Promotion effect of Ga3+ in ZnAlGa-x mixed oxides obtained from their layered double hydroxides on the enhancement in the transient photocurrent response, the inhibition in the recombination rate of photogenerated (e−, h+) charges and the photocatalytic activity in the photodegradation of 4-chlorophenol

Abstract

ZnAlGa-x (x = 0, 0.5, 0.8, 1.0, 2.0 and 3.0 mol % of Ga3+) mixed oxides (MOs) obtained by calcination of their corresponding layered double hydroxides (LDHs) were characterized and evaluated in the photodegradation of 4-chlorophenol in aqueous media (4-CP) using UV light irradiation. Structural studies by X-ray diffraction (XRD) of ZnAlGa-x MOs indicated that the incorporation of a small molar concentration of Ga3+ (0.5–0.8 mol %) within the ZnAl LDH structure changed the micro-crystalline structure to an amorphous structure. A small molar content of Ga3+ in the ZnAlGa3+ MOx promotes the formation of a high amount of structural oxygen vacancies as evidenced by Raman and EPR spectroscopy studies. Transient photocurrent response (TPC) and fluorescence spectroscopy experiments reveal that the incorporation of a small molar concentration of Ga3+ in the structure of ZnAl MO promotes the enhancement in the transient photocurrent response, the separation of photogenerated charges and the inhibition of the recombination rate of (e−, h+) pairs. Furthermore, ZnAlGa-x MOs with a small molar concentration of Ga3+ reduced their band gap energies below of 3.0 eV. ZnAl MO photodegradated 69.0 % of 4-CP after 4 h of reaction. However, the photoconversion % of 4-CP increased to 80–90 % at 3 h of reaction using ZnAlGa-x MOs with a small molar concentration of Ga3+. ZnAlGa-x with small Ga3+ concentration mineralized approximately 70–75 % of total disolved organic carbon at 3 h of reaction. The photocatalytic degradation reaction of 4-CP fitted well to a pseudo-first order kinetics of Langmuir-Hinshelwood-type. The kinetic parameters of ZnAlGa-x MOs confirmed that ZnAlGa-0.8 MO was the best photocatalyst to photodegradate 4-CP in aqueous media. The highest photocatalytic activity and efficacy of ZnAlGa-0.8 MO to mineralize 4-CP in aqueous medium may be due to its higher amount of oxygen vacancies contained in its structure promoting a better separation of charges and the inhibition of the recombination rate of photogenerated (e−, h+) charges.