Molecular Surface Functionalization of Carbon Materials via Radical-Induced Grafting of Terminal Alkenes

Yongqian Zhang; Ali A Tamijani; Megan E Taylor; Bo Zhi; Christy L Haynes; Sara E Mason; Robert J Hamers

doi:10.1021/jacs.9b02369

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Journal article

Molecular Surface Functionalization of Carbon Materials via Radical-Induced Grafting of Terminal Alkenes

Yongqian Zhang, Ali A Tamijani, Megan E Taylor, Bo Zhi, Christy L Haynes, Sara E Mason and Robert J Hamers

Journal of the American Chemical Society, Vol.141(20), pp.8277-8288

05/22/2019

DOI: 10.1021/jacs.9b02369

PMCID: PMC7733706

PMID: 31038938

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Abstract

Formation of functional monolayers on surfaces of carbon materials is inherently difficult because of the high bond strength of carbon and because common pathways such as S 2 mechanisms cannot take place at surfaces of solid materials. Here, we show that the radical initiators can selectively abstract H atoms from H-terminated carbon surfaces, initiating regioselective grafting of terminal alkenes to surfaces of diamond, glassy carbon, and polymeric carbon dots. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) demonstrate formation of self-terminating organic monolayers linked via the terminal C atom of 1-alkenes. Density functional theory (DFT) calculations suggest that this selectivity is at least partially thermodynamic in origin, as significantly less energy is needed to abstract H atoms from carbon surfaces as compared to typical aliphatic compounds. The regioselectivity favoring binding to the terminal C atom of the reactant alkenes arises from steric hindrance encountered in bond formation at the adjacent carbon atom. Our results demonstrate that carbon surface radical chemistry yields a versatile, selective, and scalable approach to monolayer formation on H-terminated carbon surfaces and provide mechanistic insights into the surface selectivity and regioselectivity of molecular grafting.

Alkenes - chemistry

Benzoyl Peroxide - chemistry

Density Functional Theory

Free Radicals - chemistry

Magnetic Resonance Spectroscopy

Models, Chemical

Nanodiamonds - chemistry

Photoelectron Spectroscopy

Quantum Dots - chemistry

Surface Properties

Thermodynamics

Details

Title: Subtitle: Molecular Surface Functionalization of Carbon Materials via Radical-Induced Grafting of Terminal Alkenes
Creators: Yongqian Zhang - Department of Chemistry , University of Wisconsin-Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States
Ali A Tamijani - Department of Chemistry , University of Iowa , Iowa City , Iowa 52242 , United States
Megan E Taylor - Department of Chemistry , University of Wisconsin-Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States
Bo Zhi - Department of Chemistry , University of Minnesota Twin Cities , 207 Pleasant Street SE , Minneapolis , Minnesota 55455 , United States
Christy L Haynes - Department of Chemistry , University of Minnesota Twin Cities , 207 Pleasant Street SE , Minneapolis , Minnesota 55455 , United States
Sara E Mason - Department of Chemistry , University of Iowa , Iowa City , Iowa 52242 , United States
Robert J Hamers - Department of Chemistry , University of Wisconsin-Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States
Resource Type: Journal article
Publication Details: Journal of the American Chemical Society, Vol.141(20), pp.8277-8288
DOI: 10.1021/jacs.9b02369
PMID: 31038938
PMCID: PMC7733706
NLM abbreviation: J Am Chem Soc
ISSN: 0002-7863
eISSN: 1520-5126
Grant note: S10 OD012245 / NIH HHS
Language: English
Date published: 05/22/2019
Academic Unit: Chemistry
Record Identifier: 9984216561202771

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