Edge effect-enhanced CO2 adsorption and photo-reduction over g-C3N4 nanosheet

doi:10.1016/S1872-2067(24)60141-5

Abstract

Abstract:

Effective CO₂ adsorption and fast electron injection are two crucial processes of photocatalysts for achieving high-efficiency CO₂ photo-reduction. However, simultaneously enhancing these processes within a single photocatalyst remains a challenging task. Herein, we propose an intriguing edge effect based on the intrinsic atomic structure of g-C₃N₄ nanosheets (NSs) to enhance their CO₂ adsorption and facilitate the transfer of photo-generated electrons to the adsorbed CO₂. By cutting large pieces of g-C₃N₄ NSs into smaller fragments, the exposure of amino groups at the edges of its repeating tri-s-triazine units can be significantly increased. These edge-exposed amino groups serve as active sites for enhancing the CO₂ capture capacity of g-C₃N₄ NSs. As we decrease the lateral size of g-C₃N₄ NSs from tens of micrometers to hundreds of nanometers, their CO₂ adsorption capacity increases from 4.74 to 8.56 cm³ g^-1. Reducing the size of g-C₃N₄ NSs also facilitates the transfer of photo-generated electrons to the edge-adsorbed CO₂. Thus, our optimized g-C₃N₄ NSs with the edge effect exhibits a 37-fold enhancement in activity for CO₂ photo-reduction compared to normal g-C₃N₄ NSs under simulated sunlight irradiation. Notably, by introducing Pt cocatalysts, we can control product selectivity from 85.9% CO to 97.9% CH₄.

Key words: Photocatalysis, CO₂ reduction, CO₂ adsorption, Edge effect, Amino group

Xuedong Jing, Xiaoyun Mi, Wei Lu, Na Lu, Shiwen Du, Guodong Wang, Zhenyi Zhang. Edge effect-enhanced CO₂ adsorption and photo-reduction over g-C₃N₄ nanosheet[J]. Chinese Journal of Catalysis, 2024, 67: 112-123.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60141-5

https://www.cjcatal.com/EN/Y2024/V67/I12/112

Figures/Tables 6

Scheme 1. (A) PDOS plot of g-C3N4 in three units, where different colors correspond to C and N atoms in different environments; (B) Structural model of g-C3N4 in three units, with a local enlarged view (right) showing the schematic diagram of electron transfer paths; (C) The optimized configurations of a single CO2 molecule adsorbed onto the surface of g-C3N4, along with the corresponding adsorption energies at the N1 (i), N2 (ii), N3 (iii) and N4 sites (iv); (D) The mechanism diagram of how the edge effect enhances photocatalytic activity.

Fig. 1. (A) Schematic diagram of edge-exposed amino groups changes in g-C3N4 nanosheets obtained through ultrasonic cutting. SEM images of CN-0 (B), CN-4 NSs (C) and CN-8 NSs (D). AFM images of CN-0 (E), CN-4 NSs (F) and CN-8 NSs (G).

Fig. 2. (A) XRD patterns. (B,C) FT-IR spectra for different nanosheets: (a) CN-0; (b) CN-2 NSs; (c) CN-4 NSs; (d) CN-6 NSs; (e) CN-8 NSs. High-resolution XPS spectra of C 1s (D), N 1s (E), and O 1s (F) core-level spectra for the samples CN-0 NSs (a) and CN-8 NSs (b). The percentage of amino peak area relative to the total peak area (G) and CO2 adsorption isotherms (H) measured on different samples: (a) CN-0; (b) CN-2 NSs; (c) CN-4 NSs; (d) CN-6 NSs; (e) CN-8 NSs. (I) The schematic illustration of the CO2 molecule adsorption mechanism on samples with varying amino group concentrations.

Fig. 3. UV-vis absorption spectra (A), Steady-state PL spectra (B) and time-resolved PL decay spectra (C) of the samples: (a) CN-0; (b) CN-2 NSs; (c) CN-4 NSs; (d) CN-6 NSs; (e) CN-8 NSs. KPFM images in dark (left) and light (right) conditions of CN-0 NSs (D,E) and CN-8 NSs (F,G). The charge difference distribution between layers of g-C3N4 NSs without amino groups (H) and g-C3N4 NSs with amino groups (I) (charge accumulation is in yellow and charge depletion is in blue). (J) The distribution and transfer of electrons among different samples exhibiting varying concentrations of amino groups.

Fig. 4. (A) Photocatalytic CO2 reduction performance of the as-synthesized samples to CO under AM 1.5 irradiation. (B) The products yield of photocatalytic CO2 reduction following 3 h irradiation for the as-synthesized samples. (C) Photocatalytic CO2 reduction to CO rate and selectivity of different samples: CN-0 (a), CN-2 NSs (b), CN-4 NSs (c), CN-6 NSs (d) and CN-8 NSs (e). (D) AQE of CN-0 (a) and CN-8 NSs (b). In-situ FTIR spectra of CO2 reduction process on different samples under the illumination process using AM 1.5 light: CN-0 (E) and CN-8 NSs (F). (G) Free energy diagram of g-C3N4 NSs with (CN-NH2) and without (CN) amino groups for photocatalytic CO2 reduction. (H) The plausible mechanism for photocatalytic reduction of CO2 to CO.

Fig. 5. HAADT-STEM images of the as-synthesized CN-8 NSs loaded with 1 wt% Pt (A) and 5 wt% Pt (B). High-resolution XPS spectra of the N 1s core-level spectra (C) and Pt 4f core-level spectra (D) of CN-8 NSs loaded with different amount of Pt NPs: (a) 0%; (b) 1%; (c) 5%. (E) Photocatalytic CO2 reduction to CH4 performance and CH4 selectivity of the CN-8 NSs with different amount of Pt loading. (F) Schematic illustration of the photocatalytic CO2 reduction reaction for different samples: (a) CN; (b) CN-NH2(rich); (c) CN-NH2(Pt).

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Edge effect-enhanced CO₂ adsorption and photo-reduction over g-C₃N₄ nanosheet

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