3D Ni and Co redox-active metal-organic frameworks based on ferrocenyl diphosphinate and 4,4′-bipyridine ligands as efficient electrocatalysts for the hydrogen evolution reaction

Khrizanforova V, Shekurov R, Miluykov V, Khrizanforov M, Bon V, Kaskel S, Gubaidullin A, Sinyashin O, Budnikova Y (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Dalton Transactions Royal Society of Chemistry

Book Volume: 49

Pages Range: 2794-2802

Journal Issue: 9

DOI: 10.1039/c9dt04834k

Abstract

New 3D Ni and Co redox-active metal-organic frameworks based on ferrocenyl diphosphinate and 4,4′-bipyridine ligands have been synthesized, characterized by single crystal X-ray diffraction and spectroscopic techniques and explored as stable electrocatalysts capable of meeting two important parameters: the overpotential and Tafel slope (TS) in the hydrogen evolution reaction (HER). The electrochemical studies suggest that the reaction kinetics of a Ni-MOF (1) catalyst is more favorable than that of a Co-MOF (2) catalyst. Particularly, Ni-MOF exhibits better HER performance with an overpotential of 350 mV at a current density of 10 mA cm^-2, a small TS of 60 mV dec^-1 and superior long-term durability (of up to 10 000 cycles), ranking it among the most active non-noble metal-based molecular electrocatalysts. The introduction of a 4,4′-bpy linker in 2 significantly changes the catalytic properties in an organic or aqueous environment compared to 1D cobalt polymers based on ferrocenyl diphosphinate. For Co-MOF 2, there is a significant decrease in the overvoltage by ∼440 mV in comparison with the 1D Co polymer in an organic medium and by 50 mV in an aqueous medium. The TS changes from 120 to 65 mV dec^-1 when moving from 1D CofcdHp to a 3D structure of 2. Thus, a 4,4′-bpy linker reduces the overvoltage and gives more favorable HER kinetics (lower TS). These results provide important guidelines for the rational design of non-precious metal electrocatalysts.

Involved external institutions

Russian Academy of Sciences / Росси́йская акаде́мия нау́к (RAS)

Russian Federation (RU) Technische Universität Dresden

Germany (DE)

How to cite

APA:

Khrizanforova, V., Shekurov, R., Miluykov, V., Khrizanforov, M., Bon, V., Kaskel, S.,... Budnikova, Y. (2020). 3D Ni and Co redox-active metal-organic frameworks based on ferrocenyl diphosphinate and 4,4′-bipyridine ligands as efficient electrocatalysts for the hydrogen evolution reaction. Dalton Transactions, 49(9), 2794-2802. https://doi.org/10.1039/c9dt04834k

MLA:

Khrizanforova, Vera, et al. "3D Ni and Co redox-active metal-organic frameworks based on ferrocenyl diphosphinate and 4,4′-bipyridine ligands as efficient electrocatalysts for the hydrogen evolution reaction." Dalton Transactions 49.9 (2020): 2794-2802.

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