Photoelectrocatalytic Urea Synthesis via co-Reduction of CO2 and $NO_{2}^{-}$ over Metallic Surface Modified TiO2

doi:10.6023/A24110345

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (3): 247-255.DOI: 10.6023/A24110345 Previous Articles Next Articles

Article

金属原子表面修饰TiO₂光电催化CO₂与 $NO_{2}^{-}$ 共还原合成尿素

王瑛琦^a^,^b,^†, 常嘉怡^a^,^b,^†, 李敏^a^,^b^,^*(), 梁红^a^,^b, 李知恒^a^,^b, 谢文富^a^,^b, 王强^a^,^b^,^*()

a 北京林业大学环境科学与工程学院水体污染源控制技术北京市重点实验室北京 100083
b 北京林业大学环境科学与工程学院污染水体源控制与生态修复技术北京市高等学校工程研究中心北京 100083

投稿日期:2024-11-13 发布日期:2025-02-03
基金资助:
国家自然科学基金(52300125); 国家自然科学基金(22109004); 中央高校基本科研业务费(BLX202259); 中央高校基本科研业务费(BLX202257)

Photoelectrocatalytic Urea Synthesis via co-Reduction of CO₂ and $NO_{2}^{-}$ over Metallic Surface Modified TiO₂

Yingqi Wang^a^,^b,^†, Jiayi Chang^a^,^b,^†, Min Li^a^,^b(), Hong Liang^a^,^b, Zhiheng Li^a^,^b, Wenfu Xie^a^,^b, Qiang Wang^a^,^b()

a Beijing Key Laboratory for Source Control Technology of Water Pollution, College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China
b Beijing Engineering Research Center of Source Control and Ecological Restoration Technology for Contaminated Water Bodies, College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China

Received:2024-11-13 Published:2025-02-03
Contact: ^*E-mail: limin2022@bjfu.edu.cn; qiangwang@bjfu.edu.cn
About author:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(52300125); National Natural Science Foundation of China(22109004); Fundamental Research Funds for the Central Universities(BLX202259); Fundamental Research Funds for the Central Universities(BLX202257)

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Abstract

Using mild photoelectrocatalytic technology to co-reduce CO₂ from the atmosphere and $NO_{2}^{-}$ from water pollutants into high-value-added chemical urea is an effective approach to achieving pollution reduction and carbon reduction goals. However, this reaction involves a 12-electron co-reduction with dual-substrate molecules, making it highly challenging with a complex pathway and high demands on the catalyst. So, there are few reports on this reaction currently. In this study, Ru, Cu, and Zn atom-modified TiO₂catalytic materials (Ru, Cu, and Zn-TiO₂) were prepared via a hydrothermal method combined with photodeposition method. The specific synthesis processes are as follows: titanium butoxide was dropwise added into a H₂O/HCl mixed solution. Then the solution and fluorine-doped tin oxide (FTO) substrate were transferred and sealed in a Teflon-lined stainless-steel autoclave and heated to 150 ℃ for 20 h. The obtained TiO₂ photoelectrode was annealed in a muffle furnace at 350 ℃ for 2 h. The TiO₂ with different metal atom surface modifications were prepared by adding metal salt solution and methanol in a beaker, placing the TiO₂ photoelectrode in the solution and irradiating it with a 300 W xenon lamp for 1 h. We conducted catalytic urea synthesis experiments by using three-electrode configuration in a H-type quartz cell equipped with pretreated Nafion 117 membrane. The as-prepared semiconductor, Ag/AgCl electrode and Pt foil were utilized as the photocathode, reference and counter electrodes, respectively. 0.1 mol•L⁻¹ KNO₂ was used as the electrolyte in both the cathode and anode compartments. CO₂ gas was injected into the cathode chamber during the photoelectrocatalytic test. The experimental results showed that Ru-TiO₂ modified with 5% (w) Ru achieved a urea yield of 50.58 μmol•g⁻¹•h⁻¹ and a Faradaic efficiency (FE) of 16.66% under 2 h light irradiation at －0.1 V (vs. RHE). The 5% (w) Ru-TiO₂ catalyst exhibits a FE 1.65 times than that of TiO₂ under identical conditions. UV-Vis diffuse reflectance spectra (DRS) and electrochemical impedance spectra (EIS) indicate that Ru atoms can effectively enhance the light absorption, charge separation and transfer of TiO₂. Photogenerated electrons transfer from TiO₂ to Ru atomic sites, participating in the C—N coupling reaction. This work provides theoretical guidance for designing and synthesizing efficient catalysts for photoelectrocatalytic urea synthesis, offering novel idea and pathway for synergetic control of environmental pollution and carbon emissions.

Key words: titanium dioxide, photoelectrocatalysis, carbon dioxide, nitrite, urea

Cite this article

Yingqi Wang, Jiayi Chang, Min Li, Hong Liang, Zhiheng Li, Wenfu Xie, Qiang Wang. Photoelectrocatalytic Urea Synthesis via co-Reduction of CO₂ and $NO_{2}^{-}$ over Metallic Surface Modified TiO₂[J]. Acta Chimica Sinica, 2025, 83(3): 247-255.

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Fig. & Tab. 12

Figure 1. XRD patterns of TiO2 and M-TiO2

Figure 2. The SEM images of TiO2

Figure 3. The SEM images and mapping images of M-TiO2: (a~d) SEM and mapping images of Cu-TiO2; (e~h) SEM and mapping images of Zn-TiO2; (i~l) SEM and mapping images of Ru-TiO2

Figure 4. (a) The XPS spectra of TiO2 and Ru-TiO2; (b~d) The XPS spectra of Ti 2p, O 1s and Ru 3d

Figure 5. (a) UV-Vis DRS diagram; (b) Energy spectra of TiO2 and Ru-TiO2

Figure 6. (a) Yield and FE of photoelectrocatalytic urea synthesis for TiO2 under different voltages; (b) Yield of photoelectrocatalytic ammonia synthesis for TiO2 under different voltages; (c) Yield and FE of photoelectrocatalytic urea synthesis for TiO2 and M-TiO2; (d) Yield of photoelectrocatalytic ammonia synthesis for TiO2 and M-TiO2

Figure 7. The LSV plots of TiO2 and M-TiO2

Figure 8. (a) Yield and FE of photoelectrocatalytic urea synthesis for Ru-TiO2 with varied metal loadings; (b) Yield of photoelectrocatalytic ammonia synthesis for Ru-TiO2 with varied metal loadings

Figure 9. (a) Yield and FE of photoelectrocatalytic urea synthesis for Ru-TiO2 at different times; (b) Yield of photoelectrocatalytic ammonia synthesis for Ru-TiO2 at different times

Figure 10. (a) EIS plots of TiO2 and 5% (w) Ru-TiO2; (b) The LSV plots of TiO2 and 5% (w) Ru-TiO2

Figure 11. (a) Analysis diagram of carbon and nitrogen source for urea synthesis; (b) Comparative urea synthesis performance in PEC, EC and PC systems

Figure 12. Mechanism diagram of urea synthesis via photoelectrocatalysis

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金属原子表面修饰TiO₂光电催化CO₂与 $NO_{2}^{-}$ 共还原合成尿素

Photoelectrocatalytic Urea Synthesis via co-Reduction of CO₂ and $NO_{2}^{-}$ over Metallic Surface Modified TiO₂

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