Department of Chemistry, Universidade Federal do Paraná (UFPR), CP 19032, CEP 81531-980, Curitiba, PR, Brazil.
Department of Chemistry, Universidade Federal do Paraná (UFPR), CP 19032, CEP 81531-980, Curitiba, PR, Brazil.
Environ Pollut. 2023 Aug 1;330:121802. doi: 10.1016/j.envpol.2023.121802. Epub 2023 May 9.
Organophosphates are a worldwide threat because of their presence in agrochemicals and chemical warfare. Situations of misuse, apprehensions of prohibited chemicals (e.g. pesticides), undesired stockpiles and chemical attacks require effective measures for neutralization and removal. Herein, a green approach is shown by functionalizing the agricultural waste rice husk with amidoximes leading to heterogeneous catalysts that were applied in the degradation/scavenging of toxic organophosphates. In aqueous medium, the waste-derived catalyst was efficient in the catalytic neutralization of a phosphotriester (increments up to 1 × 10-fold), while allying important features: selective, recyclable and lead to less toxic products. Curiously, the amidoximated rice husk behaved as a scavenger in the aprotic polar solvents MeCN and acetone by covalently bonding to the phosphoryl moiety. Upon addition of water, this bond is broken and the phosphoryl liberated (hydrolyzed) to the aqueous medium. Thus, the scavenging process is reversible and can be used to remove toxic organophosphates. P nuclear magnetic resonance spectroscopy was crucial for confirming the overall mechanisms involved. In summary, a sustainable material was synthetized from a waste source and employed as catalyst and scavenger for eliminating threatening organophosphates. This is promising for assuring chemical security such as in chemical emergencies.
有机磷化合物因其存在于农用化学品和化学战剂中而成为全球威胁。由于存在滥用情况、对违禁化学品(如杀虫剂)的担忧、意外的库存和化学袭击,需要采取有效的中和和清除措施。在此,通过将农业废弃物稻壳用羟胺官能化,制备出非均相催化剂,应用于有毒有机磷化合物的降解/清除,从而展示了一种绿色方法。在水介质中,该废催化剂在催化膦酸三酯的中和(增加 10 倍)方面非常有效,同时具有重要的特点:选择性、可回收性和导致毒性较低的产物。有趣的是,在非质子极性溶剂 MeCN 和丙酮中,羟胺化稻壳通过与磷酰基部分共价键合而作为清除剂。加入水后,该键断裂,磷酰基释放(水解)到水介质中。因此,清除过程是可逆的,可以用于去除有毒的有机磷化合物。P 核磁共振波谱对于证实所涉及的整体机制至关重要。总之,从废物来源合成了一种可持续的材料,并用作催化剂和清除剂来消除威胁性的有机磷化合物。这对于确保化学安全(如在化学紧急情况下)是有希望的。