(667a) Selective Organic Electrooxidations By Laser-Made Nanocatalysts

Selective electrocatalysis offers a sustainable approach to revolutionize chemical manufacturing by producing single products from organic molecules.¹ Selective hydrocarbon oxidations aim to convert hydrocarbons into alcohols, especially methane into methanol, without energy-intensive steam reforming. Benzaldehyde, a key building block in the chemical industry, has an estimated global benzaldehyde market valuation of >580 million U.S. dollars.² However, achieving selectivity in electrocatalysis, especially arresting reactions after the first oxidation, presents challenges due to energetics favoring further oxidations. Overcoming this challenge demands advancements in catalysts, reaction control, and electrocatalytic understanding for high selectivity for individual products with efficient activity.

We laser-synthesized earth-abundant mixed-metal nanocatalysts³ and employed them on high-surface-area carbon supports,⁴ enabling the selective electrooxidation of toluene to benzyl alcohol, or benzyl alcohol to benzaldehyde. We show how electrolyte engineering and concomitant accessibility of different mechanistic pathways led to 100 % selectivity for desired products with unprecedentedly high conversion efficiencies. We also revealed the mechanistic underpinnings of this remarkable performance of laser-made nanocatalysts for these electrooxidations.

References:

1) T. Taseska, W. Yu, M.K. Wilsey, Z. Meng, C.P. Cox, S.S. Ngarnim, A.M. Müller, Analysis of the Scale of Global Human Needs and Opportunities for Sustainable Catalytic Technologies. Top. Catal. 2023, 66, 338-374.

2) N.R. Choudhury, Benzaldehyde Market Outlook from 2024 to 2034. https://www.futuremarketinsights.com/reports/benzaldehyde-market (accessed March 23, 2024).

3) R.C. Forsythe, C.P. Cox, M.K. Wilsey, A.M. Müller, Pulsed Laser in Liquids Made Nanomaterials for Catalysis. Chem. Rev. 2021, 121, 7568-7637.

4) M.K. Wilsey, K.R. Watson, O.C. Fasusi, B.P. Yegela, C.P. Cox, P.R. Raffaelle, L. Cai, A.M. Müller, Selective Hydroxylation of Carbon Fiber Paper for Long-Lasting Hydrophilicity by a Green Chemistry Process. Adv. Mater. Interfaces 2023, 10, 2201684.