomes significantly reduced, being the key reason which is responsible for the higher photovoltage. Additionally, the coating and the compression cause modifications in the surface states and in the nature of the interfaces with the electrolyte. This induces TiO2 conduction band displacements and shifts of the relative position of the modified states that influence the performance.

Development of molecular precursors for deposition of indium sulphide thin film electrodes for photoelectrochemical applications.

Symmetrical and unsymmetrical dithiocarbamato pyridine solvated and non-solvated complexes of indium(III) with the general formula [In(S2CNRR')3]·n(py) [where py = pyridine; R,R' = Cy, n = 2 (1); R,R' = (i)Pr, n = 1.5 (2); NRR' = Pip, n = 0.5 (3) and R = Bz, R' = Me, n = 0 (4)] have been synthesized. The compositions, structures and properties of these complexes have been studied by means of microanalysis, IR and (1)H-NMR spectroscopy, X-ray single crystal and thermogravimetric (TG/DTG) analyses. The applicability of these complexes as single source precursors (SSPs) for the deposition of ß-In2S3 thin films on fluorine-doped SnO2 (FTO) coated conducting glass substrates by aerosol-assisted chemical vapour deposition (AACVD) at temperatures of 300, 350 and 400 °C is studied. All films have been characterized by powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDX) for the detection of phase and stoichiometry of the deposit. Scanning electron microscopy (SEM) studies reveal that precursors (1)-(4), irrespective of different metal ligand design, generate comparable morphologies of ß-In2S3 thin films at different temperatures. Direct band gap energies of 2.2 eV have been estimated from the UV-vis spectroscopy for the ß-In2S3 films fabricated from precursors (1) and (4). The photoelectrochemical (PEC) properties of ß-In2S3 were confirmed by recording the current-voltage plots under light and dark conditions. The plots showed anodic photocurrent densities of 1.25 and 0.65 mA cm(-2) at 0.23 V vs. Ag/AgCl for the ß-In2S3 films made at 400 and 350 °C from the precursors (1) and (4), respectively. The photoelectrochemical performance indicates that the newly synthesised precursors are highly useful in fabricating ß-In2S3 electrodes for solar energy harvesting and optoelectronic application.

Electrochromic and colorimetric properties of nickel(II) oxide thin films prepared by aerosol-assisted chemical vapor deposition.

Aerosol-assisted chemical vapor deposition (AACVD) was used for the first time in the preparation of thin-film electrochromic nickel(II) oxide (NiO). The as-deposited films were cubic NiO, with an octahedral-like grain structure, and an optical band gap that decreased from 3.61 to 3.48 eV on increase in film thickness (in the range 500-1000 nm). On oxidative voltammetric cycling in aqueous KOH (0.1 mol dm(-3)) electrolyte, the morphology gradually changed to an open porous NiO structure. The electrochromic properties of the films were investigated as a function of film thickness, following 50, 100, and 500 conditioning oxidative voltammetric cycles in aqueous KOH (0.1 mol dm(-3)). Light modulation of the films increased with the number of conditioning cycles. The maximum coloration efficiency (CE) for the NiO (transmissive light green, the "bleached" state) to NiOOH (deep brown, the colored state) electrochromic process was found to be 56.3 cm(2) C(-1) (at 450 nm) for films prepared by AACVD for 15 min followed by 100 "bleached"-to-colored conditioning oxidative voltammetric cycles. Electrochromic response times were <10 s and generally longer for the coloration than the bleaching process. The films showed good stability when tested for up to 10 000 color/bleach cycles. Using the CIE (Commission Internationale de l'Eclairage) system of colorimetry the color stimuli of the electrochromic NiO films and the changes that take place on reversibly oxidatively switching to the NiOOH form were calculated from in situ visible spectra recorded under electrochemical control. Reversible changes in the hue and saturation occur on oxidation of the NiO (transmissive light green) form to the NiOOH (deep brown) form, as shown by the track of the CIE 1931 xy chromaticity coordinates. As the NiO film is oxidized, a sharp decrease in luminance was observed. CIELAB L*a*b* coordinates were also used to quantify the electrochromic color states. A combination of a low L* and positive a* and b* values quantified the perceived deep brown colored state.

Kinetics of light-driven oxygen evolution at alpha-Fe2O3 electrodes.

The kinetics of light-driven oxygen evolution at polycrystalline alpha-Fe2O3 layers prepared by aerosol-assisted chemical vapour deposition has been studied using intensity modulated photocurrent spectroscopy (IMPS). Analysis of the frequency-dependent IMPS response gives information about the competition between the 4-electron oxidation of water by photogenerated holes and losses due to electron-hole recombination via surface states. The very slow kinetics of oxygen evolution indicates the presence of a kinetic bottleneck in the overall process. Surface treatment of the alpha-Fe2O3 with dilute cobalt nitrate solution leads to a remarkable improvement in the photocurrent response, but contrary to expectation, the results of this study show that this is not due to catalysis of hole transfer but is instead the consequence of almost complete suppression of surface recombination.

Kinetics and mechanism of light-driven oxygen evolution at thin film α-Fe2O3 electrodes.

Rate constants for recombination and hole transfer during oxygen evolution at illuminated α-Fe(2)O(3) electrodes were measured by intensity-modulated photocurrent spectroscopy and found to be remarkably low. Treatment of the electrode with a Co(II) solution suppressed surface recombination but did not catalyse hole transfer. Intermediates in the reaction were detected spectroscopically.

New insights into water splitting at mesoporous α-Fe2O3 films: a study by modulated transmittance and impedance spectroscopies.

Thin mesoporous films of α-Fe(2)O(3) have been prepared on conducting glass substrates using layer-by-layer self-assembly of ca. 4 nm hydrous oxide nanoparticles followed by calcining. The electrodes were used to study the oxygen evolution reaction (OER) in the dark and under illumination using in situ potential-modulated absorption spectroscopy (PMAS) and light-modulated absorption spectroscopy (LMAS) combined with impedance spectroscopy. Formation of surface-bound higher-valent iron species (or "surface trapped holes") was deduced from the PMAS spectra measured in the OER onset region. Similar LMAS spectra were obtained at more negative potentials in the onset region of photoelectrochemical OER, indicating involvement of the same intermediates. The impedance response of the mesoporous α-Fe(2)O(3) electrodes exhibits characteristic transmission line behavior that is attributed to slow hopping of holes, probably between surface iron species. Frequency-resolved PMAS and LMAS measurements revealed slow relaxation behavior that can be related to the impedance response and that indicates that the lifetime of the intermediates (or trapped holes) involved in the OER is remarkably long.

Electrosynthesis of cyclic carbonates from epoxides and atmospheric pressure carbon dioxide.

The use of CO(2) for the preparation of value-added compounds has dramatically increased due to increased global warming concerns. We herein report an electrochemical cell containing a copper cathode and a magnesium anode that effectively converts epoxides and carbon dioxide to cyclic carbonates under mild electrochemical conditions at atmospheric pressure.

Isostructural copper-zinc mixed metal complexes for single source deposition of Cu-ZnO composite thin films.

The mixed metal complex [Zn(TFA)(3)(µ-OH)Cu(3)(dmae)(3)Br]·THF (1) and its isostructural analogues ([Zn(TFA)(3)(µ-OH)Cu(3)(dmae)(3)Cl]·THF (2) and [Zn(TFA)(3)(µ-OH)Cu(3)(dmae)(3)Cl/Br]·THF (3)) have been prepared by a simple metal ligand assembly method and were characterized by their melting points, elemental analysis, IR spectroscopy, thermogravimetry and single crystal X-ray structures. The compounds are distinguished only by the nature of the halide ions and are made up of the same [Zn(TFA)(3)(µ-OH)Cu(3)(dmae)(3)X]·THF molecular building block with Cu(3)ZnO(4) cubane moieties as the central core in which the four metal ions and four oxygen atoms are joined together in alternate positions of the cuboid. All the complexes crystallize with similar packing and crystallographically related symmetry settings, distinguished mainly by the degree of disorder within the complexes and the ordering of the complexes in the structures. The triclinic cell of (1) emulates the monoclinic cell of (2) and is pseudomerohedrally twinned by a symmetry operation of the monoclinic cell. The molecules in (2) are 1:1 disordered around a crystallographic mirror plane. The structure of the mixed halogen compound (3) in turn is a superstructure of the less symmetric structures of (1) and (2) formed by ordering of the complexes along the longest axis of (3). Aerosol-assisted chemical vapour deposition (AACVD) experiments showed that they are promising precursors to deposit thin films of crystalline Cu/ZnO composites. The surface morphology, microstructure, chemical composition and crystallinity of the resulting Cu/ZnO composite thin films were analysed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDAX), which suggest that the films are thin, crystalline, uniform, smooth and tightly adherent to the substrates with average crystallite sizes in a range between 40.2 and 80.0 nm. Particle sizes, shapes and film morphology were investigated as a function of precursor and decomposition temperature.

Photooxidation of water by NiTiO3 deposited from single source precursor [Ni2Ti2(OEt)2(micro-OEt)6(acac)4] by AACVD.

A single-source heterobimetallic complex Ni2Ti2(OEt)2(mu-OEt)6(acac)4 (1) (acac=2,4-pentanedionate), having a low decomposition temperature and sufficient solubility in organic solvents, was synthesized by simple chemical techniques in high yield and analyzed by melting point, FTIR, single crystal X-ray analysis and thermal analysis. The TGA analysis proved that complex (1) underwent facile thermal decomposition at 500 degrees C to give NiTiO3 residue. In-house designed aerosol assisted chemical vapor deposition equipment was used to deposit high quality thin films of NiTiO3 on a SnO2 coated conducting glass substrate at 500 degrees C. An XRD analysis of the thin films proved the formation of crystalline NiTiO3 with average grain size 42 nm. Scanning electron microscopic studies (SEM) show that the thin films consist of flat, plate-like nanoparticles. The current-potential characteristics recorded under AM1.5 illumination indicate that NiTiO3 thin films are anodic and the photocurrent density at 1.23 V vs RHE (Reversible Hydrogen Electrode) is about 40 microA cm(-2).

Photosensitization of nanocrystalline TiO2 by self-assembled layers of CdS quantum dots.

CdS quantum dots can be self-assembled on high surface area nanocrystalline TiO2 electrodes; spectroscopic and photoelectrochemical studies indicate that the size, and hence the absorption edge, of the CdS particles can be controlled; efficient photosensitization of the TiO2 electrode by the Q-particles has been achieved.