Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Zhou, Jiahua; Yang, Piaoping; Kots, Pavel A.; Cohen, Maximilian; Chen, Ying; Quinn, Caitlin M.; de Mello, Matheus Dorneles; Anibal Boscoboinik, J.; Shaw, Wendy J.; Caratzoulas, Stavros; Zheng, Weiqing; Vlachos, Dionisios G.

doi:10.1038/s41467-023-37962-3

Title: Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Journal Article · 20 April 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-37962-3 · OSTI ID:1971167

Zhou, Jiahua; Yang, Piaoping;

; Cohen, Maximilian;

;

; Anibal Boscoboinik, J.;

;

Abstract Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, ¹⁵ N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; SC0001004; SC0012704

OSTI ID:: 1971167

Report Number(s):: BNL--225124-2023-JAAM; 2293; PII: 37962

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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