Topology-induced local electric polarization in 2D thiophene-based covalent organic frameworks for boosting photocatalytic H2 evolution

doi:10.1016/S1872-2067(23)64627-3

Abstract

Abstract:

2D Substoichiometric covalent organic frameworks (2D-SSCOFs) are a new kind of porous organic polymers with accurate modifiability, good stability and abundant porosity. However, the strong exciton effects and slow charge transfer in 2D-SSCOFs can severely linker hinder the efficiency of photocatalytic energy conversion. Herein, we report a brand new thiophene-based 2D-SSCOF (PTT-COF) constructed by the Schiff base reaction using thiophene-enriched tri-topic linker and tetra-topic pyrene as structural unit precursors. Interestingly, PTT-COF exhibits a novel topology, high crystallinity, abundant delocalization electrons and weak excitonic effects. Inspired by the unique structural characteristics and photoelectrical performance, PTT-COF is utilized for photocatalytic hydrogen evolution. Experimental and theoretical studies have confirmed that introducing thiophene effectively modulates the topology of the COF, inducing local charge delocalization and redistribution, thus suppressing the excitonic effect and enhancing the photocatalytic performance. In addition, the periodic, uncondensed functional groups allow PTT-COF to be accurately modified by ferrocene carboxaldehyde as organic hole transporting ligands, leading to a further 40% enhancement in hydrogen evolution rate up to 79.610 mmol g^-1 h^-1. These findings in this work not only offer a brand new 2D-SSCOF with novel topology, but also provide new opportunities and directions for the ration design of 2D-SSCOF for emerging functional applications.

Key words: Photocatalytic hydrogen evolution, Charge separation, Substoichiometric covalent organic frameworks, Topologies structure, Excitonic effect

Junxian Bai, Rongchen Shen, Guijie Liang, Chaochao Qin, Difa Xu, Haobin Hu, Xin Li. Topology-induced local electric polarization in 2D thiophene-based covalent organic frameworks for boosting photocatalytic H₂ evolution[J]. Chinese Journal of Catalysis, 2024, 59: 225-236.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64627-3

https://www.cjcatal.com/EN/Y2024/V59/I4/225

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Scheme 1. (a) The synthetic route of 2D substoichiometric PTT-COF with heart-shaped pores. (b) Post-modification route of PTT-COF by ferrocene carboxaldehyde (FC) as organic hole-transporting ligands.

Fig. 1. Structure and characterization of PTT-COF. (a) Synthesis of PTT-COF. (b) Top view and side view of the AA stacking structure of PTT-COF based on PXRD and modeling. (c) Experimental, simulated, and Pawley refined PXRD of the PTT-COF crystal structure on the basis of the AA stacking models. (d) 13C CP/MAS NMR spectrum of PTT-COF. (e) Comparison of the FTIR spectra of PTT-COF, PTT-COF-FC, and the corresponding building units. (f) Comparison of N2 adsorption isotherms of PTT-COF and PTT-COF-FC at 77 K and a graph of the pore-size distribution; inset shows its pore size distribution. (g) High-angle annular dark field transmission electron microscopic image of PTT-COF. (h) HRTEM image of PTT-COF-FC. (i) Enlarge image of the HTEM.

Fig. 2. (a) UV-vis DRS spectra of PTB-COF, PTT-COF, PTT-COF-FC and FC. (b) The optical band gap of PTB-COF, PTT-COF and PTT-COF-FC determined by Tauc plot. (c) Mott-Schottky plots for PTT-COF. (d) Valence band XPS spectra of PTT-COF. (e) Schematic energy band structures of PTB-COF, PTT-COF, PTT-COF-FC. (f) Kohn-Sham orbitals of CBM and VBM of PTT-COF (Blue for positive diffuse and yellow for negative diffuse). (g) Calculated density of states for PTT-COF.

Fig. 3. (a) Photocatalytic H2 evolution performance of PTT-COF-FC compared to PTB-COF, PTT-COF, PTT-COF/FC and FC (2 mg catalyst in 100 mL water, 3 wt% Pt, 0.1 mol L-1 ascorbic acid, λ > 420 nm). (b) The photocatalytic H2 production rate of PTT-COF, PTT-COF-FC and reported photocatalysts. (c) Cycling stability for PTT-COF-FC in photocatalytic H2 evolution. (d) Wavelength-dependent AQY of photocatalytic H2 evolution for PTT-COF. (e) Dependence of the amount of AQY for PTT-COF-FC with different mass. (f) PL spectra of PTB-COF, PTT-COF and PTT-COF-FC. Temperature-dependent PL spectra and corresponding fitting curves (inset) of PTB-COF (g), PTT-COF (h) and PTT-COF-FC (i).

Fig. 4. TA spectra excitation at 400 nm of PTB-COF (a), PTT-COF (d), and PTT-COF-FC (g). 2D mapping TA spectra of PTB-COF (b), PTT-COF (e) and PTT-COF-FC (h). (c) Transient absorption traces for PTB-COF normalized to the 500 nm exciton bands. (f) Transient absorption traces for PTT-COF normalized to the 545 nm exciton bands. (i) Transient absorption traces for PTT-COF-FC normalized to the 545 nm exciton bands.

Fig. 5. (a) PTB-COF, PTT-COF, PTT-COF-1,6 and PTT-COF-1,3 in the ground state, blue and red represented electron accumulation and depletion, respectively. The electron-hole distributions (iso-surface = 0.0006 a.u.) of PTB-COF (b), PTT-COF (c), PTT-COF-1,6 (d) and PTT-COF-1,3 (e) in the excited state, green and blue represented electron accumulation and depletion, respectively.

Fig. 6. (a) The charge centroids diagram of PTB-COF, PTT-COF, PTT-COF-1,6 and PTT-COF-1,3 in the excited state. (b) Photocurrent profiles. (c) EIS Nyquist plots, with an inset showing the electrical equivalent circuit of the Nyquist plots. (d) Polarization curves. (e) EPR spectra TEMPO-e- for PTB-COF, PTT-COF and PTT-COF-FC lighted for 10 min. (f) Schematic of the mechanism of PTT-COF-FC for photocatalytic hydrogen evolution.

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Topology-induced local electric polarization in 2D thiophene-based covalent organic frameworks for boosting photocatalytic H₂ evolution

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