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The thermodynamics on the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH was calculated and analyzed. Using Y­(NO3)3·6H2O as the precursor, a series of Y2O3 were prepared through the one-pot calcination method, which were employed to catalyze DMC synthesis. The decomposition temperature of Y­(NO3)3·6H2O was measured by thermogravimetric analysis, and Y2O3 was obtained after the precursor calcination at desired temperatures, denoted as Y2O3-T (°C). The catalysts were characterized by X-ray diffraction, Brunauer–Emmett–Teller method, transmission electron microscopy, NH3/CO2 temperature-programmed desorption, and X-ray photoelectron spectroscopy to detect the crystal phase, surface property, particle size, acidity–basicity amounts, and oxidation state, respectively. The characterization results indicated that Y2O3-750 can favor the formation of moderate acidic and basic sites and facilitate the activation of CO2 and CH3OH. The catalytic performance evaluation was experimentally investigated, and Y2O3-750 owned the highest DMC yield of 1.02 mmol/g·cat under 90 °C, 8 MPa, and 6 h, which also exhibited reliable recycle ability.

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