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oai:figshare.com:article/34028755 2026-09-30T03:05:38Z category_1 category_4 category_915 category_16 category_24 category_873 category_734 portal_63 item_type_6 month_year_09_2026

Triadic σ–π Coordination Programs Cu^δ+ Sites to Drive Sequential Dual‑N Species C–N Coupling for Efficient Urea Electrosynthesis Chao Zhao (253684) Bo-Chao Ye (25139965) Meiqi Zhu (20926368) Honghui Ou (2792803) Qi-lin Hou (25139968) Yu Jin (360487) Wen-Hao Li (4778280) Dingsheng Wang (1630807) Guidong Yang (2222821) Biophysics Biochemistry Physical Sciences not elsewhere classified Physiology Evolutionary Biology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified poor spatiotemporal synchronization membrane electrode assembly first coupling step effects improve proton coupled electron transfer conjugated microporous polymers 8 mmol g synchronized local coverages couples carbon utilization urea formation rate site engineering strategy electronically program low coordinate sequential dual δ +</ sup coordinated cu stabilizes single active sites urea </ sub sequential dual tunable single local repulsion carbon route active site − 0 x </ working state work demonstrates transferable atomic theory show stable operation site competition reduction reaction normalized tof nitrate valorization key intermediate intermediate electrocatalysis interfacial hydrogen insufficient control derived intermediates conh identified complex multi bond network Electrocatalytic CO₂/NO₃^– coreduction to urea through C–N coupling (EcnRR) offers a low-carbon route that couples carbon utilization with nitrate valorization. However, its efficiency is limited by poor spatiotemporal synchronization of C- and N-derived intermediates, site competition and local repulsion at single active sites, and insufficient control over the NO₃^– reduction reaction (NtrRR) hydrogenation. Here, we construct a series of secondary-coordination-tunable single-atom Cu–alkynyl–X sites in conjugated microporous polymers (Cu–X–CMPs, X = N, C, S), where X → Cu σ coordination and an alkynyl π channel work together through triadic σ–π coupling to electronically program low-valent Cu atomic sites (Cu^δ+). Experiments and theory show that N-coordinated Cu stabilizes the Cu^δ+ working state, enhances local interfacial polarization, and reorganizes the interfacial hydrogen-bond network. These effects improve proton-coupled electron transfer (PCET) compatibility and increase the synchronized local coverages of *CO and *NH_<i>x</i> near the active site. More importantly, Cu–N–CMPs establishes a sequential dual-N-species C–N coupling pathway initiated by *NH and completed by *NH₂, with *CONH identified as the key intermediate in the first coupling step. As a result, Cu–N–CMPs delivers a Cu-site-normalized TOF of 1321.2 h^–1 at −0.6 V_RHE. In the membrane electrode assembly (MEA) electrolyzer, it further delivers a urea formation rate of 92.8 mmol g_cat.^–1 h^–1 with 77.6% FE_urea and stable operation for 85 h. This work demonstrates that Cu site electronic programming can coordinate sequential dual-N species C–N coupling, providing a transferable atomic-site engineering strategy for complex multi-intermediate electrocatalysis. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/jacs.6c17136.s001 https://figshare.com/articles/journal_contribution/Triadic_Coordination_Programs_Cu_sup_sup_Sites_to_Drive_Sequential_Dual_N_Species_C_N_Coupling_for_Efficient_Urea_Electrosynthesis/34028755 CC BY-NC 4.0