A pyrolysis-phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles for ambient electrosynthesis of ammonia

Shengbo Zhang; Wanbing Gong; Yang Lv; Haojie Wang; Miaomiao Han; Guozhong Wang; Tongfei Shi; Haimin Zhang

doi:10.1039/c9cc06385d

A pyrolysis-phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles for ambient electrosynthesis of ammonia

Chem Commun (Camb). 2019 Oct 10;55(82):12376-12379. doi: 10.1039/c9cc06385d.

Authors

Shengbo Zhang¹, Wanbing Gong², Yang Lv¹, Haojie Wang², Miaomiao Han², Guozhong Wang², Tongfei Shi², Haimin Zhang²

Affiliations

¹ 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. zhanghm@issp.ac.cn tfshi@issp.ac.cn and University of Science and Technology of China, Hefei 230026, China.
² 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. zhanghm@issp.ac.cn tfshi@issp.ac.cn.

PMID: 31559991
DOI: 10.1039/c9cc06385d

Abstract

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.