电催化二氧化碳还原耦联氨亲核加成反应高效合成尿素

doi:10.1016/S1872-2067(26)65213-8

摘要/Abstract

摘要：

尿素是至关重要的氮肥和工业原料, 全球年产量超1亿吨. 然而, 传统Bosch-Meiser工艺合成尿素能耗巨大, 且对环境不友好. 因此, 开发温和条件下节能环保合成尿素新路径具有重要战略意义. 电催化CO₂还原耦联NH₃亲核加成反应(ECRR/NARN)是一种新兴尿素合成方法. 该方法以电催化CO₂还原过程中产生CO₂^•-中间体为碳源, 以NH₄⁺水解生成NH₃为氮源, 通过CO₂^•-中间体与NH₃发生亲核加成反应实现C-N偶联合成尿素. 相较于传统的CO₂与NO_x^-共还原路径, 该方法反应路径更加精简, 且避免了氮源经历不必要其他氧化还原过程. 理论上具有更高电子利用效率. 然而, 当前该方案面临两大关键挑战: 一是CO₂^•-中间体极易发生竞争反应转化为CO, 导致C-N偶联效率低下; 二是催化剂在实现高效还原CO₂的同时, 难以有效吸附NH₃, 使得CO₂^•-与NH₃有效碰撞概率极低, 严重制约了尿素产率的提升.
针对上述挑战, 本研究设计并构建了一种Pd团簇与Ni单原子相结合的双位点催化剂(Pd_1.0/Ni_SAs-N-C), 通过“位点分工-中间体迁移”协同催化机制, 实现了CO₂^•-中间体与NH₃的高效偶联合成尿素. 在-1.3 V vs. RHE电位下, 该催化剂在CO₂饱和的0.5 mol·L^-1NH₄HCO₃溶液中实现了3.10 mmol·L^-1·g^-1·h^-1的尿素产率, 远超过单一Ni_SAs-N-C的尿素产率(0.22 mmol·L^-1·g^-1·h^-1), 这是目前已知的通过ECRR/NARN路径合成尿素的最高产率. 实验表征与理论计算表明, Pd团簇与Ni单原子之间存在电子相互作用, 部分电子从Pd转移至Ni, 诱导了二者电子结构的重构. 一方面, Pd团簇因失去部分电子, 其轨道未占据态增加, 从而促进Pd团簇与NH₃分子中N的孤对电子发生d-p轨道杂化, 显著增强了Pd团簇对NH₃吸附能力. NH₃吸附能从Ni位点的-0.17 eV上升至Pd位点的-1.66 eV, 有效富集了反应物; 另一方面, 电荷重构使Ni单原子的d带中心下移, 从-2.516 eV降至-2.595 eV, 这一变化优化了Ni单原子对CO₂^•-的吸附强度, 使Ni单原子对CO₂^•-的吸附能从0.18 eV上升至0.32 eV, 这不仅有效抑制了CO₂^•-中间体向CO转化的副反应, 同时还促进了CO₂^•-中间体从Ni位点脱附并迁移至Pd位点, 从而显著提高了CO₂^•-中间体与NH₃的有效碰撞概率. 这种协同催化机制显著降低了C-N偶联能垒, 使其从0.40 eV降至0.24 eV, 从而加速了整体反应动力学速率. 该“位点分工-中间体迁移”机制为电催化耦合反应中多活性中心的协同设计提供了新思路.
综上, 本研究证实“位点分工-中间体迁移”机制可显著提升ECRR/NARN方式合成尿素的产率, 为突破该路径效率瓶颈提供了新思路. 随着理论计算与原位表征技术的深度融合深入揭示尿素合成反应机制, 未来高效稳定ECRR/NARN催化剂将不断涌现, 为多步串联电催化反应的多活性中心设计提供重要参考.

关键词: 尿素, 双位点催化剂, 竞争反应, 氨吸附, 中间体迁移

Abstract:

The electrocatalytic CO₂ reduction reaction coupled with nucleophilic addition reaction of NH₃ represents a promising route to synthesis urea. Relying on interfacial reactions between surface-adsorbed CO₂^•- from CO₂ reduction and dissolved NH₃. However, its efficiency is limited by competing CO formation and weak NH₃ adsorption, which restrict the C-N coupling efficiency. Thus, achieving synergistic co-adsorption of CO₂^•- and NH₃ while suppressing the CO pathway is essential. This study presents a dual-site catalyst with Pd clusters and Ni single atoms (Pd_1.0/Ni_SAs-N-C). In 0.5 mol·L^-1 NH₄HCO₃ solution at -1.3 V vs. RHE, Pd_1.0/Ni_SAs-N-C achieves a record urea production rate of 3.10 mmol·L^-1·g^-1·h^-1, substantially exceeding Ni_SAs-N-C (0.22 mmol·L^-1·g^-1·h^-1). Experimental and theoretical analyses reveal that electronic interaction between Ni and Pd sites induces charge redistribution, which enhances NH₃ adsorption on Pd via d-p orbital hybridization and optimizes CO₂^•- binding on Ni. This synergy suppresses CO formation and promotes CO₂^•- transfer to Pd sites, thereby increasing the “collision” probability between CO₂^•- and NH₃ and reducing the C-N coupling energy barrier from 0.40 to 0.24 eV, which accelerates the overall kinetics. The “site division-intermediate migration” mechanism offers a new paradigm for electrocatalytic coupling systems.

Key words: Urea, Dual-site catalyst, Competitive reactions, Ammonia adsorption, Intermediate migration

樊舒畅, 李沛泽, 孙天宇, 卫言, 于召式, 张剑东, 王鸣魁, 申燕. 电催化二氧化碳还原耦联氨亲核加成反应高效合成尿素[J]. 催化学报, 2026, 91: 135-146.

Shuchang Fan, Peize Li, Tianyu Sun, Yan Wei, Zhaoshi Yu, Jiandong Zhang, Mingkui Wang, Yan Shen. Efficient urea synthesis via electrocatalytic CO₂ reduction reaction coupled with nucleophilic addition reaction of NH₃[J]. Chinese Journal of Catalysis, 2026, 91: 135-146.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65213-8

https://www.cjcatal.com/CN/Y2026/V91/I12/135

图/表 6

Fig. 1. (a) SEM image of Pd1.0/NiSAs-N-C. (b) HAADF-STEM image of Pd1.0/NiSAs-N-C at 50 nm. (c) HAADF-STEM image of Pd1.0/NiSAs-N-C at 5 nm. AC-STEM images of NiSAs-N-C (d) and Pd1.0/NiSAs-N-C (e) (Ni single atoms are marked by red circles, and Pd clusters were marked by yellow circles). (f) HAADF-STEM image and corresponding EDS mapping of Pd1.0/NiSAs-N-C.

Fig. 2. (a) XRD patterns of N-C, NiSAs-N-C, and Pd1.0/NiSAs-N-C. (b) C 1s XPS spectrum of Pd1.0/NiSAs-N-C. (c) N 1s XPS spectrum of Pd1.0/NiSAs-N-C. (d) Ni 2p XPS spectra of NiSAs-N-C and Pd1.0/NiSAs-N-C. (e) Pd 3d XPS spectra of Pd1.0/N-C and Pd1.0/NiSAs-N-C. (f) XRD patterns of Pd0.5/NiSAs-N-C, Pd1.0/NiSAs-N-C, and Pd1.5/NiSAs-N-C.

Fig. 3. Electrochemical tests. (a) LSV curves of the Pd1.0/NiSAs-N-C electrode in different solutions. (b) Urea production rate and FEurea of the Pd1.0/NiSAs-N-C electrode at each potential. (c) The FECO comparison of the Pd1.0/NiSAs-N-C, NiSAs-N-C, N-C electrodes in a CO2-saturated 0.5 mol·L-1 NH4HCO3 solution from -0.7 to -1.7 V (vs. RHE). (d) Urea production rates of Pdx/NiSAs-N-C electrodes (x=0.5, 1.0, 1.5) at -0.7 to -1.7 V (vs. RHE). (e) Stability test of the Pd1.0/NiSAs-N-C electrode at -1.3 V vs. RHE.

Fig. 4. UV-Vis in situ absorption spectra of the NiSAs-N-C electrode (a) and Pd1.0/NiSAs-N-C electrode (b) in a CO2-saturated 0.5 mol·L-1 KHCO3 solution at -0.7 to -1.7 V (vs. RHE). (c) JCO for NiSAs-N-C, Pd1.0/NiSAs-N-C electrodes in CO2 saturated 0.5 mol·L-1 NH4HCO3 solutions at -0.7 to -1.7 V (vs. RHE). (d) UV-vis in-situ absorption spectra of the NiSAs-N-C electrode and (e) Pd1.0/NiSAs-N-C electrode in an Ar-saturated 0.5 mol·L-1 NH4HCO3 solution at -0.7 to -1.7 V (vs. RHE). (f) NH3-TPD spectra of NiSAs-N-C and Pd1.0/NiSAs-N-C.

Fig. 5. In-situ FT-IR test of the Pd1.0/NiSAs-N-C electrode in a CO2-saturated 0.5 mol·L-1 NH4HCO3 solution within the potential range of -0.6 to -1.8 V (vs. RHE) was conducted, with tests in the wavenumber ranges of 2600-3600 cm-1 (a) and 1000-1800 cm-1 (b).

Fig. 6. DFT calculations of electronic property and reaction free energy. (a) PDOS of Ni in NiSAs-N-C and Pd1.0/NiSAs-N-C. (b) After introducing NH3 into Pd1.0/NiSAs-N-C, the PDOS of Pd (d) and N (p). (c) The adsorption energies of CO2•- and NH3 on NiSAs-N-C, as well as those of CO2•- on the Ni sites of Pd1.0/NiSAs-N-C and NH3 on the Pd sites of Pd1.0/NiSAs-N-C. (d) Free energy diagrams of ECRR/NARN on NiSAs-N-C and Pd1.0/NiSAs-N-C. (e) ECRR/NARN reaction mechanism diagram.

参考文献

[1]	X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S.-Z. Qiao, Nat. Commun., 2022, 13, 5471.
[2]	H. Wang, Z. Xin, Y. Li, Top. Curr. Chem., 2017, 375, 49.
[3]	J. Qiao, Y. Liu, F. Hong, J. Zhang, Chem. Soc. Rev., 2014, 43, 631-675.
[4]	M. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev., 2014, 114, 1709-1742.
[5]	C. Smith, A. K. Hill, L. Torrente-Murciano, Energy Environ. Sci., 2020, 13, 331-344.
[6]	M. Wang, M. A. Khan, I. Mohsin, J. Wicks, A. H. Ip, K. Z. Sumon, C.-T. Dinh, E. H. Sargent, I. D. Gates, M. G. Kibria, Energy Environ. Sci., 2021, 14, 2535-2548.
[7]	X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie, D. Wang, M. Qiu, N. He, P. Zhou, W. Chen, J. Cheng, H. Lin, J. Jia, X.-Z. Fu, S. Wang, J. Am. Chem. Soc., 2022, 144, 11530-11535.
[8]	R. F. Service, Science, 2014, 345, 610.
[9]	C. Chen, D. Yan, Y. Wang, Y. Zhou, Y. Zou, Y. Li, S. Wang, Small, 2019, 15, 1805029.
[10]	S. Licht, B. Cui, B. Wang, F.-F. Li, J. Lau, S. Liu, Science, 2014, 345, 637-640.
[11]	Q. Wang, J. Guo, P. Chen, J. Energy Chem., 2019, 36, 25-36.
[12]	S. Ghavam, M. Vahdati, I. A. Grant Wilson, P. Styring, Front. Energy Res., 2021, 9, 580808.
[13]	X. Zhang, X. Zhu, S. Bo, C. Chen, M. Qiu, X. Wei, N. He, C. Xie, W. Chen, J. Zheng, P. Chen, S.-P. Jiang, Y. Li, Q. Liu, S. Wang, Nat. Commun., 2022, 13, 5337.
[14]	C. Chen, X. Zhu, X. Wen, Y. Zhou, L. Zhou, H. Li, L. Tao, Q. Li, S. Du, T. Liu, D. Yan, C. Xie, Y. Zou, Y. Wang, R. Chen, J. Huo, Y. Li, J. Cheng, H. Su, X. Zhao, W. Cheng, Q. Liu, H. Lin, J. Luo, J. Chen, M. Dong, K. Cheng, C. Li, S. Wang, Nat. Chem., 2020, 12, 717-724.
[15]	A. Adalder, K. Mitra, S. Bhowmick, U. K. Ghorai, Adv. Energy Mater., 2026, 16, e05111.
[16]	J. Mukherjee, S. Paul, A. Adalder, S. Kapse, R. Thapa, S. Mandal, B. Ghorai, S. Sarkar, U. K. Ghorai, Adv. Funct. Mater., 2022, 32, 2200882.
[17]	S. R. Waghela, A. Adalder, K. Mitra, U. K. Ghorai, ChemCatChem, 2025, 17, e202401565.
[18]	H. Li, L. Xu, S. Bo, Y. Wang, H. Xu, C. Chen, R. Miao, D. Chen, K. Zhang, Q. Liu, J. Shen, H. Shao, J. Jia, S. Wang, Nat. Commun., 2024, 15, 8858.
[19]	A. Adalder, K. Mitra, N. Barman, R. Thapa, R. Urkude, S. Das, U. K. Ghorai, Small, 2025, 21, 2505313.
[20]	T.-J. Lin, W.-S. Chen, H.-C. Li, C.-Y. Chen, H. Choi, Y. Kwon, M.-J. Cheng, J. Phys. Chem. C, 2025, 129, 3424-3436.
[21]	C. Lv, C. Lee, L. Zhong, H. Liu, J. Liu, L. Yang, C. Yan, W. Yu, H. H. Hng, Z. Qi, L. Song, S. Li, K. P. Loh, Q. Yan, G. Yu, ACS Nano, 2022, 16, 8213-8222.
[22]	C. Lv, L. Zhong, H. Liu, Z. Fang, C. Yan, M. Chen, Y. Kong, C. Lee, D. Liu, S. Li, J. Liu, L. Song, G. Chen, Q. Yan, G. Yu, Nat. Sustain., 2021, 4, 868-876.
[23]	Y. T. Wang, T. L. Li, Y. F. Yu, B. Zhang, Angew. Chem. Int. Ed., 2022, 61, e202115409.
[24]	S. Han, H. Li, T. Li, F. Chen, R. Yang, Y. Yu, B. Zhang, Nat. Catal., 2023, 6, 402-414.
[25]	F.-Y. Chen, Z.-Y. Wu, S. Gupta, D. J. Rivera, S. V. Lambeets, S. Pecaut, J. Y. T. Kim, P. Zhu, Y. Z. Finfrock, D. M. Meira, G. King, G. Gao, W. Xu, D. A. Cullen, H. Zhou, Y. Han, D. E. Perea, C. L. Muhich, H. Wang, Nat. Nanotechnol., 2022, 17, 759-767.
[26]	J. G. Chen, R. M. Crooks, L. C. Seefeldt, K. L. Bren, R. M. Bullock, M. Y. Darensbourg,P. L. Holland, B. Hoffman, M. J. Janik, A. K. Jones, M. G. Kanatzidis, P. King, K. M. Lancaster, S. V. Lymar, P. Pfromm, W. F. Schneider, R. R. Schrock, Science, 2018, 360, eaar6611.
[27]	H. Xiong, P. Yu, K. Chen, S. Lu, Q. Hu, T. Cheng, B. Xu, Q. Lu, Nat. Catal., 2024, 7, 785-795.
[28]	P. Li, Z. Zhang, X. Yang, Y. Zhu, Z. Zhou, X. Jiang, Q. Wang, X. Gao, X. Yang, Y. Shen, M. Wang, ChemCatChem, 2024, 16, e202301302.
[29]	P. Li, Y. Wei, X. Yang, Y. Zhu, Z. Zhang, X. Yang, Y. Shen, M. Wang, ACS Catal., 2024, 14, 7967-7977.
[30]	Y. Huang, T. Fan, Y. Ji, Phys. Chem. Chem. Phys., 2024, 27, 531-538.
[31]	J. Su, Y. Yang, G. Xia, J. Chen, P. Jiang, Q. Chen, Nat. Commun., 2017, 8, 14969.
[32]	S. Yuan, Z. Pu, H. Zhou, J. Yu, I. S. Amiinu, J. Zhu, Q. Liang, J. Yang, D. He, Z. Hu, G. Van Tendeloo, S. Mu, Nano Energy, 2019, 59, 472-480.
[33]	W. Miao, R. Hao, L. Gan, W. Xu, Z. Wang, W. Lin, H. Liu, Y. Lyu, Q. Li, J. Xi, A. Nie, J. Wu, H. Wang, J. Energy Chem., 2025, 101, 733-743.
[34]	Z. Jiang, Q. Pan, M. Li, T. Yan, T. Fang, Appl. Surf. Sci., 2014, 292, 494-499.
[35]	G. Novell-Leruth, A. Valcárcel, J. Pérez-Ramírez, J. M. Ricart, J. Phys. Chem. C, 2007, 111, 860-868.
[36]	E. Sälli, S. Martiskainen, L. Halonen, J. Phys. Chem. C, 2012, 116, 14960-14969.
[37]	J. Wang, S. Kattel, C. J. Hawxhurst, J. H. Lee, B. M. Tackett, K. Chang, N. Rui, C.-J. Liu, J. G. Chen, Angew. Chem. Int. Ed., 2019, 58, 6271-6275.
[38]	D. Gao, H. Zhou, F. Cai, J. Wang, G. Wang, X. Bao, ACS Catal., 2018, 8, 1510-1519.
[39]	H. Huang, H. Jia, Z. Liu, P. Gao, J. Zhao, Z. Luo, J. Yang, J. Zeng, Angew. Chem. Int. Ed., 2017, 56, 3594-3598.
[40]	C. Sun, F. Li, H. An, Z. Li, A. M. Bond, J. Zhang, Electrochim. Acta, 2018, 269, 733-741.
[41]	B. Zhang, Y. Chen, J. Wang, H. Pan, W. Sun, Adv. Funct. Mater., 2022, 32, 2202227.
[42]	H. Rong, S. Ji, J. Zhang, D. Wang, Y. Li, Nat. Commun., 2020, 11, 5884.
[43]	X. Cheng, Y. Li, L. Zheng, Y. Yan, Y. Zhang, G. Chen, S. Sun, J. Zhang, Energy Environ. Sci., 2017, 10, 2450-2458.
[44]	X. Guo, X. Wan, Q. Liu, Y. Li, W. Li, J. Shui, eScience, 2022, 2, 304-310.
[45]	F. Li, H.-J. Noh, W. Che, J.-P. Jeon, G.-F. Han, T. J. Shin, M. G. Kim, Y. Wang, Y. Bu, Z. Fu, Y. Lu, J.-B. Baek, ACS Nano, 2022, 16, 18830-18837.
[46]	Y. Guo, M. Wang, Q. Zhu, D. Xiao, D. Ma, Nat. Catal., 2022, 5, 766-776.
[47]	R. Yao, K. Sun, K. Zhang, Y. Wu, Y. Du, Q. Zhao, G. Liu, C. Chen, Y. Sun, J. Li, Nat. Commun., 2024, 15, 2218.
[48]	C.-Z. Yuan, K. Liang, X.-M. Xia, Z.-K. Yang, Y.-F. Jiang, T. Zhao, C. Lin, T.-Y. Cheang, S.-L. Zhong, A.-W. Xu, Catal. Sci. Technol., 2019, 9, 3669-3674.
[49]	S. Zhang, X. Ao, J. Huang, B. Wei, Y. Zhai, D. Zhai, W. Deng, C. Su, D. Wang, Y. Li, Nano Lett., 2021, 21, 9691-9698.
[50]	M. Zhou, Y. Jiang, G. Wang, W. Wu, W. Chen, P. Yu, Y. Lin, J. Mao, L. Mao, Nat. Commun., 2020, 11, 3188.
[51]	Y. Goto, K. Taniguchi, T. Omata, S. Otsuka-Yao-Matsuo, N. Ohashi, S. Ueda, H. Yoshikawa, Y. Yamashita, H. Oohashi, K. Kobayashi, Chem. Mater., 2008, 20, 4156-4160.
[52]	F. Petraki, V. Papaefthimiou, S. Kennou, Org. Electron., 2007, 8, 522-528.
[53]	K. Fujiwara, U. Müller, S. E. Pratsinis, ACS Catal., 2016, 6, 1887-1893.
[54]	N. Ye, Y. Bai, Z. Jiang, T. Fang, Int. J. Hydrogen Energy, 2020, 45, 32022-32038.
[55]	M. A. Albrahim, A. Shrotri, R. R. Unocic, A. S. Hoffman, S. R. Bare, A. M. Karim, Angew. Chem. Int. Ed., 2023, 62, e202308002.
[56]	Y. B. Zhu, P. Z. Li, X. J. Yang, M. Q. Wang, Y. L. Zhang, P. K. Gao, Q. K. Huang, Y. Wei, X. Yang, D. Y. Wang, Y. Shen, M. K. Wang, Adv. Energy Mater., 2023, 13, 2204143.
[57]	L. Pan, J. Wang, F. Lu, Q. Liu, Y. Gao, Y. Wang, J. Jiang, C. Sun, J. Wang, X. Wang, Angew. Chem. Int. Ed., 2023, 62, e202216835.
[58]	J. Geng, S. Ji, M. Jin, C. Zhang, M. Xu, G. Wang, C. Liang, H. Zhang, Angew. Chem. Int. Ed., 2023, 62, e202210958.
[59]	N. Meng, Y. Huang, Y. Liu, Y. Yu, B. Zhang, Cell Rep. Phys. Sci., 2021, 2, 100378.
[60]	N. J. Firet, W. A. Smith, ACS Catal., 2017, 7, 606-612.
[61]	R. Keuleers, H. O. Desseyn, B. Rousseau, C. Van Alsenoy, J. Phys. Chem. A, 1999, 103, 4621-4630.
[62]	M. Jonusas, K. Leroux, L. Krim, J. Mol. Struct., 2020, 1220, 128736.
[63]	D. Yue, Y. Jia, Y. Yao, J. Sun, Y. Jing, Electrochim. Acta, 2012, 65, 30-36.
[64]	J. Balaji, P. Srinivasan, S. Prabu, M. George, D. Sajan, J. Mol. Struct., 2020, 1207, 127750.
[65]	L. R. Winter, B. Ashford, J. Hong, A. B. Murphy, J. G. Chen, ACS Catal., 2020, 10, 14763-14774.
[66]	Y. Li, J. Ge, J. Zhu, G. Huang, C. Liu, Y. Ge, Z. Wang, L. Dai, H. Liu, ACS Nano, 2025, 19, 10489-10499.
[67]	S. Yao, S. Wang, Y. Liu, Z. Hou, J. Wang, X. Gao, Y. Sun, W. Fu, K. Nie, J. Xie, Z. Yang, Y.-M. Yan, J. Am. Chem. Soc., 2023, 145, 26699-26710.
[68]	Q. Zhang, Z. Zheng, R. Gao, X. Xiao, M. Jiao, B. Wang, G. Zhou, H.-M. Cheng, Adv. Mater., 2024, 36, 2401018.