Constructing vacancy-rich metal phosphates by the spatial effect of ionic oligomers for enhanced OER activity
- 12 April 2024
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of Materials Chemistry A
- Vol. 12 (20) , 12077-12087
Abstract
The Oxygen Evolution Reaction (OER) is a critical half-reaction in green energy devices and has become a bottleneck in improving energy conversion efficiency. Introducing vacancies in electrocatalysts is recognized as a promising method to improve their OER reactivity. However, the production of catalysts through the ion-by-ion nucleation pathway limits the generation of vacancies due to the closely-packed ionic structure. Here, we developed nickel–cobalt phosphate (NiCoPi) oligomers with an average size of 1–2 nm, which were used as building blocks for the NiCoPi catalyst. The oligomer-by-oligomer crosslinking process has a spatial effect, which could introduce more sub-nano-sized gaps between oligomer blocks. These gaps acted as the vacancies in the solid phase of NiCoPi, where the exposed oxygen largely improved the OER activity of NiCoPi (with a low overpotential of 254 mV at 10 mA cm−1 and a small Tafel slope of 45.75 mV dec−1) through lattice oxygen-mediated (LOM) reaction pathways, and this reactivity was superior to those of all the reported NiCoPi catalysts. The oligomer building blocks were extendable to more bimetallic transition metal phosphates (e.g. Ni–Fe phosphate, Co–Fe phosphate, etc.) for vacancy manufacturing in solid catalysts, and their performances exceeded those of all the analogous phosphate catalysts. This work developed an alternative way to build high performance electrocatalysts by rationally introducing vacancies. Moreover, it presented the important role of ionic oligomers in the regulation of solid structures at sub-nano-sizes.Keywords
Funding Information
- Fundamental Research Funds for the Central Universities (2022ZJJH02-01)
- National Natural Science Foundation of China (22275161)
- National Key Research and Development Program of China (2020YFA0710400)
This publication has 57 references indexed in Scilit:
- Coupling Adsorbed Evolution and Lattice Oxygen Mechanism in Fe‐Co(OH)2/Fe2O3 Heterostructure for Enhanced Electrochemical Water OxidationAdvanced Functional Materials, 2023
- Inorganic ionic polymerization: From biomineralization to materials manufacturingNano Research, 2023
- Operando deciphering the activity origins for potential-induced reconstructed oxygen-evolving catalystsApplied Catalysis B: Environment and Energy, 2022
- Electrochemical Reduction of Carbon Dioxide and Iron Oxide in Molten Salts to Fe/Fe3C Modified Carbon for Electrocatalytic Oxygen EvolutionAngewandte Chemie International Edition, 2020
- Scaled‐Up Synthesis of Amorphous NiFeMo Oxides and Their Rapid Surface Reconstruction for Superior Oxygen Evolution CatalysisAngewandte Chemie International Edition, 2019
- Enhanced activity and stability of La-doped CeO2 monolithic catalysts for lean-oxygen methane combustionEnvironmental Science and Pollution Research, 2017
- The Development of Functional Mesocrystals for Energy Harvesting, Storage, and ConversionChemistry – A European Journal, 2017
- A facile approach for the preparation of biomorphic CuO–ZrO2 catalyst for catalytic combustion of methaneApplied Catalysis A: General, 2012
- Oxygen activation on Cu/Mn–Ce mixed oxides and the role in diesel soot oxidationCatalysis Today, 2008
- Screening of amorphous metal–phosphate catalysts for the oxidative dehydrogenation of ethylbenzene to styreneApplied Catalysis B: Environment and Energy, 2007