Origin of anomalous strain effects on the molecular adsorption on boron-doped graphene

When compressive strain is applied to a single-layered material, the layer generally ripples along the third dimension to release the strain energy. In contrast, such a rippling effect is not favored when it is under tensile strain. Here, using first-principles density-functional calculations, we show that molecular adsorption on boron-doped graphene (BG) can be largely tuned by exploiting the rippling effect of the strained graphene. Under tensile strain, the adsorption energy of K2CO3, NO2, and NH3 on BG, for which the molecular adsorption is a chemisorption characterized by a covalent B-molecule bond, exhibits a superlinear dependence on the applied strain. In contrast, when microscopic ripples are present in the BG under compressive strain, the adsorption strength is significantly enhanced with increasing the strain. Such a nonlinear and asymmetric effect of strain on the molecular adsorption is a characteristic of two-dimensional systems, because a general elastic theory of molecular adsorption on three-dimensional systems gives a linear and symmetric strain effect on the adsorption strength. We provide the underlying mechanism of the anomalous strain effect on the chemical molecular adsorption on BG, in which the microscopic rippling of the graphene and the creation of the π-dangling bond state near the Dirac point play an important role. Our finding can be used to modify chemical reactivity of graphene with a wide range of application.