Diels–Alder reactions of graphene oxides: greatly enhanced chemical reactivity by oxygen-containing groups. Issue 18 (20th April 2017)

• Record Type: Journal Article
• Authors: Tang, Shaobin; Wu, Weihua; Liu, Liangxian; Cao, Zexing; Wei, Xiaoxuan; Chen, Zhongfang
• Is Part Of: Physical chemistry chemical physics. Volume 19:Issue 18(2017)
• Page Start: 11142
• Page End: 11151
• Publication Date: 2017-04-20
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c7cp01086a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Oxygen-containing groups of graphene oxides greatly enhanced the Diels–Alder (DA) reactivity of pristine graphene. Abstract : Graphene oxides (GOs) or reduced GOs (rGOs) may offer extraordinary potential for chemical functionalization of graphene due to their unique electronic and structural properties. By means of dispersion-corrected density functional theory computations, we systematically investigated the Diels–Alder (DA) chemistry of GOs. Our computations showed that the dual nature of GOs as both a diene and a dienophile is stronger than that of pristine graphene. Interestingly, the interior bonds of a graphene surface modified by oxygen-containing groups could be functionalized by maleic anhydride (MA) and 2, 3-dimethoxybutadiene (DMBD) through cycloaddition reactions, and the cycloaddition products of MA and DMBD are more favorable than the non-covalent complexes between these reagents and the GO surface. The feasibility of covalent functionalization of GOs as a diene and a dienophile strongly depends on the local structural environment of the oxygen groups, including the atomic arrangement and the number of these groups surrounding the reaction site. The exothermicities for (4+2) adducts of DMBD with GO are far larger than those of MA, which indicates that the dienophile character of the GO surface is stronger than its behavior as a diene.