Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.
Chem Commun (Camb). 2019 Oct 10;55(82):12376-12379. doi: 10.1039/c9cc06385d.
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.
我们报告了一种热解-磷化方法，使用 ZIF-67 作为前驱体制备嵌入 CoP 纳米颗粒（CoP/CNs）的碳纳米管，用于在环境条件下电催化氮气（N2）还原为氨（NH3）。结果表明，所合成的 CoP/CNs 作为电催化剂对 N2 还原反应（NRR）表现出高电催化活性，在 0.1 M Na2SO4 电解质中，在-0.4 V（相对于 RHE）下，NH3 的产率速率高达 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，所获得的 NH3 确实来自 CoP/CN 催化的 NRR 过程。我们的理论计算结果表明，N2 分子优先通过缔合的远端加氢过程吸附在 CoP(112)平面上的高不饱和三配位 Co 位点上。
