  The conversion of waste carbon dioxide (CO2) gas into valuable products and
fuels through an electrocatalytic CO2 reduction reaction (CO2RR) is a promising
approach. The sluggish kinetics of the CO2RR require the development of novel
strategies for electrocatalyst design. Two-dimensional (2D) materials emerge as
promising candidates for CO2RR due to their distinctive electronic and
structural properties. This study follows the first principles based DFT-D
method to examine the electrocatalytic competences of the defective
two-dimensional boron nitride monolayer (d-BN) material towards CO2RR.
Introducing a particular defect with nitrogen vacancies in the 2D single layer
pristine hexagonal boron nitride (VN_d-BN) can efficiently activate the CO2
molecules for hydrogenation by reducing the electronic band gap of the pristine
hBN from 6.23 eV to 3.0 eV. Therefore, VN_d-BN material can act as a large band
gap semiconductor. Our findings demonstrate that the defective regions in the
2D monolayer VN_d-BN serve as active sites (Boron) for both the adsorption and
activation of CO2. The subsequent hydrogenation steps occur sequentially once
the CO2 molecule is adsorbed on the catalytic surface. Our results indicate
that the OCHO* path is the most favorable for CH4 production. Hence, the 2D
monolayer VN_d-BN material holds a great promise as a cost-effective catalyst
for CO2RR, and it presents a viable alternative to expensive platinum (Pt)
catalysts.
