Copper and platinum dual-single-atoms supported on crystalline graphitic carbon nitride for enhanced photocatalytic CO2 reduction

doi:10.1016/S1872-2067(21)63879-2

Abstract

Abstract:

Single-atom Pt catalysts are designed to promote efficient atom utilization, whereas effective decrease of Pt loading and improvement of photocatalytic activity in monoatomic Pt-deposited systems is still ongoing. Atomically dispersed metal species in crystalline carbon nitride are still challenging owing to their high crystallization and structural stability. In this study, we developed a novel single-atomic Pt-Cu catalyst for reducing noble metal loading by combining Pt with earth-abundant Cu atoms and enhancing photocatalytic CO₂ reduction. N-vacancy-rich crystalline carbon nitride was used as a fine-tuning ligand for isolated Pt-Cu atom dispersion based on its accessible functional N vacancies as the seeded centers. The synthesized dimetal Pt-Cu atoms on crystalline carbon nitride (PtCu-crCN) exhibited high selectivity and activity for CO₂ conversion without the addition of any cocatalyst or sacrificial agent. In particular, we demonstrated that the diatomic Pt-Cu exhibited high mass activity with only 0.32 wt% Pt loading and showed excellent photocatalytic selectivity toward CH₄ generation. The mechanism of CO₂ photoreduction for PtCu-crCN was proposed based on the observations and analysis of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images, in situ irradiated X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The findings of this work provide insights for abrogating specific bifunctional atomic metal sites in noble metal-based photocatalysts by reducing noble metal loading and maximizing their effective mass activity.

Key words: Dimetal Pt-Cu atom, Crystalline carbon nitride, Photocatalytic CO₂ reduction, Low loading, Synergistic photocatalysis

Lei Cheng, Peng Zhang, Qiye Wen, Jiajie Fan, Quanjun Xiang. Copper and platinum dual-single-atoms supported on crystalline graphitic carbon nitride for enhanced photocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2022, 43(2): 451-460.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63879-2

https://www.cjcatal.com/EN/Y2022/V43/I2/451

Figures/Tables 7

Fig. 1. (a) Schematic illustration of synthetic procedure for PtCu-crCN; TEM image (b), HRTEM image (c) (the right shows partially zoomed-in images of the selected region 1), STEM image and EDS elemental mapping (d) of PtCu-crCN; (e,f) Aberration-corrected HAADF-STEM images of PtCu-crCN (the right shows partially zoomed-in images of the selected region 2, and corresponding intensity profile along the labeled line 1; scale bar: 0.1 nm).

Fig. 2. (a) The mass of Cu and Pt measured by inductively coupled plasma mass test of PtCu-crCN; XRD patterns (b), UV-vis diffuse reflection spectra (c), electrochemical impedance spectra (d), and transient photocurrent response spectra (e) of PtCu-crCN, Cu-crCN, Pt-crCN and crCN; (f) Schematic illustration of possible dynamic photocarrier transfer in crCN (i) and PtCu-crCN (ii).

Fig. 3. ISI-XPS patterns of Cu 2p (a), Pt 4f (b), C 1s (c) and N 1s (d) in the dark and under 365 nm LED irradiation, respectively.

Fig. 4. Comparable photocatalytic yield for CO (a) and CH4 (b) of PtCu-crCN, Cu-crCN, Pt-crCN and crCN under subsequently simulated solar illumination; Calculated TONs (c) and selectivity for CH4 evolution (d) of PtCu-crCN, Cu-crCN, Pt-crCN and crCN; (e) Photocatalytic recycle reaction of PtCu-crCN under subsequently simulated solar illumination for 3 cycle (each cycle lasts for 3.5 h); (f) The average yield of CO and CH4 over PtCu-crCN PtCu-crCN, Cu-crCN, Pt-crCN and crCN with reaction proceeds for 3.5 h.

Fig. 5. In situ DRIFTS spectra of CO2 and H2O interaction with PtCu-crCN in the dark (0-60 min) with different wavenumber ranges of 1000-1900 cm-1 (a), 2000-2500 cm-1 (b), and 3200-3900 cm-1 (c).

Fig. 6. In situ DRIFTS spectra of CO2 and H2O interaction with PtCu-crCN under 365 nm light irradiation (0-120 min) with different wavenumber ranges of 950-2250 cm-1 (a) and 2900-3900 cm-1 (b).

Fig. 7. Schematic illustration for photocatalytic mechanism of CO2 reduction on PtCu-crCN. The induced Pt-Cu atomic species exhibits synergistic photocatalysis with the dispersed Pt sites searving as hydrogen reservoir to hydrogenation reaction and Cu as active CO2 adsorption centers, and both of the active centers are active in accelerating the long-lived charge separation.

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Copper and platinum dual-single-atoms supported on crystalline graphitic carbon nitride for enhanced photocatalytic CO₂ reduction

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