Self-template synthesis of flower-like hierarchical graphene/copper oxide@copper(II) metal-organic framework composite f
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ORIGINAL PAPER
Self-template synthesis of flower-like hierarchical graphene/copper oxide@copper(II) metal-organic framework composite for the voltammetric determination of caffeic acid Xiaolong Tu 1,2 & Yu Xie 1 & Feng Gao 1 & Xue Ma 1 & Xinchen Lin 1 & Xigen Huang 1 & Fengli Qu 2 & Li Ping 1 & Yongfang Yu 1 & Limin Lu 1 Received: 16 October 2019 / Accepted: 24 March 2020 # Springer-Verlag GmbH Austria, part of Springer Nature 2020
Abstract Flower-like graphene/CuO@Cu-BTC (GR/CuO@Cu-BTC) composite was employed as electrode material for the voltammetric determination of caffeic acid (CA) in the wine. The composite material was prepared via the self-template method. In this synthetic process, budlike CuO not only acts as the template, but also provides Cu2+ ions for in situ growth of the Cu-BTC shell. The utilization of GR as petal greatly boosts the stability and electronic conductivity of CuO@Cu-BTC. The GR/ CuO@Cu-BTC composite possesses unique structural features with high specific surface area and good conductivity, exhibiting excellent electrocatalytic activity towards the oxidation of CA. Under optimized conditions, the sensor shows a good linear response to CA concentration over the range 0.020–10.0 μM, together with a low limit of detection (LOD) of 7.0 nM. Selectivity, reproducibility, and stability were investigated, and the method has been applied for the determination of CA in wine samples. Keywords Metal-organic framework . Graphene . Copper oxide . Heterostructures . Electrocatalysts . Signal amplification . Self-template strategy . Caffeic acid . Modified electrode . Electrochemical sensor
Introduction Caffeic acid (CA) commonly presents in a variety of fruit and vegetable and red wines [1], which has many beneficial effects on Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00604-020-04238-2) contains supplementary material, which is available to authorized users. * Xigen Huang [email protected] * Fengli Qu [email protected] * Limin Lu [email protected] 1
Key Laboratory of Crop Physiology, Ecology and Genetic Breeding, Ministry of Education, Key Laboratory of Chemical Utilization of Plant Resources of Nanchang, College of Science, Jiangxi Agricultural University, Nanchang 330045, People’s Republic of China
2
College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, People’s Republic of China
human health including anti-allergic, antibacterial, and inflammatory effects [2]. Thus, the quantitative detection of CA is more concerned for healthcare. Electrochemical methods are considered to be the most preferred methods on account of their low cost, rapid response, and high sensitivity [3, 4]. Based on the electroactivity of CA, many studies have reported the use of nanocomposite-modified sensors for CA detection, such as graphene [5], copper sulfide nanodots/graphene oxide [6]. However, there is still a need to construct unique modified electrodes with higher sensitivity and selectivity. Metal-orga
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