Autonomous closed-loop mechanistic investigation of molecular electrochemistry via automation

Abstract

Electrochemical research often requires stringent combinations of experimental parameters that are demanding to manually locate. Recent advances in automated instrumentation and machine-learning algorithms unlock the possibility for accelerated studies of electrochemical fundamentals via high-throughput, online decision-making. Here we report an autonomous electrochemical platform that implements an adaptive, closed-loop workflow for mechanistic investigation of molecular electrochemistry. As a proof-of-concept, this platform autonomously identifies and investigates an EC mechanism, an interfacial electron transfer (E step) followed by a solution reaction (C step), for cobalt tetraphenylporphyrin exposed to a library of organohalide electrophiles. The generally applicable workflow accurately discerns the EC mechanism’s presence amid negative controls and outliers, adaptively designs desired experimental conditions, and quantitatively extracts kinetic information of the C step spanning over 7 orders of magnitude, from which mechanistic insights into oxidative addition pathways are gained. This work opens opportunities for autonomous mechanistic discoveries in self-driving electrochemistry laboratories without manual intervention.

An Automated Electrochemistry Platform for Studying pH-dependent Molecular Electrocatalysis

“…[54][55][56] Recent work has shown the combination of deep learning and automated experimentation allows for fully closed-loop mechanistic studies of molecular electrochemistry, however this type of workflow has yet to be applied to electrocatalytic systems. 28 We are excited to explore such a closed-loop system for the study of molecular electrocatalysis using our new automated platform. We believe that such a system will enable rapid discovery of new effective electrocatalysts, and accelerate molecular electrocatalysis for energy conversion, fuel valorization, bioelectrochemical sensing, and other practical applications.…”

“…For example, automated and high throughput platforms for electrochemical experimentation have been used for applications ranging from energy storage 21-https://doi.org/10.26434/chemrxiv-2024-t0s3s ORCID: https://orcid.org/0000-0001-5880-9812 Content not peer-reviewed by ChemRxiv. License: CC BY 4.0 27 , electrocatalysis [28][29][30][31] , electrosynthesis [32][33][34][35][36] , and even single entity electrochemistry. 37 However, these platforms are not designed for the titration-type electrochemical experiments that are crucial in molecular electrocatalysis studies, highlighting the need for a specialized platform for this type of study.…”