Pinning Effect of Lattice Pb Suppressing Lattice Oxygen Reactivity of Pb-RuO Enables Stable Industrial-level Electrolysis

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Nov 12

PMID 39532833

Authors

Chenhui Zhou

Lu Li

Zhaoqi Dong

Fan Lv

Hongyu Guo

Kai Wang

Menggang Li

Zhengyi Qian

Na Ye

Zheng Lin

Mingchuan Luo

Shaojun Guo

Affiliations

Soon will be listed here.

Abstract

Ruthenium (Ru) is widely recognized as a low-cost alternative to iridium as anode electrocatalyst in proton-exchange membrane water electrolyzers (PEMWE). However, the reported Ru-based catalysts usually only operate within tens of hours in PEMWE because of their intrinsically high reactivity of lattice oxygen that leads to irrepressible Ru leaching and structural collapse. Herein, we report a design concept by employing large-sized and acid-resistant lattice lead (Pb) as a second element to induce a pinning effect for effectively narrowing the moving channels of oxygen atoms, thereby lowering the reactivity of lattice oxygen in Ru oxides. The Pb-RuO catalyst presents a low overpotential of 188 ± 2 mV at 10 mA cm and can sustain for over 1100 h in an acid medium with a negligible degradation rate of 19 μV h. Particularly, the Pb-RuO-based PEMWE can operate for more than 250 h at 500 mA cm with a low degradation rate of only 17 μV h. Experimental and theoretical calculation results reveal that Ru-O covalency is reduced due to the unique 6s-2p-4d orbital hybridization, which increases the loss energy of lattice oxygen and suppresses the over-oxidation of Ru for improved long-term stability in PEMWE.

Citing Articles

Significantly Enhanced Acidic Oxygen Evolution Reaction Performance of RuO Nanoparticles by Introducing Oxygen Vacancy with Polytetrafluoroethylene.

Zhang J, Wang X, Zhao X, Chen H, Jia P Polymers (Basel). 2025; 17(1.

PMID: 39795462 PMC: 11723143. DOI: 10.3390/polym17010059.

References

Xu Y, Mao Z, Zhang J, Ji J, Zou Y, Dong M . Strain-modulated Ru-O Covalency in Ru-Sn Oxide Enabling Efficient and Stable Water Oxidation in Acidic Solution. Angew Chem Int Ed Engl. 2024; 63(8):e202316029. DOI: 10.1002/anie.202316029. View

Chen X, Wang X, Le J, Li S, Wang X, Zhang Y . Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction. Nat Commun. 2023; 14(1):5289. PMC: 10468501. DOI: 10.1038/s41467-023-41030-1. View

Hao S, Liu M, Pan J, Liu X, Tan X, Xu N . Dopants fixation of Ruthenium for boosting acidic oxygen evolution stability and activity. Nat Commun. 2020; 11(1):5368. PMC: 7584605. DOI: 10.1038/s41467-020-19212-y. View

Ping X, Liu Y, Zheng L, Song Y, Guo L, Chen S . Locking the lattice oxygen in RuO to stabilize highly active Ru sites in acidic water oxidation. Nat Commun. 2024; 15(1):2501. PMC: 10954744. DOI: 10.1038/s41467-024-46815-6. View

Xu J, Jin H, Lu T, Li J, Liu Y, Davey K . IrO·HO with lattice water-assisted oxygen exchange for high-performance proton exchange membrane water electrolyzers. Sci Adv. 2023; 9(25):eadh1718. PMC: 10289644. DOI: 10.1126/sciadv.adh1718. View

Su H, Yang C, Liu M, Zhang X, Zhou W, Zhang Y . Tensile straining of iridium sites in manganese oxides for proton-exchange membrane water electrolysers. Nat Commun. 2024; 15(1):95. PMC: 10762142. DOI: 10.1038/s41467-023-44483-6. View

Hao S, Sheng H, Liu M, Huang J, Zheng G, Zhang F . Torsion strained iridium oxide for efficient acidic water oxidation in proton exchange membrane electrolyzers. Nat Nanotechnol. 2021; 16(12):1371-1377. DOI: 10.1038/s41565-021-00986-1. View

Zhang G, Qu Z, Tao W, Wang X, Wu L, Wu S . Porous Flow Field for Next-Generation Proton Exchange Membrane Fuel Cells: Materials, Characterization, Design, and Challenges. Chem Rev. 2022; 123(3):989-1039. DOI: 10.1021/acs.chemrev.2c00539. View

Shi Z, Li J, Wang Y, Liu S, Zhu J, Yang J . Customized reaction route for ruthenium oxide towards stabilized water oxidation in high-performance PEM electrolyzers. Nat Commun. 2023; 14(1):843. PMC: 9932065. DOI: 10.1038/s41467-023-36380-9. View

10.

Seitz L, Dickens C, Nishio K, Hikita Y, Montoya J, Doyle A . A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science. 2016; 353(6303):1011-1014. DOI: 10.1126/science.aaf5050. View

11.

Chen H, Ze H, Yue M, Wei D, A Y, Wu Y . Unmasking the Critical Role of the Ordering Degree of Bimetallic Nanocatalysts on Oxygen Reduction Reaction by In Situ Raman Spectroscopy. Angew Chem Int Ed Engl. 2022; 61(16):e202117834. DOI: 10.1002/anie.202117834. View

12.

Lin Y, Dong Y, Wang X, Chen L . Electrocatalysts for the Oxygen Evolution Reaction in Acidic Media. Adv Mater. 2022; 35(22):e2210565. DOI: 10.1002/adma.202210565. View

13.

Shi Z, Zhang X, Lin X, Liu G, Ling C, Xi S . Phase-dependent growth of Pt on MoS for highly efficient H evolution. Nature. 2023; 621(7978):300-305. DOI: 10.1038/s41586-023-06339-3. View

14.

Liu R, Xu Z, Li F, Chen F, Yu J, Yan Y . Recent advances in proton exchange membrane water electrolysis. Chem Soc Rev. 2023; 52(16):5652-5683. DOI: 10.1039/d2cs00681b. View

15.

Ye X, Zhao J, Das H, Sheptyakov D, Yang J, Sakai Y . Observation of novel charge ordering and spin reorientation in perovskite oxide PbFeO. Nat Commun. 2021; 12(1):1917. PMC: 7997894. DOI: 10.1038/s41467-021-22064-9. View

16.

Li L, Zhang G, Zhou C, Lv F, Tan Y, Han Y . Lanthanide-regulating Ru-O covalency optimizes acidic oxygen evolution electrocatalysis. Nat Commun. 2024; 15(1):4974. PMC: 11166638. DOI: 10.1038/s41467-024-49281-2. View

17.

Chong L, Gao G, Wen J, Li H, Xu H, Green Z . La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis. Science. 2023; 380(6645):609-616. DOI: 10.1126/science.ade1499. View

18.

Wu Z, Chen F, Li B, Yu S, Finfrock Y, Meira D . Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis. Nat Mater. 2022; 22(1):100-108. DOI: 10.1038/s41563-022-01380-5. View

19.

Zhou C, Shi J, Dong Z, Zeng L, Chen Y, Han Y . Oxophilic gallium single atoms bridged ruthenium clusters for practical anion-exchange membrane electrolyzer. Nat Commun. 2024; 15(1):6741. PMC: 11306551. DOI: 10.1038/s41467-024-51200-4. View

20.

Zhou L, Shao Y, Yin F, Li J, Kang F, Lv R . Stabilizing non-iridium active sites by non-stoichiometric oxide for acidic water oxidation at high current density. Nat Commun. 2023; 14(1):7644. PMC: 10667250. DOI: 10.1038/s41467-023-43466-x. View