Immobilization of Iron Phthalocyanine on Pyridine-Functionalized Carbon Nanotubes for Efficient Nitrogen Reduction Reaction

• An electrochemical nitrogen reduction reaction (NRR) under mild conditions offers a promising alternative to the traditional Haber-Bosch process in converting abundant nitrogen (N2) to high value-added ammonia (NH3). In this work, iron phthalocyanine (FePc) was homogeneously immobilized on pyridine-functionalized carbon nanotubes to form a well-tuned electrocatalyst with an FeN5 active center (FePc-Py-CNT). Synchrotron X-ray absorption and Fourier transform infrared spectroscopy proved the presence of an Fe-N coordination bond between FePc and surface-bound pyridine. The resulting hybrid exhibited notably enhanced electrocatalytic NRR performance compared to FePc immobilized on CNTs based on pi-pi stacking interactions (FePc-CNT), resulting in doubled NH3 yield (21.7 mu g 1 h mgcat-1h-1) and Faradaic efficiency (22.2%). Theoretical calculations revealed that the axial coordination on FePc resulted in partial electron transfer from iron to pyridine, which efficiently suppresses the adsorption of H+ and improves the chemisorption of N2 at Fe sites. Meanwhile, the interfacial electron transfer was facilitated by pyridine as an electron transfer relay between FePc and CNTs. This work provides a unique strategy for the design of highly efficient NRR electrocatalysts at the molecular level.

Ämnesord

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Nyckelord

nitrogen reduction reaction

axial coordination

Fe phthalocyanine

heterogeneous molecular electrocatalysis

interfacial electron transfer

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