Construction of 2D Zn-MOF/BiVO4 S-scheme heterojunction for efficient photocatalytic CO2 conversion under visible light irradiation

doi:10.1016/S1872-2067(21)64005-6

Abstract

Abstract:

The construction of S-scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel. However, there are still considerable challenges with regard to efficient charge transfer, the abundance of catalytic sites, and extended light absorption. Herein, an S-scheme heterojunction of 2D/2D zinc porphyrin-based metal-organic frameworks/BiVO₄ nanosheets (Zn-MOF/BVON) was fabricated for efficient photocatalytic CO₂ conversion. The optimal one shows a 22-fold photoactivity enhancement when compared to the previously reported BiVO₄ nanoflake (ca. 15 nm), and even exhibits ~2-time improvement than the traditional g-C₃N₄/BiVO₄heterojunction. The excellent photoactivities are ascribed to the strengthened S-scheme charge transfer and separation, promoted CO₂ activation by the well-dispersed metal nodes Zn₂(COO)₄in the Zn-MOF, and extended visible light response range based on the results of the electrochemical reduction, electron paramagnetic resonance, and in-situ diffuse reflectance infrared Fourier transform spectroscopy. The dimension-matched Zn-MOF/BVON S-scheme heterojunction endowed with highly efficient charge separation and abundant catalytic active sites contributed to the superior CO₂ conversion. This study offers a facile strategy for constructing S-scheme heterojunctions involving porphyrin-based MOFs for solar fuel production.

Key words: BiVO₄ nanosheet, 2D zinc porphyrin-based MOFs, modification, S-scheme heterojunction, Visible light catalysis, CO₂conversion

Zhenlong Zhao, Ji Bian, Lina Zhao, Hongjun Wu, Shuai Xu, Lei Sun, Zhijun Li, Ziqing Zhang, Liqiang Jing. Construction of 2D Zn-MOF/BiVO₄ S-scheme heterojunction for efficient photocatalytic CO₂ conversion under visible light irradiation[J]. Chinese Journal of Catalysis, 2022, 43(5): 1331-1340.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64005-6

https://www.cjcatal.com/EN/Y2022/V43/I5/1331

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Scheme 1. Schematic diagram of the synthetic process for 2D/2D Zn-MOF/BVON heterojunctions.

Fig. 1. (a) TEM and HRTEM images, (b) AFM image and the corresponding height profile, (c) HAADF image and the corresponding EDX mapping images of elemental Bi, V, O, Zn, C, N of 20Zn-MOF/BVON heterojunction.

Fig. 2. (a) Raman spectra of BVON and xZn-MOF/BVON heterojunctions with the excitation wavelength of 532 nm; (b) Raman spectra of Zn-MOF and xZn-MOF/BVON heterojunctions with the excitation wavelength of 785 nm; (c) XPS profiles of V 2p for BVON and 20Zn-MOF/BVON heterojunction; (d) XPS profiles of Zn 2p for Zn-MOF and 20Zn-MOF/BVON heterojunction.

Fig. 3. FS related to the formed •OH amount (a), photoelectrochemical I-V curves (b), photocatalytic activities (c) for CO2 conversion of BVON and xZn-MOF/BVON heterojunctions under visible-light irradiation; (d) Photocatalytic cycling test of 20Zn-MOF/BVON heterojunction.

Fig. 4. DMPO spin-trapping EPR spectra for •OH (a) and •O2- (b) under visible-light irradiation for BVON, Zn-MOF, and 20Zn-MOF/BVON heterojunction; (c) Normalized photocurrent action spectra of BVON, Zn-MOF, and 20Zn-MOF/BVON heterojunction under different monochromatic light irradiation; (d) SS-SPS responses in N2 atmosphere of BVON and 20Zn-MOF/BVON heterojunction, inset: SS-SPS responses assisted with 470 nm monochromatic beam; (e) Schematic diagram of the formation of Zn-MOF/BVON S-scheme heterojunction and the internal electric field (IEF) induced charge transfer and separation under visible-light irradiation.

Fig. 5. Electrochemical reduction curves of BVON, Zn-MOF and 20Zn-MOF/BVON heterojunction in N2-bubbled system (a) and CO2-bubbled system (b); In-situ DRIFTS for adsorbed CO2 (c) and H2O (d) of BVON and 20Zn-MOF/BVON heterojunction in dark for 30 min and under light irradiation for 15 min; (e) In-situ DRIFT spectra of 20Zn-MOF/BVON heterojunction with different light irradiation intervals.

Scheme 2. Schematic of photogenerated charges transfer in Zn-MOF/BVON heterojunctions during CO2 photoreduction process.

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Construction of 2D Zn-MOF/BiVO₄ S-scheme heterojunction for efficient photocatalytic CO₂ conversion under visible light irradiation

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