In Situ Spectroelectrochemical Studies into the Formation and Stability of Robust Diazonium-Derived Interfaces on Gold Electrodes for the Immobilization of an Oxygen-Tolerant Hydrogenase
In Situ Spectroelectrochemical Studies into the Formation and Stability of Robust Diazonium-Derived Interfaces on Gold Electrodes for the Immobilization of an Oxygen-Tolerant Hydrogenase
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DOI：
10.1021/acsami.8b02273
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发表时间：
2018-07-11
影响因子：
9.5
通讯作者：
Fischer, Anna
中科院分区：
文献类型：
--
作者：
Harris, Tomos G. A. A.;Heidary, Nina;Fischer, Anna
表面增强红外吸收光谱法用于原位测定沉积到纳米结构的薄膜金电极表面上的有机界面的电化学稳定性，所述纳米结构的薄膜金电极通过重氮盐的电化学还原。这些接口显示出在乙腈和磷酸盐缓冲液中具有宽的电化学稳定性窗口，远远超过硫醇衍生的自组装单分子膜的稳定性窗口。使用相同的原位技术，自由基清除剂的应用程序在电化学还原重氮盐显示温和的界面形成。因此，可以充分降低异质电荷转移电阻以增强固定化氧化还原活性酶与电极之间的直接电子转移。这被证明为耐氧[NiFe]氢化酶从“Knallgas”细菌Ralstonia eutropha通过将其电化学活性氢氧化的接口性能。
Surface-enhanced infrared absorption spectroscopy is used in situ to determine the electrochemical stability of organic interfaces deposited onto the surface of nanostructured, thin-film gold electrodes via the electrochemical reduction of diazonium salts. These interfaces are shown to exhibit a wide electrochemical stability window in both acetonitrile and phosphate buffer, far surpassing the stability window of thiol-derived self-assembled monolayers. Using the same in situ technique, the application of radical scavengers during the electrochemical reduction of diazonium salts is shown to moderate interface formation. Consequently, the heterogeneous charge-transfer resistance can be reduced sufficiently to enhance the direct electron transfer between an immobilized redox-active enzyme and the electrode. This was demonstrated for the oxygen-tolerant [NiFe] hydrogenase from the "Knallgas" bacterium Ralstonia eutropha by relating its electrochemical activity for hydrogen oxidation to the interface properties.