Subangstrom spatial regulation of Fe1-N4 coordination structure for remarkably efficient C‒H bond oxidation

doi:10.1016/S1872-2067(26)65096-6

Chinese Journal of Catalysis ›› 2026, Vol. 87: 305-315.DOI: 10.1016/S1872-2067(26)65096-6

• Articles • Previous Articles Next Articles

Subangstrom spatial regulation of Fe₁-N₄ coordination structure for remarkably efficient C‒H bond oxidation

Jianglin Duan^a^,¹, Pengcheng Deng^a^,¹, Huifeng Xiong^a^,¹, Na Yang^b^,^*(), Xueling Zhou^a, Jingwen Wang^a, Rui Zhang^c, Dan Feng^d, Ji Yang^e^,^*(), Yong Qin^f^,^*(), Yujing Ren^a^,^g^,^*()

^a Interdisciplinary Research Center of Biology & Catalysis, School of Life Science and Technology, Northwestern Polytechnical University, Xi’an 710072, Shaanxi, China
^b School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
^c Faculty of Chemical Engineering and Energy Technology, Shanghai Institute of Technology, Shanghai 201418, China
^d Analytical & Testing Center, Northwestern Polytechnical University, Xi’an 710072, Shaanxi, China
^e College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
^f College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^g Shenzhen Research Institute of Northwestern Polytechnical University, Shenzhen 518057, Guangdong, China

Received:2025-11-30 Accepted:2026-01-12 Online:2026-08-18 Published:2026-06-24
Contact: qinyong@qust.edu.cn (Y. Qin),
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22303031);National Natural Science Foundation of China(22472131);National Natural Science Foundation of China(22202075);National Natural Science Foundation of China(22402164);National Natural Science Foundation of China(22002118);National Key R&D Program of China(2023YFA1506603);Youth Science Foundation Project of Sichuan Province(2024NSFSC1103);Guangdong Basic and Applied Basic Research Foundation(2024A1515012109);Central Guidance for Local Scientific and Technological Development(2025ZY-XCZXZS-26)

Abstract

Abstract:

Structural regulation of heterogeneous active centers has been widely explored at the nano- and atomic-level, yet achieving subangstrom precision remains highly challenging. Here, we demonstrate subangstrom spatial regulation of the Fe‒N bond within a fully uniform Fe₁-N₄ coordination structure. Strikingly, a 0.1 Å bond compression led to nearly a 23-fold enhancement in C‒H bond oxidation. Advanced characterizations confirmed the uniform low-spin Fe₁-N₄ configuration, with the Fe‒N bond distance gradually decreasing from 2.03 to 1.93 Å during pyrolysis. This subtle structural modification originates from the concerted effect of temperature- and curvature-induced distortion on the curved carbon surface, as further supported by theoretical simulations. The Fe‒N bond distance was found to govern the electronic structure of the Fe center, where compressed coordination promotes electron accumulation. This structural modulation directly results in the high capability for peroxide group activation on Fe₁ single atoms, which affords outstanding C‒H bond oxidation, comparable to supported noble metal catalysts. This study provides the experimental demonstration of structural regulation at subangstrom scale, extending the concept of “precise chemistry” in catalyst design from the nano- and atomic- to the subangstrom scale.

Key words: Single-atom catalyst, Subangstrom spatial regulation, C?H bond oxidation, Fe₁-N₄, Structure-performance relationship

Jianglin Duan, Pengcheng Deng, Huifeng Xiong, Na Yang, Xueling Zhou, Jingwen Wang, Rui Zhang, Dan Feng, Ji Yang, Yong Qin, Yujing Ren. Subangstrom spatial regulation of Fe₁-N₄ coordination structure for remarkably efficient C‒H bond oxidation[J]. Chinese Journal of Catalysis, 2026, 87: 305-315.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65096-6

https://www.cjcatal.com/EN/Y2026/V87/I8/305

Figures/Tables 7

Fig. 1. Synthesis and structural characterizations of Fe1-N4/ND catalysts. (a) Schematic illustration of the catalyst synthesis including impregnation and thermal treatment. (b) XRD patterns of all Fe1-N4/ND catalysts with ND as reference. AC-HAADF-STEM images of Fe1-N4/ND-200 (c), Fe1-N4/ND-400 (d) and Fe1-N4/ND-600 (e) catalysts.

Fig. 2. Spectroscopic characterizations of Fe1-N4/ND catalysts. (a) 57Fe Mössbauer spectra. (b) The k3-weighted FT-EXAFS spectra of Fe1-N4/ND catalysts with Fe foil, Fe2O3 and FePc as comparison. (c) Corresponding EXAFS fitting curves in R space.

Table 1 The best-fitted EXAFS results of Fe1-N4/ND-T.

Sample	Shell	CN	R (Å)	σ² (10² Å²)	ΔE₀ (eV)	R-factor (%)
Fe Foil	Fe-Fe	12.0	2.54	—	—	—
Fe-Pc	Fe-N	4.0	1.98	—	—	—
Fe₁-N₄/ND-RT	Fe-N	3.8	2.03	0.6	‒2.4	0.4
Fe₁-N₄/ND-200	Fe-N	4.1	2.02	0.6	‒2.9	0.3
Fe₁-N₄/ND-400	Fe-N	4.0	1.96	0.8	‒7.5	0.2
Fe₁-N₄/ND-600	Fe-N	4.0	1.93	0.8	‒7.5	0.2

Fig. 3. Compression mechanism. (a) The radial distribution functions of corresponding Fe?N bond length at different temperatures during AIMD simulations of Fe1-N4 on curved graphene surface. (b) Schematic illustration for the compression of Fe?N bond on the curved graphene surface. (c) The theoretical and experimental compression ratio of different size carbon nanotubes. The structure of Fe1-N4 site on six, eight and fourteen of six-membered rings forming carbon nanotubes.

Fig. 4. Electronic structure confirmation. (a) The PDOS results of Fe-3d orbit for Fe1-N4/ND-600, Fe1-N4/ND-400 and Fe1-N4/ND-200 samples. XANES spectra (b) and corresponding average oxidation state (c) of Fe1-N4/ND-T samples.

Fig. 5. Catalytic performance evaluation results. Catalytic oxidation of TMB (a) and ethylbenzene (b) on Fe1-N4/ND-T catalysts. (c) Substrate scope for catalytic oxidations on Fe1-N4/ND-600 catalyst.

Fig. 6. The structure-activity relationship. (a) The adsorption energy (ΔE) of H2O2/OH on Fe1-N4/ND-T catalysts. (b-d) 3D (top view) and 2D (bottom view) charge density differences after OH adsorption on various Fe1-N4 models, herein, for the 3D view, charge accumulation and depletion are signified by yellow and blue isosurfaces; for the 2D view, charge accumulation and depletion are signified by red and blue areas. (e) The calculated Gibbs free energy diagram of H2O2 activation on Fe1-N4/ND-T catalysts. (f) The correlation between the activity of Fe1-N4/ND-T, the average oxidation state of Fe1 species, and compression ratio of Fe?N bond. The pentagon and circle represent TOF determined from catalytic oxidation of TMB and solvent-free C?H bond oxidation of ethylbenzene, and the star represents the average oxidation state of Fe1 species determined from XANES characterization.

References

[1]	R. Jin, G. Li, S. Sharma, Y. Li, X. Du, Chem. Rev., 2021, 121, 567-648.
[2]	F. Zaera, Chem. Rev., 2022, 122, 8594-8757.
[3]	C. Vogt, B. M. Weckhuysen, Nat. Rev. Chem., 2022, 6, 89-111.
[4]	C. Wang, Z. Wang, S. Mao, Z. Chen, Y. Wang, Chin. J. Catal., 2022, 43, 928-955.
[5]	P. Liu, N. Zheng, Natl. Sci. Rev., 2018, 5, 636-638.
[6]	C. Xie, Z. Niu, D. Kim, M. Li, P. Yang, Chem. Rev., 2020, 120, 1184-1249.
[8]	X. Duan, L. Ying, X.-Y. Li, B. Zhu, Y. Gao, J. Phys. Chem. Lett., 2023, 14, 9848-9854.
[9]	M. Li, Z. Zhao, T. Cheng, A. Fortunelli, C.-Y. Chen, R. Yu, Q. Zhang, L. Gu, B. V. Merinov, Z. Lin, E. Zhu, T. Yu, Q. Jia, J. Guo, L. Zhang, W. A. Goddard III, Y. Huang, X. Duan, Science, 2016, 354, 1414-1419.
[10]	C. Xiao, B.-A. Lu, P. Xue, N. Tian, Z.-Y. Zhou, X. Lin, W.-F. Lin, S.-G. Sun, Joule, 2020, 4, 2562-2598.
[11]	R. Wang, J. M. Lee, Small, 2024, 20, 2401546.
[12]	B. Ni, Y. Shi, X. Wang, Adv. Mater., 2018, 30, 1802031.
[13]	Y. Du, H. Sheng, D. Astruc, M. Zhu, Chem. Rev., 2020, 120, 526-622.
[14]	X.-F. Yang, A. Wang, B. Qiao, J. Li, J. Liu, T. Zhang, Acc. Chem. Res., 2013, 46, 1740-1748.
[15]	A. Wang, J. Li, T. Zhang, Nat. Rev. Chem., 2018, 2, 65-81.
[16]	X. Liang, N. Fu, S. Yao, Z. Li, Y. Li, J. Am. Chem. Soc., 2022, 144, 18155-18174.
[17]	K. McCardle, Nat. Comput. Sci., 2022, 2, 138.
[19]	S. K. Kaiser, Z. Chen, D. Faust Akl, S. Mitchell, J. Pérez-Ramírez, Chem. Rev., 2020, 120, 11703-11809.
[20]	R. Lang, X. Du, Y. Huang, X. Jiang, Q. Zhang, Y. Guo, K. Liu, B. Qiao, A. Wang, T. Zhang, Chem. Rev., 2020, 120, 11986-12043.
[21]	R. T. Hannagan, G. Giannakakis, R. Réocreux, J. Schumann, J. Finzel, Y. Wang, A. Michaelides, P. Deshlahra, P. Christopher, M. Flytzani-Stephanopoulos, M. Stamatakis, E. C. H. Sykes, Science, 2021, 372, 1444-1447.
[22]	J. Hulva, M. Meier, R. Bliem, Z. Jakub, F. Kraushofer, M. Schmid, U. Diebold, C. Franchini, G. S. Parkinson, Science, 2021, 371, 375-379.
[23]	J. Shan, C. Ye, Y. Jiang, M. Jaroniec, Y. Zheng, S.-Z. Qiao, Sci. Adv., 2022, 8, eabo0762.
[24]	X. Hai, S. Xi, S. Mitchell, K. Harrath, H. Xu, D. F. Akl, D. Kong, J. Li, Z. Li, T. Sun, H. Yang, Y. Cui, C. Su, X. Zhao, J. Li, J. Pérez-Ramírez, J. Lu, Nat. Nanotechnol., 2022, 17, 174-181.
[25]	L. L. Han, H. Cheng, W. Liu, H. Q. Li, P. F. Ou, R. Lin, H.-T. Wang, C.-W. Pao, A. R. Head, C.-H. Wang, X. Tong, C.-J. Sun, W.-F. Pong, J. Luo, J.-C. Zheng, H. L. Xin, Nat. Mater., 2022, 21, 681-688.
[26]	K. Liu, J. Fu, Y. Lin, T. Luo, G. Ni, H. Li, Z. Lin, M. Liu, Nat. Commun., 2022, 13, 2075.
[27]	M. H. Li, H. F. Wang, W. Luo, P. C. Sherrell, J. Chen, J. Yang, Adv. Mater., 2020, 32, 2001848.
[28]	L. Luo, J. Luo, H. Li, F. Ren, Y. Zhang, A. Liu, W.-X. Li, J. Zeng, Nat. Commun., 2021, 12, 1218.
[29]	P. Kumar, T. A. Al-Attas, J. Hu, M. G. Kibria, ACS Nano, 2022, 16, 8557-8618.
[30]	H. Wei, X. Liu, A. Wang, L. Zhang, B. Qiao, X. Yang, Y. Huang, S. Miao, J. Liu, T. Zhang, Nat. Commun., 2014, 5, 5634.
[31]	Y. Ma, Y. Ren, Y. Zhou, W. Liu, W. Baaziz, O. Ersen, C. Pham-Huu, M. Greiner, W. Chu, A. Wang, T. Zhang, Y. Liu, Angew. Chem. Int. Ed., 2020, 59, 21613-21619.
[32]	H. Qi, J. Yang, F. Liu, L. Zhang, J. Yang, X. Liu, L. Li, Y. Su, Y. Liu, R. Hao, A. Wang, T. Zhang, Nat. Commun., 2021, 12, 3295.
[33]	W. Liu, L. Zhang, X. Liu, X. Liu, X. Yang, S. Miao, W. Wang, A. Wang, T. Zhang, J. Am. Chem. Soc., 2017, 139, 10790-10798.
[34]	H.-Y. Zhuo, X. Zhang, J.-X. Liang, Q. Yu, H. Xiao, J. Li, Chem. Rev., 2020, 120, 12315-12341.
[35]	L. Zhang, X. Yang, J. Lin, X. Li, X. Liu, B. Qiao, A. Wang, T. Zhang, Acc. Chem. Res., 2025, 58, 1878-1892.
[36]	Y. Ren, Y. Tang, L. Zhang, X. Liu, L. Li, S. Miao, D. Su, A. Wang, J. Li, T. Zhang, Nat. Commun., 2019, 10, 4500.
[37]	J. Duan, Y. Zhou, Y. Ren, F. Liu, P. Deng, M. Yang, H. Ge, J. Gao, J. Yang, Y. Qin, ACS Catal., 2023, 13, 3308-3316.
[38]	H. Qi, Y. Jiao, J. Duan, N. F. Dummer, B. Zhang, Y. Ren, S. H. Taylor, Y. Qin, K. Junge, H. Jiao, G. J. Hutchings, M. Beller, Nat. Commun., 2025, 16, 1840.
[39]	F. L. Liu, M. Yang, J. L. Duan, Z. Y. Yin, M. Y. Shi, F. Chen, H. Xiong, X. Liu, W. Liu, Q. Xia, S. Sun, D. Feng, H. Qi, Y. Qin, Y. Ren, Chin. J. Catal., 2025, 72, 187-198.
[40]	Z. Li, Z. Wang, S. Xi, X. Zhao, T. Sun, J. Li, W. Yu, H. Xu, T. S. Herng, X. Hai, P. Lyu, M. Zhao, S. J. Pennycook, J. Ding, H. Xiao, J. Lu, ACS Nano, 2021, 15, 7105-7113.
[41]	L. Yu, Y. Li, Y. Ruan, Angew. Chem. Int. Ed., 2021, 60, 25296-25301.
[43]	Y. Zeng, X. Li, J. Wang, M. T. Sougrati, Y. Huang, T. Zhang, B. Liu, Chem Catal., 2021, 1, 1215-1233.
[44]	G.-F. Han, F. Li, A. I. Rykov, Y.-K. Im, S.-Y. Yu, J.-P. Jeon, S.-J. Kim, W. Zhou, R. Ge, Z. Ao, T. J. Shin, J. Wang, H. Y. Jeong, J.-B. Baek, Nat. Nanotechnol., 2022, 17, 403-407.
[45]	Y. Zhao, J. Wan, C. Ling, Y. Wang, H. He, N. Yang, R. Wen, Q. Zhang, L. Gu, B. Yang, Z. Xiang, C. Chen, J. Wang, X. Wang, Y. Wang, H. Tao, X. Li, B. Liu, S. Zhang, D. Wang, Nature, 2025, 644, 668-675.
[46]	J. Yang, Z. Wang, C.-X. Huang, Y. Zhang, Q. Zhang, C. Chen, J. Du, X. Zhou, Y. Zhang, H. Zhou, L. Wang, X. Zheng, L. Gu, L.-M. Yang, Y. Wu, Angew. Chem. Int. Ed., 2021, 60, 22722-22728.
[47]	U. I. Kramm, J. Herranz, N. Larouche, T. M. Arruda, M. Lefèvre, F. Jaouen, P. Bogdanoff, S. Fiechter, I. Abs-Wurmbach, S. Mukerjee, J.-P. Dodelet, Phys. Chem. Chem. Phys., 2012, 14, 11673.
[48]	M. Sola, J. Mestres, M. Duran, J. Phys. Chem., 1995, 99, 10752-10758.
[49]	G.-H. Liang, H.-S. Liu, X.-M. Zhang, J.-F. Li, S. Zheng, J. Energy Chem., 2025, 105, 608-616.
[50]	D. Liu, X. Li, S. Chen, H. Yan, C. Wang, C. Wu, Y. A. Haleem, S. Duan, J. Lu, B. Ge, P. M. Ajayan, Y. Luo, J. Jiang, L. Song, Nat. Energy, 2019, 4, 512-518.
[51]	Q. C. Wang, L. L. Lyu, X. Hu, W. Q. Fan, C. Y. Shang, Q. Huang, Z. Li, Z. Zhou, Y.-M. Kang, Angew. Chem. Int. Ed., 2025, 64, e202422920.
[52]	J. R. Polam, J. L. Wright, K. A. Christensen, F. A. Walker, H. Flint, H. Winkler, M. Grodzicki, A. X. Trautwein, J. Am. Chem. Soc., 1996, 118, 5272-5276.
[53]	F. Neese, Inorg. Chim. Acta, 2002, 337, 181-192.
[54]	M. Yang, K. Wu, S. Sun, J. Duan, X. Liu, J. Cui, S. Liang, Y. Ren, ACS Catal., 2023, 13, 681-691.
[55]	L. Su, P. Wang, X. Ma, J. Wang, S. Zhan, Angew. Chem. Int. Ed., 2021, 60, 21261-21266.
[56]	S. Ji, B. Jiang, H. Hao, Y. Chen, J. Dong, Y. Mao, Z. Zhang, R. Gao, W. Chen, R. Zhang, Q. Liang, H. Li, S. Liu, Y. Wang, Q. Zhang, L. Gu, D. Duan, M. Liang, D. Wang, X. Yan, Y. Li, Nat. Catal., 2021, 4, 407-417.
[57]	Y.-F. Liang, N. Jiao, Acc. Chem. Res., 2017, 50, 1640-1653.

[1]	Yueling Chen, Yuling Lin, Ziyan Chen, Xiangyu Kong, Jinhong Bi, Guocheng Huang, Ling Wu. Asymmetric N-Ru-S dipole within covalent organic framework enhances internal electric field for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2026, 87(8): 59-69.
[2]	Zheng Li, Ziang Zhao, Yihui Li, Yuan Lyu, Li Yan, Wenhao Cui, Shunbin Zhu, Yu Meng, Hejun Zhu, Yunjie Ding. Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co₂C-Co catalyst [J]. Chinese Journal of Catalysis, 2026, 85(6): 371-383.
[3]	Yi-Wen Han, Run-Yu Liu, Yu-Xin Zhang, Lei Ye, Phuc T. T. Nguyen, Tian-Jun Gong, Xue-Bin Lu, Yao Fu, Ning Yan. Establishing built-in electric field within single-atom-anchored hollow architectures for efficient solar-thermal regulation in plastic photoreforming [J]. Chinese Journal of Catalysis, 2026, 84(5): 301-313.
[4]	Xin Song, Zhonghua Li, Li Sheng, Yang Liu. Spin density symmetry breaking-mediated hydrogen evolution in single-atom catalysts [J]. Chinese Journal of Catalysis, 2026, 80(1): 213-226.
[5]	Gang Wang, Imran Muhammad, Hui-Min Yan, Jun Li, Yang-Gang Wang. Regulating the local environment of Ni single-atom catalysts with heteroatoms for efficient CO₂ electroreduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 120-129.
[6]	Eryu Wang, Yi-Chun Chu, Wenjun Zhang, Yanping Wei, Chuanling Si, Regina Palkovits, Xin-Ping Wu, Zupeng Chen. Sustainable co-production of H₂ and lactic acid from lignocellulose photoreforming using Pt-C₃N₄ single-atom catalyst [J]. Chinese Journal of Catalysis, 2025, 74(7): 308-318.
[7]	Xiaochun Hu, Longgang Tao, Kun Lei, Zhiqiang Sun, Mingwu Tan. Unraveling TiO₂ phase effects on Pt single-atom catalysts for efficient CO₂ conversion [J]. Chinese Journal of Catalysis, 2025, 73(6): 186-195.
[8]	Fenli Liu, Man Yang, Jianglin Duan, Zhiyu Yin, Mingyang Shi, Fuqing Chen, Huifeng Xiong, Xin Liu, Wengang Liu, Qixing Xia, Shaodong Sun, Dan Feng, Haifeng Qi, Yong Qin, Yujing Ren. Peripheral N_V-induced electron transfer to Fe₁ single atoms for highly efficient O₂ activation [J]. Chinese Journal of Catalysis, 2025, 72(5): 187-198.
[9]	Tao Ban, Jian-Wei Wang, Xi-Yang Yu, Hai-Kuo Tian, Xin Gao, Zheng-Qing Huang, Chun-Ran Chang. Machine learning-assisted screening of SA-FLP dual-active-site catalysts for the production of methanol from methane and water [J]. Chinese Journal of Catalysis, 2025, 70(3): 311-321.
[10]	Jiayi Cui, Xintao Yu, Xueyao Li, Jianmin Yu, Lishan Peng, Zidong Wei. Advances in spin regulation of M-N-C single-atom catalysts and their applications in electrocatalysis [J]. Chinese Journal of Catalysis, 2025, 69(2): 17-34.
[11]	Yangyang Li, Jingyi Yang, Botao Qiao, Tao Zhang. Size-dependent strong metal-support interaction modulation of Pt/CoFe₂O₄ catalysts [J]. Chinese Journal of Catalysis, 2025, 69(2): 292-302.
[12]	Yuxing Xu, Leilei Wang, Qin Liu, Botao Teng, Chuanqiang Wu, Binghui Ge, Wentuan Bi, Minghui Gu, Mengkai Zhang, Huan Yan, Junling Lu. Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 79(12): 68-77.
[13]	Tianyou Zhao, Fengming Hu, Meiqi Zhu, Chang-Jie Yang, Xin-Yu Wang, Yong-Zhou Pan, Jiarui Yang, Xia Zhang, Wen-Hao Li, Dingsheng Wang. Future development of single-atom catalysts in portable energy and sensor technologies [J]. Chinese Journal of Catalysis, 2025, 78(11): 100-137.
[14]	Hao Dai, Tao Song, Xian Yue, Shuting Wei, Fuzhi Li, Yanchao Xu, Siyan Shu, Ziang Cui, Cheng Wang, Jun Gu, Lele Duan. Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO₂ electroreduction to CH₄ [J]. Chinese Journal of Catalysis, 2024, 64(9): 123-132.
[15]	Jialin Wang, Kaini Zhang, Ta Thi Thuy Nga, Yiqing Wang, Yuchuan Shi, Daixing Wei, Chung-Li Dong, Shaohua Shen. Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2024, 64(9): 54-65.

Subangstrom spatial regulation of Fe₁-N₄ coordination structure for remarkably efficient C‒H bond oxidation

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics