Selective recognition of 2,4,5-trichlorophenol by temperature responsive and magnetic molecularly imprinted polymers based on halloysite nanotubes

Abstract

Fe₃O₄/Halloysite nanotube magnetic composites (MHNTs) were firstly prepared via an effective polyol-medium solvothermal method, and then the surface of the MHNTs was endowed with reactive vinyl groups through modification with 3-(methacryloyloxy)propyl trimethoxysilane (MPS). Based on the MHNTs-MPS, temperature responsive and magnetic molecularly imprinted polymers (t-MMIPs) were further synthesized by adopting methacrylic acid (MAA) and N-isopropylacrylamide (NIPAM) as the functional monomer and temperature responsive monomer, respectively. The as-prepared t-MMIPs were characterized by FT-IR, TEM, TGA and VSM, which indicated that the t-MMIPs exhibit magnetic sensitivity (M_s = 2.026 emu g⁻¹), magnetic stability (especially in the pH range of 4.0–8.0) and thermal stability and are composed of an imprinted layer. The molecular interaction between 2,4,5-trichlorophenol (TCP) and MAA was investigated by ¹H-NMR spectroscopy and ultraviolet absorption spectroscopy, which suggest that hydrogen bonding may be largely responsible for the recognition mechanism. The t-MMIPs were then applied to selectively recognise and release TCP molecules at 60 °C and 20 °C, respectively. The maximum amount of binding at 60 °C was 197.8 mg g⁻¹ and 122.6 mg g⁻¹ for t-MMIPs and temperature responsive and magnetic non-imprinted polymers (t-MNIPs), respectively. At 20 °C, about 32.3%–42.7% of TCP adsorbed by t-MMIPs was released, whereas 25.3%–39.9% of TCP was released by t-MNIPs. The selective recognition experiments demonstrated the high affinity and selectivity of t-MMIPs towards TCP over competitive phenolic compounds, and the specific recognition of binding sites may be based on the distinct size, structure and functional group to the template molecules.