LAUSR

The spontaneous reaction between Zn and H2O is of critical importance and could plausibly be used to produce H2 gas, especially under neutral conditions. However, this reaction has long been overlooked owing to its sluggish kinetics and Zn consumption. Herein, a unique self‐co‐electrolysis system (SCES) is reported, which uses a Zn anode, a CoP‐based catalytic cathode, and a neutral phosphate buffer solution (PBS) as the electrolyte. In this SCES, Zn is not only a sacrificial anode but also an important precursor of high‐value‐added NaZnPO4. Additionally, the composition and phase structure of NaZnPO4 can be well regulated. In this study, a high‐performance N,Cu‐CoP/carbon cloth (CC) catalyst is synthesized to catalyze the cathodic hydrogen evolution reaction (HER) at an especially low overpotential of 64.7 mV at 10 mA cm−2. H2 gas (13.7 mL cm−2 h−1) and NaZnPO4 (3.73 mg cm−2 h−1) are obtained at the cathode and anode, respectively, in the N,Cu‐CoP/CC||Zn SCES spontaneously. Moreover, the SCES has a favorable open‐circuit voltage (OCV) of 0.79 V and a maximum power density of 1.83 mW cm−2. Density functional theory (DFT) calculations are performed to elucidate the electronic structure and HER catalytic mechanism of the N and Cu co‐doped CoP catalysts.