Improvement in the activity of Ru/ZrO2 for CO2 methanation by the enhanced hydrophilicity of zirconia

Menghui Liu, Rui Zou, Chang-jun Liu
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Abstract

Increasing interests in the supported Ru catalysts for CO methanation can be recently found in the literature. In this work, we demonstrated that the enhanced surface hydrophilicity of ZrO via air plasma treatment has significant effects on the properties of Ru/ZrO catalyst for CO methanation. At the same CO conversions, the reaction temperature over the catalysts on ZrO with enhanced hydrophilicity is 20–70 °C lower than those on untreated ZrO. The catalyst characterization confirms that the enhanced hydrophilicity leads to more hydroxyl groups and oxygen vacancies on the support, which further promotes CO adsorption and activation, facilitating the conversion of CO to HCO* and HCOO* in formate pathway. The enhanced hydrophilicity also causes a high Ru dispersion with stronger electronic interaction between Ru and ZrO, which forms more interfacial active sites and improves the adsorption and dissociation of H, promoting the linear-CO-Ru adsorption in CO* pathway.
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氧化锆亲水性的增强提高了 Ru/ZrO2 对 CO2 甲烷化的活性
最近,人们对用于一氧化碳甲烷化的支撑型 Ru 催化剂的兴趣日益浓厚。在这项工作中,我们证明了通过空气等离子体处理增强 ZrO 表面亲水性对 Ru/ZrO 催化剂甲烷化 CO 的性能有显著影响。在相同的 CO 转化率下,亲水性增强的 ZrO 催化剂的反应温度比未经处理的 ZrO 催化剂低 20-70 ℃。催化剂表征证实,亲水性的增强会在载体上产生更多的羟基和氧空位,从而进一步促进 CO 的吸附和活化,促进 CO 通过甲酸途径转化为 HCO* 和 HCOO*。亲水性的增强还能使 Ru 高度分散,Ru 和 ZrO 之间的电子相互作用更强,从而形成更多的界面活性位点,改善 H 的吸附和解离,促进 CO* 途径中的线性-CO-Ru 吸附。
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