常温常压下N2、CO2和H2O体系TiO2机械化学合成尿素的实验与理论研究

doi:10.6023/A25040118

摘要/Abstract

作为重要的化学品, 尿素的应用广泛, 然而传统Bosch-Meiser尿素生产工艺存在高能耗、高排放问题. 本工作提出在常温常压的条件下, 以N₂、CO₂和H₂O为原料, 通过机械化学合成尿素的新策略. 利用二氧化锆球磨罐和磨球, 分别研究了TiO₂、ZnO、Cu₂O、Nb₂O₅、Fe₂O₃作为催化剂的机械化学合成尿素的催化作用. 其中TiO₂表现出最佳的机械催化活性, 加入TiO₂在相同条件下尿素的产率能够达到133.59 μg•L^-1•h^-1, 相对于无催化剂提升了2.2倍. 利用透射电子显微镜(TEM)、能量色散X射线能谱(EDS)、X射线衍射(XRD)、X射线光电子能谱(XPS)、电子顺磁共振(EPR)、Raman光谱对机械球磨合成尿素后的TiO₂进行表征, 发现在机械球磨后TiO₂中氧空位的含量上升. 利用傅里叶变换红外光谱(FT-IR)等技术检测了TiO₂表面吸附的残余基团, 提出了可能的反应机理. 通过密度泛函理论计算研究了反应过程, H₂O在催化剂表面的裂解和N₂的活化是机械球磨合成尿素过程中两个重要步骤. TiO₂中的氧空位不但能够促进对N₂吸附和活化, 而且有助于H₂O的裂解, 以释放出自由H. 在尿素合成的反应过程中, H₂O裂解和*N₂与*CO之间发生的C—N偶联反应是尿素合成过程中的共速控步. 本工作提出了一种以N₂、CO₂和H₂O为原料通过机械化学合成尿素的方法, 初步揭示了TiO₂对机械化学合成尿素的催化作用机理.

关键词: 尿素合成, 机械化学, TiO₂催化剂, N₂活化, 密度泛函理论

As an important chemical, urea has a wide range of applications. However, the conventional Bosch-Meiser process suffers from high energy consumption and substantial carbon emissions. This study proposes a novel mechanochemical strategy for urea synthesis under ambient temperature and pressure using N₂, CO₂, and H₂O as feedstocks. Five transition metal oxide catalysts (TiO₂, ZnO, Cu₂O, Nb₂O₅, Fe₂O₃) were investigated for their mechanocatalytic effects in a ZrO₂ jar equipped with ZrO₂ balls, with TiO₂ exhibiting the highest performance. Urea production rate was up to 133.59 μg•L^-1•h^-1 with the presence of TiO₂, which is 2.2 times larger than that the catalyst-free conditions. TiO₂ was characterized using transmission electron microscope (TEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and Raman spectroscopy, revealing an increase in oxygen vacancies after the mechanochemical reaction. Fourier transform infrared spectroscopy (FT-IR) analysis was used to detect the adsorbed species on the TiO₂ surface, providing mechanistic insights. Density functional theory (DFT) calculations identified H₂O dissociation and N₂ activation as critical steps. The oxygen vacancies (Vo) in TiO₂ not only enhanced the adsorption of N₂ and H₂O but also facilitated H₂O dissociation to release free H atoms and weakened the N≡N bond. Both the H₂O dissociation and the C—N coupling between *N₂ and *CO were determined to be the rate-limiting step in urea formation. This study presents a green and energy-efficient mechanochemical approach for urea synthesis and elucidates the catalytic role of titanium dioxides in the process.

Key words: urea synthesis, mechanochemistry, TiO₂ catalyst, N₂ activation, density functional theory

引用此文

楼一淳, 何承溧, 王霖锐, 崔晓莉. 常温常压下N₂、CO₂和H₂O体系TiO₂机械化学合成尿素的实验与理论研究[J]. 化学学报, 2026, 84(1): 73-85.

Yichun Lou, Chengli He, Linrui Wang, Xiaoli Cui. Mechanochemical Urea Synthesis Using Nitrogen, Water and Carbon Dioxide with TiO₂ under Mild Conditions: An Experimental and Theoretical Study[J]. Acta Chimica Sinica, 2026, 84(1): 73-85.

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图/表 17

图1. 加入0.5 g不同的过渡金属催化剂后机械球磨合成尿素的产率. 标为“None”的表示不加入催化剂的条件下进行机械化学合成尿素. 使用ZrO2材质的磨球和球磨罐, 磨球装载量为140 g, 转速为650 r/min, 研磨时间为1.0 h

Figure 1. The mechanochemical urea yield rate with the addition of 0.5 g different metal oxide catalysts. The label “None” means performing mechanochemical urea synthesis without any additional catalysts. The grinding balls and grinding jar made of ZrO2 material were used, with a ball loading of 140 g, a rotation speed of 650 r/min, and a grinding time of 1.0 h

图2. N2、CO2和H2O体系机械化学合成尿素性能研究(100 mL ZrO2球磨罐和140 g磨球). (a)机械球磨尿素产量和球磨时间的关系; (b)机械球磨尿素产率和球磨转速的关系

Figure 2. The performance of mechanochemical synthesis of urea from N2, CO2 and H2O (100 mL ZrO2 ball milling jar and 140 g grinding balls). (a) Relationship between urea yield and ball milling time; (b) Relationship between urea yield and ball milling speed

图3. 球磨前TiO2的(a) TEM图和(b) HRTEM图, 球磨后收集到的TiO2样品的(c) TEM图和(d) HRTEM图(650 r/min, 140 g磨球, 球磨时长2.5 h)

Figure 3. (a) TEM image, (b) HRTEM image of TiO2 before milling, and (c) TEM image, (d) HRTEM image of TiO2 after milling (650 r/min, 140 g milling balls, and ball milling for 2.5 h)

图4. 机械化学合成尿素0, 0.5, 1.0, 1.5, 2.0, 2.5 h后催化剂TiO2的XRD图(650 r/min, 70 g磨球)

Figure 4. The XRD patterns of the TiO2 solid powders after the mechanochemical urea synthesis process for 0, 0.5, 1.0, 1.5, 2.0, 2.5 h (650 r/min, 70 g milling balls)

图5. 球磨前后的TiO2粉末的(a) XPS全谱以及(b) Ti 2p, (c) O 1s, (d) N 1s高分辨谱(650 r/min, 140 g磨球, 2.5 h)

Figure 5. (a) XPS spectra of TiO2 before and after milling and corresponding high-resolution spectra of (b) Ti 2p, (c) O 1s, and (d) N 1s of TiO2 powders (650 r/min, 140 g milling balls, 2.5 h)

图6. 机械球磨合成尿素0, 0.5, 1.0, 1.5, 2.0, 2.5 h TiO2的(a)拉曼光谱和(b) 400 cm-1到500 cm-1处的局部放大图(650 r/min, 70 g磨球)

Figure 6. (a) Raman spectra and (b) local magnification in the range of 400 cm-1 to 500 cm-1 of solid powders obtained after mechanical ball milling synthesis of urea for 0, 0.5, 1.0, 1.5, 2.0, and 2.5 h (650 r/min, 70 g grinding balls)

图7. 机械催化反应后TiO2粉末的电子顺磁共振波谱(球磨时间2.5 h)

Figure 7. Electron paramagnetic resonance spectrum of TiO2 powders obtained after mechanochemical urea synthesis for 2.5 h

图8. TiO2机械球磨合成尿素0 h, 2.5 h后所得的固体粉末的红外光谱. (a) 3800~2400 cm-1区域, (b) 1800~1200 cm-1区域

Figure 8. FT-IR spectra of solid powders obtained after TiO2-catalyzed mechanochemical urea synthesis for 0 and 2.5 h. (a) 3800~2400 cm-1 region, (b) 1800~1200 cm-1 region

图9. 通过CO2和N2机械化学合成尿素的不同机理及其中间物. 从CO2生成*CO的途径, N2以(a)侧向吸附或(b)端向吸附[52]. 路径中的H•和e-代表机械能诱导的活性氢与局域电子, 由H2O裂解及缺陷位点提供, 非电化学过程

Figure 9. Different mechanisms of mechanochemical urea synthesis from CO2 and N2 and corresponding intermediate: the formation pathway of *CO from CO2, the adsorption way of N2 via (a) side-on and (b) end-on[52]. The H• and e- present in the pathway denote mechanically induced active hydrogen species and localized electrons, originating from water (H2O) splitting and defect sites, respectively; this mechanism operates independently of electrochemical processes

图10. 分别使用A: 2 g (COOH)2, N2和30 mL H2O以及B: N2和30 mL H2O以及C: CO2和30 mL H2O为原料机械球磨合成尿素(球磨时间1.0 h, 650 r/min, 140 g磨球)

Figure 10. Control experiments of mechanical ball mill urea synthesis. Urea synthesized via A: 2 g (COOH)2, N2, with 30 mL H2O, B: N2, with 30 mL H2O, and C: CO2, with 30 mL H2O (1.0 h ball milling time, 650 r/min, 140 g milling balls)

图11. 在TiO2 (101)表面上可能形成的两种Vo(灰色小球代表Ti, 红色小球代表O)

Figure 11. Two types of Vo that may form on TiO2 (101) surface (grey balls represent Ti and red balls represent O)

图12. H2O在Vo-TiO<H2O在Vo-TiO2 (101)表面的化学吸附和解离(每一步的形成能在图中已标出). (a)邻近Vo的Ti位点, (b)远离Vo的Ti位点(灰色小球代表Ti, 红色小球代表O, 白色小球代表H)

Figure 12. The pathway of H2O molecules chemisorbed and dissociated on the Vo-TiO2 (101) surface (Each step has its corresponding formation energy value marked). (a) Ti sites adjacent to Vo, and (b) Ti sites away from Vo (grey balls represent Ti, red balls O, white balls H)

图13. 几何优化后N2吸附在富含氧空位的TiO2 (101)表面上不同吸附构型: (a)在Vo上的侧向吸附方式和(b)端向吸附方式, (c)邻近Vo的端向吸附方式(对应吸附构型的吸附能已在图中标出, 灰色小球代表Ti, 红色小球代表O, 蓝色小球代表N)

Figure 13. The adsorption structu The adsorption structure of N2 molecules on the TiO2 (101) surface with the presence of oxygen vacancies (Vo) after geometry optimization, with different adsorption sites: (a) side-on adsorption and (b) end-on adsorption at Vo site, and (c) end-on adsorption adjacent to Vo (The adsorption energies corresponding to these configurations are marked in the figure, grey balls represent Ti, red balls O, blue balls N)

图14. N2在Vo-TiO2 (101)表面于Vo上侧向吸附时机械化学合成尿素可能的演变路线(灰色小球代表Ti, 红色小球代表O, 蓝色小球代表N, 白色小球代表H, 深灰色小球代表C)

Figure 14. The possible evolution pathway for the mechanochemical synthesis of urea with the side-on adsorption of N2 on the Vo site of the Vo-TiO2 (101) surface (grey balls represent Ti, red balls O, blue balls N, white balls H, dark-grey balls C)

图15. N2在Vo-TiO2 (101)表面于Vo上端向吸附时机械化学合成尿素可能的演变路线(灰色小球代表Ti, 红色小球代表O, 蓝色小球代表N, 白色小球代表H, 深灰色小球代表C)

Figure 15. The possible evolution pathway for the mechanochemical synthesis of urea with the end-on adsorption of N2 on the Vo site of the Vo-TiO2 (101) surface (grey balls represent Ti, red balls O, blue balls N, white balls H, dark-grey balls C)

图16. N2在Vo-TiO2 (101)表面上以侧向吸附和端向吸附时机械球磨合成尿素过程中各反应步骤之间形成能的变化

Figure 16. The formation energy between each reaction step during the mechanical ball milling synthesis of urea with N2 adsorbed on the Vo-TiO2 (101) surface via side-on and end-on adsorption

图17. TiO2 (101)晶面结构(几何优化后所得的结果): (a)俯视图, (b)侧视图, (c)主视图(灰色小球表示Ti, 红色小球表示O)

Figure 17. The structure of TiO2 (101) surface (the result from geometry optimization): (a) top view, (b) side view, (c) main view (grey balls represent Ti, red balls represent O)

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常温常压下N₂、CO₂和H₂O体系TiO₂机械化学合成尿素的实验与理论研究

Mechanochemical Urea Synthesis Using Nitrogen, Water and Carbon Dioxide with TiO₂ under Mild Conditions: An Experimental and Theoretical Study

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