Designed electron transport path via Fe-O-Ni atomic bond for high CO2 reduction

doi:10.1016/S1872-2067(24)60230-5

Abstract

Abstract:

The assembly of different Metal organic framework (MOFs) into hybrid heterostructures has proven to be a promising strategy that can effectively break through the limited regulatory capacity of single metal sites. Here, an S-scheme heterostructure (Fe₃Ni-MOF) based on homologous ligands (1,4-phthalic acid) of ultra-thin Ni-MOF and Fe-MOF nanoparticles with directional electron transport channels, was developed and used it for photoreduction of CO₂. Under the S-scheme electric field mechanism, the photogenerated carrier can achieve efficient directional separation through Fe-O-Ni atomic bond, which significantly reduces the energy barrier of the rate-determining step. Results show that the performance of Fe₃Ni-MOF (63.5 μmol g^-1) was 20 and 3.2 times higher than that of Ni-MOF and Fe-MOF, respectively, and exhibits excellent CO selectivity (96.4%) and stability. Transmission electron microscopy and atomic force microscopy revealed the two-molecular-layers structure of Ni-MOF and the micro-assembly structure of Fe₃Ni-MOF, which can shorten the electron transport distance and increase the molecular mass transfer rate. X-ray photoelectron spectroscopy, electron spin resonance and electron density difference calculations reveal that interfacial electric fields and atomic bonds work together to promote directional carrier separation, resulting in the accumulation of holes on Ni-MOF and electrons on Fe-MOF. The Gibbs free energy calculation and in-situ Fourier transformed infrared spectroscopy validate that the micro-assembled S-scheme heterostructures with directional electron transport channels can significantly reduce the activation energy barrier of the reaction. This study not only proves the feasibility of constructing MOFs S-scheme heterostructures using homologous ligands, but also provides a new way to overcome the limitations of monometallic MOFs. This strategy is expected to open up a new avenue to design efficient photocatalysts.

Key words: Ultra-thin 2D structure, S-scheme electron transfer, Atomic transfer channel, Photocatalytic CO₂ conversion, MOF-on-MOF

Mengyang Xu, Bingqing Chang, Jinze Li, Huiqin Wang, Pengwei Huo. Designed electron transport path via Fe-O-Ni atomic bond for high CO₂ reduction[J]. Chinese Journal of Catalysis, 2025, 71: 114-127.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60230-5

https://www.cjcatal.com/EN/Y2025/V71/I4/114

Figures/Tables 11

Scheme 1. Schematic illustration of the preparation process for Fe3Ni-MOF.

Fig. 1. SEM images of Ni-MOF (a), Fe3Ni-MOF (b), and Fe-MOF (c). TEM (d) and AFM (e) of Ni-MOF. (f) TEM of Fe-MOF. (g-i) TEM and local magnification TEM images of Fe3Ni-MOF. (j) Element mapping diagram of Fe3Ni-MOF (Ni, Fe, O, C).

Fig. 2. XRD (a), FT-IR (b) and Raman (c) spectra of Ni-MOF, Fe3Ni-MOF, and Fe-MOF. HR-XPS spectra of Fe 2p (d), Ni 2p (e) and O 1s (f).

Fig. 3. UV-vis spectra (a), instantaneous photocurrent response intensity (b) and Nyquist (EIS) curve (c) of Ni-MOF, Fe-MOF and FeNi-MOF series samples. (d) TR-PL spectra of Ni-MOF, Fe-MOF and Fe3Ni-MOF.

Fig. 4. (a) Photocatalytic activity test results for the Ni-MOF, Fe-MOF, and FeNi-MOF series samples. (b) Relationship between the proportion of Fe elements and performance. (c) Cycling stability test for Fe3Ni-MOF. (d) Control experiments under varying conditions for Fe3Ni-MOF. (e) Isotopic analysis using 13C. (f) Quantum efficiency measurements for Ni-MOF, Fe-MOF, and Fe3Ni-MOF at wavelengths of 360, 420, and 560 nm.

Fig. 5. ESR test after 5 min of illumination: DMPO-?OH (a) and DMPO-?O2- (b). (c) Bandgaps of Ni-MOF and Fe-MOF obtained from Tauc's plot. (d) Mott Schottky curves of Ni-MOF and Fe-MOF at different frequencies. (e) The photogenerated carrier transfer mode before and after Ni-MOF and Fe-MOF recombination under light.

Fig. 6. Work functions of Ni-MOF (a) and Fe-MOF (b). (c) Differential charge density calculation of Fe3Ni-MOF (blue regions are electrons, yellow regions are holes). (d) The Gibbs free energy (ΔG) of Ni-MOF and Fe-MOF adsorbed CO2 was calculated. (e) Calculate ΔG of CO2 adsorbed on the Ni-MOF side and Fe-MOF side of Fe3Ni-MOF.

Fig. 7. Kelvin Probe Force Microscopy (KPFM) of Ni-MOF (a,b), Fe3Ni-MOF (c,d) and Fe-MOF (e,f).

Fig. 8. In-situ FT-IR adsorption tests of CO2 for Ni-MOF (a), Fe3Ni-MOF (b), and Fe-MOF (c). (d) Nitrogen adsorption and desorption test.

Fig. 9. (a) Gibbs free energy calculation for Ni-MOF, Fe3Ni-MOF and Fe-MOF during photoreduction of CO2. In-situ FT-IR spectra of Ni-MOF (b) Fe3Ni-MOF (c) and Fe-MOF (d) under light.

Fig. 10. In situ XPS measurements of Fe3Ni-MOF under dark conditions, during light irradiation, and after the light source was turned off. (a) HR-XPS of Ni 2p; (b) HR-XPS of Fe 2p.

References

[1]	J. Fu, K. Liu, H. Li, J. Hu, M. Liu, Environ. Chem. Lett., 2021, 20, 243-262.
[2]	M. Jafarzadeh, K. Daasbjerg, ACS Appl. Energy Mater., 2023, 6, 6851-6882.
[3]	J. Yang, Y. Guo, W. Lu, R. Jiang, J. Wang, Adv. Mater., 2018, 30,1802227.
[4]	H. Wang, X. Li, X. Zhao, C. Li, X. Song, P. Zhang, P. Huo, X. Li,, Chin. J. Catal., 2022, 43, 178-214.
[5]	H. L. Zheng, S. L. Huang, M. B. Luo, Q. Wei, E. X. Chen, L. He, Q. Lin, Angew. Chem. Int. Ed., 2020, 59, 23588-23592.
[6]	B. Zhu, J. Sun, Y. Zhao, L. Zhang, J. Yu, Adv. Mater., 2024, 36, 2310600.
[7]	X. Zu, Y. Zhao, X. Li, R. Chen, W. Shao, L. Li, P. Qiao, W. Yan, Y. Pan, Q. Xu, J. Zhu, Y. Sun, Y. Xie, Angew. Chem. Int. Ed., 2022, 62, e202215247.
[8]	Q. Zuo, R. Cui, L. Wang, Y. Wang, C. Yu, L. Wu, Y. Mai, Y. Zhou, Sci. China Chem., 2023, 66, 570-577.
[9]	Q. Zuo, T. Liu, C. Chen, Y. Ji, X. Gong, Y. Mai, Y. Zhou, Angew. Chem. Int. Ed., 2019, 58, 10198-10203.
[10]	Y.-L. Dong, H.-R. Liu, S.-M. Wang, G.-W. Guan, Q.-Y. Yang, ACS Catal., 2023, 13, 2547-2554.
[11]	T. Araya, M. Jia, J. Yang, P. Zhao, K. Cai, W. Ma, Y. Huang, Appl. Catal. B, 2017, 203, 768-777.
[12]	J. Zhao, G. Ren, X. Meng, Nano Energy, 2024, 130, 110109.
[13]	W. Wang, D. Wang, H. Song, D. Hao, B. Xu, J. Ren, M. Wang, C. Dai, Y. Wang, W. Liu, Chem. Eng. J., 2023, 455, 140909.
[14]	J. Di, J. Xiong, H. Li, Z. Liu, Adv. Mater., 2018, 30, 1704548.
[15]	W. Yang, X. Lin, W.-J. Shi, J.-H. Zhang, Y.-C. Wang, J.-H. Deng, D.-C. Zhong, T.-B. Lu, J. Mater. Chem. A, 2023, 11, 2225-2232.
[16]	R. Chen, Y. Wang, Y. Ma, A. Mal, X.-Y. Gao, L. Gao, L. Qiao, X.-B. Li, L.-Z. Wu, C. Wang, Nat. Commun., 2021, 12, 1354.
[17]	Y. Li, S. Wu, J. Zheng, Y.-K. Peng, D. Prabhakaran, R. A. Taylor, S. C. E. Tsang, Mater. Today, 2020, 41, 34-43.
[18]	Y. Xiao, J. Liu, J. Leng, Z. Yin, Y. Yin, F. Zhang, C. Sun, S. Jin, ACS Energy Lett., 2022, 7, 2323-2330.
[19]	W. Wang, Y. Yu, Y. Jin, X. Liu, M. Shang, X. Zheng, T. Liu, Z. Xie, J. Nanobiotechnol., 2022, 20, 207.
[20]	B. Han, X. Ou, Z. Deng, Y. Song, C. Tian, H. Deng, Y. J. Xu, Z. Lin, Angew. Chem. Int. Ed., 2018, 57, 16811-16815.
[21]	N.-Y. Huang, Z.-Y. Chen, F.-L. Hu, C.-Y. Shang, W. Wang, J.-R. Huang, C. Zhou, L. Li, Q. Xu, Nano Res., 2023, 16, 7756-7760.
[22]	B. He, Y.-J. Wang, X. Bai, H. Bian, Y. Xie, R. Li, J.-R. Li, Chem. Eng. J., 2024, 48, 149000.
[23]	T. Le Huec, A. Lopez-Frances, I. Abanades Lazaro, S. Navalon, H. G. Baldovi, M. Gimenez-Marques, ACS Nano, 2024, 18, 20201-20212.
[24]	F. Li, J. Li, L. Zhou, S. Dai, Sustainable Energy Fuels, 2021, 5, 1095-1102.
[25]	Q. Wang, J. Lu, Y. Jiang, S. Yang, Y. Yang, Z. Wang, Chem. Eng. J., 2022, 143, 136483.
[26]	Q. Wu, M. S. Siddique, W. Yu, J. Hazard. Mater., 2021, 401, 123261.
[27]	M. Wang, Y. Li, D. Yan, H. Hu, Y. Song, X. Su, J. Sun, S. Xiao, Y. Gao, Chin. J. Catal., 2024, 65, 103-112.
[28]	Q. Zhu, W. Huang, J. Shen, H. Jiang, Y. Zhu, C. Li, Chem. Eng. J., 2024, 499, 156663.
[29]	C. F. Li, L. J. Xie, J. W. Zhao, L. F. Gu, H. B. Tang, L. Zheng, G. R. Li, Angew. Chem. Int. Ed., 2022, 61, e202116934.
[30]	Y. Bao, H. Ru, Y. Wang, K. Zhang, R. Yu, Q. Wu, A. Yu, D.S. Li, C. Sun, W. Li, J. Tu, Adv. Funct. Mater., 2024, 34, 2314611.
[31]	Y. Zou, E. Rukundo, S. Feng, X. Chen, Y. Liu, Chem. Eng. J., 2024, 492, 152435.
[32]	K. Lai, Y. Sun, N. Li, Y. Gao, H. Li, L. Ge, T. Ma, Adv. Funct. Mater., 2024, 2409031.
[33]	L. Chen, Q. Liu, J. Yang, Y. Li, G. Li, Chin. Chem. Lett., 2023, 34, 107335.
[34]	X. Li, J. Yu, M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603-2636.
[35]	M. Hu, J. Liu, S. Song, W. Wang, J. Yao, Y. Gong, C. Li, H. Li, Y. Li, X. Yuan, Z. Fang, H. Xu, W. Song, Z. Li, ACS Catal., 2022, 12, 3238-3248.
[36]	J. Liang, H. Zhang, Q. Song, Z. Liu, J. Xia, B. Yan, X. Meng, Z. Jiang, X. W. Lou, C. S. Lee, Adv. Mater., 2024, 36, 2303287.
[37]	Z.-W. Huang, K.-Q. Hu, X.-B. Li, Z.-N. Bin, Q.-Y. Wu, Z.-H. Zhang, Z.-J. Guo, W.-S. Wu, Z.-F. Chai, L. Mei, W.-Q. Shi, J. Am. Chem. Soc., 2023, 145, 18148-18159.
[38]	K. Wang, T. Sun, H. Ma, Y. Wang, Z.-H. He, H. Wang, W. Wang, Y. Yang, L. Wang, Z.-T. Liu, Chem. Eng. J., 2024, 497, 154711.
[39]	Y. Xiao, H. T. Zhang, M. T. Zhang, J. Am. Chem. Soc., 2024, 146, 28832-28844.
[40]	J. Li, Y. Li, M. Han, Y. Yamauchi, G. Zhang, Chem. Eng. J., 2024, 499, 156429.
[41]	X. Liu, Y. Wu, Y. Li, X. Yang, Q. Ma, J. Luo, Chem. Eng. J., 2024, 485, 149855.
[42]	Z.-X. Pan, S. Yang, X. Chen, J.-X. Luo, R.-Z. Zhang, P. Yang, Q. Xu, J.-Y. Yue, Chem. Eng. J., 2024, 493, 152798.
[43]	L. Zhang, G. Zhou, G. Chen, H. Wang, Q. Zhao, W. Yin, J. Yi, X. Zhu, X. Wang, X. Ning, Chem. Eng. J., 2024, 497, 154701.
[44]	Z. Zhang, X. Wang, H. Tang, D. Li, J. Xu, Chin. J. Catal., 2023, 55, 227-240.
[45]	Y. A. Chen, Y. Nakayasu, Y. C. Lin, J. C. Kao, K. C. Hsiao, Q. T. Le, K. D. Chang, M. C. Wu, J. P. Chou, C. W. Pao, T. F. M. Chang, M. Sone, C. Y. Chen, Y. C. Lo, Y. G. Lin, A. Yamakata, Y. J. Hsu, Adv. Funct. Mater., 2024, 34, 2402392.
[46]	M. Dai, Z. He, P. Zhang, X. Li, S. Wang, J. Mater. Sci. Technol., 2022, 122, 231-242.
[47]	Y. Zhang, J. Li, W. Zhou, X. Liu, X. Song, S. Chen, H. Wang, P. Huo, Appl. Catal. B, 2024, 342, 123449.
[48]	M. Liu, J. Wen, R. Xiao, R. Tan, Y. Qin, J. Li, Y. Bai, M. Xi, W. Yang, Q. Fang, L. Hu, W. Gu, C. Zhu, Nano Lett., 2023, 23, 5358-5366.
[49]	H. Zhao, L. Wang, G. Liu, Y. Liu, S. Zhang, L. Wang, X. Zheng, L. Zhou, J. Gao, J. Shi, Y. Jiang, ACS Catal., 2023, 13, 6619-6629.
[50]	Y. Zhang, L. Hu, Y. Zhang, X. Wang, H. Wang, Appl. Catal. B, 2022, 315, 121540.
[51]	W. Yu, J. Liu, M. Yi, J. Yang, W. Dong, C. Wang, H. Zhao, H.S.H. Mohamed, Z. Wang, L. Chen, Y. Li, B.L. Su, J. Colloid Interf. Sci., 2020, 565, 207-217.
[52]	W. Ling, J. Ma, M. Hong, R. Sun, Chem. Eng. J., 2024, 493, 152729.
[53]	D. Liu, L. Jiang, D. Chen, Z. Hao, B. Deng, Y. Sun, X. Liu, B. Jia, L. Chen, H. Liu, ACS Catal., 2024, 14, 5326-5343.
[54]	Y. Che, B. Weng, K. Li, Z. He, S. Chen, S. Meng, Appl. Catal. B, 2025, 361, 124656.
[55]	Y. An, W. Liu, Y. Zhang, J. Zhang, Z. Lu, Acta Phys.-Chim. Sin., 2024, 40, 2407021.
[56]	S. Yin, Y. Liu, W. Zhou, H. Wang, X. Song, H. Wang, P. Huo, Chem. Eng. J., 2023, 477, 147292.
[57]	C. Liu, Y. Xiao, W. Wan, Y. Wei, Y. Cao, L. Hong, Y. Wang, J. Chen, Q. Zhang, H. Jing, Appl. Catal. B, 2023, 325, 122394.
[58]	J. Qin, Y. An, Y. Zhang, Acta Phys.-Chim. Sin., 2024, 40, 2408002.
[59]	E.-M. Köck, M. Kogler, T. Bielz, B. Klötzer, S. Penner, J. Phys. Chem. C, 2013, 117, 17666-17673.
[60]	Z. Li, J. Xiong, Y. Huang, Y. Huang, G.I.N. Waterhouse, Z. Wang, Y. Mao, Z. Liang, X. Luo, Chem. Eng. J., 2024, 495, 153310.
[61]	J. Liang, H. Yu, J. Shi, B. Li, L. Wu, M. Wang, Adv Mater., 2023, 35, 2209814.

Designed electron transport path via Fe-O-Ni atomic bond for high CO₂ reduction

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