Hu Yanan, Gong Chenhao, Chen Peng, Li Yuanzhe, Zhu Wenjie, Liu Jiangping, Luo Yongming
Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China; Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China; The Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, China.
Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China; The Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, China.
J Hazard Mater. 2025 May 5;488:137496. doi: 10.1016/j.jhazmat.2025.137496. Epub 2025 Feb 4.
Unraveling the water activation is essential in the catalytic hydrolysis of organic sulfur compounds, yet its intrinsic mechanism of the water-promoting effect is still unclear. In this work, we describe novel findings of oxygen vacancy (V) engineering by facile regulating CeO nanocatalysts with different shapes (rod, octahedral, sphere, and cube) for COS hydrolysis at lower temperature, aiming at understanding the structural origin of the excellent catalytic hydrolysis activity. Unexpectedly, among CeO catalysts with different morphologies, spherical CeO (CeO-S) catalysts can achieve completely conversion of COS at 60 ℃ and maintain 30 hours of non-deactivation, which is a significant improvement in catalytic activity and reaction temperature compared to previously reported catalysts. Through various characterizations and results analysis, it is obvious to see that the more spontaneous formation V on CeO-S catalysts synergistically induced the water activation and dissociation thus result in the generation of more surface active hydroxyl groups (-OH), which contributes to the enhanced performance of COS catalytic hydrolysis at lower temperature. The promoting effect of catalyst morphology changes on COS hydrolysis were furthering analyzed using in situ DRIFTS and DFT calculations, and revealed that the exposed (111) crystal plane of CeO exhibits the strongest adsorption capacity for COS. Notably, CeO-S also exhibited good catalytic performance and stability towards to other typical organic sulfur compounds (COS and CS), which is beneficial for the wide application at complex operating conditions. This study provides new insights for designing OH-rich CeO catalysts to remove single as well as multi-component organic sulfur compounds for different applications at lower temperatures.
揭示水活化过程对于有机硫化合物的催化水解至关重要，但其促进水作用的内在机制仍不清楚。在这项工作中，我们描述了通过简便地调控不同形状（棒状、八面体、球形和立方体）的CeO纳米催化剂进行氧空位（V）工程的新发现，以实现低温下COS水解，旨在了解优异催化水解活性的结构起源。出乎意料的是，在不同形貌的CeO催化剂中，球形CeO（CeO-S）催化剂在60℃时可实现COS的完全转化，并保持30小时无失活，与先前报道的催化剂相比，这在催化活性和反应温度方面有显著提高。通过各种表征和结果分析，可以明显看出CeO-S催化剂上更自发形成的V协同诱导了水的活化和解离，从而导致产生更多的表面活性羟基（-OH），这有助于在较低温度下增强COS催化水解的性能。利用原位漫反射红外傅里叶变换光谱（DRIFTS）和密度泛函理论（DFT）计算进一步分析了催化剂形貌变化对COS水解的促进作用，并揭示了CeO暴露的（111）晶面对COS具有最强的吸附能力。值得注意的是，CeO-S对其他典型有机硫化合物（COS和CS）也表现出良好的催化性能和稳定性，这有利于在复杂操作条件下的广泛应用。这项研究为设计富含-OH的CeO催化剂以在较低温度下去除单组分和多组分有机硫化合物用于不同应用提供了新的见解。
