TY - JOUR
T1 - Modified potentiometric titration method to distinguish and quantify oxygenated functional groups on carbon materials by pKa and chemical reactivity
AU - Zhang, Zhongyao
AU - Flaherty, David W.
N1 - Funding Information:
We acknowledge Ms. Pranjali Priyadarshini and Mr. Daniel T. Bregante for their careful reviews of the manuscript and Flaherty group members for discussions and help. Jennifer Wilson and Brian Kitt from Spirit AeroSystems, Inc. also provide helpful opinions for this work. Authors acknowledge Spirit AeroSystems, Inc. for funding this project.
Funding Information:
We acknowledge Ms. Pranjali Priyadarshini and Mr. Daniel T. Bregante for their careful reviews of the manuscript and Flaherty group members for discussions and help. Jennifer Wilson and Brian Kitt from Spirit AeroSystems, Inc. also provide helpful opinions for this work. Authors acknowledge Spirit AeroSystems , Inc. for funding this project.
Publisher Copyright:
© 2020 Elsevier Ltd
PY - 2020/9/30
Y1 - 2020/9/30
N2 - The presence and form of oxygenated functions on carbons lead to significant differences in material properties that impact surface chemistry, catalysis, electronic, and mechanical properties. Titration methodologies, specifically potentiometric and Boehm titrations, classify the types of acidic functions present on carbon materials into broad categories described as carboxylic, lactonic, and phenolic functions based upon the measured or estimated acid dissociation constants (pKa). The accuracy of these methods depends, however, on the estimates for pKa values and suffers when multiple possible species possess similar pKa values. Here, we improve upon past methods by combining potentiometric and chemical titrations, which involves identifying acidic functions by pKa values but also examining how functional groups react with alkaline titrants. Specifically, Brønsted acids like carboxylic and phenolic groups deprotonate reversibly when contacted with alkaline titrant solutions; however, lactonic functions undergo hydrolysis to form carboxylic acids and hydroxyls during identical treatments. Consequently, comparisons between sequential potentiometric titrations can be used to discriminate between functional groups by examining their pKa values but also their reactivity. Tests on probe compounds and functionalized carbon materials show our method successfully distinguishes lactones from other acidic functions on carbon surfaces and suggests the methodology complements other characterization techniques for carbon materials.
AB - The presence and form of oxygenated functions on carbons lead to significant differences in material properties that impact surface chemistry, catalysis, electronic, and mechanical properties. Titration methodologies, specifically potentiometric and Boehm titrations, classify the types of acidic functions present on carbon materials into broad categories described as carboxylic, lactonic, and phenolic functions based upon the measured or estimated acid dissociation constants (pKa). The accuracy of these methods depends, however, on the estimates for pKa values and suffers when multiple possible species possess similar pKa values. Here, we improve upon past methods by combining potentiometric and chemical titrations, which involves identifying acidic functions by pKa values but also examining how functional groups react with alkaline titrants. Specifically, Brønsted acids like carboxylic and phenolic groups deprotonate reversibly when contacted with alkaline titrant solutions; however, lactonic functions undergo hydrolysis to form carboxylic acids and hydroxyls during identical treatments. Consequently, comparisons between sequential potentiometric titrations can be used to discriminate between functional groups by examining their pKa values but also their reactivity. Tests on probe compounds and functionalized carbon materials show our method successfully distinguishes lactones from other acidic functions on carbon surfaces and suggests the methodology complements other characterization techniques for carbon materials.
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U2 - 10.1016/j.carbon.2020.05.040
DO - 10.1016/j.carbon.2020.05.040
M3 - Article
AN - SCOPUS:85085659431
VL - 166
SP - 436
EP - 445
JO - Carbon
JF - Carbon
SN - 0008-6223
ER -