Tröger’s base derived 3D-porous aromatic frameworks with efficient exciton dissociation and well-defined reactive site for near-unity selectivity of CO2 photo-conversion

doi:10.1016/S1872-2067(23)64474-2

Abstract

Abstract:

The overall photocatalytic conversion of CO₂ and H₂O to fuel and O₂is challenging. In this study, a series of three-dimensional Tröger’s base-derived porous aromatic frameworks (3D-X-TB-PAFs (X = TEPE, TEPM, SPF)) featuring designated reaction sites and unique charge transfer properties were developed. The incorporation of V-shaped Tröger’s base (TB) units and aromatic alkynes imparts the polymers with permanent porosity, additional photon scattering cross-sections, and enhanced CO₂ adsorption/activation capabilities. Density functional theory calculations and optoelectronic measurements revealed the formation of intramolecular built-in polarization and electron-trap sites induced by TB, which modulated charge separation and customized reaction sites in collaboration with 3D networks. In addition, product allocation during the photoreduction of CO₂was regulated by the photooxidation of H₂O. Among the as-prepared 3D-PAFs, the most efficient electron transport channel was demonstrated by the TEPE-TB-PAF with fully conjugated TEPE-T. In the absence of cocatalysts and sacrificial agents, TEPE-TB-PAF exhibits a competitive CO formation rate (194.50 μmol g^-1 h^-1) with near-unity selectivity (99.74%). Significantly, the low energy barrier for CO desorption and the high energy barrier for *CHO formation contribute to the high efficiency of TEPE-TB-PAF, as demonstrated by computational exploration and in situ diffuse reflectance infrared Fourier transform spectra. This work offers efficient building blocks for the synthesis of multifunctional organic photocatalysts and groundbreaking insights into the simultaneous enhancement of photocatalytic reactivity and selectivity.

Key words: CO₂ photoreduction, Porous aromatic frameworks, Tröger's base, 3D networks, Intramolecular built-in polarization

Nan Yin, Weibin Chen, Yong Yang, Zheng Tang, Panjie Li, Xiaoyue Zhang, Lanqin Tang, Tianyu Wang, Yang Wang, Yong Zhou, Zhigang Zou. Tröger’s base derived 3D-porous aromatic frameworks with efficient exciton dissociation and well-defined reactive site for near-unity selectivity of CO₂ photo-conversion[J]. Chinese Journal of Catalysis, 2023, 51: 168-179.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64474-2

https://www.cjcatal.com/EN/Y2023/V51/I8/168

Figures/Tables 5

Fig. 1. (a) Structures of monomers and the typical synthesis of X-TB-PAF (X = TEPE, TEPM, SPF) via Sonogashira-Hagihara cross-coupling. (b) Comparative FT-IR spectra of X-TB-PAF (X = TEPE, TEPM, SPF) and TB. (c) Solid-state 13C NMR spectra of the polymer networks. (d?f) SEM images of TEPM-TB-PAF, TEPE-TB-PAF, and SPF-TB-PAF.

Fig. 2. (a) UV-vis diffusion reflectance spectra of polymers. (b) The estimated band gap from Tauc plots. (c) Mott-Schottky curves of samples tested at 1000 Hz in 0.5 mol L?1 Na2SO4 solution. (d) Experimentally determined band structures of X-TB-PAF (X = TEPE, TEPM, SPF).

Fig. 3. (a) Time-dependent CO production based on polymers. (b) Average gas production rates over X-TB-PAF (X = TEPE, TEPM, SPF) upon 6 h of irradiation. (c) Wavelength-specific quantum efficiency of TEPE-TB-PAF using band-pass filters during CO2PRR. (d) Durability tests of CO2PRR over TEPE-TB-PAF. (e) The isotope analysis of 13CO using 13CO2 as atmosphere by GC-MS (inset: the mass spectrum of 13CO). (f) The isotope analysis of oxidation half-reaction using H218O by GC-MS (inset: the mass spectrum of produced O2).

Fig. 4. (a?c) Electric dipole moment of TEPM-TB-PAF, SPF-TB-PAF, and TEPE-TB-PAF. (d) Photoluminescence (PL) emission spectra of each material. (e) Time-resolved fluorescence decay traces and the average lifetime of TEPE-TB-PAF, TEPM-TB-PAF, and SPF-TB-PAF. (f) Transient photocurrent signals for target polymers. (g) EIS Nyquist plots of X-TB-PAF (X = TEPE, TEPM, SPF) under light-on conditions.

Fig. 5. (a) CO2 adsorption isotherms of target polymers collected at 273.15 K. (b) In-situ DRIFT spectra during CO2 photoconversion over different PAFs. (c) Calculated free energy diagrams for CO2-CO reduction by optimized models. (d) Proposed mechanisms for photocatalytic CO2PRR with TEPE-TB-PAF.

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Tröger’s base derived 3D-porous aromatic frameworks with efficient exciton dissociation and well-defined reactive site for near-unity selectivity of CO₂ photo-conversion

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