The CO₂-assisted oxidative dehydrogenation of n-butane to 1,3-C₄H₆ offers a perspective process for producing valuable chemicals while simultaneously utilizing CO₂. In this work, iron-based ZnFe₂O_x and Fe₂O₃ catalysts with high 1,3-C₄H₆ selectivity were prepared and their corresponding structure–activity relationships were investigated in detail. On basis of the in situ spectroscopic characterization, hydrogen-assisted CO₂ activation pathway was captured. Kinetic studies show that Fe₂O₃ catalyst displays a higher reaction order depending on CO₂ concentration than that of ZnFe₂O_x catalyst. Fe₂O₃ is evidenced to serve as an effective mediator for oxygen exchange between CO₂ and n-butane based on temperature-programmed experiments and deactivation kinetics analysis. Rapid deactivation is observed over ZnFe₂O_x due to its strong CO₂ adsorption ability, which triggers the reforming reaction accompanied by severe coke deposition. Interestingly, self-healing phenomena for catalytic performance are found on Fe₂O₃ catalyst after several test cycles. The reaction/regeneration cycles are proved to drive the surface reconstruction which greatly enhance its resistance to over reduction and coking. This study provides a fundamental insight into Fe-based catalysts in the CO₂-assisted oxidative dehydrogenation reactions.

CO ₂辅助的正丁烷氧化脱氢生成1,3-C ₄ H _{6为在利用CO 2}的同时生产有价值的化学品提供了一种有前景的方法。本工作制备了具有高1,3-C ₄ H _{6选择性的铁基ZnFe 2} O _x和Fe ₂ O ₃催化剂，并详细研究了它们相应的构效关系。在原位光谱表征的基础上，捕获了氢辅助CO _{2活化途径。}动力学研究表明Fe ₂ O _{3取决于CO 2}浓度，催化剂表现出比ZnFe ₂ O _x催化剂更高的反应级数。基于程序升温实验和失活动力学分析，Fe ₂ O ₃被证明是CO _{2和正丁烷之间氧交换的有效介体。}由于其较强的CO ₂吸附能力， ZnFe ₂ O _x会发生快速失活，从而引发重整反应并伴有严重的焦炭沉积。_{有趣的是，在 Fe 2} O ₃上发现了催化性能的自修复现象经过多次测试循环后的催化剂。事实证明，反应/再生循环可驱动表面重构，从而大大增强其对过度还原和结焦的抵抗力。这项研究为CO ₂辅助的氧化脱氢反应中的铁基催化剂提供了基本的见解。