Facile Synthesis of Novel CaIn₂S₄/ZnIn₂S₄ Composites with Efficient Performance for Photocatalytic Reduction of Cr(VI) under Simulated Sunlight Irradiation.

A series of novel and efficient heterostructured composites CaIn₂S₄/ZnIn₂S₄ have been synthesized using a facile hydrothermal method. XRD patterns indicate the as-prepared catalysts are two-phase composites of cubic phase CaIn₂S₄ and hexagonal phase ZnIn₂S₄. FESEM (field emission scanning electron microscope) images display that the synthesized composites are composed of flower-like microspheres with wide diameter distribution. UV⁻Vis diffuse reflectance spectra (DRS) show that the optical absorption edges of the CaIn₂S₄/ZnIn₂S₄ composites shift toward longer wavelengths with the increase of the CaIn₂S₄ component. The photocatalytic activities of the as-synthesized composites are investigated by using the aqueous-phase Cr(VI) reduction under simulated sunlight irradiation. This is the first report on the application of the CaIn₂S₄/ZnIn₂S₄ composites as stable and efficient photocatalysts for the Cr(VI) reduction. The fabricated CaIn₂S₄/ZnIn₂S₄ composites possess higher photocatalytic performance in comparison with pristine CaIn₂S₄ or ZnIn₂S₄. The CaIn₂S₄/ZnIn₂S₄ composite with a CaIn₂S₄ molar content of 30% exhibits the optimum photocatalytic activity. The primary reason for the significantly enhanced photoreduction activity is proved to be the substantially improved separation efficiency of photogenerated electrons/holes caused by forming the CaIn₂S₄/ZnIn₂S₄ heterostructured composites. The efficient charge separation can be evidenced by steady-state photoluminescence spectra (PLs) and transient photocurrent response. Based on the charge transfer between CaIn₂S₄ and ZnIn₂S₄, an enhancement mechanism of photocatalytic activity and stability for the Cr(VI) reduction is proposed.