A Comprehensive Pyrolysis Mechanism of Binuclear Chromium-Based Complexes for Superior OER Activity

Abstract

Transition metal oxides are widely pursued as potent electrocatalysts for the oxygen evolution reaction (OER). However, single-metal chromium catalysts remain underexplored due to their intrinsic activity limitations. Herein, we successfully synthesize mixed-valence, nitrogen-doped Cr 2 O 3 /CrO 3 /CrN@NC nanoelectrocatalysts via one-step targeted pyrolysis techniques from a binuclear Cr-based complex (Cr 2 (Salophen) 2 (CH 3 OH) 2 ), which is strategically designed as a precursor. Comprehensive pyrolysis mechanisms were thoroughly delineated by using coupled thermogravimetric analysis and mass spectrometry (TG−MS) alongside X-ray diffraction. Below 800 °C, the generation of a reducing atmosphere was noted, while continuous pyrolysis at temperatures exceeding 800 °C promoted highly oxidized CrO 3 species with an elevated +6 oxidation state. The optimized catalyst pyrolyzed at 1000 °C (Cr 2 O 3 /CrO 3 /CrN@NCs-1000) demonstrated remarkable OER activity with a low overpotential of 290 mV in 1 M KOH and excellent stability. Further density functional theory (DFT) calculations revealed a much smaller reaction energy barrier of CrO 3 than the low oxidation state species for OER reactivity. This work reveals fresh strategies for rationally engineering chromium-based electrocatalysts and overcoming intrinsic roadblocks to enable efficient OER catalysis through a deliberate oxidation state and compositional tuning.