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ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction.

Howard Yi Fan SimJaslyn Ru Ting ChenCharlynn Sher Lin KohHiang Kwee LeeXuemei HanGia Chuong Phan-QuangJing Yi PangChee Leng LaySrikanth PedireddyIn Yee PhangEdwin Kok Lee YeowXing Yi Ling
Published in: Angewandte Chemie (International ed. in English) (2020)
The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst-H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mgcat -1  h-1 under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst-N2 interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-NZIF interaction is key to enable strong N2 adsorption over H atom.
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