A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction
A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction
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DOI：
10.1021/jacs.1c00595
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发表时间：
2021-05-18
影响因子：
15
通讯作者：
Liu, Jinyong
中科院分区：
文献类型：
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作者：
Ren, Changxu;Yang, Peng;Liu, Jinyong
高氯酸盐(ClO4-)是地球和火星上普遍存在的一种有害的惰性阴离子。目前的ClO4还原技术要么需要苛刻的条件，要么需要多组分的酶过程。本文报道了一种由双齿氮配体(L)-Na_2MoO_4和Pd/C直接制备的多相(L)Mo-Pd/C催化剂，在室温下以1atm的H-2将水中的ClO_4-还原为Cl-。一系列的仪器表征和探测反应表明，Mo-VI前驱体和L以1：1的最佳比例原位转化为碳-水界面上的低聚Mo-IV活性中心。对于每个Mo位，氧原子从ClOx衬底转移的初始周转频率(TOF0)达到165h(-1)。单批减少100 mm ClO4-后，成交量(吨)达到3840个。这项研究为水净化和太空探索提供了一种水相容、高效和坚固的催化剂来降解和利用ClO4-。
Perchlorate (ClO4-) is a pervasive, harmful, and inert anion on both Earth and Mars. Current technologies for ClO4- reduction entail either harsh conditions or multicomponent enzymatic processes. Herein, we report a heterogeneous (L)Mo-Pd/C catalyst directly prepared from Na2MoO4, a bidentate nitrogen ligand (L), and Pd/C to reduce aqueous ClO4- into Cl- with 1 atm of H-2 at room temperature. A suite of instrument characterizations and probing reactions suggest that the Mo-VI precursor and L at the optimal 1:1 ratio are transformed in situ into oligomeric Mo-IV active sites at the carbon-water interface. For each Mo site, the initial turnover frequency (TOF0) for oxygen atom transfer from ClOx- substrates reached 165 h(-1). The turnover number (TON) reached 3840 after a single batch reduction of 100 mM ClO4-. This study provides a water-compatible, efficient, and robust catalyst to degrade and utilize ClO4- for water purification and space exploration.