Catalytic Ru- or Fe-complexes bearing two ligands L1, L2, where L1 = phosphine and L2 = Schiff-base ligand, present remarkable H₂ production efficiency from Formic Acid (FA) than their single-ligand counterparts. The optimum L1RuL2 and L1FeL2 catalysts were obtained using a phosphine = P(CH₂CH₂PPh₂)₃ (or PP₃) as L1 and a Schiff-base ligand (abbreviated L_γ herein) as L2, while the using of amino functionalized nanoparticle H₂N@SiO₂ as cocatalyst further promotes the H₂ production efficiency. In long term stability experiments [RuPP₃L_γ]/H₂N@SiO₂ and [FePP₃L_γ]/H₂N@SiO₂ achieve a total TONs >17,367 and >29,372 respectively without deactivation. Thermodynamic and spectroscopic data reveal a common catalytic mechanism for both Fe and Ru based systems, involving synergism between L1, L2 in order to promote the rate-limiting steps. The present work is the first example of “double-ligand catalyst” concept as a novel route for high-efficiency, HCOOH dehydrogenation catalysts, which can be operative for either noble-metal or earth-abundant metals.

带有两个配体L1，L2（其中L1 =膦和L2 = Schiff碱配体）的催化Ru-或Fe复合物，与单配体相比，甲酸（FA）的H ₂生产效率显着提高。使用膦= P（CH得到最佳L1RuL2和L1FeL2催化剂₂ CH ₂ P博士₂）₃（或PP ₃）作为L1和席夫碱配体（简写大号_γ本文中）为L2，而使用氨基的功能化的纳米颗粒H ₂ N @ SiO ₂作为助催化剂进一步提高了H _2的生产效率。在长期稳定性实验中[RuPP ₃ L_γ ] / H ₂ N - [的SiO ₂和[FePP ₃大号_γ ] / H ₂ N - [的SiO ₂共实现吨> 17367和分别> 29372无失活。热力学和光谱数据揭示了基于Fe和Ru的系统的共同催化机理，涉及L1，L2之间的协同作用以促进限速步骤。目前的工作是“双配体催化剂”概念的第一个实例，它是高效的HCOOH脱氢催化剂的新颖途径，可用于贵金属或富稀土金属。