A pyrolysis-phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles for ambient electrosynthesis of ammonia
A pyrolysis-phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles for ambient electrosynthesis of ammonia
复制标题
热解-磷化方法制备嵌入 CoP 纳米颗粒的碳纳米管，用于常温电合成氨
DOI：
10.1039/c9cc06385d
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发表时间：
2019
影响因子：
4.9
通讯作者：
Zhang Haimin
中科院分区：
文献类型：
--
作者：
Zhang Shengbo;Gong Wanbing;Lv Yang;Wang Haojie;Han Miaomiao;Wang Guozhong;Shi Tongfei;Zhang Haimin
我们报告了一种热解-磷化方法，使用 ZIF-67 作为前体，在环境条件下电催化氮 (N2) 还原为氨 (NH3)，制造嵌入 CoP 纳米颗粒 (CoP/CNs) 的碳纳米管。结果表明，合成的CoP/CNs作为电催化剂对N2还原反应（NRR）表现出较高的电催化活性，在0.1 M Na2SO4电解质中，在-0.4 V（相对于RHE）下，NH3产率高达48.9 μg h−1 mgcat.−1，法拉第效率（FE）为8.7%。 15N同位素标记实验证实获得的NH3确实来自CoP/CN催化的NRR过程。我们的理论计算结果表明，在缔合远端氢化过程后，N2 分子更倾向于吸附在 CoP(112) 平面的高度不饱和的三个配位 Co 位点上。
We report a pyrolysis–phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles (CoP/CNs) using ZIF-67 as a precursor for electrocatalytic nitrogen (N2) reduction to ammonia (NH3) under ambient conditions. The results demonstrate that the as-synthesized CoP/CNs as electrocatalysts exhibit high electrocatalytic activity toward the N2 reduction reaction (NRR), affording a large NH3 yield rate of 48.9 μg h−1 mgcat.−1 with a faradaic efficiency (FE) of 8.7% at −0.4 V (vs. RHE) in 0.1 M Na2SO4 electrolyte. The 15N isotopic labelling experiments confirm that the NH3 obtained is indeed from the CoP/CN catalyzed NRR process. Our theoretical calculation results reveal that the N2 molecules prefer to be adsorbed on the highly unsaturated three coordinated Co sites of the CoP(112) plane following an associative distal hydrogenation process.