2D Phthalocyanine-based covalent organic frameworks for infrared light-mediated photocatalysis

doi:10.1016/S1872-2067(24)60196-8

Abstract

Abstract:

Covalent organic frameworks (COFs) based photocatalysts utilizing infrared light remains unexplored due to the limitation of electronic absorption. Herein, two novel two-dimensional (2D) polyimide-linked phthalocyanine COFs, namely MPc-DPA-COFs (M = Zn/Cu), were prepared from the imidization reaction of metal tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato (M(TAPc)) with 9,10-diphenyl anthracene (DPA). Both COFs possess highly crystalline eclipsed AA stacking structure with neighboring layer distance of 0.33 nm on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy. Effective π-π interaction between phthalocyanine chromophores in neighboring layers of 2D COFs leads to significant bathochromic-shift of narrow Q band from 697 nm for M(TAPc) to the infrared light absorption range of 760-1000 nm for MPc-DPA-COFs according to solid UV-vis diffuse reflectance spectra. This endows them in particular ZnPc-DPA-COF with excellent reactive oxygen species of ^•O₂⁻ and ¹O₂ generation activity under infrared light radiation (λ > 760 nm) based on the electron spin resonance spectroscopy measurement, in turn resulting in the excellent photocatalytic capacity towards oxidation of sulfides under infrared light radiation. Corresponding quenching experiments reveal the contribution of both ^•O₂⁻ and ¹O₂ to the oxidation of sulfides, but the former ^•O₂⁻ species plays a leading role in this photocatalytic process. The present result not only provides a new efficient infrared light photocatalyst but also unveils the good potentials of phthalocyanine-based COFs in photocatalysis.

Key words: Covalent organic framework, Infrared light, Photocatalysis, Reactive oxygen species, Oxidation of sulfides

Xiaoning Zhan, Yucheng Jin, Bin Han, Ziwen Zhou, Baotong Chen, Xu Ding, Fushun Li, Zhiru Suo, Rong Jiang, Dongdong Qi, Kang Wang, Jianzhuang Jiang. 2D Phthalocyanine-based covalent organic frameworks for infrared light-mediated photocatalysis[J]. Chinese Journal of Catalysis, 2025, 69: 271-281.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60196-8

https://www.cjcatal.com/EN/Y2025/V69/I2/271

Figures/Tables 7

Scheme 1. Synthesis of ZnPc-DPA-COF and CuPc-DPA-COF.

Fig. 1. PXRD patterns of ZnPc-DPA-COF (a) and CuPc-DPA-COF (b). Simulated packing structures of ZnPc-DPA-COF (c,d) and CuPc-DPA-COF (e,f) via π-π interactions (C: gray; N: cyan; O: red; Zn: violet; Cu: orange; H: white). SEM, TEM, HRTEM, and EDS mapping photos for ZnPc-DPA-COF (g?j) and CuPc-DPA-COF (k?n).

Fig. 2. FT-IR spectra (a), XPS spectrum (b), and N2 adsorption (solid) and desorption (hollow) curves (c) at ?196 °C of ZnPc-DPA-COF. XANES spectra (d) and EXAFS curves (e) of Zn foil, ZnPc, and ZnPc-DPA-COF at Zn K-edge. (f) The experimental and fitting EXAFS curves of ZnPc-DPA-COF. WT-EXAFS of ZnPc-DPA-COF (g), ZnPc (h), and Zn foil (i).

Fig. 3. (a) EIS curves. Solid and liquid UV-vis spectra (Insert: Nyquist plots) of ZnPc-DPA-COF (b) and CuPc-DPA-COF (c). Mott-Schottky plots of ZnPc-DPA-COF (d) and CuPc-DPA-COF (e). (f) Experimental energy levels of ZnPc-DPA-COF and CuPc-DPA-COF.

Fig. 4. (a) Time-dependent catalytic efficiency of ZnPc-DPA-COF under infrared light. (b) Selective oxidation of organic sulfide yield by photocatalysis of ZnPc-DPA-COF for 4.0 h in O2 atmosphere. (c) Recycling test of ZnPc-DPA-COF. (d) The number of photocatalysts reported for sulfide oxidation reactions under different types of light irradiation in the past three years. ESR detection of 1O2 generation trapped by TEMP (e) and ?O2? generation trapped by DMPO (f). (g) Quenching experiments on the photocatalytic oxidation of methylphenyl-sulfide. (h) Plausible mechanism for this photocatalytic oxidation reaction.

Table 1 Photocatalytic oxidation of sulfides to sulfoxide under different conditions a.

Entry	Substrate	Time (h)	Conv.^b (%)	Sel. (%)	TOF (mmol g⁻¹ h⁻¹)
1	R = H	8	>99	>99	6.25
2^c	R = H	8	trace	trace	trace
3^d	R = H	8	trace	trace	trace
4^e	R = H	8	trace	trace	trace
5^f	R = H	8	trace	trace	trace
6^g	R = H	8	83	>99	5.19
7^h	R = H	8	trace	trace	trace
8	R = CH₃	7	>99	>99	7.14
9	R = OCH₃	4	>99	>99	12.5
10	R = Cl	8	69	>99	4.31
11	R = NO₂	8	53	>99	3.31

Fig. 5. (a) The distribution of orbital electron wavefunctions of ZnPc-DPA-COF. The charge density of ZnPc-DPA-COF (b) and CuPc-DPA-COF (c). The EDD diagram of ZnPc-DPA-COF (d) and CuPc-DPA-COF (e). (f) The ESP diagram of ZnPc-DPA-COF. (g) O2 adsorption models. (h) The differential charge density maps of ZnPc-DPA-COF and CuPc-DPA-COF and the charge density differences of adsorbed O2 on ZnPc-DPA-COF and CuPc-DPA-COF. The cyan and yellow areas represented electron increase and decrease, respectively. (i) The overlap of O (2p) & Zn (3dz2) in pDOS. (j) The Gibbs free energy diagram for the reaction pathways.

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