3D Fe-MOF embedded into 2D thin layer carbon nitride to construct 3D/2D S-scheme heterojunction for enhanced photoreduction of CO2

doi:10.1016/S1872-2067(22)64115-9

Abstract

Abstract:

Regulating charge transfer to achieve specific transfer path can improve electron utilization and complete efficient photoreduction of CO₂. Here, we fabricated a S-scheme heterojunction of CN/Fe-MOF by an in-situ assembly strategy. The S-scheme charge transfer mechanism was confirmed by band structure, electron spin resonance (ESR) and work function (Φ) analysis. On the one hand, the response of Fe-MOF in the visible region improved the utilization of light energy, thus increasing the ability of CN/Fe-MOF to generate charge carriers. On the other hand, CN, as the active site, not only had strong adsorption capacity for CO₂, but also retained photogenerated electrons with high reduction capacity because of S-scheme charge transfer mechanism. Hence, in the absence of any sacrificial agent and cocatalyst, the optimized 50CN/Fe-MOF obtained the highest CO yield (19.17 μmol g^-1) under UV-Vis irradiation, which was almost 10 times higher than that of CN. In situ Fourier transform infrared spectra not only revealed that the photoreduction of CO₂ occurred at the CN, but also demonstrated that the S-scheme charge transfer mechanism enabled 50CN/Fe-MOF to have a stronger ability to generate HCOO^- than CN.

Key words: Thin layer porous g-C₃N₄, S-Scheme heterojunction, Photocatalytic CO₂ reduction, Fe-MOF, Surface intermediate

Xiaoxue Zhao, Mengyang Xu, Xianghai Song, Weiqiang Zhou, Xin Liu, Pengwei Huo. 3D Fe-MOF embedded into 2D thin layer carbon nitride to construct 3D/2D S-scheme heterojunction for enhanced photoreduction of CO₂[J]. Chinese Journal of Catalysis, 2022, 43(10): 2625-2636.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64115-9

https://www.cjcatal.com/EN/Y2022/V43/I10/2625

Figures/Tables 14

Scheme 1. Schematic of synthesis of CN/Fe-MOF.

Fig. 1. (a) XRD of all samples. (b) FT-IR spectra of CN, Fe-MOF and 50CN/ Fe-MOF.

Fig. 2. (a,b) SEM of Fe-MOF. (c) SEM of 50CN/Fe-MOF. (d-i) The element mappings of 50CN/Fe-MOF. (j) TEM of 50CN/Fe-MOF.

Fig. 3. (a) N2 adsorption-desorption isotherms. (b-d) BJH mesopore size distributions.

Table 1 SBET, pore volume and pore diameter of CN, Fe-MOF and 50CN/Fe-MOF.

Sample	S_BET (m² g^-1)	Average pore size (nm)	Pore volume (cm³ g^-1)
CN	48.021	22.923	0.344
Fe-MOF	7.545	15.554	0.049
50CN/Fe-MOF	203.470	9.340	0.459

Fig. 4. XPS spectra of samples. (a) C 1s; (b) Fe 2p; (c) O 1s; (d) N 1s.

Fig. 5. (a) CO evolution amount vs. illumination time. (b) AQY values for photocatalytic CO2 reduction over the 50CN/Fe-MOF at various wavelengths. (c) Evolution of CO under various reaction conditions. (d) Mass spectrum of the 13CO generated from the photoreduction of 13CO2 isotopic experiment.

Fig. 6. The PL (a) and TRPL (b) of CN, Fe-MOF and 50CN/ Fe-MOF. The TPR (c) and EIS (d) of all the photocatalysts. (e) The LSV of CN, Fe-MOF and 50CN/Fe-MOF in CO2. (f) The LSV of 50CN/Fe-MOF in N2 and CO2.

Table 2 The fitted parameters obtained from decay curves of the samples.

Sample	τ₁ (ns)	A₁ (%)	τ₂ (ns)	A₂ (%)	τ_av (ns)
CN	8.79	73.02	96.29	26.98	9.33
Fe-MOF	8.41	58.75	84.10	41.25	8.82
50CN/Fe-MOF	7.24	36.56	60.35	63.44	7.39

Fig. 7. The 3D color-mapped surface map with projection (a,d), in situ FT-IR spectra (b,e) and Partial enlarged view (c,f) for 50CN/Fe-MOF (a-c) and CN (d-f).

Fig. 8. (a) UV-vis diffuse reflectance spectra of all photocatalysts. (b) Tauc plots of CN, Fe-MOF and 50CN/Fe-MOF derived from the corresponding DRS.

Fig. 9. Mott-Schottky curves of CN (a) and Fe-MOF (b). The schematic diagram of the band structure of CN and Fe-MOF (c).

Fig. 10. (a) UPS spectra of CN and Fe-MOF. (b) The work functions of CN and Fe-MOF before/after contact and the formation of internal electric field. DMPO/•O2- (c) and DMPO/•OH (d) of ESR detection.

Fig. 11. The mechanism of S-scheme 3D/2D CN/Fe-MOF as a photocatalyst for CO2 reduction.

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3D Fe-MOF embedded into 2D thin layer carbon nitride to construct 3D/2D S-scheme heterojunction for enhanced photoreduction of CO₂

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