Defects and morphology engineering for constructing V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S nanotube heterojunction arrays toward efficient bifunctional electrocatalyst for overall water splitting

The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube heterojunction arrays were in-situ grown on copper foam(V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF)for efficient electrocatalytic overall water splitting.With the merits of nanotube arrays and efficient electronic mod-ulation drived by the OD vacancy defect and 2D heterojunction defect,the resultant V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF electrocatalyst exhibits excellent electrocatalytic activity with a low overpotential of 47 mV for the hydrogen evolution reaction(HER)at 10 mA cm^(-2) current density,and 263 mV for the oxygen evolution reaction(OER)at 50 mA cm^(-2) current density,as well as a cell voltage of 1.48 V at 10 mA cm^(-2).Moreover,the nanotube heterojunction arrays endows V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF with outstanding stability in long-term catalytic processes,as confirmed by the continuous chronopotentiom-etry tests at current densities of 10 mA cm^(-2) for 100 h.

Fabrication of quantum-sized Cd S-coated Ti O2 nanotube array with efficient photoelectrochemical performance using modified successive ionic layer absorption and reaction(SILAR) method

Quantum-sized CdS-coated TiO2 nanotube array （Q-CdS-TiO2 NTA） was fabricated by the modified successive ionic layer absorption and reaction method. Scanning electron microscope and transmission electron microscope images showed the regular structure of TiO2 NTA, where quantum-sized CdS （diameter 〈10nm） deposited on both the inside and outside of TiO2 nanotube wall. Fabrication conditions including immersing cycles, calcination temperature and drying process were well optimized, and the Q-CdS-TiO2 NTA and its photoelectrochemical （PEC） properties were characterized by X-ray fluorescence spectrometer, UV-Vis diffuse reflectance spectra and photovoltage. Distinct increases in visible light absorption and photocurrent were observed as the immersing cycle was increased from 5 to 20 times. The additional drying process accelerated the CdS crystal growth rate, and thus, the fabrication time could be shortened accordingly. Calcination temperature influenced the PEC property of Q-CdS-TiO2 NTA deeply, and the optimized calcination temperature was found as 500 ℃. As the Q-CdS-TiO2 NTA was fabricated under such condition, the visible photocurrent density increased to 2.8 mA/cm and the photovoltage between 350 and 480 nm was enhanced by 2.33 times than that without calcination. This study is expected to optimize Q-CdS-TiO2 NTA fabrication conditions for the purpose of improving its PEC performance.