Citation: Bo YAN, Wenjuan JI, Lu XU, Wenzhuang LEI, Haiying YANG, Yunlong FU. Highly sensitive electrochemical detection for 4-aminophenol based on pore-confined nitrogen-rich tetranuclear cobalt-oxo cluster metal-organic framework[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(6): 1175-1189. doi: 10.11862/CJIC.20250375 shu

Highly sensitive electrochemical detection for 4-aminophenol based on pore-confined nitrogen-rich tetranuclear cobalt-oxo cluster metal-organic framework

Bo YAN ¹ ,
Wenjuan JI ^1,, ,
Lu XU ¹ ,
Wenzhuang LEI ¹ ,
Haiying YANG ^2,, ,
Yunlong FU ^1,,

1.
Key Laboratory of Magnetic Molecules and Magnetic Information Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China
2.
Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, China

Corresponding author: Wenjuan JI, jiwj@sxnu.edu.cn Haiying YANG, hyyang@ycu.edu.cn Yunlong FU, yunlongfu@sxnu.edu.cn
Received Date: 15 December 2025
Revised Date: 16 April 2026

Figures(12)

A mixed-ligand strategy was employed to construct a novel 3D metal-organic framework (MOF) with rhombic channels, namely [Co₄(μ₃-OH)₂(ABTC)(INA)₂(DMF)₂]_n (SXNU-6-Co, DMF=N, N-dimethylformamide, SXNU=Shanxi Normal University), by the hydrothermal assembly of cobalt nitrate with isonicotinic acid (HINA) and the rigid ligand 3, 3′, 5, 5′-azobenzenetetracarboxylic acid (H₄ABTC). The well-defined pore channels of SXNU-6-Co are decorated with abundant azo groups and pyridine nitrogen active sites, while the tetranuclear metal-oxygen clusters provide reversible Co²⁺/Co³⁺ redox pairs with different coordination numbers. The synergistic effect of these structural features enables precise regulation of 4-aminophenol (4-AP) adsorption and electrocatalytic performance. An electrochemical sensor was fabricated by modifying a glassy carbon electrode (GCE) with SXNU-6-Co, which exhibited a wide linear response range of 0.2-328 μmol·L^-1 towards 4-AP, with a low detection limit of 10.47 nmol·L^-1 (S/N=3). Grand canonical Monte Carlo (GCMC) simulations confirm that the strong interactions between 4-AP molecules and the SXNU-6-Co framework are mainly driven by π-π stacking and hydrogen bonding with the nitrogen-containing sites, significantly enhancing substrate affinity. The SXNU-6-Co/GCE sensor was successfully applied to detect 4-AP in real water samples, demonstrating high sensitivity, excellent selectivity, and long-term stability.
- 4-aminophenol,
- metal-organic framework,
- electrochemical sensor,
- mixed-ligand strategy,
- tetranuclear cluster
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