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

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.