Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(24)60075-6

Abstract

Abstract:

Covalent organic frameworks (COFs) are promising materials for converting solar energy into green hydrogen. However, limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction (HER). In this study, the intrinsically tunable internal bond electric field (IBEF) at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field (IMEF) induced by the donor-acceptor (D-A) structure for an efficient HER. The aligned orientation of IBEF and IMEF resulted in a remarkable H₂ evolution rate of 57.3 mmol·g^-1·h^-1 on TNCA, which was approximately 520 times higher than that of TCNA (0.11 mmol·g^-1·h^-1) with the opposing electric field orientation. The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer, kinetically facilitating the migration of photogenerated electrons from D to A. Furthermore, theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only provides a strong driving force for carrier transfer but also effectively hinders the return of free electrons to the valence band, improving the utilization of photoelectrons. This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.

Key words: Covalent organic framework, Internal molecular electric field, Internal bond electric field, Photocatalysis, Hydrogen evolution

Chao Li, Shuo Wang, Yuan Liu, Xihe Huang, Yan Zhuang, Shuhong Wu, Ying Wang, Na Wen, Kaifeng Wu, Zhengxin Ding, Jinlin Long. Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2024, 63: 164-175.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60075-6

https://www.cjcatal.com/EN/Y2024/V63/I8/164

Figures/Tables 9

Fig. 1. (a) Schematic representation of the synthesis of TNCA and TCNA. Front view of TNCA (b) and TCNA (c) with opposite direction of electron transfer in imine linkage (Orange: nitrogen, Green: triazine carbon, Yellow: triphenylamine carbon, White: hydrogen).

Scheme 1. The synthetic procedure of TNCA.

Scheme 2. The synthetic procedure of TCNA.

Scheme 3. The synthetic procedure of TNNA.

Fig. 2. PXRD patterns of TNCA (a) and TCNA (b) with the Pawley refined in black cross, Experimental profiles in red and black, differences in blue, Braggs diffractions in green, and simulated AA stacking in purple. (c) FT-IR spectra of TNCA, TCNA, and relevant monomers. (d) 13C NMR pattern of TNCA and TCNA. (e) TEM image of TNCA, Inset: enlarged HR-TEM image from the yellow square selected area.

Fig. 3. (a) Solid state UV-vis DRS spectra of TNCA and TCNA. (b) Time-dependent hydrogen evolution production of TNCA and TCNA for 10 h under visible light irradiation. (c) Long-term HER activity for TNCA in 50 h recorded every 10 h for five times. (d) Steady-state photoluminescence spectra of TNCA and TCNA. (e) Time-resolved photoluminescence spectra of TNCA and TCNA. (f) EPR spectra of TEMPO for free electron detection in TNCA and TCNA under visible light irradiation using 300 W Xe lamp (λ > 420 nm).

Fig. 4. Time-resolved transient absorption spectra of TNCA (a,b) and TCNA (c,d) under 400 nm excitation in solid state. Comparison of the kinetic tendency of TNCA (e) and TCNA (f) at the appointed wavelength.

Fig. 5. Calculated surface electrostatic potential of TNCA (a) and TCNA (b). Local dipole moment of TNCA (c) and TCNA (d). Mulliken charge of TNCA (e) and TCNA (f).

Fig. 6. Calculated density of states and electronic band structures for TNCA (a,c) and TCNA (b,d). (e) Proposed reaction mechanism for photocatalytic hydrogen evolution over TNCA and TCNA.

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