Professors Mingdi Yan and Lawrence Wolf of the University of Massachusetts Lowell are supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry to develop experimental and computationally guided approaches to enhance the reactivity of pristine graphene (a defect-free single layer, two-dimensional carbon material). The integration of theory with experiment provides a comprehensive, fundamental understanding of the reactions leading to the acceleration of discovery. The results have a direct impact on the practical utilization of this material, which exhibit extraordinary mechanical, electrical and thermal properties. Pristine graphene has the potential to impact many technologically important applications, such as in display screens, nanoelectronics, solar cells, and various others. Pristine graphene offers advantages over other forms of graphene, which are either oxidized or contain many defects. The computational modeling techniques used are incorporated in the curriculum of new computational chemistry courses offered to both undergraduate and graduate students. The students involved in the project receive training in research planning and evaluation through individualized development plans. Under-represented and female undergraduate students are recruited to participate in the project.

This project aims to expand the chemical space of pristine graphene. Specifically, the impacts of substrate and interface on the reactivity of pristine graphene in cycloaddition reactions is investigated both experimentally and computationally. Pristine graphene is fabricated on different surfaces by chemical vapor deposition or by transfer. Cycloaddition reactions, with initial focus on the (2+1) cycloaddition with perfluoroaryl azides, are carried out and the products are characterized. The study aims to shed light on the relationship between the reactivity of graphene and its supporting substrate interface. The reactivity of pristine graphene in other cycloaddition reactions is also a subject of this investigation. The theoretical underpinnings of the cycloaddition substrate/reactivity relationships with pristine graphene is established using density functional theory through the development and application of modern reactivity models. Pristine graphene is fairly inert chemically due to the large resonance stabilization resulting from the delocalization of its conjugated pi electrons over the entire two-dimensional network. Overcoming these inherent reactivity challenges offers the ability to introduce into pristine graphene well-defined functionalities. Other benefits include modulating graphene solubility and bandgap, and enabling its integration into high performance composite materials and devices.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

Agency
National Science Foundation (NSF)
Institute
Division of Chemistry (CHE)
Type
Standard Grant (Standard)
Application #
1808671
Program Officer
George Janini
Project Start
Project End
Budget Start
2018-08-01
Budget End
2021-07-31
Support Year
Fiscal Year
2018
Total Cost
$359,977
Indirect Cost
Name
University of Massachusetts Lowell
Department
Type
DUNS #
City
Lowell
State
MA
Country
United States
Zip Code
01854