Graphitization with Suppressed Carbon Loss for High-Quality Reduced Graphene Oxide.

Abstract

An efficient reduction method to obtain high-quality graphene sheets from mass-producible graphene oxide is highly desirable for practical applications. Here, we report an <i>in situ</i> deoxidation and graphitization mechanism for graphene oxide that allows for high-quality reduced graphene oxide sheets under the low temperature condition (<300 °C) by utilizing a well-known Fischer-Tropsch reaction catalyst (CuFeO₂). By applying modified FTR conditions, where graphene oxide was reduced on the catalyst surface under the hydrogen-poor condition, deoxidation with much suppressed carbon loss was possible, resulting in high-quality graphene sheets. Our experimental data and density functional theory calculations proved that reduction which occurred on the CuFeO₂ surface preferentially removed adsorbed oxygen atoms in graphene oxide sheets, leaving dissociated carbon structures to be restored to a near-perfect few-layer graphene sheet. TGA-mass data revealed that GO with catalysts released 92.8% less carbon-containing gases than GO without catalysts during the reduction process, which suggests that this process suppressed carbon loss in graphene oxide sheets, leading to near-perfect graphene. The amount of oxygen related to the epoxide group in the basal plane of GO significantly decreased to near zero (from 43.84 to 0.48 at. %) in catalyst-assisted reduced graphene oxide (CA-rGO). The average domain size and the density of defects of CA-rGO were 4 times larger and 0.1 times lower than those for thermally reduced graphene oxide (TrGO), respectively. As a result, CA-rGO had a 246 and 8 times lower electrical resistance than TrGO and CVD-graphene. With these performances, CA-rGO coated paper connected to a coin-cell battery successfully lit an LED bulb, and CA-rGO itself acted as an efficient catalyst for both the hydrogen evolution reaction and the oxygen evolution reaction.