Efficient and selective photocatalytic CO2 conversion enabled by FePc nanosheets in a dye-sensitized system

doi:10.1016/S1872-2067(26)65061-9

Abstract

Abstract:

Solar-driven photocatalytic CO₂ conversion offers a sustainable solution for greenhouse gas mitigation and renewable energy storage. While metal phthalocyanines (MPc) exhibit excellent CO₂ reduction capabilities, their practical application in dispersed photocatalytic systems faces limitations of the stacking of MPc molecules that reduces active site accessibility, and inefficient electron transfer limited by diffusive mass transport. To address these challenges, we developed a bioinspired dye-sensitized RuP-TiO₂-FePc nanosheets (NSs) hybrid system, where ultrathin FePc NSs obtained by liquid-phase ultrasonic exfoliation enhance active site exposure and mass transfer, while TiO₂ serves as a mediator to facilitate electron transfer between the photosensitizer and FePc NSs. Time-resolved spectroscopic studies demonstrate that TiO₂ plays a dual role: it spatially organizes functional components to enable surface electron transfer by shortening intermolecular distances, while also functioning as a semiconductor bridge to facilitate charge transport. This synergistic design achieves a remarkable CO production rate of 27.3 mmol g^-1 h^-1 (> 98% selectivity) and exceptional stability (TON_CO = 1363 over 100 h), outperforming many noble-metal-based systems. Our work demonstrates a robust strategy for optimizing bulk catalysts through 2D exfoliation and controlled heterogenization, offering a versatile platform for efficient and durable artificial photosynthesis.

Key words: CO₂ reduction, FePc nanosheets, Dye-sensitized photocatalysis, Electron transfer, Artificial photosynthesis

Hua Gao, Yong Zhu, Zhibing Wen, Ran Zhao, Zhi Chen, Siyao Wang, Shuanglin He, Kuang Peng, Yiwen Tang, Licheng Sun, Fei Li. Efficient and selective photocatalytic CO₂ conversion enabled by FePc nanosheets in a dye-sensitized system[J]. Chinese Journal of Catalysis, 2026, 86: 350-362.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65061-9

https://www.cjcatal.com/EN/Y2026/V86/I7/350

Figures/Tables 9

Scheme 1. Evolution of photocatalytic systems from natural photosynthesis to artificial interfaces. The schematic illustrates the progression from natural photosynthetic systems to "soft interface" vesicle systems and then to "hard interface" TiO2 systems, highlighting the key advantages of the latter. SED stands for sacrificial electron donor.

Scheme 2. Schematic illustration of photocatalytic CO2 reduction over RuP-TiO2-FePc NSs under light irradiation.

Fig. 1. TEM images of multi-layer stacked B-FePc (a) and FePc NSs (b). (c) Tyndall effect observed in a colloidal solution of FePc NSs. (d) HAADF-STEM image and corresponding EDS elemental mapping of FePc NSs. (e) AFM image of FePc NSs. UV-vis spectra (f), FT-IR spectra (g), and Raman spectra (h) of B-FePc and FePc NSs.

Fig. 2. (a) TEM and HRTEM images of TiO2-FePc NSs. (b) The corresponding EDS mapping of TiO2-FePc NSs. UV-vis spectra (c), FT-IR spectra (d), and Raman spectra (e) of TiO2 and TiO2-FePc NSs.

Fig. 3. (a) XPS survey spectra of TiO2-FePc NSs. (b) Fe 2p of FePc and TiO2-FePc NSs. C 1s (c), N 1s (d), O 1s (e), and Ti 2p (f) spectra of TiO2-FePc NSs.

Fig. 4. Photocatalytic CO2 reduction performance under illumination (λLED = 450 nm, 5 mg samples, 25 mmol L-1 BIH, 0.1 mol L-1 phenol). (a) RuP-TiO2-FePc NSs (1 wt%) with different H+. (b) Time dependent products yield of CO2 reduction with different systems: heterogeneous (Hete) system of RuP-TiO2-FePc NSs (1 wt%) and semi-homogeneous (Homo) system of [Ru(bpy)3]Cl2·6H2O and FePc NSs with the same molar amounts as Hete. CO2 reduction performance of RuP-TiO2-FePc NSs (1 wt%) under both long-term continuous (c) and multiple cycling illumination (d) conditions.

Fig. 5. Transient photocurrent response (a) and EIS Nyquist plots (b) of RuP-TiO2 and RuP-TiO2-FePc NSs. TRPL lifetime spectra in DMF of RuP-Al2O3, RuP-TiO2, RuP-TiO2-FePc NSs, RuP-TiO2-FePc NSs + BIH (c) and RuP-Al2O3, RuP-Al2O3-FePc NSs (d). Transient absorption spectroscopy measurements of ground-state bleach recovery kinetics for RuP monitored at 450 nm in DMF: RuP-TiO2-FePc NSs (e), and RuP-TiO2-FePc NSs + BIH (f). The transient traces were analyzed using a triple-exponential decay model (Table S5, τ = ∑ Biτi2/∑ Biτi).

Fig. 6. In-situ FT-IR spectra of RuP-TiO2-FePc NSs during photocatalytic CO2 reduction.

Scheme 3. Schematic illustration of possible mechanism for CO2-to-CO conversion in a ternary hybrid system (RuP-TiO2-FePc NSs).

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Efficient and selective photocatalytic CO₂ conversion enabled by FePc nanosheets in a dye-sensitized system

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