The defect chemistry of doped-ceria is vital but tangled for sustainable conversion of biomass resources. In this work, a group of Zr-doped CeO solid solutions were prepared and the defect chemistry in CeZrO (0.02 ≤ ≤ 5) catalyst was elucidated over the oxidative coupling of lignin-based aniline and benzyl alcohol. Varying the Zr molar fraction enabled to successfully adjust the defect sites of catalysts and further influence their catalytic performances. In addition, the optimal CeZrO catalyst exhibited a flexible temperature adaptability, wide substrate scope and superior reusability. Various characterizations, kinetic investigations, controlled experiments, DFT calculations and DRIFT-IR technique were used to unravel the roles of Ce and oxygen defects and the reaction mechanism. It was disclosed that Zr-doped defects can obviously increase surface Ce cations, oxygen species (peroxide and superoxide anions) and oxygen vacancies. These coordinatively unsaturated sites were shown to play critical roles in absorbing and activating substrates hence can accelerate the formation rate of bio-based imines.

中文翻译：

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揭示木质素基苯胺和苯甲醇氧化偶联的掺杂二氧化铈催化剂的化学缺陷


掺杂二氧化铈的缺陷化学至关重要，但对于生物质资源的可持续转化来说却很复杂。在这项工作中，制备了一组Zr掺杂CeO固溶体，并阐明了CeZrO (0.02≤≤5)催化剂在木质素基苯胺和苯甲醇氧化偶联过程中的缺陷化学。改变Zr摩尔分数能够成功调整催化剂的缺陷位点并进一步影响其催化性能。此外，优化的CeZrO催化剂表现出灵活的温度适应性、广泛的底物范围和优异的可重复使用性。使用各种表征、动力学研究、对照实验、DFT 计算和 DRIFT-IR 技术来揭示 Ce 和氧缺陷的作用以及反应机制。研究表明，Zr掺杂缺陷可以明显增加表面Ce阳离子、氧物种（过氧化物和超氧阴离子）和氧空位。这些配位不饱和位点在吸收和活化底物中发挥着关键作用，因此可以加速生物基亚胺的形成速率。