Co4+ in porous ZIF-67-derives intercalating-bridging adsorption of 2-reaction sites for simultaneous 2-electron transfer toward sensitive detection of uric acid

Li Peng Gan; Juan Li; Fan Shi; Zhuo Zou; Ke Jiang Li; Zhuan Zhuan Shi; Xiao Shuai Wu; Yun Peng Li; Wei Sun; Zhi Song Lu; Tao Hu; Liming Dai; Chang Ming Li

doi:10.1016/j.aca.2024.342614

Co⁴⁺ in porous ZIF-67-derives intercalating-bridging adsorption of 2-reaction sites for simultaneous 2-electron transfer toward sensitive detection of uric acid

Anal Chim Acta. 2024 Jun 15:1308:342614. doi: 10.1016/j.aca.2024.342614. Epub 2024 Apr 25.

Authors

Li Peng Gan¹, Juan Li¹, Fan Shi², Zhuo Zou³, Ke Jiang Li⁴, Zhuan Zhuan Shi², Xiao Shuai Wu², Yun Peng Li², Wei Sun⁵, Zhi Song Lu⁶, Tao Hu⁷, Liming Dai⁸, Chang Ming Li⁹

Affiliations

¹ Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, China; Institute for Clean Energy and Advanced Materials, School of Materials & Energy, Southwest University, China; Chongqing Key Laboratory for Advanced Materials and Technologies of Clean Energies, Chongqing, 400715, China; Institute of Materials Science & Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China.
² Institute of Materials Science & Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China.
³ Institute of Materials Science & Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China; Australian Carbon Materials Centre (A-CMC), School of Chemical Engineering, University of New South Wales, Sydney, NSW, 2052, Australia.
⁴ Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, China; Institute for Clean Energy and Advanced Materials, School of Materials & Energy, Southwest University, China; Chongqing Key Laboratory for Advanced Materials and Technologies of Clean Energies, Chongqing, 400715, China.
⁵ College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571158, China.
⁶ Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, China; Institute for Clean Energy and Advanced Materials, School of Materials & Energy, Southwest University, China; Chongqing Key Laboratory for Advanced Materials and Technologies of Clean Energies, Chongqing, 400715, China. Electronic address: zslu@swu.edu.cn.
⁷ Institute of Materials Science & Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China. Electronic address: thu@usts.edu.cn.
⁸ Australian Carbon Materials Centre (A-CMC), School of Chemical Engineering, University of New South Wales, Sydney, NSW, 2052, Australia. Electronic address: 1.dai@unsw.edu.au.
⁹ Institute of Materials Science & Devices, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China. Electronic address: ecmli@swu.edu.cn.

PMID: 38740455
DOI: 10.1016/j.aca.2024.342614

Abstract

Metal-organic frameworks (MOFs) have been used to detect uric acid (UA), but still very challenging to achieve a low detection limit due to the low inferior conductivity of MOFs. Herein, three different N-doped ZIF-67-derived carbons were synthesized for the first time by one-step co-pyrolysis of 2-methylimidazole with cobalt nitrate (CN), cobalt acetate (CA) or cobalt chloride (CC) toward UA sensing. Afterwards, the cobalt nitrate-derived Co particle (Co/CN) supported by N-doped ZIF-67-derived carbon displays extremely low detection limit and high sensitivity for UA, outperformed all reported MOFs-based UA sensors. More interestingly, it was discovered that the high valence Co⁴⁺ within the Co/CN sample produced in high-acidic environment can intercalate in the frame for a bridge adsorption between two reaction sites, which boosted simultaneous 2-electron transfer, while Co³⁺ only allows an end-adsorption structure for one-electron transfer being the rate determining step. Furthermore, the bridge adsorption mode of UA on Co⁴⁺ -based catalyst was also verified by theoretical DFT calculations and XPS experiment. This work holds great promise for a selective and sensitive UA sensor for practical bioscience and clinic diagnostic applications while shedding lights in fundamental research for innovative designs and developments of high-sensitive electrochemical sensors.

Keywords: Cobalt acetate; Cobalt chloride; Cobalt nitrate; DFT calculation; Metal-organic framework; Uric acid.