Abstract The effect of proton transfer on water oxidation has hardly been measurably established in heterogeneous electrocatalysts. Herein, two isomorphous manganese phosphates (NH4MnPO4 ⋅ H2O and KMnPO4 ⋅ H2O) were designed to form an ideal platform to study the effect of proton transfer on water oxidation. The hydrogen‐bonding network in NH4MnPO4 ⋅ H2O has been proven to be solely responsible for its better activity. The differences of the proton transfer kinetics in the two materials indicate a fast proton hopping transfer process with a low activation energy in NH4MnPO4 ⋅ H2O. In addition, the hydrogen‐bonding network can effectively promote the proton transfer between adjacent Mn sites and further stabilize the MnIII−OH intermediates. The faster proton transfer results in a higher proportion of zeroth‐order in [H+] for OER. Thus, proton transfer‐affected electrocatalytic water oxidation has been measurably observed to bring detailed insights into the mechanism of water oxidation.
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