One-Pot Synthesis of Hexamethylenetetramine Coupled with H 2 Evolution from Methanol and Ammonia by a Pt/TiO 2 Nanophotocatalyst.

Utilization of solar energy for photocatalytic H 2 evolution coupled with value-added chemical synthesis is a promising avenue to address energy and environmental crises. Here, we report the hexamethylenetetramine (HMT) synthesis and H 2 evolution from methanol and ammonia in one pot using a nanophotocatalyst of the conventional semiconductor TiO 2 (P25) loaded with Pt (Pt/P25). The addition of ammonia inhibits byproduct ethylene glycol formation, promotes H 2 evolution, and obtains HMT with high selectivity (>99.0%). The Pt valence state is regulated by calcination and reduction treatment, indicating that Pt/P25 is a stable catalyst for the photocatalytic synthesis of HMT from methanol and ammonia. The optimized formation rates of H 2 and HMT are 71.53 and 11.39 mmol g cat -1 h -1 , respectively. This work provides a green and sustainable pathway for the photocatalytic HMT synthesis coupled with H 2 evolution under mild conditions.