In the chemical vapor deposition (CVD) synthesis of graphene, the surficial chemical state of the metal substrate has exerted key roles in all elemental reaction steps determining the growth mechanism of graphene. Herein, a CO2-participated annealing procedure is designed to construct catalytic Cu2O/Cu sites on Cu foil for the graphene CVD synthesis with CO2/CH4 as carbon sources. These Cu2O/Cu species can catalyze the CH4 decomposition and subsequent C─C coupling to form C2 intermediates for fast growth of monolayer hexagonal graphene domains with a diameter of ≈30µm within 0.5min. The graphene growth kinetics can be bidirectionally regulated merely with the variation of CO2 flow rate during annealing and growth stages, in association with the Cu+/Cu0 ratio, enabling simultaneous control over the size and shape of graphene domains. Density functional theory (DFT) calculations indicate that the catalytic Cu2O/Cu sites reduce the activation energy by ≈0.13eV for the first dehydrogenation of CH4, allowing the growing rate of graphene driven by coupling of C2 intermediates faster than their etching rate by O-containing *O and *OH species. The work provides novel insights into heterostructured nano-catalyst consisting of zero valent metal and variably valent metal oxide that facilitate the controllable synthesis of graphene materials.
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