Etching of halloysite nanotubes hollow imprinted materials as adsorbent for extracting of Zearalenone from grain samples

•Etching technique combined with molecularly imprinted technology.•Hollow imprinted materials were prepared by etching technique.•Coumarin-3-carboxylicacid and pentadecanolide were used as the dummy templates.•Self-made SPE column coupled with HPLC-FD for analysis of ZEN in grain samples. The halloysite nanotubes surface molecularly imprinted polymers (HNTs-SMIPs) were prepared by precipitation polymerization, using halloysite nanotubes as the carrier material, coumarin-3-carboxylic acid and pentadecanolide as dummy templates of zearalenone, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. Then, the HNTs-SMIPs were treated with etching technique to obtain halloysite nanotubes hollow molecularly imprinted polymers (HNTs-HMIPs). HNTs-SMIPs and HNTs-HMIPs were characterized by scanning electron microscope, transmission electron microscope, fourier transform infrared spectrum and X-ray diffraction. The adsorption capacity of HNTs-HMIPs was compared with HNTs-SMIPs. The developed HNTs-HMIPs were applied as absorbents for solid phase extraction. A new method was established by combining with high performance liquid chromatography-fluorescence detector for the detection of zearalenone. The method was developed with a recovery of 77.13–102.4% and a relative standard deviation of less than 5.59%. The limit of detection of oats and wheat were 1.67 μg kg−1 and 0.5 μg kg−1, respectively. The performance of self-made solid phase extraction column was compared with immune affinity column. The developed method has been successfully applied to the detection of zearalenone in complex grain matrices.