Lawrence Elliot J, Oganesyan Vasily S, Hughes David L, Ashley Andrew E, Wildgoose Gregory G
School of Chemistry, University of East Anglia , Norwich Research Park, Norwich, NR4 7TJ, United Kingdom.
J Am Chem Soc. 2014 Apr 23;136(16):6031-6. doi: 10.1021/ja500477g. Epub 2014 Apr 10.
Frustrated Lewis pairs have found many applications in the heterolytic activation of H2 and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H2 can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H2 oxidation by 610 mV (117.7 kJ mol(-1)). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology.
受阻路易斯酸碱对已在氢气的异裂活化以及随后通过传递生成的质子和氢化物等价物对小分子进行氢化反应中得到了许多应用。在此，我们描述了如何使用经典的受阻路易斯酸碱对化学方法对氢气进行预活化，并将其与所得硼氢化物的非水原位电化学氧化相结合。我们的方法能够使氢气原位干净地转化为两个质子和两个电子，并将非水氢气氧化的电位（所需的能量驱动力）降低610 mV（117.7 kJ mol⁻¹）。这种显著的能量降低为非水氢能技术的发展开辟了道路。
