Electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance due to preferential catalyst-H formation and the consequential hydrogen evolution reaction (HER). Herein, we electronically modify PtAu electrocatalyst d-band structure using zeolitic-imidazole framework (ZIF) to achieve a faradaic efficiency (FE) of >44% with high ammonia yield rate of >161 µg.mg cat -1 .h -1 at ambient conditions. Our strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron deficient sites to kinetically drive NRR by promoting catalyst-N 2 interaction. The ZIF coating on electrocatalyst doubles as a hydrophobic layer to suppress HER, further improves FE by >44-fold compared to without ZIF (~1%). Experimental and in-silico studies reveal PtAu-N ZIF interaction is key to enable strong N 2 adsorption over H atom. Our electrocatalytic design is universal and can be extended across metal electrocatalysts for diverse applications in NRR and air-to-fuel conversion.
KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This research is supported by the Ministry of Education, Singapore, under Tier 1 (RG11/18) and Tier 2 (MOE2016-T2-1-043) grants, and Max Planck Institute-Nanyang Technological University Joint Lab. H. Y. F. S., C. S. L. K. and G. C. P-Q. thank scholarship support from Nanyang Technological University, Singapore. J. R. T. C. and J. Y. P. thank CN Yang scholarship. H. K. L. thanks the International Postdoctoral Scholarship support from Nanyang Technological University, Singapore, and Singapore Ministry of Education. We thank Mr. Poh Chong Lim, A*STAR, for XRD analysis.