Selective CO2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer

• Published in: Nature energy Vol. 5; no. 12; pp. 1032 - 1042
• Main Authors: Kim, Dohyung, Yu, Sunmoon, Zheng, Fan, Roh, Inwhan, Li, Yifan, Louisia, Sheena, Qi, Zhiyuan, Somorjai, Gabor A., Frei, Heinz, Wang, Lin-Wang, Yang, Peidong
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01-12-2020; Nature Publishing Group
• Subjects: 639/301/299/886; 639/301/357/354; 639/4077/909/4101/4102; Carbon dioxide; Catalysis; Catalysts; Cations; Configurations; Economics and Management; Electrocatalysis; Energy; Energy Policy; Energy Storage; Energy Systems; Enzymes; Interlayers; Ligands; Metal surfaces; Metals; Nanoparticles; Renewable and Green Energy; Selectivity
• ISSN: 2058-7546; 2058-7546
• DOI: 10.1038/s41560-020-00730-4

Enzymes feature the concerted operation of multiple components around an active site, leading to exquisite catalytic specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. Here, we report a nanoparticle/ordered-ligand interlayer that contains a multi-component catalytic pocket for high-specificity CO
2
electrocatalysis. The nanoparticle/ordered-ligand interlayer comprises a metal nanoparticle surface and a detached layer of ligands in its vicinity. This interlayer possesses unique pseudocapacitive characteristics where desolvated cations are intercalated, creating an active-site configuration that enhances catalytic turnover by two orders and one order of magnitude against a pristine metal surface and nanoparticle with tethered ligands, respectively. The nanoparticle/ordered-ligand interlayer is demonstrated across several metals with up to 99% CO selectivity at marginal overpotentials and onset overpotentials of as low as 27 mV, in aqueous conditions. Furthermore, in a gas-diffusion environment with neutral media, the nanoparticle/ordered-ligand interlayer achieves nearly unit CO selectivity at high current densities (98.1% at 400 mA cm
−2
).
The complex, multi-component environments found in enzymes induce high catalytic specificity, but are difficult to achieve in synthetic catalysts. Now, researchers report a catalyst comprising a dynamic, ordered layer of ligands above a nanoparticle surface that creates a pocket to facilitate CO
2
electroreduction.