KCl flux-induced growth of isometric crystals of cadmium-containing early transition-metal (Ti4+, Nb5+, and Ta5+) oxides and nitridability to form their (oxy)nitride derivatives under an NH3 atmosphere for water splitting application

In this study, we have attempted to experimentally validate the results of previous theoretical calculations predicting the possible formation of the CdTiO3-xNy, CdNbO2N, and CdTaO2N phases by applying conventional one- and two-step fabrication methods under an NH3 flow. For the two-step method, CdTiO3, Cd2Nb2O2, and Cd2Ta2O7 crystals were first grown by a KCl flux method, and the effects of solute concentration and cooling rate on the crystal growth were studied. The formability of their (oxy)nitride derivatives was investigated by changing the nitridation temperature (750-950 degrees C) and time (1-10 h) of oxide precursors. It was found that the CdTiO3-xNy, CdNbO2N, and CdTaO2N phases cannot be formed by the applied conventional methods due to the low volatilization temperature of cadmium and the susceptibility of titanium and niobium to reduction under an NH3 atmosphere. Under high-temperature NH3 atmosphere, only Cd2Ta2O2 was fully converted to single-phase Ta3N5. The results from the photocatalytic O-2 evolution test of bare and CoOx-loaded Ta3N5 crystalline structures, converted from Cd2Ta2O2 (Cd-Ta3N5) and Na2CO3-treated Ta2O3 (Na-Ta3N5) and Cd2Ta2O2 (Na-Cd-Ta3N5) crystals by nitridation at 850 degrees C for 20h under an NH3 flow, revealed that the CoOx-loaded Ta3N5 showed more than two times higher O-2 evolution rate (655 mu mol), whereas the CoOx-loaded Cd-Ta3N5 and Na-Cd-Ta3N5 exhibited nearly four (501 mu mol) and three (422 mu mol) times higher O-2 evolution rates at 5 h compared with their bare counterparts. An improved photocatalytic activity for O-2 evolution is related to the higher density of nucleation centers of CoOx nanoparticles in the form of dangling bonds in porous Ta3N5 structures and long-lived photogenerated holes, as attested by time-resolved absorption spectroscopy. (C) 2015 Elsevier B.V. All rights reserved.