Ruthenium Complex Hydride Catalysts as a Platform for Ammonia Synthesis

Abstract

Mild-condition ammonia synthesis from N2 and H2 is a long-sought-after scientific goal and a practical need, especially for the intensively pursued “Green Ammonia” production using renewable H2. Under this context, there have been growing interests in the development of new catalysts for effectively catalyzing N2+H2 to NH3. Particular attention has been given to Ru-based catalysts because they are well known to be more active at lower temperatures and pressures than non-noble-metal based catalysts. Here, we demonstrate that a series of Ru complex hydrides An[RuHm], where A is alkali or alkaline earth metal, n= 2, 3 or 4 and m = 6 or 7, exhibit universal and high catalytic activities that far exceed the benchmark Ru metal catalysts under mild conditions. Detailed investigations on the ternary Ru complex hydride catalytic system disclose that the kinetic behaviors depend strongly on the identity of alkali or alkaline earth metal cations. In clear contrast to the closed packed Ru metal catalyst, the unique configuration and synergized scenario of the Ru complex hydride center prefer a non-dissociative mechanism for N2 activation and hydrogenation, which provides a new platform for the design and development of efficient NH3 synthesis catalysts.