Mattsson Stefan, Senges Gene, Riedel Sebastian, Paulus Beate
Institut für Chemie und Biochemie, Freie Universität Berlin, Arnimallee 22, 14195, Berlin, Germany.
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34-36, 14195, Berlin, Germany.
Chemistry. 2020 Aug 21;26(47):10781-10786. doi: 10.1002/chem.202000881. Epub 2020 Jul 21.
The Simons process, otherwise known as the electrochemical fluorination (ECF) method, is widely used in industry to electrolytically synthesize chemicals for various purposes. Even to this day, the exact mechanism of the ECF reaction remains unknown, but is believed to involve the formation of an anodic nickel fluoride film with highly oxidized nickel centers. In this study, experiments and density functional theory calculations are combined to characterize the initial anodic peak occurring at potentials typically required in an ECF cell. NiF is believed to form a passivating layer at low potentials. The calculations show that a potential of +3.1 V is required to oxidize surface Ni centers to Ni . This is in good agreement with the measured anodic peak at +3.57 V.
西蒙斯法，又称电化学氟化（ECF）法，在工业上被广泛用于电解合成各种用途的化学品。即使在今天，ECF反应的确切机制仍然未知，但据信涉及形成具有高度氧化镍中心的阳极氟化镍膜。在本研究中，将实验与密度泛函理论计算相结合，以表征在ECF电池通常所需电位下出现的初始阳极峰。据信NiF在低电位下形成钝化层。计算表明，需要+3.1 V的电位才能将表面镍中心氧化为Ni 。这与在+3.57 V处测得的阳极峰非常吻合。
