Self-photosensitizing metal complexes for photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(26)65050-4

Abstract

Abstract:

Combining organic photosensitive center with dinuclear-metal catalytic center through covalent bonds to synthesize supramolecular catalysts for photocatalytic hydrogen evolution is a cost-efficient approach to convert solar to hydrogen energy, while it has been rarely explored. Herein, we constructed a self-photosensitizing pyrene-decorated dinuclear cobalt(II) molecular photocatalyst [Co₂(pyrene-L)₂] via covalent bonds, which can accelerate photogenerated electron transfer from pyrene center to dinuclear cobalt(II) center, achieving efficiently photocatalytic hydrogen evolution in the absence of any noble metal photosensitizers. The photocatalytic activity of Co₂(pyrene-L)₂ is more than 3-fold over that of the physically mixed sample. Moreover, owing to the synergistic effect of dinuclear cobalt(II) centers, the activity of Co₂(pyrene-L)₂ is 10-fold higher than that of mononuclear counterpart (Co(pyrene-L)₂). As the first example of self-photosensitizing pyrene-decorated dinuclear metal molecular catalyst, it not only features multi-functions of photosensitivity, photoreduction and photooxidation, but also possesses synergistic dinuclear metal centers to improve catalytic activity, which gives new insights for researchers in designing high-performance photocatalysts for hydrogen evolution.

Key words: Dinuclear metal complex, Photocatalytic hydrogen evolution, Synergistic catalysis, Self-photosensitizing, Pyrene

Mingyu Ma, Zongyang Liu, Kuo Yuan, Zheyuan Liu, Jiaxin Wang, Qingqing Lin, Di-Chang Zhong, Tong-Bu Lu. Self-photosensitizing metal complexes for photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 86: 375-383.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65050-4

https://www.cjcatal.com/EN/Y2026/V86/I7/375

Figures/Tables 5

Fig. 1. Schematic of catalysts (Cat) and photosensitizers (PS) are physically mixed and dissolved in solution (pervious work), and the Cat and PS covalently connected (this work) (a), as well as synthetic path of Co2(pyrene-L)2 (b).

Fig. 2. (a) Chemical structures of CoL2 and Co(pyrene-L)2 photocatalysts. FT-IR spectra of L, 1-pyrenecarboxaldehyde, pyrene-L (b) and Co2L2, Co2(pyrene-L)2 (c). (d) Schematic diagram of the photoexcited electron transfer process of self-photosensitizing dinuclear molecule. UV-vis spectra of Co2(pyrene-L)2 (e) and Co(pyrene-L)2 (f).

Fig. 3. (a) Results of photocatalytic H2 evolution by Co2(pyrene-L)2 (30 μmol L-1), Co(pyrene-L)2 (30 μmol L-1), (Co2L2&pyrene) (30 μmol L-1) and (Co2L2&[Ru(phen)3](PF6)2) (30 μmol L-1). (b) Effect of pyrene concentration on photocatalytic H2 evolution performance. (c) The photocatalytic activity of Co2(pyrene-L)2 and Co(pyrene-L)2 at different concentration ratio. (d) Control experiments for the photocatalytic H2 evolution. All photocatalytic reactions were conducted under 12 h of irradiation.

Fig. 4. NTO analysis of Co2L2&pyrene (a) and Co2(pyrene-L)2 (b). (c) XPS spectra of Co2L2 and Co2(pyrene-L)2 in dark condition. (d) XPS spectra of Co2L2&pyrene and Co2(pyrene-L)2 under light. (e) Photoluminescence spectra with the excitation wavelength of 350 nm. (f) Time-resolved photoluminescence spectroscopy of Co2(pyrene-L)2 and Co2L2&pyrene.

Fig. 5. (a) CV curves of Co2(pyrene-L)2. (b) DPV of Co2(pyrene-L)2. (c) Fluorescence spectra of pyrene by the addition of BIH. (d) Plots of fluorescence intensity ratio vs. the concentration of BIH with linear fitting. (e) Fluorescence spectra of pyrene by the addition of Co2L2. (f) Plots of fluorescence intensity ratio vs. the concentration of Co2L2 with linear fitting.

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