Department of Chemistry, Yale University, New Haven, CT, 06520, USA.
Energy Sciences Institute, Yale University, West Haven, CT, 06516, USA.
Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9111-9115. doi: 10.1002/anie.201704700. Epub 2017 Jul 4.
Main-group complexes are shown to be viable electrocatalysts for the H -evolution reaction (HER) from acid. A series of antimony porphyrins with varying axial ligands were synthesized for electrocatalysis applications. The proton-reduction catalytic properties of TPSb(OH) (TP=5,10,15,20-tetra(p-tolyl)porphyrin) with two axial hydroxy ligands were studied in detail, demonstrating catalytic H production. Experiments, in conjunction with quantum chemistry calculations, show that the catalytic cycle is driven via the redox activity of both the porphyrin ligand and the Sb center. This study brings insight into main group catalysis and the role of redox-active ligands during catalysis.
主族配合物被证明是酸性条件下氢析出反应（HER）的可行电催化剂。为了进行电催化应用，合成了一系列具有不同轴向配体的锑卟啉。详细研究了具有两个轴向羟基配体的 TPSb(OH)（TP=5,10,15,20-四(对甲苯基)卟啉）的质子还原催化性能，证明了催化产氢。实验结合量子化学计算表明，催化循环是通过卟啉配体和 Sb 中心的氧化还原活性驱动的。这项研究深入了解了主族催化以及在催化过程中氧化还原活性配体的作用。
