Gradient energy alignment drives catalytic cascades for synergistic nitrate-to-ammonia electro-conversion

doi:10.1016/S1872-2067(26)65150-9

Abstract

Abstract:

Although tandem-site multiphase catalysts have been explored for the electrochemical conversion of nitrate to ammonia (NH₃), achieving genuine phase synergy remains challenging due to energetic mismatches across the interface. Herein, a pre-infusing pyrolytic fusion strategy is developed to construct partially polarized Ag clusters on a Co₃O₄ support (PP-Ag/Co₃O₄). Strong interfacial electronic coupling stabilizes Ag^δ⁺ sites. These Ag^δ⁺ construct the relay sites with a gradient energy alignment feature, thereby facilitating a catalytic cascade enabling effective coupling between nitrate activation on Ag and subsequent hydrogenation on Co₃O₄. Experimental results demonstrate that PP-Ag/Co₃O₄ achieves a notable NH₃ Faradaic efficiency of 96.2%, a yield rate of 12.3 mg h^-1 cm^-2 under neutral conditions. Furthermore, the constructed Zn-NO₃^- battery based on PP-Ag/Co₃O₄ delivers an impressive power density of 5.42 mW cm^-2. This work highlights energy alignment engineering as an effective strategy for advancing efficient ammonia electrosynthesis.

Key words: Electrocatalytic nitrate reduction, Energy alignment, Catalytic cascades, Ag/Co₃O₄ heterointerface, Zn-NO₃^- battery

Zhihao Wang, Yuang Zhang, Xu Zhang, Yuting Jiang, Xinyue Li, Ying Xie, Zhiyu Ren, Zhimin Chen. Gradient energy alignment drives catalytic cascades for synergistic nitrate-to-ammonia electro-conversion[J]. Chinese Journal of Catalysis, 2026, 90: 287-297.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65150-9

https://www.cjcatal.com/EN/Y2026/V90/I11/287

Figures/Tables 5

Fig. 1. Structural characterizations of PP-Ag/Co3O4. (a) Schematic synthesis process. (b) HRTEM image. (c) FFT pattern and corresponding STEM-EDS elemental mapping. (d) XRD patterns of PP-Ag/Co3O4 and control samples.

Fig. 2. Electronic structure and interfacial coupling of PP-Ag/Co3O4. (a) High-resolution Ag 3d XPS spectra. (b) Co 2p XPS spectra. (c) O 1s XPS spectra. (d) Co K-edge XANES spectra. (e) FT k3-weighted EXAFS spectra. (f) WT contour plots.

Fig. 3. Electrocatalytic NitRR and Zn-NO3- battery performance of PP-Ag/Co3O4. (a) LSV curves. (b) Potential-dependent Faradaic efficiencies. NH3 Faradaic efficiencies (c) and yield rates (d). (e) Cycling stability. (f) Performance comparison with reported Ag/Co-based catalysts. (g) Polarization and power density curves of Zn-NO3- battery. (h) Galvanostatic discharge curves and NH3 yields. (i) Charge-discharge cycling stability.

Fig. 4. Mechanistic verification and in situ analyses of PP-Ag/Co3O4. Reaction potentials (a) and Tafel slopes (b) in different electrolytes. (c) In-situ ATR-SEIRAS spectra and local magnification revealing intermediate evolution. (d) In-situ EIS confirming accelerated charge and mass transfer.

Fig. 5. DFT investigation of energy alignment on PP-Ag/Co3O4. (a) Calculated *NO2 adsorption energies on Ag and Co sites. Free-energy diagrams for *NO2 desorption (b) and relay-mediated hydrogenation (c). (d) Differential and plane-averaged charge density. (e) PDOS of Ag, PP-Ag/Co3O4, and Co3O4. (f) Schematic illustration of *NO2 relay pathway on Ag-Agδ+/Co3O4 heterointerface.

References

[1]	X. Fu, J. B. Pedersen, Y. Zhou, M. Saccoccio, S. Li, R. Sažinas, K. Li, S. Z. Andersen, A. Xu, N. H. Deissler, J. B. V. Mygind, C. Wei, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov, I. Chorkendorff, Science, 2023, 379, 707-712.
[2]	C. Smith, A. K. Hill, L. Torrente-Murciano, Energy Environ. Sci., 2020, 13, 331-344.
[3]	T.-N. Ye, S.-W. Park, Y. Lu, J. Li, M. Sasase, M. Kitano, T. Tada, H. Hosono, Nature, 2020, 583, 391-395.
[4]	D. Tonelli, L. Rosa, P. Gabrielli, A. Parente, F. Contino, Nat. Food, 2024, 5, 469-479.
[5]	K. H. R. Rouwenhorst, F. Jardali, A. Bogaerts, L. Lefferts, Energy Environ. Sci., 2021, 14, 2520-2534.
[6]	X. Song, C. Basheer, J. Xu, R. N. Zare, Sci. Adv., 2024, 10, eads4443.
[7]	P. H. van Langevelde, I. Katsounaros, M. T. M. Koper, Joule, 2021, 5, 290-294.
[8]	J. Liang, Z. Li, L. Zhang, X. He, Y. Luo, D. Zheng, Y. Wang, T. Li, H. Yan, B. Ying, S. Sun, Q. Liu, M. S. Hamdy, B. Tang, X. Sun, Chem, 2023, 9, 1768-1827.
[9]	A. Aminu, J. Shaya, M. A. Jaoude, B. M. Pirzada, I. Yildiz, A. Qurashi, Nano Res. Energy, 2026, 5, e9120183.
[10]	K. Wang, R. Mao, R. Liu, J. Zhang, H. Zhao, W. Ran, X. Zhao, Nat. Water, 2023, 1, 1068-1078.
[11]	X. Fu, J. Zhang, Y. Kang, Chem Catal., 2022, 2, 2590-2613.
[12]	L. Li, L. Xu, H. Wang, H. Wei, C. Tang, G. Li, Y. Dou, H.-K. Liu, S.-X. Dou, Energy Environ. Sci., 2024, 17, 9027-9050.
[13]	X. Fan, C. Liu, X. He, Z. Li, L. Yue, W. Zhao, J. Li, Y. Wang, T. Li, Y. Luo, D. Zheng, S. Sun, Q. Liu, L. Li, W. Chu, F. Gong, B. Tang, Y. Yao, X. Sun, Adv. Mater., 2024, 36, 2401221.
[14]	L. Barrera, R. Silcox, K. Giammalvo, E. Brower, E. Isip, R. Bala Chandran, ACS Catal., 2023, 13, 4178-4192.
[15]	Y. Xue, Q. Yu, J. Fang, Y. Jia, R. Wang, J. Fan, Small, 2024, 20, 2400505.
[16]	R. Zhang, C. Li, H. Cui, Y. Wang, S. Zhang, P. Li, Y. Hou, Y. Guo, G. Liang, Z. Huang, C. Peng, C. Zhi, Nat. Commun., 2023, 14, 8036.
[17]	L. Chen, Y. Hao, J. Chu, S. Liu, F. Bai, W. Luo, Chin. J. Catal., 2024, 58, 25-36.
[18]	Z. Jin, K. Liu, Z. Pan, X. Shan, F. Cai, D. Yang, P. Li, G. Yu, M. Zhou, J. Am. Chem. Soc., 2026, 148, 622-631.
[19]	H. Jiang, T. Li, Y. Gao, J. Fan, D. Gan, S. Yuan, L. Hong, Y. Feng, J. Sun, Q. Song, T. Zhang, A. R. Jalili, P. J. Cullen, R. Zhou, J. Energy Chem., 2025, 105, 630-668.
[20]	P. Li, R. Li, Y. Liu, M. Xie, Z. Jin, G. Yu, J. Am. Chem. Soc., 2023, 145, 6471-6479.
[21]	Y. Ren, C. Zhang, H. Wang, J.-X. Liang, C. Zhu, H.-S. Hu, J. Li, Chin. J. Struct. Chem., 2025, 44, 100649.
[22]	L. Ouyang, J. Liang, Y. Luo, D. Zheng, S. Sun, Q. Liu, M. S. Hamdy, X. Sun, B. Ying, Chin. J. Catal., 2023, 50, 6-44.
[23]	X. H. Deng, Y. P. Yang, L. Wang, X. Z. Fu, J. L. Luo, Adv. Sci., 2021, 8, 2004523.
[24]	S. Liang, X. Teng, H. Xu, L. Chen, J. Shi, Angew. Chem. Int. Ed., 2024, 63, e202400206.
[25]	Z. Wang, X. Zhang, Z. Ren, Z. Chen, J. Energy Chem., 2025, 109, 210-230.
[26]	X. Fan, D. Zhao, Z. Deng, L. Zhang, J. Li, Z. Li, S. Sun, Y. Luo, D. Zheng, Y. Wang, B. Ying, J. Zhang, A. Ali Alshehri, Y. Lin, C. Tang, X. Sun, Y. Zheng, Small, 2023, 19, 2208036.
[27]	D. Qin, S. Song, Y. Liu, K. Wang, B. Yang, S. Zhang, Angew. Chem. Int. Ed., 2023, 62, e202304935.
[28]	K. Fan, W. Xie, J. Li, Y. Sun, P. Xu, Y. Tang, Z. Li, M. Shao, Nat. Commun., 2022, 13, 7958.
[29]	C. Zhou, Y. Zhang, C. Xie, J. Bai, J. Li, H. Zhang, H. Zhu, M. Long, B. Zhou, G. Zheng, Environ. Sci. Technol., 2024, 58, 14940-14948.
[30]	Z. Feng, Y. He, Y. Cui, Y. Qu, G. Ding, X. Chen, C. Sui, Q. Wei, Z. Wang, Q. Jiang, Nano Lett., 2024, 24, 11929-11936.
[31]	Z. Fan, C. Cao, X. Yang, W. Yuan, F. Qin, Y. Hu, X. Sun, G. Liu, Y. Tian, L. Xu, Angew. Chem. Int. Ed., 2024, 63, e202410356.
[32]	X. Li, S. Mitchell, Y. Fang, J. Li, J. Pérez-Ramírez, J. Lu, Nat. Rev. Chem., 2023, 7, 754-767.
[33]	Q. Jiang, M. Gu, S. Pei, T. Wang, F. Liu, X. Yang, D. Zhang, Z. Wu, Y. Wang, L. Wei, H. Li, J. Am. Chem. Soc., 2025, 147, 26029-26039.
[34]	P. Buffat, J.-P. Borel, Phys. Rev. A, 1976, 13, 2287-2298.
[35]	S. Chen, Z. Zhu, K. Song, H. Zhang, D. Luo, T. Cao, Y. Zou, C. Liu, L. Gan, D. Zhang, Y. Han, J. Huang, J. Am. Chem. Soc., 2025, 147, 36494-36507.
[36]	R. Zhang, Z. Sun, C. Zong, Z. Lin, H. Huang, K. Yang, J. Chen, S. Liu, M. Huang, Y. Yang, W. Zhang, Q. Chen, Nano Energy, 2019, 57, 753-760.
[37]	H. Yu, C. Guo, X. Zhang, X. Cheng, Y. Xu, S. Gao, L. Huo, Small Struct., 2022, 3, 2100166.
[38]	K. Hakouk, P. Deniard, L. Lajaunie, C. Guillot-Deudon, S. Harel, Z. Wang, B. Huang, H.-J. Koo, M.-H. Whangbo, S. Jobic, R. Dessapt, Inorg. Chem., 2013, 52, 6440-6449.
[39]	Y. Liang, X. Fan, X. He, D. Zheng, S. Sun, Y. Luo, H. Chen, X. Sun, Nano Res., 2025, 18, 94907344.
[40]	R. Zhang, S. Zhang, Y. Guo, C. Li, J. Liu, Z. Huang, Y. Zhao, Y. Li, C. Zhi, Energy Environ. Sci., 2022, 15, 3024-3032.
[41]	Y. Li, Z. Lu, L. Zheng, X. Yan, J. Xie, Z. Yu, S. Zhang, F. Jiang, H. Chen, Energy Environ. Sci., 2024, 17, 4582-4593.
[42]	L. Deng, S.-F. Hung, Z.-Y. Lin, Y. Zhang, C. Zhang, Y. Hao, S. Liu, C.-H. Kuo, H.-Y. Chen, J. Peng, J. Wang, S. Peng, Adv. Mater., 2023, 35, 2305939.
[43]	Y. Zhou, L. Zhang, M. Wang, X. Shen, Z. Zhu, T. Qian, C. Yan, J. Lu, Nat. Commun., 2025, 16, 7915.
[44]	L. An, H. Zhang, J. Zhu, S. Xi, B. Huang, M. Sun, Y. Peng, P. Xi, C.-H. Yan, Angew. Chem. Int. Ed., 2023, 62, e202214600.
[45]	S. Zhu, K. Liu, Z. Feng, H. Jiang, J. Lin, Nano Res. Energy, 2025, 4, e9120188.
[46]	X. Chen, W. Jin, X. Zhong, H. Lin, J. Ding, X. Liu, H. Wang, F. Chen, Y. Xiong, C. Ding, Z. Jin, M. Jiang, Chin. J. Catal., 2025, 79, 78-90.
[47]	B. Lei, B. Li, Y. Wang, W. Wang, L. Chen, X. Wu, B.-H. Zhao, W. Wang, J.-G. Ma, P. Cheng, J. Am. Chem. Soc., 2026, 148, 13774-13784.
[48]	Q. Cheng, S. Liu, Y. He, M. Wang, H. Ji, Y. Huan, T. Qian, C. Yan, J. Lu, Nat. Commun., 2025, 16, 3717.
[49]	C. Huang, C. A. Triana, B. Jia, R. Erni, H. Zhao, G. R. Patzke, ACS Catal., 2025, 15, 11407-11416.
[50]	R. Zhang, H. Hong, X. Liu, S. Zhang, C. Li, H. Cui, Y. Wang, J. Liu, Y. Hou, P. Li, Z. Huang, Y. Guo, C. Zhi, Angew. Chem. Int. Ed., 2023, 62, e202309930.
[51]	X. Sun, Y. He, M. Wang, Q. Cheng, Y. Huan, S. Liu, J. Liu, T. Qian, C. Yan, J. Lu, ACS Nano, 2025, 19, 8189-8199.
[52]	H. Huang, Y. Zhang, W. Chen, J. Chen, X. Zou, J.-J. Lv, X. Chen, Z. Shen, Z. Ge, L. Guo, Y. Yao, Y. Wang, Adv. Energy Mater., 2025, 15, 2405534.
[53]	S. Niu, Y. Wu, J. Wang, J. Gu, X.-Z. Liu, J. Zhang, L. Chen, J. Z. Liu, W.-J. Jiang, J.-S. Hu, X. Wu, Angew. Chem. Int. Ed., 2025, 64, e202508227.
[54]	W. Liao, J. Wang, Y. Tan, X. Zi, C. Liu, Q. Wang, L. Zhu, C.-W. Kao, T.-S. Chan, H. Li, Y. Zhang, K. Liu, C. Cai, J. Fu, B. Xi, E. Cortés, L. Chai, M. Liu, Nat. Commun., 2025, 16, 5715.
[55]	B. Zhou, Y. Tong, Y. Yao, W. Zhang, G. Zhan, Q. Zheng, W. Hou, X.-K. Gu, L. Zhang, Proc. Natl. Acad. Sci. U. S. A., 2024, 121, e2405236121.
[56]	R. Hao, L. Tian, C. Wang, L. Wang, Y. Liu, G. Wang, W. Li, G. A. Ozin, Chem Catal., 2022, 2, 622-638.
[57]	H. Xu, J. H. Peng, P. Q. Li, X. C. Feng, J. W. Hu, G. J. Han, J. C. Xu, D. Wang, Z. J. Lu, G. S. Li, J. P. Yang, Angew. Chem. Int. Ed., 2026, 65, e22410.
[58]	J. Ran, K. Fang, Y.-L. Sun, X. Lv, H. Wang, X. Feng, R. Li, F. Chen, Z. Ma, Y. Hu, Adv. Energy Mater., 2026, 16, e05148.
[59]	Z. Zhang, V. Du, Z. Lu, Phys. Rev. E, 2023, 107, L012102.
[60]	S. Luo, H. Guo, T. Li, H. Wu, F. Zhang, C. Tang, G. Chen, G. Yang, Y. Zhou, Appl. Catal. B, 2024, 351, 123967.
[61]	M. Yi, P. Wang, R. Shi, W. Guo, D. Yang, P. Li, G. Yu, Z. Jin, Angew. Chem. Int. Ed., 2026, 65, e21345.
[62]	X. Zhang, J. Sun, S. Du, H. Li, L. Qian, Adv. Funct. Mater., 2023, 33, 2301402.
[63]	T. Musso, P. V. Kumar, J. C. Grossman, A. S. Foster, Adv. Electron. Mater., 2017, 3, 1600318.