Accelerated Development and Optimization of Adiponitrile Production via Kolbe Electrolysis of Biomass-Derived Precursors
Authors: Mathison Ricardo , Patel Meera , Rani Elina , Modestino Miguel A 
Published: August 2024

Environmental and societal pressures are demanding a transition from fossil-based resources to renewable and sustainable feedstocks for the production of materials. In this context, biomass streams emerge as scalable candidates for creating sustainable chemicals. Electrocatalytic transformation of biomass can facilitate the production of chemicals under mild conditions and can be easily integrated with renewable energy sources. These transformations could lead to the production of sustainable monomers and polymers from biomass, significantly enhancing the sustainability of plastics production. Amongst a large number of plastics manufactured by the chemical industry, Nylon 6,6 is one of the most important fossil-derived polymers for the production of high-performance textiles and structural materials. Central to Nylon 6,6 production is adiponitrile (ADN), predominantly synthesized via energy-intensive thermochemical processes. An alternative route, electrochemical hydrodimerization of acrylonitrile (AN), although successful, still depends on fossil feedstocks. A promising sustainable source for ADN is renewable glutamic acid, derived from hydrolysis of waste proteins.1,2 This process involves transforming glutamic acid to 3-cyanopropanoic acid (CPA) and then to ADN through Kolbe electrolysis, a reaction with a historical background and multiple pathways. Our study utilizes an electrochemical reaction engineering approach to examine the Kolbe electrolysis of CPA to ADN and AN, focusing on a hierarchical research methodology. This approach allowed us to simultaneously accelerate the exploration of numerous reaction parameters while also conducting detailed studies under optimal conditions. This method has enabled us to gain deeper insights into the factors controlling reaction selectivity. We discovered that platinum electrodes favor ADN formation, with selectivity increasing at higher current densities. Optimal CPA concentrations, the presence of larger alkali cations, solvent composition, and controlled pH levels significantly influence ADN production, reducing side reactions such as the oxygen evolution reaction (OER). When using graphite electrodes, an increase in AN production was observed, with the solvent composition playing a crucial role in determining the rate of ADN formation. Our investigation has led to a deeper understanding of the electrochemical conversion of CPA to ADN, revealing key parameters that influence reaction selectivity and rate. The insights obtained from this study are not only pivotal for the specific case of ADN production but also have broader implications for a range of electrochemical decarboxylation reactions. The hierarchical research approach employed here demonstrates its potential for speeding the development of sustainable electrochemical processes. Our insights and methodology used for the electrosynthesis of ADN from biomass-derived feedstocks can be deployed to the deployed to the development of other biomass transformations advancing our ability to produce essential chemicals sustainably.
References
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337, 695-699 (2012).
2. Dai, J. J., Huang, Y. B., Fang, C., Guo, Q. X. & Fu, Y. Electrochemical synthesis of adiponitrile from the renewable raw material glutamic acid. ChemSusChem
5, 617-620, doi:10.1002/cssc.201100776 (2012).

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