High-spin configuration of asymmetric CoN1C2 coordination for boosting d-p orbital hybridization in Fenton-like reactions

doi:10.1016/S1872-2067(25)64674-2

Abstract

Abstract:

Asymmetric single-atom catalysts (ASACs) have attracted much attention owing to their excellent catalytic properties. However, the relationship between asymmetric coordination and the spin states of metal sites remains unclear. Additionally, the modulation of reactive oxygen species in Fenton-like reactions remains challenging. Herein, a novel strategy is reported for the rational design of highly loaded Co ASACs (CoN₁C₂/C₂N) immobilized on three-dimensional flower-like C₂N using an in situ-generated carbon defect method. In particular, the asymmetrically tricoordinated CoN₁C₂/C₂N exhibited excellent catalytic activity for sulfachloropyridazine degradation, with a turnover frequency of 36.8 min^-1. Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration (t_2g⁶e_g¹) to the high-spin configuration (t_2g⁵e_g²) owing to asymmetric coordination. The high-spin Co 3d orbital in CoN₁C₂/C₂N possessed more unpaired electrons and therefore, had a strong ability to gain electrons from the O 2p orbitals of HSO₅^-, boosting d-p orbital hybridization. More importantly, the spin-electron filling in the σ* orbital of high-spin Co 3d−O 2p accelerated the desorption of ^*SO₅^•−, which acted as a rate-limiting step in the reaction, thus facilitating more ¹O₂ generation. This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state, paving the way for advancements in environmental remediation and energy conversion applications.

Key words: Asymmetric coordination, C₂N, High-spin configuration, d-p orbital hybridization, Fenton-like reaction

Qian Bai, Juanjuan Qi, Rongzhe Zhang, Zhiyuan Chen, Zihao Wei, Zhiyi Sun, Ziwei Deng, Xudong Yang, Qiangwei Li, Wenxing Chen, Lidong Wang. High-spin configuration of asymmetric CoN₁C₂ coordination for boosting d-p orbital hybridization in Fenton-like reactions[J]. Chinese Journal of Catalysis, 2025, 73: 334-346.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64674-2

https://www.cjcatal.com/EN/Y2025/V73/I6/334

Figures/Tables 6

Fig. 1. Synthesis and characterization of CoN1C2/C2N. (a) Schematic illustration of the synthesis of CoN1C2/C2N. (b) SEM images of CoN1C2/C2N. (c) TEM image of CoN1C2/C2N showing the 2D sheet structure. (d) Element-mapping of CoN1C2/C2N. (e) HAADF-STEM image of CoN1C2/C2N. (f) The enlarged image of the yellow area in (e) shows that single atoms are dispersed on C2N. (g) 3D model of isolated single-Co atoms (seen as bright spots) and corresponding intensity profiles along the red dotted line in (f).

Fig. 2. Electronic structure of CoN1C2/C2N. (a) Soft XANES spectrum of the C K side of CoN1C2/C2N. (b) Soft XANES spectrum of the N K side of CoN1C2/C2N. (c) Co K-edge XANES spectra of CoN1C2/C2N and the three comparison samples. (d) FT-EXAFS spectra of CoN1C2/C2N and the remaining three comparison samples. (e) WT analysis of EXAFS signaling spectra. (f) FT-EXAFS fitting curve of CoN1C2/C2N in K-space. (g) FT-EXAFS fitting curve of CoN1C2/C2N in R-space. (h) Atomic structure model of CoN1C2/C2N.

Fig. 3. Spin state of CoN1C2/C2N and CoN2/C2N. (a) XPS fine spectra of C 1s. (b) XPS fine spectra of N 1s. (c) XPS fine spectra of Co 2p. (d) M-T curves of CoN1C2/C2N and CoN2/C2N. (e) Schematic representation of the spin transition of Co with different coordination environments. (f) Co L-edge XANES spectra of CoN1C2/C2N and CoN2/C2N. (g) The PDOS of CoN1C2/C2N and CoN2/C2N. (h) CDD of CoN1C2/C2N.

Fig. 4. Fenton-like properties of CoN1C2/C2N. (a) Degradation of SCP in different catalytic systems. (b) k1 values of SCP in different catalytic systems. (c) Effect of initial pH. (d) Effects of adding anions, cations, or NOM to CoN1C2/C2N/PMS systems on SCP degradation within 3 min. (e) Pollutant removal efficiencies of the current and other recently reported catalysts versus PMS dosage. (f) Degradation k1 values of different pollutants in CoN1C2/C2N/PMS system and structural formula of organics. (g) Correlation between the corresponding k1 values and the N index. (h) Cyclic and regenerative properties of CoN1C2/C2N/PMS system for SCP removal. Reaction condition: [catalyst] = 0.1 g L-1, [PMS] = 0.1 g L-1, [Pollutants] = 20.0 mg L-1, [anions and cation] = 1 mmol L-1, [HA] = 1 mM, and initial pH = 7.0-10.5±0.2.

Fig. 5. Detection of active substances of three catalysts. (a) Quenching experiments in CoN1C2/C2N/PMS system. (b) Quenching experiments in CoN2/C3N4/PMS system. (c) Removal efficiency of different quenchers in different PMS systems after 3 min. (d) EPR spectra of SO4?? and ?OH. (e) EPR spectra of 1O2. (f) An overview of the relationship among substrate, ROS, coordination environment, spin state, and catalytic properties. Reaction condition: [catalyst] = 0.1 g L-1, [PMS] = 0.1 g L-1, [Pollutants] = 20.0 mg L-1, [MeOH, TBA] = 200 mmol L-1, [L-histidine] = 5 mmol L-1, and initial pH = 7.0±0.2.

Fig. 6. DFT calculations and data analysis of the catalysts before and after reaction. (a) CDD, adsorption energy, and number of transferred electrons after PMS adsorption. (b) Schematic diagram of electron transfer ability in different coordination environments. (c) Orbital interactions between HSO5? and single-atom Co catalysts. (d) XPS of CoN1C2/C2N catalyst after reaction. (e) Free energy of different coordination structures. (f) XRD patterns of the CoN1C2/C2N catalyst after reaction.

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High-spin configuration of asymmetric CoN₁C₂ coordination for boosting d-p orbital hybridization in Fenton-like reactions

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