Shu-Lin Meng, Chen Zhang, Chen Ye, Jia-Hao Li, Shuai Zhou, Lei Zhu, Xu-Bing Li, Chen-Ho Tung and Li-Zhu Wu
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引用次数: 4
Abstract
Herein, we demonstrate cobaloximes as a bioinspired molecular platform for exclusive ammonia synthesis via electrocatalytic NO2? reduction (eNO2?RR), which attained 98.5% faradaic efficiency (FE) under close-to-neutral conditions. Mechanistic studies illustrated that cobaloximes furnished effective binding with NO2? and nitrogenous intermediates, along with continuous, rapid 6e?/8H+ transfer with an intramolecular hydrogen bonding framework. As the cobaloxime skeleton displayed tunable structures on axial and equatorial sites for selective NO2? to NH4+ transformation, integrating cobaloximes with multi-walled carbon nanotubes (MWCNTs) as working electrodes attained advantageous ammonia yields of 19.3 mg h?1 mgCat?1 with >95% FE at ?0.5 V vs. RHE. More strikingly, cobaloxime-catalyzed NO2? to NH4+ transformation was coupled with plasma-driven N2 oxidation (pNOR) to convert ambient air into NH4Cl at a mmol-scale. This work demonstrates promising prospects of bioinspired molecular catalytic platforms for effective and selective ammonia and nitrogenous chemical synthesis via NOx?.
在此,我们证明了钴胺肟作为一个生物启发的分子平台,通过电催化NO2?还原(eNO2?RR),在接近中性的条件下达到98.5%的法拉第效率。机制研究表明,钴酰肟与NO2?含氮中间体,以及持续快速的6e?/8H+转移与分子内氢键框架。由于钴胺骨架在轴位和赤道位上对选择性NO2?将钴酰肟与多壁碳纳米管(MWCNTs)结合作为工作电极,可获得19.3 mg h?1 mgCat ?1在- 0.5 V vs. RHE下使用>95% FE。更引人注目的是,钴胺素催化的NO2?向NH4+转化与等离子体驱动的N2氧化(pNOR)相结合,将环境空气转化为毫摩尔级的NH4Cl。这项工作表明,生物启发的分子催化平台在通过NOx进行有效和选择性的氨和氮化学合成方面具有广阔的前景。
期刊介绍:
Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences."
Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).