Habets Thomas, Speller Sylvia, Elemans Johannes A A W
Radboud University, Institute for Molecules and Materials (IMM), 6525 AJ Nijmegen, Netherlands.
University of Rostock, Institute of Physics, Albert-Einstein-Straße 23, 18059 Rostock, Germany.
Beilstein J Nanotechnol. 2020 Aug 24;11:1264-1271. doi: 10.3762/bjnano.11.110. eCollection 2020.
In a liquid-STM setup environment, the redox behavior of manganese porphyrins was studied at various solid-liquid interfaces. In the presence of a solution of Mn(III)Cl porphyrins in 1-phenyloctane, which was placed at a conductive surface, large and constant additional currents relative to a set tunneling current were observed, which varied with the magnitude of the applied bias voltage. These currents occurred regardless of the type of surface (HOPG or Au(111)) or tip material (PtIr, Au or W). The additional currents were ascribed to the occurrence of redox reactions in which chloride is oxidized to chlorine and the Mn(III) center of the porphyrin moiety is reduced to Mn(II). The resulting Mn(II) porphyrin products were identified by UV-vis analysis of the liquid phase. For solutions of Mn(III) porphyrins with non-redox active acetate instead of chloride axial ligands, the currents remained absent.
在液体扫描隧道显微镜（liquid-STM）设置环境中，研究了锰卟啉在各种固液界面的氧化还原行为。在置于导电表面的1-苯基辛烷中的Mn(III)Cl卟啉溶液存在下，观察到相对于设定隧道电流有大且恒定的附加电流，该电流随施加偏置电压的大小而变化。这些电流的出现与表面类型（高定向热解石墨（HOPG）或金（111））或尖端材料（铂铱、金或钨）无关。附加电流归因于氧化还原反应的发生，其中氯离子被氧化为氯，卟啉部分的Mn(III)中心被还原为Mn(II)。通过对液相进行紫外可见分析鉴定了生成的Mn(II)卟啉产物。对于具有非氧化还原活性的醋酸根而非氯离子轴向配体的Mn(III)卟啉溶液，未观察到电流。
