Dynamic proton migration in dual linkage-engineered D-π-A system for photosynthesis H2O2 generation

doi:10.1016/S1872-2067(24)60159-2

Abstract

Abstract:

Accelerated charge migration and proton transfer to the reaction site are critical factors for improving photocatalytic efficiency. However, realizing both simultaneously is challenging because of the sluggish water (proton source) oxidation kinetics and interdependent redox reactions. Herein, we design an imide and hydrogen bond to connect carbon nitride ports of the D-π-A system with the dual-engineered linkages. The system uses an acetylene functional group and an imidazole ring as spatially separated water oxidation and oxygen reduction reaction (ORR) catalytic centers for photogenerated charge separation, respectively. The imine bond is a bridge grafted to the oxidation site to act as a hydrogen proton trap, and the hydrogen bond formed between reduction site and carbon nitride is used as the channel for instantaneous proton delivery to the reduction center. In situ characterization confirms that the linking sites protonation optimizes the pathway of ORR to H₂O₂ and facilitates the *OOH intermediates generated. It is concluded that proton transport plays a critical role in optimizing photocatalytic H₂O₂ production. Our work provides a strategy to improve dynamic proton transfer mechanisms.

Key words: Graphite carbon nitride, Proton migration, Redox site, H₂O₂ photosynthesis

Zhihan Yu, Dainan Zhang, Chenbing Ai, Jianjun Zhang, Quanjun Xiang. Dynamic proton migration in dual linkage-engineered D-π-A system for photosynthesis H₂O₂ generation[J]. Chinese Journal of Catalysis, 2024, 67: 71-81.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60159-2

https://www.cjcatal.com/EN/Y2024/V67/I12/71

Figures/Tables 8

Fig. 1. Structural characterizations. (a) The synthesis process of ABE/IL-CN. The imine bond is formed between carbon nitride (CN) and 4-acetylene benzaldehyde (ABE) by coupling an amino group with an aldehyde group. Imidazole cations are present in 1,3-dimethylimidazole tetrafluoroborate (IL), and the hydrogen atoms bonded by carbon atoms act as hydrogen donors to form hydrogen bonds with the more electronegative sp2 N atoms. FTIR spectra (b), high-resolution C 1s XPS (c), and Raman shift (d) of ABE/IL-CN, ABE-CN, IL-CN, and CN. (e) Solid-state 13C NMR spectra of ABE/IL-CN.

Fig. 2. Photocatalytic performance of H2O2 generation. (a) Comparison of photocatalytic H2O2 production rates of ABE/IL-CN, ABE-CN, IL-CN, and CN in water under O2 bubbling. (b) Photocatalytic H2O2 evolution rate of nABE/IL-CN under 1 h visible light irradiation, n indicates the ABE concentration (0.5, 1.0, 2.0, and 4.0 mmol L−1) of ethyl acetate solution used for the synthesis of ABE graft samples, the molar ratio of ABE to IL is constant 2:1. (c) Visible light-driven photocatalytic H2O2 production by ABE/IL-CN under different conditions of air + MeOH, air, N2 + NaIO3, and N2. (d) Cycling time course of ABE/IL-CN under visible-light irradiation in O2-saturated pure water generated H2O2. (e) H2O2 decomposition curves of ABE/IL-CN, ABE-CN, IL-CN, and CN under light irradiation (C0 = 1 mmol L−1 H2O2, N2 bubbling). (f) The wavelength-dependent apparent quantum yield of ABE/IL-CN in overall water splitting for H2O2 production.

Fig. 3. In-situ structural evolution of the photocatalysts. In-situ DRIFTS spectra of ABE/IL-CN (a), ABE-CN (b), and IL-CN (c) recorded during photocatalytic H2O2 production in O2 atmosphere. (d) The key reaction sites and intermediates of WOR and ORR are obtained by in-situ DRIFTS spectra. (e) Time-resolved transient PL decay of ABE-CN, IL-CN, and ABE/IL-CN.

Table 1 The related parameter of TRPL in ABE-CN, IL-CN, and ABE/IL-CN.

Sample	τ₁/ns	A₁/%	τ₂/ns	A₂/%	τ_ave/ns
ABE-CN IL-CN ABE/IL-CN	3.14 2.58 3.10	100.89 92.33 102.08	21.13 14.79 20.31	66.34 9.47 6.54	8.71 7.10 8.19

Fig. 4. Proton transfer at the reaction sites. (a) The contents of O2 and H2 gases formed by ABE-CN and IL-CN after the addition of excess electron sacrifice agent (NaIO3) and hole sacrifice agent (TEOA), respectively. (b) Visible light-driven photocatalytic H2O2 production of ABE-CN and IL-CN under different conditions. (c) H2O2 generation rate over ABE/IL-CN and protonated ABE/IL-CN (H-ABE/IL-CN-m) in the protic solvent (ethanol), aprotic solvent (acetone) and water; m indicates the IL concentration (1.0 and 1.25 mmol L-1) of methanol solution used for the synthesis of IL graft samples, the molar number of ABE was constant (2.0 mmol L-1). (d) Mechanism of ABE/IL-CN and H-ABE/IL-CN-m for photocatalytic H2O2 formation in acetone solvent. The colors of the balls correspond to different atoms, gray: carbon; blue: nitrogen; pink: boron; cyan: fluorine; red: oxygen; white and yellow: hydrogen.

Table 2 Photocatalytic H2O2 generation performance of a series of protonation/aprotonation photocatalysts as comparison in protic/aprotic solution under air atmosphere.

Photocatalyst	Protonation	ABE:IL	Solution	H₂O₂ production (μmol L^-1 h^-1)
ABE/IL-CN H-ABE/IL-CN-1 H-ABE/IL-CN-1.25	Aprotonation Protonation Protonation	2:1 2:1 2:1.25	water aprotic solvent (acetone) protic solvent (ethanol) water aprotic solvent (acetone) protic solvent (ethanol) water aprotic solvent (acetone) protic solvent (ethanol)	219.5 0 394.2 206.9 315.4 473.0 278.5 243.1 408.3

Fig. 5. Charge carrier dynamics analysis. Two-dimensional TA spectra images of ABE/IL-CN (a), ABE-CN (b), and IL-CN (c). Femtosecond transient absorption spectra of ABE/IL-CN (d), ABE-CN (e), and IL-CN (f). Decay dynamics traces at 405 nm for ABE/IL-CN (g), ABE-CN (h), and IL-CN (i).

Fig. 6. Illustration of the proposed photocatalytic mechanism of H2O2 photosynthesis over ABE/IL-CN under UV-vis light irradiation. The colors of the balls correspond to different atoms, gray: carbon; blue: nitrogen; pink: boron; cyan: fluorine; red: oxygen; white and yellow: hydrogen.

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Dynamic proton migration in dual linkage-engineered D-π-A system for photosynthesis H₂O₂ generation

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