Bioinspired Ruthenium-Porphyrin Electrocatalysts with Atomic N<sub>4</sub>/N<sub>2</sub> Proximal Sites for Efficient Proton-Coupled Electron Transfer in Water Electrolysis.
basic_science · Level V
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- Record sourced from PubMed, PMID 40340420.
- Also identified by DOI 10.1021/acs.nanolett.5c01504.
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Abstract
Mimicking the proton-coupled electron transfer (PCET) pathways of natural enzymes, we engineer a porphyrin-based ruthenium coordination polymer (Ru-PCPN) with precisely positioned atomic-level N<sub>4</sub>/N<sub>2</sub> proximal sites through molecular-scale coordination engineering. This bioinspired architecture establishes a dual-site relay mechanism where the Ru-N<sub>2</sub> center accelerates water dissociation kinetics while the adjacent Ru-N<sub>4</sub> site optimizes hydrogen recombination. Experimental and theoretical results reveal that the sub-nanometer-proximate N<sub>4</sub>/N<sub>2</sub> sites function as proton donor-acceptor pairs, enabling directional proton transfer via PCET and synergistically enhancing water electrolysis. When integrated with carbon substrates, the Ru-PCPN@CB catalyst demonstrates exceptional hydrogen evolution performance in alkaline conditions, achieving a low overpotential at 10 mA cm<sup>-2</sup> (42 mV, comparable to 44 mV of Pt/C), high mass activity and TOF of 9.02 A mg<sup>-1</sup> and 4.73 s<sup>-1</sup> (∼7.0 and 3.6 times of Pt/C), and good stability. This work establishes atomic-scale coordination proximity as a new paradigm for breaking scaling relationships in multistep electrocatalysis.