新型电化学-质谱平台及其在电化学反应机理研究中的应用

Investigating mechanisms of electrochemical reactions is not only fundamental and important to electrochemistry and related researches, but also extremely challenging, because it often requires state-of-the-art techniques and methods to detect and characterize the reaction products and/or short-lived intermediates. To this end, we recently employed a hybrid theta pipette containing one empty micro-channel and one carbon-filled micro-channel for a nanospray emitter and a micro-electrochemical cell, along with a piezoelectric pistol for inducing relay spray ionization, to have constructed a new platform for combined electrochemistry-mass spectrometry (EC-MS) study. Here, we propose to improve the performance of this EC-MS setup by making necessary adjustments and modifications. We will also build and test new EC-MS devices. The common goal is that the response time of our EC-MS platform will be shortened from the current order of milliseconds to the order of microseconds, so that extremely short-lived reaction intermediates can be captured. With the improved capability, our EC-MS platform will allow us to address some remaining issues in the mechanisms of electrochemical luminescence proposed by Bard et al., and it will also provide us with a useful tool to study the mechanisms of some other very interesting electrochemical reactions.

探究电化学的反应机理，对电化学以及相关的研究来说，不仅基础和重要，而且非常具有挑战性，因为它往往需要发展先进的技术和方法, 去检测和表征反应过程中的产物和/或者短寿命的反应中间体。为此, 我们最近利用一半中空、一半由碳材料装填的杂化双管，既作为纳喷雾喷针，又用作微型电化学反应池，以及一把诱导接力喷雾离子化的压电枪, 搭建了一个新的电化学-质谱（EC-MS）研究平台。本项目中，我们计划对这个EC-MS平台进行必要的调整和改进，搭建和测试新的EC-MS装置，将我们的EC-MS分析平台的响应时间从目前的毫秒量级缩短至微秒量级，使得非常短寿命的反应中间体能被EC-MS平台所捕获，解决Bard等以前在电化学发光反应机理研究中遗留的一些问题，同时也为其他一些非常有意思的电化学反应机理的研究提供一种有用的工具。

探究电化学的反应机理，对电化学以及相关的研究来说，不仅基础和重要，而且非常具有挑战性，因为它往往需要发展先进的技术和方法，去检测和表征反应过程中的产物和/或者短寿命的反应中间体。为此，我们搭建了一个电化学-中性物种再电离-质谱（EC-NR-MS）平台，可在线检测电化学反应过程中的离子型中间体，尤其能够在线检测短寿命的、中性的中间体，包括在线检测和表征了长期未被直接检测到的三丙胺、2-（二丁基胺）乙醇、以及三乙醇胺的中性自由基，为阐明一些复杂的电化学反应过程提供了更明确的质谱证据，从而帮助澄清了过去一些未经完全证实的电化学发光反应机理，为将来其他具有挑战性的电化学反应研究工作的开展提供了一个非常有用的平台。