具有供体-桥接效应的高熵合金FeCoNiCuPt用于增强二氧化碳和硝酸盐的尿素电合成

doi:10.1016/S1872-2067(26)64981-9

摘要/Abstract

摘要：

目前, 尿素的工业化生产主要依赖哈伯-博世法合成氨,|再经由博世-迈耶法将氨转化为尿素. 这些工艺均需在高温高压下运行, 不仅消耗大量化石燃料, 还伴随着显著的二氧化碳排放,|因而面临高能耗与环境污染的双重压力. 而利用可再生电能驱动二氧化碳(CO₂)和硝酸根离子(NO₃⁻)的共还原反应来电合成尿素, 成为一种极具前景的绿色替代路线. 该过程在常温常压下即可进行, 不仅能将温室气体CO₂和水体污染物NO₃⁻转化为高附加值产品, 实现“变废为宝”, 还能有效降低对化石能源的依赖. 然而, 该反应路径极为复杂, 涉及多种含碳和含氮中间体的吸附、活化及最终的C‒N键偶联, 因此要求催化剂具备多功能且能协同作用的活性位点. 开发能够同时高效活化两种反应物并精准促进C‒N耦合的新型催化剂, 是该领域发展的关键瓶颈.

本文的设计思路是构建一种具有独特电子结构的多组分高熵合金催化剂, 解决CO₂和NO₃^-共还原至尿素过程中反应路径复杂、中间体吸附能不匹配以及C-N耦合困难等关键问题. 其核心创新在于选择了原子半径相近的Fe, Co, Ni, Cu并引入贵金属Pt, 成功制备了具有单一面心立方结构的FeCoNiCuPt高熵合金纳米颗粒, 并在该体系中明确提出了“电子给体-桥联效应”机制, 即Pt作为电子给体, 而Fe, Co, Ni, Cu等原子作为电子转移的桥梁, 共同促进电子向反应中间体的转移. 采用X-射线衍射、球差扫描透射电镜和元素面扫描证实了其均匀的单相高熵结构. X-射线光电子能谱和X-射线吸收精细结构分析揭示了合金内部的电子重排以及Pt与其他金属的配位环境, 为“给体-桥联”效应提供了结构基础. 此外, 该催化剂在‒0.7 V (vs. RHE)下实现了49.26 mmol h^-1 g_cat^-1的尿素产率和25.51%的法拉第效率, 性能显著优于单金属及不含Pt的FeCoNiCu中熵合金, 并展现出优异的稳定性. 同位素实验(使用¹⁵NO₃^-和KH¹³CO₃)通过¹H核磁共振谱确认了尿素中的N和C原子分别来源于NO₃^-和CO₂. 在机理研究方面, 密度泛函理论计算表明, FeCoNiCuPt对CO₂的最强吸附发生在Pt-M桥位点, 其吸附能强于对比样品, CO₂-程序升温脱附实验也证实了这一点; 而对于NO₃^-, Pt的引入使Fe, Co, Ni, Cu的d带中心下移, 适度削弱了整体吸附强度, 避免了活性位点中毒. 差分电荷计算直接证实了在CO₂吸附时电子主要由Pt原子提供, 确立了Pt的“电子给体”角色, 而其他金属原子充当了电子转移的“桥梁”. 自由能计算确定*NO₂与*CO的首次C-N耦合为决速步, 并在FeCoNiCuPt的Pt-M位点上发现了更低的耦合能垒. 原位红外光谱检测到了*NO₂, *COOH, *NH₂等关键中间体, 并发现FeCoNiCuPt体系中的*NO₂信号更强且溶液中NO₂^-副产物更少, 表明其表面的*NO₂更易参与耦合而非脱附, 与理论计算相互印证. 本文揭示了FeCoNiCuPt高熵合金通过其多活性位点协同以及独特的“电子给体-桥联效应”, 不仅优化了CO₂和NO₃^-的吸附行为, 更关键的是显著促进了C-N耦合这一决速步骤, 从而实现了高效、稳定的尿素电合成.

综上, 本研究深入解析多活性位点的协同机制与动态演化过程, 并揭示其“电子给体-桥联”新机制, 为理解并设计多组分催化剂用于复杂的C-N耦合反应提供了关键的原理性证明和可行的材料设计范式, 推动CO₂和NO₃^-共还原合成高值化学品的基础研究发展, 并为设计用于多分子串联反应的高效电催化剂提供了新的理论依据和设计策略.

关键词: 电子供体-桥体效应, 高熵合金, 尿素电合成, d带中心, 二氧化碳还原

Abstract:

Electrocatalytic co-reduction of nitrate (NO₃^-) and carbon dioxide (CO₂) offers a promising route for sustainable urea synthesis, yet the process remains limited by the complexity of intermediate species and poorly understood C-N coupling mechanisms. Herein, we report a high-entropy alloy (HEA) FeCoNiCuPt catalyst that enables efficient and selective urea production through donor-bridge-acceptor interactions. Benefiting from the atomic-level disorder of the HEA, the catalyst provides a diverse array of active sites capable of accommodating the distinct adsorption and activation pathways of NO₃^- and CO₂ intermediates. At -0.7 V vs. RHE, the FeCoNiCuPt catalyst achieves a urea yield of 49.26 mmol h^-1 g_cat^-1 and a Faradaic efficiency of 25.51%, outperforming most reported systems. Mechanistic studies show that Pt sites act as electron donors, while neighboring transition metal atoms serve as electron bridges, enhancing electron transfer toward critical *NO₂ and *CO₂ species. This donor-bridge facilitates C-N coupling and promotes efficient urea formation, offering new insights into catalyst design for tandem small-molecule electrosynthesis.

Key words: Electron donor-bridge effect, High-entropy alloy, Urea electrosynthesis, D-band center, CO₂ reduction

郭威, 莫贞林, 徐来季, 章宇, 杨明辉, 刘宝军. 具有供体-桥接效应的高熵合金FeCoNiCuPt用于增强二氧化碳和硝酸盐的尿素电合成[J]. 催化学报, 2026, 84: 159-174.

Wei Guo, Zhenlin Mo, Laiji Xu, Yu Zhang, Minghui Yang, Baojun Liu. High-entropy alloy FeCoNiCuPt with donor-bridge effect for enhancing urea electrosynthesis from CO₂ and nitrate[J]. Chinese Journal of Catalysis, 2026, 84: 159-174.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)64981-9

https://www.cjcatal.com/CN/Y2026/V84/I5/159

图/表 6

Fig. 1. (a) Diagram of the preparation process of the FeCoNiCuPt. (b) XRD pattern of the FeCoNiCuPt. (c) AC-STEM image with the fast Fourier transform (FFT) pattern. (d) HAADF-HRTEM image and corresponding elemental maps (Fe, Ni, Co, Cu, Pt. Scale Bar: 10 nm) of the HEA. (e) 3D surface intensity profile of atoms in the selection of Fig. (d). (f) AC-STEM-EDX mapping images and ratio of the elements (inset). (g) The elemental proportions of the FeCoNiCuPt alloy obtained by electron microscopy at different scales, ICP, and XPS test.

Fig. 2. (a-e) The high-resolution XPS spectra of Fe 2p, Co 2p, Ni 2p, Cu 2p, and Pt 4f. (f) XANES spectra of Pt atomic and its corresponding metallic foil at the Pt L3-edge. (g) FT-EXAFS spectra of Pt L3-edge. (h) WTs of EXAFS spectra of metallic foil, HEA-Pt and PtO. (i) Fitting results of the magnitude of the Fourier transform of the k3-weighted EXAFS spectra for HEA-Pt. (j) The electrostatic potential (ESP) and electron localization function (ELF) surrounding the Pt metal atom. (k) The PDOS of the 3d orbitals of Fe, Co, Ni, Cu atoms coordinated with Pt atoms.

Fig. 3. Electrochemical performance for urea synthesis. (a) Yield rate of urea. (b)Faraday efficiency (FE). (c) Comparison of properties between FeCoNiCuPt alloy with monometal Fe, Ni, Co, Cu. (d) LSV curves of FeCoNiCuPt alloy and monometal Fe, Ni, Co, Cu. (e) Cdl plots obtained from CV curves (Inset Fig. S9). (f) 1H NMR spectra of urea obtained by using K15NO3 and K14NO3 as the reactants. Electrocatalytic stability test of the FeCoNiCuPt alloy by intermittent (g) and non-intermittent (h) electrolyte replacement testing.

Fig. 4. (a) Variation trend of CO2 adsorption energy on the FeCoNiCuPt alloy and monometal Fe, Ni, Co, Cu, and Pt. (b) The adsorption energy of CO2 at different adsorption sites on the surface of the FeCoNiCu alloy. (c) CO2-TPD profiles of the FeCoNiCuPt and the FeCoNiCu alloy. (d) Differential charge distribution and profile of the Pt-M (M = Fe, Ni, Co, or Cu) bridge adsorption sites of CO2. (e) The gain or loss charge distribution diagram along the Z direction. (f) Schematic diagram of the electron donor-bridge effect for enhanced CO2 adsorption. (g) Variation trend of NO3- adsorption energy on the FeCoNiCuPt, the FeCoNiCu alloy and monometal Fe, Ni, Co, Cu, and Pt. (h) Comparison of the average d-band centers of metal atom. (i) The charge difference and transfer amount of FeCoNiCuPt and FeCoNiCu alloys when adsorbing NO3-. (j) Dynamic process snapshots of electrolyte solutions on the FeCoNiCuPt alloy surface at different simulation times.

Fig. 5. Comparison of yield (a) and Faraday efficiency (b) of the alloys with different Pt contents (FeCoNiCuPtn: n represents the theoretical proportion of metal Pt content) in electrocatalytic urea synthesis. (c) The urea synthesis performance of catalysts with different alloys of Pt. The change of in-situ FTIR spectra with time using the FeCoNiCu (d) and the FeCoNiCuPt (e) alloys as catalysts. The change of in-situ FTIR spectra with applied voltage (FeCoNiCu (f), FeCoNiCuPt (g)). (h) Variation of NO2- concentration with applied voltage during electrocatalytic urea synthesis using the FeCoNiCu alloy and the FeCoNiCuPt alloy, respectively. (i) The adverse effect of easily desorbed NO2- on C-N coupling.

Fig. 6. (a) Free energy change of co-reduction of NO3- and CO2 to urea by the FeCoNiCu and the FeCoNiCuPt alloys catalyst. (b) Comparison of overcoming energy barriers for first C-N coupling at different CO2 adsorption sites on the FeCoNiCu alloy and the FeCoNiCuPt alloy. (c) The differential charge during the first C-N coupling reaction. (d) Schematic diagram of electron donor-bridge transfer during the first coupling reaction of C-N. (e) Diagram of the reaction path of urea synthesis.

参考文献

[1]	J. Lim, C. A. Fernández, S. W. Lee, M. C. Hatzell, ACS Energy Lett., 2021, 6, 3676-3685.
[2]	S. Paul, A. Adalder, U. K. Ghorai, Mater. Chem. Front., 2023, 7, 3820-3854.
[3]	X. Zhu, X. Zhou, Y. Jing, Y. Li, Nat. Commun., 2021, 12, 4080.
[4]	G. Estiu, K. M. Merz, J. Am. Chem. Soc., 2004, 126, 11832-11842.
[5]	G. Ibáñez-Redín, G. Rosso Cagnani, N. O. Gomes, P. A. Raymundo-Pereira, S. A. S. Machado, M. A. Gutierrez, J. E. Krieger, O. N. Oliveira Jr, Biosens. Bioelectron., 2023, 223, 114994.
[6]	G. Soloveichik, Nat. Catal., 2019, 2, 377-380.
[7]	S.-K. Geng, Y. Zheng, S.-Q. Li, H. Su, X. Zhao, J. Hu, H.-B. Shu, M. Jaroniec, P. Chen, Q.-H. Liu, S.-Z. Qiao, Nat. Energy, 2021, 6, 904-912.
[8]	M. Capdevila-Cortada, Nat. Catal., 2019, 2, 1055-1055.
[9]	S. Paul, S. Sarkar, A. Adalder, A. Banerjee, U. K. Ghorai, J. Mater. Chem. A, 2023, 11, 13249-13254.
[10]	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.
[11]	S. R. Waghela, A. Adalder, K. Mitra, U. K. Ghorai, ChemCatChem, 2025, 17, e202401565.
[12]	X. Peng, L. Zeng, D. Wang, Z. Liu, Y. Li, Z. Li, B. Yang, L. Lei, L. Dai, Y. Hou, Chem. Soc. Rev., 2023, 52, 2193-2237.
[13]	Y. Ou, C. Roney, J. Alsalam, K. Calvin, J. Creason, J. Edmonds, A. A. Fawcett, P. Kyle, K. Narayan, P. O’Rourke, P. Patel, S. Ragnauth, S. J. Smith, H. McJeon, Nat. Commun., 2021, 12, 6245.
[14]	Z. Mo, J. Mu, B. Liu, Adv. Powder Mater., 2024, 3, 100245.
[15]	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.
[16]	S. Yao, S.-Y. Jiang, B.-F. Wang, H.-Q. Yin, X.-Y. Xiang, Z. Tang, C.-H. An, T.-B. Lu, Z.-M. Zhang, Angew. Chem. Int. Ed., 2025, 64, e202418637.
[17]	H. Li, J. Lai, Z. Li, L. Wang, Adv. Funct. Mater, 2021, 31, 2106715.
[18]	R. Maity, B. S. Birenheide, F. Breher, B. Sarkar, ChemCatChem, 2021, 13, 2337-2370.
[19]	T. A. A. Batchelor, J. K. Pedersen, S. H. Winther, I. E. Castelli, K. W. Jacobsen, J. Rossmeisl, Joule, 2019, 3, 834-845.
[20]	Y. Zhou, M. Wang, L. Zhang, N. Li, T. Qian, C. Yan, J. Lu, ACS Nano, 2025, 19, 7273-7282.
[21]	X. Chen, Y. Tan, J. Yuan, S. Zhai, L. Su, Y. Mou, W.-Q. Deng, H. Wu, Adv. Energy Mater., 2025, 15, 2500872.
[22]	H. Li, Y. Han, H. Zhao, W. Qi, D. Zhang, Y. Yu, W. Cai, S. Li, J. Lai, B. Huang, L. Wang, Nat. Commun., 2020, 11, 5437.
[23]	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.
[24]	Z.-S. Sun, X.-Y. Xiang, Q.-P. Zhao, Z. Tang, S.-Y. Jiang, T.-B. Lu, Z.-M. Zhang, B. Wang, H.-Q. Yin, Chin. J. Catal., 2024, 65, 153-162.
[25]	B. Rhimi, M. Zhou, Z. Yan, X. Cai, Z. Jiang, Nano-Micro. Lett., 2024, 16, 64.
[26]	H. Zhong, M. Ghorbani-Asl, K. H. Ly, J. Zhang, J. Ge, M. Wang, Z. Liao, D. Makarov, E. Zschech, E. Brunner, I. M. Weidinger, J. Zhang, A. V. Krasheninnikov, S. Kaskel, R. Dong, X. Feng, Nat. Commun., 2020, 11, 1409.
[27]	H. Huang, J. Zhao, H. Guo, B. Weng, H. Zhang, R. Ali Saha, M. Zhang, F. Lai, Y. Zhou, R.-Z. Juan, P.-C. Chen, S. Wang, J. A. Steele, F. Zhong, T. Liu, J. Hofkens, Y.-M. Zheng, J. Long, M. B. J. Roeffaers, Adv. Mater., 2024, 36, 2313209.
[28]	M. Wei, Y. Sun, J. Zhang, F. Ai, S. Xi, J. Wang, Energy Environ. Sci., 2023, 16, 4009-4019.
[29]	C. Zhan, Y. Xu, L. Bu, H. Zhu, Y. Feng, T. Yang, Y. Zhang, Z. Yang, B. Huang, Q. Shao, X. Huang, Nat. Commun., 2021, 12, 6261.
[30]	M. Bondesgaard, N. L. N. Broge, A. Mamakhel, M. Bremholm, B. B. Iversen, Adv. Funct. Mater., 2019, 29, 1905933.
[31]	S. Bhowmick, A. Adalder, A. Maiti, S. Kapse, R. Thapa, S. Mondal, U. K. Ghorai, Chem. Sci., 2025, 16, 4806-4814.
[32]	Y. Yu, J. Han, H. Li, H. Diao, Y. Shi, G. Jin, H. Li, G. A. Bagliuk, L. Wang, J. Lai, Adv. Mater., 2025, 37, 2419738.
[33]	Y. Yu, Y. Sun, J. Han, Y. Guan, H. Li, L. Wang, J. Lai, Energy Environ. Sci., 2024, 17, 5183-5190.
[34]	H.-Q. Yin, Z.-S. Sun, Q.-P. Zhao, L.-L. Yang, T.-B. Lu, Z.-M. Zhang, J. Energy Chem., 2023, 84, 385-393.
[35]	X. Wang, S. Wang, H. Wang, W. Tu, Y. Zhao, S. Li, Q. Liu, J. Wu, Y. Fu, C. Han, F. Kang, B. Li, Adv. Mater., 2021, 33, 2007945.
[36]	J. Hao, Z. Zhuang, K. Cao, G. Gao, C. Wang, F. Lai, S. Lu, P. Ma, W. Dong, T. Liu, M. Du, H. Zhu, Nat. Commun., 2022, 13, 2662.
[37]	H. Cai, H. Yang, S. He, D. Wan, Y. Kong, D. Li, X. Jiang, X. Zhang, Q. Hu, C. He, Angew. Chem. Int. Ed., 2025, 64, e202423765.
[38]	K. Huang, B. Zhang, J. Wu, T. Zhang, D. Peng, X. Cao, Z. Zhang, Z. Li, Y. Huang, J. Mater. Chem. A, 2020, 8, 11938-11947.
[39]	X. Sun, Y. Sun, Chem. Soc. Rev., 2024, 53, 4400-4433.
[40]	P. Xie, Y. Yao, Z. Huang, Z. Liu, J. Zhang, T. Li, G. Wang, R. Shahbazian-Yassar, L. Hu, C. Wang, Nat. Commun., 2019, 10, 4011.
[41]	C.-Y. Wu, Y.-C. Hsiao, Y. Chen, K.-H. Lin, T.-J. Lee, C.-C. Chi, J.-T. Lin, L.-C. Hsu, H.-J. Tsai, J.-Q. Gao, C.-W. Chang, I.-T. Kao, C.-Y. Wu, Y.-R. Lu, C.-W. Pao, S.-F. Hung, M.-Y. Lu, S. Zhou, T.-H. Yang, Sci. Adv., 2024, 10, eadl3693.
[42]	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.
[43]	S. Chen, S. Lin, L.-X. Ding, H. Wang, Small Methods, 2023, 7, 2300003.
[44]	X. Du, J. Huang, J. Zhang, Y. Yan, C. Wu, Y. Hu, C. Yan, T. Lei, W. Chen, C. Fan, J. Xiong, Angew. Chem. Int. Ed., 2019, 58, 4484-4502.
[45]	K. Odbadrakh, L. Enkhtor, T. Amartaivan, D. M. Nicholson, G. M. Stocks, T. Egami, J. Appl. Phys., 2019, 126, 095104.
[46]	J. K. Pedersen, T. A. A. Batchelor, A. Bagger, J. Rossmeisl, ACS Catal., 2020, 10, 2169-2176.
[47]	Z.-W. Chen, J. Li, P. Ou, J. E. Huang, Z. Wen, L. Chen, X. Yao, G. Cai, C.-C. Yang, C. V. Singh, Q. Jiang, Nat. Commun., 2024, 15, 359.
[48]	D. Zhang, Y. Shi, H. Zhao, W. Qi, X. Chen, T. Zhan, S. Li, B. Yang, M. Sun, J. Lai, B. Huang, L. Wang, J. Mater. Chem. A, 2021, 9, 889-893.
[49]	A. Adalder, S. Paul, N. Barman, A. Bera, S. Sarkar, N. Mukherjee, R. Thapa, U. K. Ghorai, ACS Catal., 2023, 13, 13516-13527.
[50]	A. Adalder, K. Mitra, N. Barman, R. Thapa, S. Bhowmick, U. K. Ghorai, Adv. Energy Mater., 2024, 14, 2470185.
[51]	D. Yin, B. Li, B. Gao, M. Chen, D. Chen, Y. Meng, S. Zhang, C. Zhang, Q. Quan, L. Chen, C. Yang, C.-Y. Wong, J. C. Y. Ho, Adv. Mater., 2025, 37, 2415739.
[52]	K. Chen, D. Ma, Y. Zhang, F. Wang, X. Yang, X. Wang, H. Zhang, X. Liu, R. Bao, K. Chu, Adv. Mater., 2024, 36, 2402160.
[53]	J. Sun, B. Wu, Z. Wang, H. Guo, G. Yan, H. Duan, G. Li, Y. Wang, J. Wang, Energy Environ. Sci., 2025, 18, 1027-1037.
[54]	Y. Wang, X. Zhu, Q. An, X. Zhang, X. Wei, C. Chen, H. Li, D. Chen, Y. Zhou, Q. Liu, H. Shao, S. Wang, Angew. Chem. Int. Ed., 2024, 63, e202410938.
[55]	Y. Wan, Z. Zhang, X. Wang, X. Yang, H. Zhang, K. Chu, Adv. Funct. Mater., 2024, 34, 2406438.
[56]	Z. Xu, Z. Yang, H. Lu, J. Zhu, J. Li, M.-H. Fan, Z. Zhao, X. Kong, K. Wang, Z. Geng, Nano Lett., 2024, 24, 11730-11737.
[57]	A. Adalder, K. Mitra, N. Barman, R. Thapa, R. Urkude, S. Das, U. K. Ghorai, Small, 2025, 21, 2505313.