Efficient Photoelectrochemical Water Splitting over Anodized <i>p</i>‑Type NiO Porous Films

NiO photocathodes were fabricated by alkaline etching-anodizing nickel foil in an organic-based electrolyte. The resulting films have a highly macroporous surface structure due to rapid dissolution of the oxide layer as it is formed during the anodization process. We are able to control the films’ surface structures by varying the anodization duration and voltage. With an onset potential of +0.53 V versus the reversible hydrogen electrode (RHE), the photocurrent efficiency of the NiO electrodes showed dependencies on their surface roughness factor, which determines the extent of semiconductor-electrolyte interface and the associated quality of the NiO surface sites. A maximum incident photon-to-current conversion efficiency (IPCE_max) of 22% was obtained from NiO film with a roughness factor of 8.4. Adding an Al₂O₃ blocking layer minimizes surface charge recombination on the NiO and hence increased the IPCE_max to 28%. The NiO/Al₂O₃ films were extremely stable during photoelectrochemical water splitting tests lasting up to 20 h, continuously producing hydrogen and oxygen in the stoichiometric 2:1 ratio. The NiO/Al₂O₃ and NiO films fabricated using the alkaline anodization process produced 12 and 6 times as much hydrogen, respectively, as those fabricated using commercial NiO nanoparticles

Investigation of the Exchange Kinetics and Surface Recovery of Cd_<i>x</i>Hg_1–<i>x</i>Te Quantum Dots during Cation Exchange Using a Microfluidic Flow Reactor

Detailed analyses of coupled photoluminescence, emission lifetime, and absorption measurements have been made on the products of cation exchange reactions between CdTe nanocrystals and Hg²⁺ salt/ligand solutions in a microfluidic flow reactor and capillary measurement cell to probe the reaction kinetics over the seconds to hours time scale and to establish the influence of the reaction conditions on the spatial distribution of the mixed cations within the resulting Cd_<i>x</i>Hg_1–<i>x</i>Te colloidal quantum dots. The establishment of the evolution of the radiative and nonradiative rates allowed the recovery of the emission quantum yield in Cd_<i>x</i>Hg_1–<i>x</i>Te quantum dots to be quantified to almost 50% and the necessary time scales to be determined for each set of reaction conditions. The reaction kinetics showed clear indication of a fast surface exchange process followed by a slower internal rearrangement of the cation distribution