Abstract ZrO2 is known as a prospective catalyst for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol, which is important for CO2 utilization and green chemicals production. To identify the relationship between catalytic activity and surface acid–base properties, here, hydroxylated tetragonal (t) and monoclinic (m) zirconia are explored using density function theory (DFT) calculations combined with catalytic activity tests, as well as various characterization techniques, including in situ Fourier transform infrared (FTIR) spectra and temperature-programmed desorption of CO2 and NH3. DMC is formed from the combination of methyl and methyl carbonates on both catalysts, and m-ZrO2 exhibits higher DMC yield than t-ZrO2. The amount and strength of surface Bronsted acid sites, rather than Lewis base sites and Lewis acid sites, strongly affect catalytic performance of ZrO2. In addition, compared with t-ZrO2, m-ZrO2 displays a smaller band gap which also facilitates its catalytic activity for DMC synthesis.

中文翻译：

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ZrO2 表面酸碱性质对 CO2 和甲醇直接合成 DMC 的影响：DFT 和实验相结合的研究

摘要 ZrO2 被认为是由 CO2 和甲醇直接合成碳酸二甲酯 (DMC) 的潜在催化剂，对 CO2 的利用和绿色化学品生产具有重要意义。为了确定催化活性和表面酸碱性质之间的关系，在这里，使用密度函数理论 (DFT) 计算结合催化活性测试以及各种表征技术探索了羟基化四方晶 (t) 和单斜晶 (m) 氧化锆，包括原位傅里叶变换红外 (FTIR) 光谱和 CO2 和 NH3 的程序升温解吸。DMC 由甲基和甲基碳酸酯在两种催化剂上的组合形成，并且 m-ZrO2 表现出比 t-ZrO2 更高的 DMC 产率。表面布朗斯台德酸中心的数量和强度，而不是路易斯碱中心和路易斯酸中心，强烈影响 ZrO2 的催化性能。此外，与 t-ZrO2 相比，m-ZrO2 显示出更小的带隙，这也有利于其对 DMC 合成的催化活性。