Autonomous closed-loop mechanistic investigation of molecular electrochemistry via automation

Sheng, Hongyuan; Sun, Jingwen; Rodríguez, Oliver; Hoar, Benjamin B.; Zhang, Weitong; Xiang, Danlei; Tang, Tianhua; Hazra, Avijit; Min, Daniel S.; Doyle, Abigail G.; Sigman, Matthew S.; Costentin, Cyrille; Gu, Quanquan; Rodríguez-López, Joaquín; Liu, Chong

doi:10.1038/s41467-024-47210-x

Autonomous closed-loop mechanistic investigation of molecular electrochemistry via automation

Journal Article · Sat Mar 30 04:00:00 EDT 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-47210-x· OSTI ID:2331328

; ; Rodríguez, Oliver; Hoar, Benjamin B.; ; Xiang, Danlei; Tang, Tianhua; ; Min, Daniel S.; ; ; ; ; ;

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.

View Journal Article

Sponsoring Organization:: USDOE

OSTI ID:: 2331328

Alternate ID(s):: OSTI ID: 2470262

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (51)

Elements of Molecular and Biomolecular Electrochemistry: An Electrochemical Approach to Electron Transfer Chemistry Savéant, Jean‐Michel; Costentin, Cyrille https://doi.org/10.1002/9781119292364	journal	June 2019
A Multifunctional Microfluidic Platform for High‐Throughput Experimentation of Electroorganic Chemistry Mo, Yiming; Rughoobur, Girish; Nambiar, Anirudh M. K. Angewandte Chemie International Edition, Vol. 59, Issue 47 https://doi.org/10.1002/anie.202009819	journal	September 2020
Chemical catalysis of the electrochemical reduction of alkyl halides Lexa, D.; Savéant, J. M.; Soufflet, J. P. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 100, Issue 1-2 https://doi.org/10.1016/S0022-0728(79)80158-8	journal	June 1979
What and how can machine learning help to decipher mechanisms in molecular electrochemistry? Sun, Jingwen; Liu, Chong Current Opinion in Electrochemistry, Vol. 39 https://doi.org/10.1016/j.coelec.2023.101306	journal	June 2023
Combinatorial micro electrochemistry. Part 4: Cyclic voltammetric redox screening of homogeneous ruthenium(II) hydrogenation catalysts Lindner, Ekkehard; Lu, Zhong-Lin; Mayer, Hermann A. Electrochemistry Communications, Vol. 7, Issue 10 https://doi.org/10.1016/j.elecom.2005.07.002	journal	October 2005
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. Nicholson, R. S.; Shain, Irving Analytical Chemistry, Vol. 36, Issue 4, p. 706-723 https://doi.org/10.1021/ac60210a007	journal	April 1964
Semiempirical Procedure for Measuring with Stationary Electrode Polarography Rates of Chemical Reactions Involving the Product of Electron Transfer. Nicholson, R. S. Analytical Chemistry, Vol. 38, Issue 10 https://doi.org/10.1021/ac60242a030	journal	September 1966
Autonomous Chemical Experiments: Challenges and Perspectives on Establishing a Self-Driving Lab Seifrid, Martin; Pollice, Robert; Aguilar-Granda, Andrés Accounts of Chemical Research, Vol. 55, Issue 17 https://doi.org/10.1021/acs.accounts.2c00220	journal	August 2022
Hard Potato: A Python Library to Control Commercial Potentiostats and to Automate Electrochemical Experiments Rodríguez, Oliver; Pence, Michael A.; Rodríguez-López, Joaquín Analytical Chemistry, Vol. 95, Issue 11 https://doi.org/10.1021/acs.analchem.2c04862	journal	March 2023
Automatically Identifying Electrode Reaction Mechanisms Using Deep Neural Networks Kennedy, Gareth F.; Zhang, Jie; Bond, Alan M. Analytical Chemistry, Vol. 91, Issue 19 https://doi.org/10.1021/acs.analchem.9b01891	journal	August 2019
Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis Malapit, Christian A.; Prater, Matthew B.; Cabrera-Pardo, Jaime R. Chemical Reviews, Vol. 122, Issue 3 https://doi.org/10.1021/acs.chemrev.1c00614	journal	November 2021
A Practical Beginner’s Guide to Cyclic Voltammetry Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D. Journal of Chemical Education, Vol. 95, Issue 2 https://doi.org/10.1021/acs.jchemed.7b00361	journal	November 2017
High-Throughput Electrochemistry: State of the Art, Challenges, and Perspective Wills, Alfie G.; Charvet, Sylvain; Battilocchio, Claudio Organic Process Research & Development, Vol. 25, Issue 12 https://doi.org/10.1021/acs.oprd.1c00167	journal	August 2021
Electrochemical Screening for Electroorganic Synthesis Gütz, Christoph; Klöckner, Bernhard; Waldvogel, Siegfried R. Organic Process Research & Development, Vol. 20, Issue 1 https://doi.org/10.1021/acs.oprd.5b00377	journal	December 2015
The Evolution of High-Throughput Experimentation in Pharmaceutical Development and Perspectives on the Future Mennen, Steven M.; Alhambra, Carolina; Allen, C. Liana Organic Process Research & Development, Vol. 23, Issue 6 https://doi.org/10.1021/acs.oprd.9b00140	journal	May 2019
Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor Rein, Jonas; Annand, James R.; Wismer, Michael K. ACS Central Science, Vol. 7, Issue 8 https://doi.org/10.1021/acscentsci.1c00328	journal	August 2021
Electrochemical Mechanistic Analysis from Cyclic Voltammograms Based on Deep Learning Hoar, Benjamin B.; Zhang, Weitong; Xu, Shuangning ACS Measurement Science Au, Vol. 2, Issue 6 https://doi.org/10.1021/acsmeasuresciau.2c00045	journal	August 2022
Automated Measurement of Electrogenerated Redox Species Degradation Using Multiplexed Interdigitated Electrode Arrays Pence, Michael A.; Rodríguez, Oliver; Lukhanin, Nikita G. ACS Measurement Science Au, Vol. 3, Issue 1 https://doi.org/10.1021/acsmeasuresciau.2c00054	journal	November 2022
Legion: An Instrument for High-Throughput Electrochemistry Gerroll, Benjamin H. R.; Kulesa, Krista M.; Ault, Charles A. ACS Measurement Science Au, Vol. 3, Issue 5 https://doi.org/10.1021/acsmeasuresciau.3c00022	journal	July 2023
High-Throughput Experimentation for Electrochemistry Rein, Jonas; Lin, Song; Kalyani, Dipannita ACS Symposium Series https://doi.org/10.1021/bk-2022-1419.ch010	book	November 2022
Parallel Electrosynthesis of α-Alkoxycarbamates, α-Alkoxyamides, and α-Alkoxysulfonamides Using the Spatially Addressable Electrolysis Platform (SAEP) Siu, Tung; Li, Wei; Yudin, Andrei K. Journal of Combinatorial Chemistry, Vol. 2, Issue 5 https://doi.org/10.1021/cc000035v	journal	September 2000
Separation of polar and resonance substituent effects in the reactions of acetophenones with bisulfite and of benzyl halides with nucleophiles Young, P. R.; Jencks, W. P. Journal of the American Chemical Society, Vol. 101, Issue 12 https://doi.org/10.1021/ja00506a025	journal	June 1979
Concerted Displacement Reactions. VI. m- and p-Substituent Effects as Evidence for a Unity of Mechanism in Organic Halide Reactions¹ Swain, C. Gardner; Langsdorf, William P. Journal of the American Chemical Society, Vol. 73, Issue 6 https://doi.org/10.1021/ja01150a113	journal	June 1951
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242 https://doi.org/10.1021/ja303560c	journal	June 2012
Monovalent Nickel-Mediated Radical Formation: A Concerted Halogen-Atom Dissociation Pathway Determined by Electroanalytical Studies Lin, Qiao; Fu, Yue; Liu, Peng Journal of the American Chemical Society, Vol. 143, Issue 35 https://doi.org/10.1021/jacs.1c05255	journal	August 2021
Machine-Learning-Guided Discovery of Electrochemical Reactions Zahrt, Andrew F.; Mo, Yiming; Nandiwale, Kakasaheb Y. Journal of the American Chemical Society, Vol. 144, Issue 49 https://doi.org/10.1021/jacs.2c08997	journal	December 2022
Mechanistic Studies into the Oxidative Addition of Co(I) Complexes: Combining Electroanalytical Techniques with Parameterization Sandford, Christopher; Fries, Lydia R.; Ball, Tyler E. Journal of the American Chemical Society, Vol. 141, Issue 47 https://doi.org/10.1021/jacs.9b10771	journal	November 2019
Kinetics and mechanism of benzylation of anilines Ballistreri, Francesco P.; Maccarone, Emanuele; Mamo, Antonino The Journal of Organic Chemistry, Vol. 41, Issue 21 https://doi.org/10.1021/jo00883a005	journal	October 1976
Hammett and Broensted-type relationships in reactions of 9-substituted fluorenyl anions with benzyl halides Bordwell, Frederick G.; Hughes, David L. The Journal of Organic Chemistry, Vol. 45, Issue 16 https://doi.org/10.1021/jo01304a036	journal	August 1980
Autonomous optimization of non-aqueous Li-ion battery electrolytes via robotic experimentation and machine learning coupling Dave, Adarsh; Mitchell, Jared; Burke, Sven Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32938-1	journal	September 2022
Electrochemical and spectroscopic methods for evaluating molecular electrocatalysts Lee, Katherine J.; Elgrishi, Noémie; Kandemir, Banu Nature Reviews Chemistry, Vol. 1, Issue 5 https://doi.org/10.1038/s41570-017-0039	journal	May 2017
Accelerating the discovery of materials for clean energy in the era of smart automation Tabor, Daniel P.; Roch, Loïc M.; Saikin, Semion K. Nature Reviews Materials, Vol. 3, Issue 5 https://doi.org/10.1038/s41578-018-0005-z	journal	April 2018
Controlling an organic synthesis robot with machine learning to search for new reactivity Granda, Jarosław M.; Donina, Liva; Dragone, Vincenza Nature, Vol. 559, Issue 7714 https://doi.org/10.1038/s41586-018-0307-8	journal	July 2018
Closed-loop optimization of fast-charging protocols for batteries with machine learning Attia, Peter M.; Grover, Aditya; Jin, Norman Nature, Vol. 578, Issue 7795 https://doi.org/10.1038/s41586-020-1994-5	journal	February 2020
A mobile robotic chemist Burger, Benjamin; Maffettone, Phillip M.; Gusev, Vladimir V. Nature, Vol. 583, Issue 7815 https://doi.org/10.1038/s41586-020-2442-2	journal	July 2020
Bayesian reaction optimization as a tool for chemical synthesis Shields, Benjamin J.; Stevens, Jason; Li, Jun Nature, Vol. 590, Issue 7844 https://doi.org/10.1038/s41586-021-03213-y	journal	February 2021
Automation and computer-assisted planning for chemical synthesis Shen, Yuning; Borowski, Julia E.; Hardy, Melissa A. Nature Reviews Methods Primers, Vol. 1, Issue 1 https://doi.org/10.1038/s43586-021-00022-5	journal	March 2021
The rise of self-driving labs in chemical and materials sciences Abolhasani, Milad; Kumacheva, Eugenia Nature Synthesis, Vol. 2, Issue 6 https://doi.org/10.1038/s44160-022-00231-0	journal	January 2023
Inorganic Electrochemistry Zanello, Piero; Connelly, Neil G. Royal Society of Chemistry https://doi.org/10.1039/9781847551146	book	August 2003
Concertedness in proton-coupled electron transfer cleavages of carbon–metal bonds illustrated by the reduction of an alkyl cobalt porphyrin Costentin, Cyrille; Passard, Guillaume; Robert, Marc Chem. Sci., Vol. 4, Issue 2 https://doi.org/10.1039/C2SC21788K	journal	January 2013
A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms Sandford, Christopher; Edwards, Martin A.; Klunder, Kevin J. Chemical Science, Vol. 10, Issue 26 https://doi.org/10.1039/C9SC01545K	journal	January 2019
Analyzing mechanisms in Co(i) redox catalysis using a pattern recognition platform Tang, Tianhua; Sandford, Christopher; Minteer, Shelley D. Chemical Science, Vol. 12, Issue 13 https://doi.org/10.1039/D0SC06725C	journal	January 2021
Electrocatalysis as an enabling technology for organic synthesis Novaes, Luiz F. T.; Liu, Jinjian; Shen, Yifan Chemical Society Reviews, Vol. 50, Issue 14 https://doi.org/10.1039/D1CS00223F	journal	January 2021
Inclusion of multiple cycling of potential in the deep neural network classification of voltammetric reaction mechanisms Gundry, Luke; Kennedy, Gareth; Bond, Alan M. Faraday Discussions, Vol. 233 https://doi.org/10.1039/D1FD00050K	journal	January 2022
198. Nucleophilic reactivity. Part II. The reaction between substituted thiophenols and benzyl bromides Hudson, R. F.; Klopman, G. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/JR9620001062	journal	January 1962
Accelerated Electrosynthesis Development Enabled by High-Throughput Experimentation Mo, Yiming; Chen, Huijie Synthesis, Vol. 55, Issue 18 https://doi.org/10.1055/a-2072-2617	journal	May 2023
Deep Residual Learning for Image Recognition He, Kaiming; Zhang, Xiangyu; Ren, Shaoqing 2016 IEEE Conference on Computer Vision and Pattern Recognition (CVPR) https://doi.org/10.1109/CVPR.2016.90	conference	June 2016
A platform for automated nanomole-scale reaction screening and micromole-scale synthesis in flow Perera, Damith; Tucker, Joseph W.; Brahmbhatt, Shalini Science, Vol. 359, Issue 6374 https://doi.org/10.1126/science.aap9112	journal	January 2018
Organic synthesis in a modular robotic system driven by a chemical programming language Steiner, Sebastian; Wolf, Jakob; Glatzel, Stefan Science, Vol. 363, Issue 6423 https://doi.org/10.1126/science.aav2211	journal	November 2018
A robotic platform for flow synthesis of organic compounds informed by AI planning Coley, Connor W.; Thomas, Dale A.; Lummiss, Justin A. M. Science, Vol. 365, Issue 6453 https://doi.org/10.1126/science.aax1566	journal	August 2019
Object-detecting deep learning for mechanism discernment in multi-redox cyclic voltammograms Hoar, Benjamin; Zhang, Weitong; Chen, Yuanzhou ChemRxiv https://doi.org/10.26434/chemrxiv-2023-r2v1k	preprint	December 2023

Similar Records

Autonomous Electrochemistry Platform with Real-Time Normality Testing of Voltammetry Measurements Using ML

Conference · Sun Sep 01 00:00:00 EDT 2024 · OSTI ID:2448173

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Journal Article · Fri Mar 20 00:00:00 EDT 2020 · Angewandte Chemie · OSTI ID:1633671

Autonomous closed-loop mechanistic investigation of molecular electrochemistry via automation

Citation Formats

References (51)

Similar Records

Related Subjects