Ab initio characterization and experimental validation on the roles of oxygen-containing groups in graphene based...

The development of formaldehyde (HCHO) sensors employing reduced graphene oxide (rGO) as sensing materials calls for a profound, atomic level understanding on the roles of oxygen-containing groups. In this work, the performances of rGO-based HCHO sensors were investigated using ab initio calculations and experimental validation. Density functional theory (DFT) simulations were performed to calculate the adsorption energy (E_ads) and charge transfer (ΔQ) for the adsorption of HCHO on pristine graphene, rGO with epoxides, rGO with hydroxyl groups, and rGO with carboxyl groups. The results show that the incorporation of oxygen-containing groups leads to an obvious increase of E_ads and ΔQ values, with an order of carboxyl group > hydroxyl group > epoxides > pristine graphene. The increase of E_ads and ΔQ values could increase the variation in the concentration of charge carriers, the change of conductance of the sensing materials, and hence the sensor response. The experimental measurements indicate that with a decrease in the C/O atomic ratio from 16.2 to 6.6, the sensor response to 1 ppm HCHO increases from 0.10% to 0.73%, confirming the DFT calculation results. Moreover, even with a certain C/O atomic ratio of ∼6.6, rGO with 6.80% carboxyl groups exhibits a distinctly larger response to 0.2-3 ppm HCHO, compared with the counterpart with 3.09% carboxyl groups. The as-obtained insights into the effects of oxygen-containing groups on the response of rGO to HCHO could be instructive for preparing rGO-based HCHO sensors for advanced performances.