Low Pt Loading on Wolframite-Type NiWO4 to Excel the Electrocatalytic Water Splitting and Ammonia Oxidation Reaction

Hydrogen production via water-splitting or ammonia electrolysis using transition metal-based electrodes is one of the most cost-effective approaches. Herein, ca. 1-4% of Pt atoms are stuffed into a wolframite-type NiWO4 lattice to improve the electrocatalytic efficiency. The co-existence of atomically dilute quantities of Pt0 and PtIV atoms in the NiWO4 without altering the lattice structure is established via powder X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), core-level X-ray photoelectron spectroscopy, and other spectroscopic studies. While the undoped NiWO4 and a physical mixture of Pt0 (2 wt %) and NiWO4 exhibit poor oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and ammonia oxidation reaction (AOR) activities, 3-4% Pt-enriched NiWO4 depict improved electrocatalytic performances with at least 50 mV overpotential drop for both the OER and HER. The 3%Pt/NiWO4 electrode showcases a long-term (for 110 h) chronoamperometric/chronopotentiometric OER and HER performance, delivering high current at a low working potential. The bifunctional behavior of the material leads to the development of a water-splitting electrolyzer, 3%Pt/NiW/NF(-)/(+)3%Pt/NiW/NF, achieving >90% Faradaic efficiency for H2 production. The onset potential for the AOR is also cathodically shifted for 3%Pt/NiW and 4%Pt/NiW compared to the NiWO4 itself. Electrokinetic study through a rotating ring-disk electrode (RRDE) experiment and the Koutecký-Levich study provides an observed rate constant (kobs) of 1.68 × 10-3 cm s-1 of AOR with a 6e- count from the kinetic current region, highlighting [NO2]- as the major product. The electrolysis of 1 M NH3 using 4%Pt/NiW/NF as a working electrode produces predominantly [NO2]- (FE: 53%) and [NO3]- (FE: 30%). The improved electrocatalytic activity of 3-4% Pt-enriched NiWO4 can be due to the low Tafel slope and charge transfer resistance (Rct). Pt0 being electron-rich induces facile electronic conduction during electrocatalysis and enhances a better binding of the analytes such as H2O, [OH]-, and NH3. At the same time, the PtIV centers present adjacent to the NiII sites can polarize the electron density to stabilize NiIII species and enhance the possibility of OER and AOR. This study demonstrates the effect of hetero-metal doping to tune the electronic structure to improve the electrochemical activity. The low-Pt-doped NiWO4 material is presented here as a multimodal electrocatalyst that can efficiently electrolyze water or ammonia to produce hydrogen.