Photo-Current Enhancement in Carbon Quantum Dots Functionalized Titania Nanotube Arrays.

Highly aligned, vertically oriented, TiO2 nanotube arrays fabricated by electrochemical anodization were functionalised by carbon quantum dots (CQD) synthesized by an electrochemical reduction technique. Here, we report the photo-electrochemical properties of such TiO2 nanotubes array-CQD composite material and it has been found that the properties are significantly enhanced compared to that in pristine (bare) nanotubes. The TiO2 nanotubes were characterized by X-ray diffraction and scanning electron microscopy, whereas the CQD samples were characterized by transmission electron microscopy, optical absorption spectroscopy. CQDs synthesized under two different conditions showed a distinct size difference and corresponding absorption spectra revealed concominant shift in the absorption edges. Furthermore, the photo-electrochemical measurements were carried out with the help of photo-current, incident photon to current conversion efficiency (IPCE), Mott-Schottky plots and the impedance analysis. The photo-current data revealed 30% improvement in TiO2-CQD samples compared to bare TiO2 nanotubes samples. A higher photo-conversion efficiency was observed along with the shifting of the peak value towards visible wavelengths. The Mott-Schottky plots revealed shift in the flat-band potential in the CQD-TiO2 samples and corresponding lowering of the charge transfer resistance was observed through the impedance spectroscopy.

Stable hydrogen generation from Ni- and Co-based co-catalysts in supported CdS PEC cell.

To improve the limited efficiency and stability of CdS photoanodes in a photoelectrochemical (PEC) cell, the nanostructured CdS photoanode was modified with Ni(OH)2, NiO, Co(OH)2, and Co3O4 water-oxidation-nano co-catalysts (WOC). Co(OH)2 nanorice and Ni(OH)2 nanosheet co-catalysts were obtained by a simple chemical precipitation method. Modification by the co-catalysts gives longer stability (>8 h) to CdS electrodes, and facilitates impulsive H2 evolution in PEC cells. Nano-NiO modification yields a two-fold increase in photocurrent density and the highest H2 evolution of 2.5 mmol h(-1). A dual role for Ni related co-catalysts over CdS surface, that is forming a p-n junction and acting as an effective co-catalyst, improves the photocurrent and hydrogen evolution rate, respectively. Improvement in stability was measured using X-ray photoelectron spectroscopy and prolong chronoamperometry measurements. The present report focuses on exploration of chemically synthesized earth-abundant and cost-effective co-catalysts for PEC H2 generation.

Nanoniobia modification of CdS photoanode for an efficient and stable photoelectrochemical cell.

Herein we report the surface modification of a CdS film by niobia nanoparticles via thioglycerol as an organic linker and thus fabricate an efficient and a stable photoanode for a photoelectrochemical (PEC) cell. We have synthesized three differenly sized (∼3, ∼6 ,and ∼9 nm) niobia nanoparticles by a hydrothermal synthesis approach and have further investigated the particle-size-dependent PEC performance of the nanoparticle-modified CdS photoanode. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirm the formation of Nb2O5 nanoparticles that are prepared via decomposition of the niobium peroxo complex during the hydrothermal reaction and reveal the presence of surface OH(-) groups over niobia nanoparticles that impart a high catalytic property to a material. The nano-Nb2O5-modified photoanode displayed a 23-fold higher power conversion efficiency compared to that of CdS. This modified structure increases the open circuit voltage (OCV) from 0.65 to 0.77 V, which is attributed to the nano-Nb2O5-induced surface passivation effect over bare CdS. Linking of nanoparticles on the CdS surface improves the photocorrosion stability of the CdS photoanode for even longer than 4 h in contrast to the tens of minutes for the base CdS surface. The uniform coverage of the CdS photoanode surface by niobia nanoparticles is thus found to be the controlling parameter for achieving a higher PEC performance and stability of the photoanode. This finding directed us to design an improved CdS photoanode for efficient and prolonged PEC hydrogen generation from a PEC cell.