Citation: Hongyan Liu, Duan Peng, Yingyue Zhao, Wenzheng Guo, Chongde Tang, Yamin Nie, Yanmei Zhou. Defect engineering enabling ultralow-potential, high-efficiency cathodic electrochemiluminescence in electron-deficient metal-organic frameworks for biosensing[J]. Chinese Chemical Letters, ;2026, 37(8): 112310. doi: 10.1016/j.cclet.2025.112310 shu

Defect engineering enabling ultralow-potential, high-efficiency cathodic electrochemiluminescence in electron-deficient metal-organic frameworks for biosensing

State Key Laboratory of Antiviral Drugs, Henan Joint International Research Laboratory of Environmental Pollution Control Materials, College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, China

ymnie@henu.edu.cn

zhouyanmei@henu.edu.cn

Received Date: 4 August 2025
Revised Date: 30 October 2025
Accepted Date: 22 December 2025
Available Online: 22 December 2025

Figures(5)

Metal-organic frameworks (MOFs) hold promise as electrochemiluminescence (ECL) emitters but are limited by high operating potentials and low efficiencies, leading to substantial electrochemical interference and reduced sensitivity. Here, we report a defect-rich Fe(Ⅲ)-based MOF (De-Fe(Ⅲ)-MOF) that exhibits highly efficient ECL triggered at an ultralow potential (-0.3 V vs. Ag/AgCl). Prepared using electron-deficient 3,4,9,10-perylenetetracarboxylic acid (PTCA) as ligands and H₃PO₄ as the acid modulator, De-Fe(Ⅲ)-MOF features abundant open-metal catalytic sites, which achieves an exceptional cathodic ECL efficiency of 553.06%, even using classical Ru(bpy)₃Cl₂/S₂O₈²⁻ system triggered at -1.2 V as a standard. This outstanding performance is attributed to three key factors: (1) The abundant Fe(Ⅲ) active sites that efficiently catalyze S₂O₈²⁻ to produce SO₄^{•^-} radicals at ultralow potentials; (2) the electron-deficient PTCA ligand that enables simultaneous reduction at similarly low potentials; and (3) the unified porous frame that facilitates efficient electron transfer through an ultrashort pathway, enhancing ECL efficiency. These features collectively minimize electrochemical side reactions and significantly enhance the sensitivity of the sensing platform. To demonstrate its practical application, we constructed an ECL sensor for carboxylesterase activity, achieving a limit of detection of 6.6 × 10^–7 U/L with minimal interference.
- Biosensors,
- Electrochemiluminescence,
- Luminescent metal-organic frameworks,
- Defect engineering,
- Ultralow-potential electrochemiluminescence,
- Carboxylesterase activity
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沈阳化工大学材料科学与工程学院沈阳 110142