The economical manufacturing of high-quality graphene has been a significant challenge in its large-scale application. Previously, we used molten Sn and Cu as the heat-transfer agent to produce multilayer graphene on the surface of gas bubbles in a bubble column. However, element Sn and Cu have poor catalytic activity toward methane pyrolysis. To further improve the yield of graphene, we have added active Ni into Sn to construct a Sn–Ni alloy in this work. The results show that Sn–Ni alloy is much more active for methane pyrolysis, and thus more graphene is obtained. However, the graphene product is more defective and thicker because of the faster growth rate. By using 300 ml molten Sn–Ni alloy (70 mm height) and 500 sccm source gas ( CH4:Ar = 1:9), this approach produces graphene with a rate of 0.61 g/hr and a conversion rate of methane to carbon of 37.9% at 1250 ℃ and ambient pressure. The resulting graphene has an average atom layer number of 22, a crumpled structure and good electrical conductivity.

We report a highly sensitive NO2 gas sensor based on multi-layer graphene (MLG) films synthesized by a chemical vapor deposition method on a microheater-embedded flexible substrate. The MLG could detect low-concentration NO2 even at sub-ppm (<200 ppb) levels. It also exhibited a high resistance change of ~6% when it was exposed to 1 ppm NO2 gas at room temperature for 1 min. The exceptionally high sensitivity could be attributed to the large number of NO2 molecule adsorption sites on the MLG due to its a large surface area and various defect-sites, and to the high mobility of carriers transferred between the MLG films and the adsorbed gas molecules. Although desorption of the NO2 molecules was slow, it could be enhanced by an additional annealing process using an embedded Au microheater. The outstanding mechanical flexibility of the graphene film ensures the stable sensing response of the device under extreme bending stress. Our large-scale and easily reproducible MLG films can provide a proof-of-concept for future flexible NO2 gas sensor devices.