High-ammonia selective metal-organic framework-derived Co-doped Fe/Fe(2)O(3) catalysts for electrochemical nitrate reduction.
High-ammonia selective metal-organic framework-derived Co-doped Fe/Fe(2)O(3) catalysts for electrochemical nitrate reduction.
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DOI：
10.1073/pnas.2115504119
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发表时间：
2022-02-08
影响因子：
11.1
通讯作者：
Liu X
中科院分区：
文献类型：
--
作者：
Zhang S;Li M;Li J;Song Q;Liu X
电化学还原水中的硝酸盐污染物为增值铵对于现代农业和工业是必不可少的，并且代表了替代传统Haber-Bosch工艺的潜在可持续战略。然而，在环境条件下的硝酸盐还原反应（NO3−RR）过程通常具有低选择性。在这里，我们开发了一种调整电子结构的策略，用于制备钴掺杂的Fe@Fe2O3电催化剂。钴掺杂调谐Fe d-带中心，从而调节中间体的吸附能并抑制氢的产生。因此，电催化剂表现出上级NO3−RR活性，具有高硝酸盐去除能力（100.8 mg N gcat−1 h−1）、NH3选择性（99.0 ± 0.1%）和法拉第效率（85.2 ± 0.6%）。该策略为NO3−RR的先进材料设计提供了一种方法。氨（NH3）是未来可持续氢经济中理想的无碳能源，可满足不断增长的能源需求。电化学硝酸盐还原反应（NO3−RR）是一种在环境条件下去除硝酸盐和生产NH3的有前途的方法，但缺乏有效的电催化剂。在这里，我们提出了一种金属有机框架（MOF）衍生的钴掺杂Fe@Fe2O3（Co-Fe@ Fe 2 O3）NO3−RR催化剂，用于电化学能生产。该催化剂的硝酸盐去除能力为100.8 mg N gcat−1 h−1，铵选择性为99.0 ± 0.1%，是所有已报道研究中最高的。此外，NH3的产生速率为1，505.9 μg h−1 cm−2，最大法拉第效率为85.2 ± 0.6%。实验和计算结果表明，Co-Fe@ Fe 2 O 3的高性能来自于钴掺杂，其调谐Fe d-带中心，使得中间体的吸附能能够被调制并抑制氢的产生。因此，本研究提供了一个策略，在电化学硝酸盐还原的电催化剂的设计。
Electrochemical reduction of nitrate pollution in water into value-added ammonium is essential for modern agriculture and industry and represents a potentially sustainable strategy to replace the traditional Haber–Bosch process. However, the nitrate reduction reaction (NO3−RR) process under ambient conditions often suffers from low selectivity. Here, we developed a strategy of tuning an electronic structure for preparing cobalt-doped Fe@Fe2O3 electrocatalysts. Cobalt doping tunes the Fe d-band center, thereby modulating the adsorption energies of intermediates and suppressing hydrogen production. Therefore, the electrocatalysts exhibit superior NO3−RR activity with a high nitrate removal capacity (100.8 mg N gcat−1 h−1), NH3 selectivity (99.0 ± 0.1%), and faradaic efficiency (85.2 ± 0.6%). This strategy provides an approach to design advanced materials for NO3−RR. Ammonia (NH3) is an ideal carbon-free power source in the future sustainable hydrogen economy for growing energy demand. The electrochemical nitrate reduction reaction (NO3−RR) is a promising approach for nitrate removal and NH3 production at ambient conditions, but efficient electrocatalysts are lacking. Here, we present a metal–organic framework (MOF)–derived cobalt-doped Fe@Fe2O3 (Co-Fe@Fe2O3) NO3−RR catalyst for electrochemical energy production. This catalyst has a nitrate removal capacity of 100.8 mg N gcat−1 h−1 and an ammonium selectivity of 99.0 ± 0.1%, which was the highest among all reported research. In addition, NH3 was produced at a rate of 1,505.9 μg h−1 cm−2, and the maximum faradaic efficiency was 85.2 ± 0.6%. Experimental and computational results reveal that the high performance of Co-Fe@Fe2O3 results from cobalt doping, which tunes the Fe d-band center, enabling the adsorption energies for intermediates to be modulated and suppressing hydrogen production. Thus, this study provides a strategy in the design of electrocatalysts in electrochemical nitrate reduction.
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影响因子：
29.4
作者：
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通讯作者：
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影响因子：
15
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影响因子：
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作者：
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22.1
作者：
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