Bimetallic Ni–Mn Electrocatalysts for Stable Oxygen Evolution Reaction in Simulated/Alkaline Seawater and Overall Performance in the Splitting of Alkaline Seawater

Abstract

The perfect strategy for the generation of green and renewable hydrogen (H2) fuels is the direct electrocatalytic splitting of plentiful seawater rather than scarce freshwater. One of the half-reactions taking place during the electrocatalytic splitting of seawater is oxygen evolution (OER). However, the OER is affected by slow four-electron transfer kinetics as well as competitive chlorine evolution reactions (CERs) in seawater. To overcome the kinematic and competitive barriers of seawater splitting and achieve an excellent overall performance of seawater splitting, we herein report a facile, low-cost, one-step fabrication procedure of 3D structured nickel–manganese (NiMn) coatings using a dynamic hydrogen bubble template (DHBT) technique. The electrocatalytic activities of the thus synthesized catalytic materials for OER in simulated seawater (0.5 M NaCl + 1 M KOH, denoted as SSW) and alkaline natural seawater (natural seawater + 1 M KOH, denoted as ASW) were investigated using linear sweep voltammetry (LSV) at varying temperatures from 25 to 75 °C. Scanning electron microscopy (SEM) and inductively coupled plasma–optical emission spectroscopy (ICP–OES) were used to examine the surface morphology and composition of the prepared catalysts. It was found that the prepared NiMn/Ti-1 catalyst in a plating bath containing a molar ratio of 1:1 Ni2+:Mn2+ and having the lowest Mn loading of 13.43 µg cm−2 exhibited quite reasonable activity for OER in Cl− ion rich SSW and ASW. To achieve the benchmark current density of 10 mA cm−2 in SSW and ASW, the NiMn/Ti-1 electrocatalyst requires overpotentials of 386 and 388 mV, respectively. In addition, this optimal bimetallic electrocatalyst also demonstrated superior long-run stability at 1.81 V (vs. RHE) and 10 mA cm−2 for 24 h in both working electrolytes. Impressively, the two-electrode electrolyzer—NiMn/Ti-5(−)||NiMn/Ti-1(+)—needs only 1.619 V to deliver 10 mA cm−2 current density for overall alkaline seawater electrolysis, which is even 0.075 V lower than the noble metal-based electrolyzer (Pt(−)||NiMn/Ti-1(+)).