Hierarchical porous carbon heterojunction flake arrays derived from metal organic frameworks and ionic liquid for H 2 O

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Hierarchical porous carbon heterojunction flake arrays derived from metal organic frameworks and ionic liquid for H2O2 electrochemical detection in cancer tissue Yan Zhang1, Qiying Lv1, Kai Chi2, Qilin Li1, Huiling Fan1, Bo Cai1, Fei Xiao2 (), Shuai Wang2 (), Zheng Wang1 (), and Lin Wang () 1 2

Union Hospital, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430022, China Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 Received: 1 July 2020 / Revised: 3 October 2020 / Accepted: 11 October 2020

ABSTRACT The development of hierarchical nanostructure is demonstrated as an effective strategy to improve catalytic activity and stability of electrocatalysts. Herein, a novel leaf-like hierarchically porous heterojunction flake arrays (FAs), integrated graphitic N-doped carbon (NC) with amorphous B,N-doped carbon (BNC), has been designed and grown on flexible carbon fiber (CF) using metal–organic framework (MOF) FAs and green ionic liquids as precursors. The hierarchical heterojunction structure possesses micro- and nano-scaled pores, large surface areas, and exposed high-density catalytic active sites, which enhances electronic conductivity and offers accessible transport channels for effectively decreasing mass transport resistance. The results of discrete Fourier transform (DFT) calculations and experiments also suggest that the catalytic activity has been promoted by the heterojunction structure through narrowing the banding gap. Consequently, the resultant nanohybrid microelectrode exhibits remarkable electrochemical sensing performance towards H2O2 with a low detection limit of 50 nM, and a high sensitivity of 213 μA·mM–1·cm–2, as well as good anti-interference capability. The practical application of nanohybrid fiber microelectrode has been explored by real-time monitoring H2O2 released from live colon cells and surgically-resected fresh colon cancer tissue, which can provide important information for the identification of different types of cells as well as distinguish cancer cells from normal ones. We believe this research will pave the way towards the development of advanced carbon nanomaterials for application in the fields of electrochemistry, biosensing, and cancer diagnosis.

KEYWORDS carbon heterojunction structure, hierarchical flake arrays, heteroatoms doping, electrochemical sensor, cancer biomarker detection

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Introduction

Ultrasensitive detection of cancer biomarkers in human samples becomes increasingly important due to the growing demand for early diagnosis of cancer [1–3]. To achieve this goal, electrochemical sensors with fast response, ease of operation, high sensitivity and specificity, and miniaturization are intensively explored. As a core element fo