Synthesis of Nanoporous Metals, Oxides, Carbides, and Sulfides: Beyond Nanocasting

Abstract

Nanoporous metal-based solids are of particular interest because they combine a large quantity of surface metal sites, interconnected porous networks, and nanosized crystalline walls, thus exhibiting unique physical and chemical properties compared to other nanostructures and bulk counterparts. Among all of the synthetic approaches, nanocasting has proven to be a highly effective method for the syntheses of metal oxides with three-dimensionally ordered porous structures and crystalline walls. A typical procedure involves a thermal annealing process of a porous silica template filled with an inorganic precursor (often a metal nitrate salt), which converts the precursor into a desired phase within the silica pores. The final step is the selective removal of the silica template in either a strong base or a hydrofluoric acid solution. In the past decade, nanocasting has become a popular synthetic approach and has enabled the syntheses of a variety of nanoporous metal oxides. However, there is still a lack of synthetic methods to fabricate nanoporous materials beyond simple metal oxides. Therefore, the development of new synthetic strategies beyond nanocasting has become an important direction. This Account describes new progress in the preparation of novel nanoporous metal-based solids for heterogeneous catalysis. The discussion begins with a method called dealloying, an effective method to synthesize nanoporous metals. The starting material is a metallic alloy containing two or more elements followed by a selective chemical or electrochemical leaching process that removes one of the preferential elements, resulting in a highly porous structure. Nanoporous metals, such as Cu, Ag, and CuTi, exhibit remarkable electrocatalytic properties in carbon dioxide reduction, oxygen reduction, and hydrogen evolution reactions. In addition, the syntheses of metal oxides with hierarchical porous structures are also discussed. On the basis of the choice of hard template, nanoporous metal oxides with bimodal pore size distributions can be obtained. Combining nanocasting with chemical etching, a cobalt oxide with a hierarchical porous structure was synthesized, which possessed a surface area up to 250 m(2) g(-1), representing the highest surface area reported to date for nanoporous cobalt oxides. Lastly, this Account also covers the syntheses of nanoporous metal carbides and sulfides. The combination of in situ carburization and nanocasting enabled the syntheses of two ordered nanoporous metal carbides, Mo2C and W2C. For nanoporous metal sulfides, an "oxide-to-sulfide" synthetic strategy was proposed to address the large volume change issue of converting metal nitrate precursors to metal sulfide products in nanocasting. The successful syntheses of ordered nanoporous FeS2, CoS2, and NiS2 demonstrated the feasibility of the "oxide-to-sulfide" method. Concluding remarks include a summary of recent advances in the syntheses of nanoporous metal-based solids and a brief discussion of future opportunities in the hope of stimulating new interests and ideas.