Diethyl pentane-1,5-diyldicarbamate (PDC), a bio-based intermediate used for isocyanate and polyurethanes, was synthesized by the direct carbonylation of CO₂ and pentanediamine (PDA) with 2-cyanopyridine (2-CP) over Zr-doped CeO₂. In this study, Zr-doped CeO₂ catalysts with different contents of Zr are successfully synthesized to produce PDC from PDA, CO₂, and ethanol. Among them, Zr_0.05Ce exhibits enhanced reaction activity and the productivity reached 6.0 mmol·g⁻¹·h⁻¹. Characterizations based on X-ray photoelectron spectroscopy, Raman, and CO₂/NH₃-temperature-programmed desorption prove that the doping of Zr atoms into CeO₂ regulates the acid–base sites and promotes oxygen vacancy formation, which is primarily responsible for the formation of monoethyl carbonate, an intermediate for diethyl carbonate (DEC). In-situ diffuse reflectance Fourier-transform spectrometry and Fourier-transform infrared spectroscopy reveal that PDA reacts with 2-CP to form N, N'-(pentane-1,5-diyl)dipicolinamide, which are transformed into PDC. Finally, the catalytic activity could be regenerated after calcination. This study presents a green route for producing bio-based carbamate by constructing C-N bond using CO₂ as a carbonyl source, which can replace carbamates derived from petrochemical resources in the future.

1,5-二基二氨基甲酸二乙酯 (PDC) 是一种用于异氰酸酯和聚氨酯的生物基中间体，通过 CO 2 和戊二胺 (PDA) 与_2-氰基吡啶 (2-CP) 在 Zr 掺杂上直接羰基化合成二氧化_铈。本研究成功合成了不同Zr含量的Zr掺杂CeO _{2催化剂，以PDA、CO 2}和乙醇为原料生产PDC。其中Zr _0.05 Ce反应活性增强，产率达到6.0 mmol·g ^-1 ·h ^-1。基于 X 射线光电子能谱、拉曼和 CO ₂ /NH _3的表征程序升温脱附证明Zr原子掺杂到CeO ₂中可以调节酸碱位点并促进氧空位的形成，这主要是碳酸单乙酯（碳酸二乙酯（DEC）的中间体）的形成的原因。原位漫反射傅里叶变换光谱和傅里叶变换红外光谱表明PDA与2-CP反应生成N,N'-(戊烷-1,5-二基)吡啶二酰胺，并转化为PDC。最后，煅烧后催化活性可以再生。_{本研究提出了一条以CO 2}作为羰基源构建CN键生产生物基氨基甲酸酯的绿色路线，未来可以替代石化资源衍生的氨基甲酸酯。