Theoretical and Experimental Studies of Molecular Interactions between Engineered Graphene and Phosphate Ions for Graphene-Based Phosphate Sensing.

Fundamental understanding of the interactions of nanoscale materials with molecules of interest is essential for the development of electronic devices, such as sensors. In particular, structures and molecular interaction properties of engineered graphenes are still largely unexplored, despite these materials' great potential to be used as molecular sensors. As an example of end user application, the detection of phosphorus in the form of phosphate in a soil environment is important for soil fertility and plant growth. However, due to the lack of an affordable technology, it is currently hard to measure the amount of phosphate directly in the soil; therefore, suitable sensor technologies need to be developed for phosphate sensors. In this work, pristine graphene and several modified graphene materials (oxygenated graphene, graphene with vacancies, and curved graphene) were studied as candidates for phosphate sensor materials using density functional theory (DFT) calculations. Our calculations showed that both pristine graphene and functionalized graphene were able to adsorb phosphate species strongly. In addition, these graphene nanomaterials showed selectivity of adsorption of phosphate with respect to nitrate, with stronger adsorption energies for phosphate. Furthermore, our calculations showed significant changes in electrical conductivities of pristine graphene and functionalized graphenes after phosphate species adsorption, in particular, on graphene with oxygen (hydroxyl and epoxide) functional groups. Experimental measurements of electrical resistivity of graphene before and after adsorption of dihydrogen phosphate showed an increase in resistivity upon adsorption of phosphate, consistent with the theoretical predictions. Our results recommend graphene and functionalized graphene-based nanomaterials as good candidates for the development of phosphate sensors.