<p>Replacing energy- and cost-intensive Solvay process with innovative manufacture protocol, such as <i>operando</i>-electrified synthesis, would provide a simpler, scale-flexible pathway to produce NaHCO₃. However, the commercialization of such technique is hampered by the bottleneck problem of small productivity, which is two orders of magnitude below traditional Solvay process. This might be attributed to the gap in conditions between embedded processes inside the system, especially low concentrations of local alkaine, which are generated relatively slowly from one-electron hydrogen chemistry, leading to a small CO₂–to–HCO₃⁻ conversion ratio. Guided by octet rule, here we embed eight-electron nitrogen chemistry into Solvay process, maximizing local alkalines generation for CO₂ conversion. By further breaking the stumbling scaling relationship with a liquid metal-derived catalyst, the system achieves productivity up to 3.63 mol L⁻¹ h⁻¹.</p>