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Ir(III)-PC(sp3)P Bifunctional Catalysts for Production of H2 by Dehydrogenation of Formic Acid: Experimental and Theoretical Study
ACS Catalysis ( IF 11.3 ) Pub Date : 2017-10-31 00:00:00 , DOI: 10.1021/acscatal.7b02482
Shirel Cohen 1 , Veniamin Borin 2 , Igor Schapiro 2 , Sanaa Musa 1 , Sophie De-Botton 1 , Natalia V. Belkova 3 , Dmitri Gelman 1
Affiliation  

Reversible storage of hydrogen in the form of stable and relatively harmless chemical substances such as formic acid (FA) is one of the cornerstones of a fossil-fuel-free economy. Recently, Ru(III)-PC(sp3)P (where PC(sp3)P = modular dibenzobarrelene-based pincer ligand possessing a pendant functional group) complex 1 has been reported as a mild and E-selective catalyst in semihydrogenation of alkynes with stoichiometric neat formic acid. Discovery of the additive-free protocol for dehydrogenation of FA launched further studies aiming at the rational design of highly efficient catalysts for this reaction operating under neutral conditions. We now report the results of our investigation on a series of bifunctionl PC(sp3)P complexes equipped with different outer-sphere auxiliaries, that allowed us to identify an amine-functionalized Ir(III)-PC(sp3)P complex 3, as a clean and efficient catalyst for the FA dehydrogenation. The catalyst is suitable for fuel-cell applications demonstrating a TON up to 5 × 105 and TOF up to 2 × 104 h–1 (3.8 × 105 and 1.2 × 104 h–1 with no additives). In addition to the practical value of the catalyst, experimental and computational mechanistic studies provide rationale for the design of improved next-generation catalysts.

中文翻译:

通过甲酸脱氢生产H 2的Ir(III)-PC(sp 3)P双功能催化剂:实验和理论研究

以稳定且相对无害的化学物质(例如甲酸(FA))形式可逆地存储氢是无化石燃料经济的基础之一。最近,据报道Ru(III)-PC(sp 3)P(其中PC(sp 3)P =具有侧基官能团的基于模块化二苯并barrelene的钳式配体)配合物1是一种温和的E-选择性催化剂,可用于半加氢精制。化学计量纯甲酸的炔烃。FA脱氢的无添加剂方案的发现启动了进一步研究,旨在合理设计高效催化剂,以在中性条件下进行该反应。现在,我们报告一系列双功能PC(sp 3)的调查结果。)P配合物配有不同的外层助剂,使我们能够确定胺官能化的Ir(III)-PC(sp 3)P配合物3,作为一种清洁高效的FA脱氢催化剂。该催化剂适用于燃料电池应用,其TON最高可达5×10 5,TOF最高可达2×10 4 h –1(无添加剂的3.8×10 5和1.2×10 4 h –1)。除了催化剂的实用价值之外,实验和计算机理研究还为改进的下一代催化剂的设计提供了理论依据。
更新日期:2017-10-31
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