Direct Synthesis of Conformal Layered Protonated Titanate Nanoarray Coatings on Various Substrate Surfaces Boosted by Low-Temperature Microwave-Assisted Hydrothermal Synthesis.

Layered protonated titanates (LPTs) are promising support materials for catalytic applications because their high surface area and cation exchange capacity provide the possibility of achieving a high metal dispersion. However, the reported LPT nanomaterials are mainly limited to free-standing nanoparticles (NPs) and usually require high temperature and pressure conditions with extended reaction time. In this work, a high-throughput microwave-assisted hydrothermal method was developed for the direct synthesis of conformal LPT nanoarray coatings onto the three-dimensional honeycomb monoliths as well as other substrate surfaces at low temperature (75-95 °C) and pressure (1 atm). Using TiCl as the titanium source, HO as the oxidant, and hydrochloric acid as the pH controller, a peroxotitanium complex (PTC) was formed and identified to play an essential role for the formation of LPT nanoarrays. The gaseous O released during the decomposition of PTC promotes the mass transfer of the precursors, making this method applicable to substrates with complex geometries. With the optimized conditions, a growth rate of 42 nm/min was achieved on cordierite monolith substrates. When loaded with Pt NPs, the LPT nanoarray-based monolithic catalysts showed excellent low-temperature catalytic activity for CO and hydrocarbon oxidation as well as satisfactory hydrothermal stability and mechanical robustness. The low temperature and pressure requirements of this facile hydrothermal method overcome the size- and pressure-seal restrictions of the reactors, making it feasible for scaled production of LPT nanoarray-based devices for various applications.