Abstract
Catalytic carbon-nitrogen (C–N) coupling reactions offer a sustainable and environmentally friendly route for the production of high value-added hexamethylenetetramine (HMTA). However, it still suffers from limited chemisorption, low activation kinetics, and unfavorable thermodynamics, resulting in low HMTA Faradaic efficiency (FEHMTA) and yield rate. Here, by physically constructing hierarchically tip and mesoporous structure, copper mesoporous nanotips (Cu MNTs) realize efficient HMTA synthesis by an electrochemical-chemical cascade catalysis. Unlike traditional catalysts, tip-enhanced site of Cu MNTs electrochemically favors NO3− chemisorption and further electroreduction into *NH3 radicals, while its confined mesoporous nanoreactor ensures cascade chemical C–N coupling and subsequent cyclization to HMTA. With minor byproducts, Cu MNTs deliver a FEHMTA of 94.2% and a yield rate of 0.227 mmol h−1 cm−2. Moreover, this route enables efficient HMTA synthesis in a flow cell electrolyzer with high economic feasibility and market potential for industrial application. This work thus deepens the physical design strategies of hierarchically structural catalysts that promote electrochemical-chemical cascade C–N coupling reactions for efficient synthesis of various important chemicals and feedstocks.
Acknowledgements
The authors would like to thank Dr. Feng Yang (the Comprehensive Training Platform of the Specialized Laboratory, College of Chemistry, Sichuan University) for her assistance with TEM/STEM imaging, Dr. Yanhong Liu (the Comprehensive Training Platform of the Specialized Laboratory, College of Chemistry, Sichuan University) for her assistance of Raman tests, and Dr. Yanping Huang (the Center of Engineering Experimental Teaching, School of Chemical Engineering, Sichuan University) for her help of SEM imaging.
Funding
This work was financially supported by the National Natural Science Foundation of China (22575159, B.L., and 22505167, L.S.), the China National Postdoctoral Program for Innovative Talents (BX20250117, L.S.), the China Postdoctoral Science Foundation (2025M781000, L.S.), the Natural Science Foundation of Sichuan Province (2025ZNSFSC0903, L.S.), the Sichuan University Postdoctoral Interdisciplinary Innovation Fund (L.S.), and the Fundamental Research Funds for the Central Universities (B.L.).
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Sun, L., Jing, Y. & Liu, B. Electrochemical and chemical cascade catalysis for efficient hexamethylenetetramine synthesis over mesoporous copper nanotips. Nat Commun (2026). https://doi.org/10.1038/s41467-026-73384-7
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DOI: https://doi.org/10.1038/s41467-026-73384-7
