Effect of palladium chemical states on CO2 photocatalytic reduction over g-C3N4: Distinct role of single-atomic state in boosting CH4 production

doi:10.1016/S1872-2067(22)64199-8

Abstract

Abstract:

Cocatalyst decoration has been recognized as an effective strategy in photocatalysis, yet the critical role of sing-atomic state on CO₂ photocatalytic reduction, distinguished from the oxide and elemental states, remains a mystery hitherto. Herein, single-atom Pd (Pd-SA), Pd oxides (PdO_x), and Pd nanoparticles (Pd-NP), were homogeneously anchored on g-C₃N₄ (CN) to investigate their CO₂ reduction behaviors under visible-light irradiation. Performance tests showed Pd species decoration improved the CH₄ production of CN, with Pd/CN-SA exhibiting the optimum yields (2.25 μmol g^-1), markedly higher than that of PdO_x/CN (1.08 μmol g^-1) and Pd/CN-NP (0.44 μmol g^-1). After comprehensive mechanism analysis with various characterization techniques, in-situ DRIFT spectra and DFT calculations, it was found that the conducive activation of CO₂, negative conduction band potentials, and excellent •H utilization efficiency, collaboratively contributed to the superior CH₄ production of Pd/CN-SA. Despite the larger electron density of Pd/CN-NP and PdO_x/CN, the moderate reduction ability of their photogenerated electrons restricted the further reduction of adsorbed CO₂ species and CO intermediate, limiting the enhancement of CO₂ reduction activity. Furthermore, the CH₄ evolutions of Pd/CN-NP and PdO_x/CN were also limited by the poor •H supply and inferior •H utilization efficiency, respectively. It is expected that the effect of chemical states, especially the critical role of single-atomic state, revealed in this work can inspire the rational design of more advanced photocatalysts for CO₂ reduction.

Key words: CO₂ photocatalytic reduction, Chemical states, Palladium, G-C₃N₄, Atomic hydrogen utilization

Qian Li, Qijun Tang, Peiyao Xiong, Dongzhi Chen, Jianmeng Chen, Zhongbiao Wu, Haiqiang Wang. Effect of palladium chemical states on CO₂ photocatalytic reduction over g-C₃N₄: Distinct role of single-atomic state in boosting CH₄ production[J]. Chinese Journal of Catalysis, 2023, 46: 177-190.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64199-8

https://www.cjcatal.com/EN/Y2023/V46/I3/177

Figures/Tables 10

Fig. 1. TEM and HRTEM images of CN (a), PdOx/CN (b), Pd/CN-NP (c), Pd/CN-SA (d). (e) HAADF-STEM image of Pd/CN-SA. (f) FT-EXAFS spectra of Pd/CN-SA, bulk palladium foil, and PdO at the Pd K-edge.

Fig. 2. High-resolution XPS spectra of Pd 3d (a), C 1s (c), N 1s (d). (b) XANES spectra of Pd/CN-SA, bulk Pd foil, and PdO at the Pd K-edge.

Fig. 3. 8-h Cumulative productions of CO and CH4 over Pd/CN (x h) (a), CN, Pd/CN-SA, Pd/CN-NP, PdOx/CN (b). (c) CO and CH4 selectivity of as-prepared samples. (d) Cycling tests of Pd/CN-SA under visible-light irradiation.

Fig. 4. (a) UV-vis diffuse reflectance spectra. (b) EPR spectra in the presence of TEMPO under visible-light irradiation. PL spectra (c), time-resolved PL spectra (d), photocurrent responses (e) and EIS spectra (f) for CN, Pd/CN-SA, Pd/CN-NP, and PdOx/CN.

Fig. 5. Energy band structures and plausible charge transfer modes of CN, PdO/CN, Pd/CN-NP and Pd/CN-SA.

Fig. 6. CO2 TPD profiles (a) and CO2 adsorption curves (b) of CN, Pd/CN-SA, Pd/CN-NP, and PdOx/CN.

Fig. 8. (a) H2 uptake tests. CO (b) and CH4 (c) production in CO2 photocatalytic reduction performance tests using H2 instead of H2O as the reductant. (d) Detained adsorption and dissociation process of H2O IS, TS and FS on the surface of Pd/CN-SA (d-1), Pd/CN-NP (d-2) and PdOx/CN (d-3). (e) Reaction coordinate for H2O adsorption and dissociation.

Fig. 9. In-situ DRIFT spectra of CN, Pd/CN SA, PdOx/CN and Pd/CN NP after adequate adsorption with CO2 and H2O.

Fig. 7. DMPO spin-trapping electron spin resonance spectra for ?OH (a) and ?O2? (b) radicals over as-prepared samples in dark and under illumination.

Fig. 10. In-situ DRIFT spectra for CN (a,e), Pd/CN-SA (b,f), PdOx/CN (c,g) and Pd/CN-NP (d,h) before and after visible-light irradiation for 2 h when exposed to CO2+H2O (a?d) and CO+H2O (e?h).

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Effect of palladium chemical states on CO₂ photocatalytic reduction over g-C₃N₄: Distinct role of single-atomic state in boosting CH₄ production

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