Issue 8, 2024

Structure sensitivity of the electrochemical hydrogenation of cis,cis-muconic acid to hexenedioic acid and adipic acid

Abstract

The global market of fossil carbon-derived adipic acid (AA) was over 3 million tons in 2022, emitting 3.1 million tons of the potent greenhouse gas N2O. Alternative biomass-derived feedstocks offer a sustainable option to replace fossil carbon, but alternative pathways for AA synthesis are also required to curb the substantial emissions associated with the process. A novel and sustainable approach to synthesize AA is by coupling biomanufacturing and electrocatalysis. Biologically-produced cis,cis-muconic acid (ccMA) from sugars and lignin monomers has recently gained significant attention as a precursor to AA, as it can be electrochemically hydrogenated to AA using water-derived (instead of fossil-derived) hydrogen and electricity generated from wind energy. For the first time in literature, we demonstrate appreciable electrochemical production of AA using supported palladium nanoparticles. The performance of this system contrasts with that of palladium foil or platinum-based catalysts, which produced little AA. Density functional theory calculations on model surfaces of palladium and platinum suggest that the reduction of ccMA to trans-3-hexenedioic acid occurs through an outer sphere proton-coupled electron transfer mechanism, while subsequent reduction to AA preferentially occurs on surface terrace sites. Our calculations also explain the exceptional performance of palladium nanoparticles compared to palladium- and platinum-based foils, attributing the more favorable activation energy barriers found on palladium terraces to the relatively moderate binding strength of adsorbed species. These results suggest structure-sensitive catalyst design strategies that maximize the exposure of terrace atoms for further improvement of the ccMA electrochemical hydrogenation process.

Graphical abstract: Structure sensitivity of the electrochemical hydrogenation of cis,cis-muconic acid to hexenedioic acid and adipic acid

Supplementary files

Article information

Article type
Paper
Submitted
11 Aug 2023
Accepted
22 Dec 2023
First published
29 Dec 2023
This article is Open Access
Creative Commons BY-NC license

Green Chem., 2024,26, 4506-4517

Structure sensitivity of the electrochemical hydrogenation of cis,cis-muconic acid to hexenedioic acid and adipic acid

D. M. Patel, P. T. Prabhu, G. Gupta, M. N. Dell'Anna, S. Kling, H. T. Nguyen, J. Tessonnier and L. T. Roling, Green Chem., 2024, 26, 4506 DOI: 10.1039/D3GC03021K

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements