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Updated: Jun 25, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
A Comprehensive Pyrolysis Mechanism of Binuclear Chromium-Based Complexes for Superior OER Activity
Meixing Gan1, Li Li1, Xixian Yang1
1Collaborative Innovation Center for Advanced Organic Chemical Materials Co-constructed by the Province and Ministry, College of Chemistry & Chemical Engineering, Research Institute of Qianjiang Industry Technology, Hubei University, No. 368 Youyi Avenue, Wuhan 430062, P. R. China.
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 Cr2O3/CrO3/CrN@NC nanoelectrocatalysts via one-step targeted pyrolysis techniques from a binuclear Cr-based complex (Cr2(Salophen)2(CH3OH)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 CrO3 species with an elevated +6 oxidation state. The optimized catalyst pyrolyzed at 1000 °C (Cr2O3/CrO3/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 CrO3 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.
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