What is Electrosynthesis?

Electrosynthesis uses an electrochemical cell to drive a chemical transformation. It provides an alternative to conventional chemical oxidizing or reducing agents, many of which are toxic or expensive. Reactions can also be performed under milder conditions and often require fewer purification steps and generate less hazardous waste¹ because electrons act as the reagent as they are supplied or removed directly at the electrode surface^2,3.

In electrosynthesis, an electrical potential is applied between two electrodes in an electrolyte containing the substrate. The substrate then either loses electrons (anodic oxidation) or gains electrons (cathodic reduction), generating a reactive intermediate, which then can form the desired product.

A typical electrosynthesis cell consists of the following:

Working electrode (anode or cathode): Where the target electron-transfer reaction takes place. Electrode material (e.g., platinum, glassy carbon, nickel, or boron-doped diamond) strongly influences selectivity and efficiency⁴.

Counter electrode: Completes the circuit by carrying out the complementary reaction, often of the solution or a sacrificial species.

Reference electrode: Used in three-electrode setups to accurately monitor and control the working electrode potential, allowing selective control over which species react.

Electrolyte: Conducts ions between the electrodes and, in organic electrosynthesis, is often a supporting salt dissolved in an organic solvent to keep the medium conductive without itself being the reactant.

Membrane or bridge: In divided cells, these separates the anodic and cathodic half-cells to prevent unwanted side reactions between the products formed at each electrode.

Figure 1: Simplified diagram of  divided (right)  and undivided (left) electrosynthesis cells, and schematic showing substrate oxidation or reduction (either directly or via mediator) at the electrode.

Electrosynthesis reactions are generally classified as:

Direct electrolysis, where the substrate itself is oxidized or reduced directly at the electrode surface.

Indirect or mediated electrolysis, where a redox mediator is oxidized or reduced at the electrode and then reacts with the substrate in solution, regenerating itself in the process. Mediators are useful when the substrate would otherwise require an electrode potential high enough to cause unwanted side reactions or solvent breakdown⁵.

Reaction outcome depends on several interlinked parameters, including applied potential (or current), electrode material, electrolyte composition, cell design (divided vs. undivided), and mass transport conditions at the electrode surface.

Electrocatalysis vs. Electrosynthesis

Electrosynthesis and electrocatalysis are closely related but describe different things. Electrosynthesis refers to the overall process of using electricity to make a target product; electrocatalysis refers to the use of a catalyst — often built into the electrode itself — to lower the energy barrier of a specific electron-transfer step and make it proceed faster, more selectively, or at a lower overpotential².

Reactions such as CO2 reduction or other small-molecule activations are usually far too sluggish or unselective without a dedicated electrocatalyst, so catalyst design becomes central to making the synthesis viable. Not all electrocatalysis is aimed at synthesis either — much electrocatalyst development (e.g., hydrogen evolution, oxygen evolution, oxygen reduction for fuel cells) targets energy conversion and storage rather than isolating a chemical product.

Applications

Electrosynthesis is used across a wide range of chemistries and applications, from small functional-group interconversions to the formation of new carbon–carbon and carbon–heteroatom bonds⁶.

One of the oldest and best-known examples is the Kolbe electrolysis (see below), in which carboxylic acids are anodically decarboxylated to form radicals that couple into new C–C bonds — a reaction still studied today as a route to symmetrical and unsymmetrical hydrocarbons.

Electrosynthesis is also increasingly explored for:

Pharmaceutical and fine chemical intermediates, where mild, selective electrochemical oxidations and reductions can replace hazardous stoichiometric reagents and reduce the number of synthetic steps⁷.

Polymer synthesis, including the electropolymerization of conducting polymers such as polypyrrole and polyaniline directly onto electrode surfaces.

Biomass valorization, converting renewable feedstocks like lignin or furfural derivatives into value-added chemicals using electricity rather than harsh chemical oxidants.

Small-molecule activation, through this process smaller, energetically stable molecules are used as feedstock for more valuable molecules. Examples include electrochemical reduction of CO₂ into fuels and chemical feedstocks (see our article, What is CO2 electrolysis?) or the conversion of NO₃^– to NH₃⁸

Benefits & Challenges

Because electrosynthesis typically avoids stoichiometric chemical oxidants/reductants, it aligns well with green chemistry principles: fewer hazardous reagents, less waste, and — when paired with renewable electricity — a lower overall carbon footprint[9].

Despite its promise, electrosynthesis faces hurdles on the path to wider adoption. Reaction selectivity can be difficult to control, particularly when multiple oxidizable or reducible groups are present in the substrate. Mass transport to the electrode surface can limit reaction rate and become a bottleneck when scaling up from milligrams to kilograms. Electrode fouling and passivation over extended electrolysis can reduce efficiency and reproducibility. Finally, translating a promising bench-scale reaction into a continuous, cost-effective industrial process requires careful engineering of cell design, current distribution, and mass transport — work that depends on rigorous electrochemical characterization at every stage.

How is Electrosynthesis Researched?

Developing an electrosynthetic process means moving progressively from understanding fundamental electron-transfer mechanisms to validating a reaction at bench scale and, eventually, engineering it for larger-scale production. BioLogic’s instrumentation supports each of these stages.

Figure 2: Range of BioLogic instruments used throughout electrosynthesis research, from molecular-scale mechanistic studies to reactor-scale process development.

Molecular scale. When exploring a new synthetic route, understanding the elementary electron-transfer steps and reaction pathway is essential. Techniques like cyclic voltammetry performed on BioLogic’s Premium Potentiostats (e.g., the SP-200) give the high-resolution electrochemical control needed to identify redox potentials, detect reaction intermediates, and screen mediators before committing to a synthetic route.
For spatially resolved feedback on reactivity, the M470 provides SECM and SDC modes, helping you connect molecular-level mechanisms to macroscopic electrode behavior

Electrode scale. Once a mechanism is understood, the role of the electrode material and the electrode-electrolyte interface becomes central, especially when an electrocatalyst is involved. Rotating Disk Electrode (RDE) and Rotating Ring-Disk Electrode (RRDE) techniques on the BluRev help characterize how electrode material and mass transport affect selectivity and efficiency, while Electrochemical Impedance Spectroscopy (EIS) provides insight into interfacial kinetics

Lab reaction scale. Demonstrating the feasibility of an electrosynthetic process at bulk scale requires proving not only that a reaction proceeds, but that it does so with the expected selectivity and yield over extended electrolysis. BioLogic’s modular Premium Potentiostats along with internal and external boosters can be configured to deliver the higher currents needed for preparative-scale electrolysis, while EC-Lab^® software’s ability to modify test plans on the fly and set safety limits supports the longer, less predictable runs typical of bulk electrolysis.

Reactor scale. As a process moves toward optimization and eventual commercialization, increasing reaction productivity and improving mass transport to the electrodes become the priority. BioLogic’s Essential Potentiostat range with boosters (up to ±60 V with the FlexP 0060) helps keep the applied potential within a safe operating window, avoiding electrolyte decomposition and supporting stable, reproducible conversion.

Across all these scales, EC-Lab^® software provides consistent data collection, and analysis tools — including ZFit for equivalent circuit modeling and Levich/Koutecky-Levich analysis for kinetic studies — support both mechanistic understanding and process optimization from the very first cyclic voltammogram through to reactor-scale validation.

Conclusion

Electrosynthesis offers a versatile and increasingly green alternative to conventional chemical synthesis, replacing hazardous stoichiometric reagents with electrons delivered directly at an electrode. From classic reactions like the Kolbe electrolysis to modern applications in pharmaceutical synthesis, biomass valorization, small molecule activation, and CO2 conversion, electrosynthesis continues to expand in scope and industrial relevance.

Realizing this potential depends on rigorous electrochemical research at every stage of development — from understanding fundamental mechanisms to engineering a scalable process. BioLogic’s range of potentiostats, boosters, and EC-Lab^® software support researchers throughout this journey, from the molecular scale to the reactor scale.

References

1. Hashmi, S. M. et al. Towards sustainable chemistry: Advances, challenges and opportunities in organic electrosynthesis. Chemical Engineering Journal (2023).
2. Leech, M. C. & Lam, K. A practical guide to electrosynthesis. Nature Reviews Chemistry 6, 275–286 (2022).
3. Yan, M., Kawamata, Y. & Baran, P. S. Synthetic Organic Electrochemical Methods Since2000: On the Verge of a Renaissance. Chemical Reviews 117, 13230–13319 (2017).
4. Pletcher, D., Green, R. A. & Brown, R. C. D. Flow Electrolysis Cells for the Synthetic Organic Chemistry Laboratory. Chemical Reviews 118, 4573–4591 (2018).
5. Francke, R. & Little, R. D. Redox catalysis in organic electrosynthesis: basic principles and recent developments. Chemical Society Reviews 43, 2492–2521 (2014).
6. Martins, G. M. & de Oliveira, K. T. Emerging trends of organic electrosynthesis in Brazil. Química Nova 48, (2024).
7. Sperry, J. B. & Wright, D. L. The application of cathodic reductions and anodic oxidations in the synthesis of complex molecules. Chemical Society Reviews 35, 605–621 (2006).
8. Guiet A, et al. Reversible transition of an amorphous Cu-Al oxyfluoride into a highly active electrocatalyst for NO3− reduction to NH3. Chem Catalysis, Volume 3, Issue 5, 100595 (2023)
9. Möhle, S. et al. Modern Electrochemical Aspects for the Synthesis of Value-Added Organic Products. Angewandte Chemie International Edition 57, 6018–6041 (2018).