A Use-Store-Reuse (USR) Concept in Catalytic HCOOH Dehydrogenation: Case-Study of a Ru-Based Catalytic System for Long-Term USR under Ambient O2

Commercial use of H2 production catalysts requires a repeated use/stop/store and reuse of the catalyst. Ideally, this cycle should be possible under ambient O2. Herein we exemplify the concept of Use-Store-Reuse (USR) of a (Ru-phosphine) catalyst in a biphasic catalytic system, for H2 production via dehydrogenation of HCOOH. The catalytic system can operate uninterrupted for at least four weeks, including storage and reuse cycles, with negligible loss of its catalytic efficiency. The catalytic system consisted of a RuP(CH2CH2PPh2)3 (i.e. RuPP3) in (tri-glyme/water) system, using KOH as a cocatalyst, to promote HCOOH deprotonation. In a USR cycle of 1 week, followed by storage for three weeks under ambient air and reuse, the system achieved in total TONs > 90,000 and TOFs > 4000 h−1. Thus, for the first time, a USR concept with a readily available stable ruthenium catalyst is presented, operating without any protection from O2 or light, and able to retain its catalytic performance.