Key factors affecting photoelectrochemical performance of g-C3N4 polymer films.

We investigated the relationship between crystallinity, deep trap states and PEC performance of g-C3N4 photoelectrodes. Long-lived charge carriers were present in the more poorly crystalline samples, due to deeper trap states, which inversely correlated with photoelectrochemical performance. The charge diffusion length in a compact g-C3N4 film was determined to be ca. 1000 nm.

Spin Selective Charge Transport through Cysteine Capped CdSe Quantum Dots.

This work demonstrates that chiral imprinted CdSe quantum dots (QDs) can act as spin selective filters for charge transport. The spin filtering properties of chiral nanoparticles were investigated by magnetic conductive-probe atomic force microscopy (mCP-AFM) measurements and magnetoresistance measurements. The mCP-AFM measurements show that the chirality of the quantum dots and the magnetic orientation of the tip affect the current-voltage curves. Similarly, magnetoresistance measurements demonstrate that the electrical transport through films of chiral quantum dots correlates with the chiroptical properties of the QD. The spin filtering properties of chiral quantum dots may prove useful in future applications, for example, photovoltaics, spintronics, and other spin-driven devices.

Helicenes--A New Class of Organic Spin Filter.

Chiral helicene, a fully conjugated system without stereogenic carbon, can filter spins effectively at room temperature, a consequence of the chiral-induced spin-selectivity effect. The chirality dictates the spin of the electrons transferred through helicene, and magnetoresistance devices based on these molecules show antisymmetric magnetoresistance versus H plots.

Role of the Electron Spin Polarization in Water Splitting.

We show that in an electrochemical cell, in which the photoanode is coated with chiral molecules, the overpotential required for hydrogen production drops remarkably, as compared with cells containing achiral molecules. The hydrogen evolution efficiency is studied comparing seven different organic molecules, three chiral and four achiral. We propose that the spin specificity of electrons transferred through chiral molecules is the origin of a more efficient oxidation process in which oxygen is formed in its triplet ground state. The new observations are consistent with recent theoretical works pointing to the importance of spin alignment in the water-splitting process.

New one-step thiol functionalization procedure for Ni by self-assembled monolayers.

This article reports on a facile and fast strategy for the self-assembled monolayer (SAM) functionalization of nickel surfaces, employing cyclic voltammetry (CV) cycling of a suitable tailored solution containing the species to be adsorbed. Results are presented for ultrathin films formed on Ni by 1-hexadecanethiol (C16), L-cysteine (L-cys), and the poly{methyl (2R)-3-(2,2'-bithiophen-4-ylsulfanyl)-2-[(tert-butoxycarbonyl)amino]propanoate} (PCT-L) thiophene-based chiral polymer. The effective formation of high-quality ultrathin organic films on the nickel was verified both electrochemically and by exploiting typical surface characterization techniques such as contact angle, ellipsometry, atomic force microscopy (AFM), polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS).

Active guests in the MoS2/MoSe2 host lattice: efficient hydrogen evolution using few-layer alloys of MoS(2(1-x))Se(2x).

Few-layer transition metal dichalcogenide alloys based on molybdenum sulphoselenides [MoS2(1-x)Se2x] possess higher hydrogen evolution (HER) activity compared to pristine few-layer MoS2 and MoSe2. Variation of the sulphur or selenium content in the parent dichalcogenides reveals a systematic structure-activity relationship for different compositions of alloys, and it is found that the composition MoS1.0Se1.0 shows the highest HER activity amongst the catalysts studied. The tunable electronic structure of MoS2/MoSe2 upon Se/S incorporation probably assists in the realization of high HER activity.

Few-layer borocarbonitride nanosheets: platinum-free catalyst for the oxygen reduction reaction.

The present study demonstrates the use of few-layer borocarbonitride nanosheets synthesized by a simple method as non-platinum cathode catalysts for the oxygen reduction reaction (ORR) in alkaline medium. Composition-dependent ORR activity is observed and the best performance was found when the composition was carbon-rich. Mechanistic aspects reveal that ORR follows the 4 e(-) pathway with kinetic parameters comparable to those of the commercial Pt/C catalyst. Excellent methanol tolerance is observed with the BCN nanosheets unlike with Pt/C.

Facile synthesis of carbon doped TiO2 nanowires without an external carbon source and their opto-electronic properties.

The present study demonstrates a simple protocol for the preparation of one dimensional (1D) oxidized titanium carbide nanowires and their opto-electronic properties. The oxidized titanium carbide nanowires (Ox-TiC-NW) are prepared from TiC nanowires (TiC-NW) that are in turn synthesized from micron sized TiC particles using the solvothermal technique. The Ox-TiC-NW is characterized by X-ray diffraction, UV-Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectroscopy. Thermal oxidation of TiC-NW yields carbon doped TiO2-NW (C-TiO2-NW), a simple methodology to obtain 1D C-TiO2-NW. Temperature dependent Raman spectra reveal characteristic bands for TiO2-NW. Electrical characterization of individual C-TiO2-NW is performed by fabricating a device structure using the focused ion beam deposition technique. The opto-electronic properties of individual C-TiO2-NW demonstrate visible light activity and the parameters obtained from photoconductivity measurements reveal very good sensitivity. This methodology opens up the possibility of using C-TiO2-NW in electronic and opto-electronic device applications.

Morphology dependent oxygen reduction activity of titanium carbide: bulk vs. nanowires.

Titanium carbide (TiC) possesses fascinating properties like high electrical conductivity and high mechanical strength coupled with high corrosion resistance and stability in acidic and alkaline environments. The present study demonstrates the tunability of mechanistic aspects of oxygen reduction reaction (ORR) using TiC nanostructures. One dimensional TiC nanostructures (TiC-NW) have been synthesized using a simple, hydrothermal method and used as a catalyst for ORR. Shape dependent electroactivity is demonstrated by comparing the activity of TiC-NW with its bulk counterparts. Comparative studies reveal higher ORR activities in the case of 1D TiC-NW involving ~4 electrons showing efficient reduction of molecular oxygen. Excellent stability and high methanol tolerance with good selectivity for ORR is reported.

Enhanced Raman spectroscopy of molecules adsorbed on carbon-doped TiO2 obtained from titanium carbide: a visible-light-assisted renewable substrate.

Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO(2) (C-TiO(2)) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO(2) substrates are synthesized by varying experimental conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction, and X-ray photoelectron spectroscopic techniques. C-TiO(2) in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO(2), improves the intensities of Raman signals, compared to undoped TiO(2). Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO(2) is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn, triggers charge transfer between TiO(2) and analyte. The C-TiO(2) substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h.