Remarkably improved hydrogen storage properties of nanocrystalline TiO2-modified NaAlH4 and evolution of Ti- containing species during dehydrogenation/hydrogenation

Adding a small amount of nanocrystalline TiO2@C （TiO2 supported on nano- porous carbon） composite dramatically decreases the operating temperatures and improves the reaction kinetics for hydrogen storage in NaAlH4. The nano- crystalline TiO2@C composite synthesized at 900 ℃ （referred as TiO2@C-900） exhibits superior catalytic activity to other catalyst-containing samples. The onset dehydrogenation temperature of the TiO2@C-900-containing sample is lowered to 90 ℃; this is 65 ℃ lower than that of the pristine sample. The dehydrogenated sample is completely hydrogenated at 115 ℃ and 100 bar of hydrogen pressure with a hydrogen capacity of 4.5 wt.%. Structural analyses reveal that the Ti undergoes a reduction process of Ti^4＋→Ti^3＋→Ti^2＋→Ti during the ball milling and heating processes, and further converts to Ti hydrides or forms Ti-Al species after rehydrogenation. The catalytic activities of Ti-based catalytic species decrease in the order Al-Ti-species 〉 TiH0.71 〉 TiH2 〉 TiO2. This understanding guides further improvement in hydrogen storage properties of metal alanates using nanocrvstalline transition metal-based additives.

Time-resolved Microwave Conductivity Studies on the Chemical Treatment of the Nanocrystalline Porous TiO2 Films

Effect of Ti(iso-C3H7O)4 treatment on the photoinduced charge carrier kinetics of nanocrystalline porous TiO2 films is studied by time-resolved microwave conductivity measurements. Analysis of the transient photoconductivity decays indicates that Ti(iso-C3H7O)4 treatment leads to an increased concentration of photogenerated charge carriers and a fast interfacial transfer rate of holes via the surface modification of the freshly growing TiO2 nanocrystallites.

A Dye-sensitized Nanocrystalline Solid State Photovoltaic Cell

A new type of dye-sensitized nanocrystalline solid state photovoltaic cell based on the wide band gap n-TiO2/p-CuI heterojunction was fabricated. Tetra-carboxyphenyl porphyrine (TPP-(COOH)(4)), squarylium cyanine derivative (SQ-(CH2),(SO3Py+)-Py-.) and ruthenium bipyridyl complex (RuL2(NCS)(2)) were used as photosensitizers. Larger photocurrents and photovoltages were shown in the cell sensitized by ruthenium bipyridyl complex and can be further increased by intercalation of a TiO2 thin underlayer.

A Novel Nanocrystalline TiO_2 Thin Film Electrodes Prepared at Low Temperature

Nanocrystalline TiO2 thin films were successfully prepared by a new “water-cooked” method on both conductive glass substrates and flexible substrates at low temperature. Dye-sensitized solar cells based on these films have exhibited high overall light-to-electricity conversion efficiencies of 4.67 % and 1.94 % on conductive glass substrate and flexible substrate, respectively, under the illumination at 100 mW/cm2.

Atomic Force Microscopy Studies on the Chemical Treatment of Nanocrystalline Porous TiO_2 Films

AFM has been utilized to study the surface topography and the local conductivity of nanocrystalline TiO2 films. Improving the local conductivity by Ti(iso-C3H7O)4 treatment is characterized by quantitative analysis of the simultaneous current image. The mechanism of Ti(iso C3H7O)4 treatment is discussed.

Sensitization of Microporous Nanocrystalline TiO_2 Electrode with Quantum Sized RuS2 Particles

The microporous nanocry'sta1line TiO2 electrode with large surface roughness factor hasbeen prepared on a conducting glass support. Modification of the TiO2 electrode by in situ preparingquantum sized RuS2 particles on the surface of TiO2 electrode extends the optical absorptionspectrum and photocurrent action specmim into visible region. In addition, compared with RuS2 bulknlaterials- a blue shifi in both absorption spectrum and photocurrent action speCtrum of RuS2rriO2elcctrode is obserived and explained in terms of quantum sized effect.

Photoelectrochemical Character of TiO_2 Nanocrystalline Electrodes Sensitized by Aluminum Phthalocyanines Modified with Sulfonate Groups

Particular kinds of TiO2 nanocrystalline electrodes were sensitized by aluminum phthalocyanines modified with sulfonate groups [ Al（OH） PcSm ]. It was found that in the red region, the electrodes show obvious photoelectrical responses. The surface photovoltage spectra and photocurrent action spectra indicate that in the red region, the monomers of aluminum phthalocyanines have a greater influence on the determination of the photoelectrical response of TiO2 electrodes than the dimers. The dye-sensitized solar cells were obtained by using the aluminum phthalocyaninessensitized TiO2 electrodes and Pt electrodes, which have an open circuit photovoltage of 360 mV, a short circuit photocurrent of 39. 4 μA/cm^2 , a fill factor of 0. 54 and a maximum power output of 7.65 μW/cm^2 under a light intensity of 50 mW/cm^2.

Photoelectric properties of thin Eu^(3+)-doped TiO_2 films sensitized by cis-RuL_2(SCN)_2·2H_2O

Thin nanocrystalline TiO2 films doped by europium ions (Eu3+) were obtained by the sol-gel method. The photoelectric properties of Eu3+-doped TiO2 film electrode sensitized by cis-RuL2(SCN)2·2H2O (L=cis-2,2′-bipyridine-4,4′-dicarboxlic acid) ruthenium complex were studied. The thin films were characterized by X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy. Effect of doping Eu3+ on microscopic structure and photoelectrical properties were discussed. The result shows that doping europium ions makes specific surface area of these films larger, which contributes to improving the photoelectric properties. It is found that an optimal composition doped with 0.2 mol.% Eu3+ exhibits the highest photoelectric properties. Isc is 0.37 mA·cm-2, which is 0.17 mA·cm-2 bigger than that of un-doped films; Voc is 405 mV, which is 50 mV bigger than that of un-doped films.

Efficiency Enhancement of Dye-Sensitized Solar Cells： Using Salt CuI as an Additive in an Ionic Liquid

Energy conversion efficiency of the dye-sensitized solar cell is improved from 3.5% to 4.5% by adding a small amount of CuI into an ionic liquid electrolyte. It is found that other copper-I salts, for example, CuBr, have the same effect for the dye-sensitized solar cell. Experimental results show that no Cu^2＋ ions exist in this electrolyte. It is suggested that this improvement is caused by the adsorption of Cu^＋ onto the TiO2 porous film.

Enhancement of Overall Photovoltaic Efficiency by Changing the Position of the Attaching Group-RSO3^-on the Hemicyanine Dye Molecules

A new photoresponsive D--A dye, mPS, has been designed and synthesized. Compared to the parent dye PS, IPCE values in the region from 400 nm to 560 nm was greatly improved upon changing the attaching group from the p- position to the o- position of the p-conjugation bridge. A solar cell based on mPS generated a remarkably high overall yield of 5.4% under irradiation of 80.0 mW cm-2 white light from a Xe lamp. Compared with PS, the overall yield ?increased by 64%.

Review on development of electrolytes for dye-sensitized solar cells

Since the prototype of a dye-sensitized solar cell(DSSC)was reported in 1991 by M. Gratzel,it has aroused intensive interest over the past decade due to its low cost and simple preparation procedure.The typical cell consists of a dye-coated mesoporous nanocrystalline TiO_2 film sandwiched between two transparent electroldes.A liquid electrolyte,traditionally containing the trioidide/iodide redox couple,fills the pores of the mesoporous nanocrystalline TiO_2 film and contacts the nanoparticles.Photoexcite...

Influence of Modification of Counter Electrode on PhotoelectricProperties of Dye-sensitized TiO_2 Solar Cells

A dye-sensitized nanocrystalline TiO 2 solar cell(DYSC) was assembled, of which counter electrode was modified already by platinum, nickel and carbon. It was found that the DYSC had better photoelectric performance when the electrode was modified by platinum than by nickel and carbon. The influence of the incidence light wavelength on the incidence monochromatic photoelectric conversion efficiency(IPCE) was investigated. The result shows that the IPCE mainly depends on the short-circuit current density(I SC) of a DYSC, and the IPCE reaches 48.32% under the irradiation with the wavelength of 560 nm when the counter electrode of a DYSC was modified by platinum. The influence of incident light intensity on the photoelectric properties of a DYSC was also investigated. It was found that the I SC and open-circuit voltage(V OC) increased and the fill factor(f f) of the DYSC decreased with the increase of the incident light intensity.

Electrochemical impedance spectra of CdSe quantume dots sensitized nanocrystalline TiO_2 solar cells

Quantum dots sensitized nanocrystalline Tit2 solar cells （QDSSCs） are promising third-generation pbotovoltalc devices. In comparison with conventional dye-sensitized solar cells （DSSCs）, the efficiency of QDSSCs is still very low （about 3%）. In this paper, the electrochemical impedance spectroscopy technology has been adopted to investigate the quasi-Fermi level and the cartier dynamics of the colloidal CdSe QDs sensitized Tit2 eletrode with S2-/Sf redox electrolytes and the series resistance of the QDSSCs. In comparison with the conventional DSSCs with I^-3/Г as redox electrolytes, the energy difference between the conduction band edge and the quasi-Fermi levels of the Tit2 films （or the Fermi levels of the redox electrolytes） in QDSSCs has been decreased by about 0.3 V, resulting in the decrease of Voc by this value. The increases of the electrolyte dif- fussion resistance and the charge transfer resistance between Pt counter electrodes and S2-/Sx redox electrolytes were attributed to the decrease of the fill factors. However, the electron lifetime and electron diffussion length for QDSSCs are longer than those for DSSCs due to the retardation of the electron recombination by the adsorbed cysteine at the surfaces of the TiO2 films. It is indicated that electron recombination at the TiO2/electrolyte interface is not the main reason for the lower Jsc of the colloidal QDs sensitized QDSSCs. Improving light harvesting efficiency and photoelectron injection efficiency should be considered in the future for such kind of QDSSCs.

Electrolytic Fixation of CO_2 by Electrocarboxylation of RX on Nanocrystalline TiO_2-Pt Cathode

Electrolytic fixation of CO2 was investigated by electrocarboxylation of organic halides (RX), and four esters (I, II, III, IV) were obtained in moderate yields. Electrochemical reduction esterifications of RX in the presence of CO2 were carried out on nanocrystalline TiO2-Pt electrode. The electrochemical behavior of RX in the presence of CO2 was investigated by the technique of cyclic voltammetry, and the probable reaction mechanism was proposed.

Nanocrystalline TiO_2-HClO_4:A novel,efficient and recyclable catalyst for the chemoselective N-Boc protection of amines under solvent-free conditions

Nanocrystalline TiO2-HClO4, as newly reported catalyst, has been used as an efficient and reusable catalyst for the chernoselective N-Boc protection of amines. The clean, mild acidity condition, quantitative yields of products, short reaction time and low reaction temperature are attractive features of this reaction. In practice, this method is a combination of a satisfactory synthesis and more significantlv easy 13roduct isolation and 13urification.