A Room-Temperature Reactive-Template Route to Mesoporous ZnGa2O4 with Improved Photocatalytic Activity in Reduction of CO2

TLDR: A novel direct method for preparing mesoporous ZnGa2O4 with a wormhole framework by an ion-exchange reaction at room temperature involving a mesoborous NaGaO2 colloid precursor is reported, which provides a means to overcome the problems associated with synthesizing multimetal Mesoporous materials.

Abstract: Mesoporous materials are of scientific and technological interest due to their potential applications in various areas. Over the past two decades, significant effort has been devoted to the synthesis of mesoporous materials. For instance, mesoporous silica and phosphate metal oxides have been synthesized and applied widely in many industrial processes. However, little progress has been made in the synthesis of mesoporous metal oxides containing more than one type of metal. To date, a limited number of routes including evaporation-induced self-assembly (EISA) and nonaqueous solvent methods have been developed to synthesize multimetallic mesoporous materials such as Pb3Nb4O13, [3] Bi20TiO32, [4] SrTiO3, MgTa2O6, CoxTi1 xO2 x, [5] and Ce1 xZrxO2. [6] In these routes, introducing surfactant molecules or a template is a general method used to construct the mesostructures. Challenges in using the template method to synthesize multimetallic mesoporous materials are uncontrolled phase separation in the multicomponent reactions and poor thermal and chemical stability of the resulting mesoporous structure. Maintaining the complete mesostructure during removal of the template by heating or chemical treatment is a key process for obtaining the expected mesostructures, and increases the uncertainty in a given synthetic route. In addition, to obtain a crystalline mesoporous material, high-temperature heat treatment is usually required for crystallization of the product. However, this process probably induces collapse of mesostructures. Recently, we developed a synthetic route to mesoporous multimetal oxides that uses the inorganic starting reactants directly as pore makers which aid in building the mesoporous structures of multimetal oxides and improve the thermal stability of the resulting mesostructure. However, in these reported synthetic routes, postcrystallization and introducing or removing an exotemplate are usually needed. In recent years, a route that does not require template removal, which was named “reactive hard templating”, was developed to synthesize porous TiN/carbon composite materials. In this route, the template consists of nanostructures of porous graphitic C3N4, which thermally decomposes completely during formation of porous TiN. This route provides a means to overcome the problems associated with synthesizing multimetal mesoporous materials. A simplified soft-chemistry route based on a reactive template is expected to allow synthesis to proceed at room temperature without requiring the introduction or removal of a template. Here we report a novel direct method for preparing mesoporous ZnGa2O4 with a wormhole framework by an ion-exchange reaction at room temperature involving a mesoporous NaGaO2 colloid precursor. The method does not require any additional processes and can be extended to prepare other porous materials, such as CoGa2O4 and NiGa2O4. The X-ray diffraction (XRD) pattern of NaGaO2 powder, which can be indexed as the orthorhombic phase (JCPDS 762151), is presented in Figure 1. Scanning electron microscopy (SEM) revealed that the powder particles are irregular in shape with little agglomeration, and most of the particles are larger than 500 nm in diameter (see Supporting Information). The as-prepared NaGaO2 powder can be dispersed in water to form a suspension. When the NaGaO2 suspension is illuminated with a 532 nm laser, a Tyndall effect is observed, that is, the suspension behaves as a colloid (see Supporting Information). Multimodal measurements of particle size distribution by dynamic light scattering show that the NaGaO2 colloidal particles exhibit two peak distributions: 20 % of the particles have an average size of 70 nm, and 80 % an average size of 335 nm. Most particulate or macroscopic materials in contact with a liquid acquire an electric charge on their surfaces. The zeta potential is an important and useful indicator of this charge that can be used to predict the stability of colloidal suspensions. The zeta potential of NaGaO2 colloidal particles is 21.57 mV (pH 6). This is lower than the critical zeta potential of 30 mV for maintaining colloid stability in an aqueous system, that is, the colloidal particles are slightly [*] S. C. Yan, J. Gao, M. Yang, X. X. Fan, L. J. Wan, Prof. Y. Zhou, Prof. Z. G. Zou Ecomaterials and Renewable Energy Research Center National Laboratory of Solid State Microstructures, Nanjing University, 22 Hankou Road, Nanjing 210093 (China) E-mail: zgzou@nju.edu.cn