Metal-free fluorinated carbon nitride with piezo-boosted hydrogen-bonding networks enable 100% CO selectivity in CO2 reduction

doi:10.1016/S1872-2067(26)65035-8

Abstract

Abstract:

The efficient conversion of CO₂into industrial fuels via piezocatalysis is a compelling solution to carbon emissions but often suffers from low activity and poor selectivity. While many piezocatalysts contain metals, the metal-free and low-cost graphitic carbon nitride (g-C₃N₄) is a promising alternative. However, its modest piezoelectric response and intrinsically low surface activity are unfavorable for efficient CO₂ activation. Here, we demonstrate that halogen doping transforms its catalytic capability by creating highly active hybridized p-states near the Fermi level. Fluorine doping introduces F 2p orbitals that hybridize with C 2p states, forming a new, higher-energy valence band maximum. This modification simultaneously creates electronically potent sites for CO₂ activation and enhances the driving force for charge separation. The resulting F-C₃N₄ converts CO₂ exclusively to CO with 100% selectivity and a high production rate of 201.7 µmol g^-1 h^-1 under ultrasonic vibration without sacrificial agents. Mechanistic investigations reveal macroscopic piezoelectric polarization synergizes with a fluorine-induced local field to drive directional charge separation. Critically, reconstructed interfacial hydrogen-bond networks facilitate CO₂ adsorption and activation, significantly lowering the energy barrier for *COOH formation. This dynamic coupling provides a new paradigm for designing high-efficiency CO₂ reduction systems.

Key words: Carbon nitride, Hydrogen-bonding networks, CO₂ reduction, Piezocatalytic, Selectivity

Xingchen He, Junhui Shao, Najun Li, Dongyun Chen, Hua Li, Qingfeng Xu, Haozhi Wang, Jianmei Lu. Metal-free fluorinated carbon nitride with piezo-boosted hydrogen-bonding networks enable 100% CO selectivity in CO₂ reduction[J]. Chinese Journal of Catalysis, 2026, 85: 130-142.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65035-8

https://www.cjcatal.com/EN/Y2026/V85/I6/130

Figures/Tables 6

Fig. 1. (a) TDOS for F-C3N4. (b) Comparison of theoretical bandgaps calculated from the TDOS for X-C3N4. (c) PDOS for F-C3N4. (d) Charge density difference plots for X-C3N4, visualizing the charge redistribution and polarization effects induced by halogen doping. (e) Calculated electrostatic potential maps for F-C3N4. (f) Planar-averaged electrostatic potential plot for F-C3N4. (g) Work functions for X-C3N4 (X = F, Cl, Br, I).

Fig. 2. (a) Schematic illustration of the preparation process for X-C3N4. (b) SEM image of F-C3N4. (c) TEM image of F-C3N4. (d) EDS elemental mapping of F-C3N4. (e) XRD patterns. (f) High-resolution N 1s XPS spectra. (g) High-resolution F 1s XPS spectrum of F-C3N4.

Fig. 3. (a) Yields of CO2 reduction products obtained via piezoelectric catalysis with different samples. (b) Control experiments for piezoelectric CO2 reduction using F-C3N4 under various conditions. (c) Recycling stability test of F-C3N4 for piezoelectric CO2 reduction over multiple cycles. (d) Comparison of CO generation performance of this work (photocatalyst is carbon nitride-based materials). (e) LSV curves of F-C3N4 recorded in a CO2-saturated electrolyte under static, stirring, and ultrasonic conditions. (f) Mass spectrometry verification of CO production from CO2 using F-C3N4 via 13CO2 isotope-labeling experiment. (g) CO2 adsorption isotherms for the different samples.

Fig. 4. (a) PFM topography image of F-C3N4. (b) PFM amplitude image of F-C3N4. (c) PFM phase image of F-C3N4. (d) PFM butterfly amplitude loop and phase hysteresis loop obtained for F-C3N4. (e) Piezoelectric current response curves under periodic mechanical stress. (f) EIS Nyquist plot. (g) KPFM surface potential map. (h) Calculated electronic band structure. (i) DFT calculated Gibbs free energy profiles for CO generation pathways on halogen-doped carbon nitride catalysts. (Detailed optimized geometric structures and adsorption configurations of the reaction intermediates are provided in Fig. S35.)

Fig. 5. (a) In-situ FTIR spectra of C3N4. (b) In-situ FTIR spectra of F-C3N4. (c) Enlarged view of the H2O characteristic peaks region from the in-situ FTIR spectra presented in (a) and (b). (d) DFT calculated changes in key bond lengths and angles on F-C3N4 after CO2 adsorption. (e) DFT calculated Gibbs free energy profile for the complete hydrogen evolution reaction pathway on F-C3N4 considering the participation of different numbers of H2O molecules. (f) DFT calculated Gibbs free energy profiles for CO generation pathways on F-C3N4, considering the participation of different numbers of H2O molecules. (Detailed optimized geometric structures and adsorption configurations of the reaction intermediates are provided in Fig. S36.)

Fig. 6. Proposed schematic diagram illustrating the piezocatalytic CO2 reduction mechanism on F-C3N4.

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Metal-free fluorinated carbon nitride with piezo-boosted hydrogen-bonding networks enable 100% CO selectivity in CO₂ reduction

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