Elucidating the NH₂OH–Mediated Pathway for Photoelectrocatalytic C–N Coupling toward Solar-Driven Hexamethylenetetramine Synthesis
Date
2026
Authors
Liu, J.
Han, C.
Yuwono, J.A.
Pan, J.
Shan, Y.
Deng, S.
Vongsvivut, J.
Pickford, R.
Song, N.
Zhou, S.
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Journal article
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Journal of the American Chemical Society, 2026; 148(11):1179-1189
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Jiarong Liu, Chen Han, Jodie A. Yuwono, Jian Pan, Yihao Shan, Shuo Deng, Jitraporn Vongsvivut, Russell Pickford, Ning Song, Shujie Zhou and Rose Amal
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Abstract
The sustainable construction of multiple C–N bonds remains a fundamental challenge, particularly for complex carbon–nitrogen molecules that require multielectron and multistep processes. Hexamethylenetetramine (HMTA) is an essential chemical feedstock, while its conventional synthesis is energy and carbon-emission intensive. Recent studies indicate the promise of Cu-based catalysts for electrochemical HMTA formation, yet a single Cu site is inherently limited in coordinating the multiple hydrogenation and condensation steps necessary for simultaneously forming the two key HMTA precursors (i.e., (CH₂NH)₃ and N(CH₂OH)₃). Herein, we report a sustainable photoelectrocatalytic (PEC) approach for HMTA synthesis via coupling NO₃– and HCHO using a Si-based photocathode integrated with hierarchical Cu/Co nanoarray cocatalysts (Cu/Co–Si). This architecture decouples light absorption and catalytic reaction, delivering a high HMTA faradaic efficiency of 80.62% at 0.2 VRHE, over 3.2 times that of Cu–Si, and a yield rate of 5.43 μmol h–1 cm–2. Importantly, *NH₂OH generated on Co sites during NO₃– reduction is identified as a key intermediate that couples directly with *HCHO to form an oxime (*CH₂═NOH), accelerating the formation of (CH₂NH)₃. Meanwhile, Cu sites favor the NH₃–HCHO condensation pathway to generate N(CH₂OH)₃. The rational dual-site strategy and photovoltaic compatibility offer a scalable, sustainable platform for solar-driven C–N coupling toward high-value chemicals.
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© 2026 American Chemical Society