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Restructuring Metal–Organic Frameworks to Nanoscale Bismuth Electrocatalysts for Highly Active and Selective CO2 Reduction to Formate

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Recently, a large number of nanostructured metal-containing materials have been developed for the electrochemical CO2 reduction reaction (eCO2RR). However, it remains a challenge to achieve high activity and selectivity with respect to the metal load due to the limited concentration of surface metal atoms. Here, it is reported that the bismuth-based metal–organic framework Bi(1,3,5-tris(4-carboxyphenyl)benzene), herein denoted Bi(btb), works as a precatalyst and undergoes a structural rearrangement at reducing potentials to form highly active and selective catalytic Bi-based nanoparticles dispersed in a porous organic matrix. The structural change is investigated by electron microscopy, X-ray diffraction, total scattering, and spectroscopic techniques. Due to the periodic arrangement of Bi cations in highly porous Bi(btb), the in situ formed Bi nanoparticles are well-dispersed and hence highly exposed for surface catalytic reactions. As a result, high selectivity over a broad potential range in the eCO2RR toward formate production with a Faradaic efficiency up to 95(3)% is achieved. Moreover, a large current density with respect to the Bi load, i.e., a mass activity, up to 261(13) A g−1 is achieved, thereby outperforming most other nanostructured Bi materials.

Original languageEnglish
Article number1910408
JournalAdvanced Functional Materials
Number of pages11
Publication statusPublished - Apr 2020

    Research areas

  • bismuth electrocatalysts, electrocatalysis, formate production, metal–organic frameworks, selective CO reduction

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