Highly Advanced Degradation of Thiamethoxam by Synergistic Chemisorption-Catalysis Strategy Using MIL(Fe)/Fe-SPC Composites with Ultrasonic Irradiation

Yanan Wei; Bingfeng Wang; Xinfang Cui; Yaseen Muhammad; Yanjuan Zhang; Zuqiang Huang; Xuesheng Li; Zhenxia Zhao; Zhongxing Zhao

doi:10.1021/acsami.8b12908

Highly Advanced Degradation of Thiamethoxam by Synergistic Chemisorption-Catalysis Strategy Using MIL(Fe)/Fe-SPC Composites with Ultrasonic Irradiation

ACS Appl Mater Interfaces. 2018 Oct 17;10(41):35260-35272. doi: 10.1021/acsami.8b12908. Epub 2018 Oct 8.

Authors

Yanan Wei, Bingfeng Wang¹, Xinfang Cui, Yaseen Muhammad², Yanjuan Zhang, Zuqiang Huang, Xuesheng Li, Zhenxia Zhao, Zhongxing Zhao

Affiliations

¹ Department of Applied Chemistry, College of Materials and Energy , South China Agricultural University , Guangzhou 510642 , China.
² Institute of Chemical Sciences , University of Peshawar , Peshawar 25120 , Khyber Pakhtunkhwa , Pakistan.

PMID: 30260206
DOI: 10.1021/acsami.8b12908

Abstract

MIL(Fe)/Fe-doped nanospongy porous biocarbon (Fe-SPC) composite was fabricated from MIL-100(Fe) via in situ growth on a unique Fe-doped nanospongy porous biocarbon (Fe-SPC) and was used as Fenton-like catalyst for advanced degradation of thiamethoxam (THIA). Fe was loaded on silkworm excrement and calcined to Fe-SPC with nanospongy and high sp² C structure. The in situ growth strategy embedded the Fe-SPC into MIL-100(Fe) crystals and formed conductive heterojunctions with an intensified interface by Fe-bridging effect, which was confirmed by negative shift of Fe³⁺ binding energy in X-ray photoelectron spectroscopy. MIL(Fe)/Fe-SPC composites exhibited high degree of crystallinity and surface area (Brunauer-Emmett-Teller: 1730 m²/g). Liquid chromatography-mass spectrometry and density functional theory simulations demonstrated that THIA was converted to a relatively stable compound (C₄H₅N₂SCl), which could be captured by MIL-100(Fe) with strong chemical bonding energy (Fe-N, -587 kJ/mol), followed by a significant geometric distortion, resulting in a thorough degradation. Efficient charge separation and synergistic chemisorption-catalysis strategy resulted in the high catalytic activity of MIL(Fe)/Fe-SPC. The composite catalyst concurrently exhibited high mineralization ratio with 95.4% total organic carbon removal (at 25 °C and 180 min) and good recycling ability under wider neutral/alkaline conditions. Endorsing to these intriguing properties, MIL(Fe)/Fe-SPC can be deemed an efficient contender for removal of hard-degradable pesticides and other environmental pollutants in practical applications.

Keywords: DFT simulation; MIL(Fe)/Fe-SPC catalyst; efficient charge separation; synergistic chemisorption-catalysis strategy; thiamethoxam advanced degradation.