Elucidation of the role of metals in the adsorption and photodegradation of herbicides by metal-organic frameworks
Elucidation of the role of metals in the adsorption and photodegradation of herbicides by metal-organic frameworks
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DOI：
10.1038/s41467-024-45546-y
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发表时间：
2024-02-17
影响因子：
16.6
通讯作者：
Stylianou，Kyriakos C.
中科院分区：
文献类型：
--
作者：
Chiu，Nan Chieh;Lessard，Jacob M.;Stylianou，Kyriakos C.
在这里，四个MOFs，即Sc-TBAPy，Al-TBAPy，Y-TBAPy，和Fe-TBAPy（TBAPy：1，3，6，8-四（对苯甲酸）芘），表征和评价其修复草甘膦（GP）的能力。在这些材料中，Sc-TBAPy在GP的吸附和降解方面均表现出上级性能。在光照射5分钟后，Sc-TBAPy完全降解1.5mM水溶液中的100%的GP。飞秒瞬态吸收光谱表明，Sc-TBAPy表现出增强的电荷转移特性相比，其他的MOFs，以及抑制形成的发射准分子，可能会阻碍荧光。这一发现进一步得到了析氢半反应（HER）实验的支持，该实验证明了Sc-TBAPy对于水裂解的上级催化活性。除了其更快的吸附和更有效的GP光降解之外，Sc-TBAPy还遵循GP氧化的选择性途径，避免了用其他M3+-TBAPy M0 F观察到的有毒氨甲基膦酸的形成。为了研究用Sc-TBAPy观察到的选择性，采用电子自旋共振、贫氧条件和与D2 O的溶剂交换来阐明不同活性氧物种对GP光降解的作用。研究结果表明，单线态氧（1 O2）在Sc-TBAPy实现的选择性光降解途径中发挥着关键作用。
Here, four MOFs, namely Sc-TBAPy, Al-TBAPy, Y-TBAPy, and Fe-TBAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoic acid)pyrene), were characterized and evaluated for their ability to remediate glyphosate (GP) from water. Among these materials, Sc-TBAPy demonstrates superior performance in both the adsorption and degradation of GP. Upon light irradiation for 5 min, Sc-TBAPy completely degrades 100% of GP in a 1.5 mM aqueous solution. Femtosecond transient absorption spectroscopy reveals that Sc-TBAPy exhibits enhanced charge transfer character compared to the other MOFs, as well as suppressed formation of emissive excimers that could impede photocatalysis. This finding was further supported by hydrogen evolution half-reaction (HER) experiments, which demonstrated Sc-TBAPy’s superior catalytic activity for water splitting. In addition to its faster adsorption and more efficient photodegradation of GP, Sc-TBAPy also followed a selective pathway towards the oxidation of GP, avoiding the formation of toxic aminomethylphosphonic acid observed with the other M3+-TBAPy MOFs. To investigate the selectivity observed with Sc-TBAPy, electron spin resonance, depleted oxygen conditions, and solvent exchange with D2O were employed to elucidate the role of different reactive oxygen species on GP photodegradation. The findings indicate that singlet oxygen (1O2) plays a critical role in the selective photodegradation pathway achieved by Sc-TBAPy.