Nanoparticle Assembly Induced Ligand Interactions for Enhanced Electrocatalytic CO2 Conversion

Yu, Sunmoon; Kim, Dohyung; Qi, Zhiyuan; Louisia, Sheena; Li, Yifan; Somorjai, Gabor A.; Yang, Peidong

doi:10.1021/jacs.1c09777

Nanoparticle Assembly Induced Ligand Interactions for Enhanced Electrocatalytic CO₂ Conversion

Journal Article · Tue Nov 16 00:00:00 EST 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c09777· OSTI ID:1833365

^[1]; ^[1]; ^[2]; Louisia, Sheena ^[1]; ^[1]; ^[1]; ^[3]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

The microenvironment in which the catalysts are situated is as important as the active sites in determining the overall catalytic performance. Recently, it has been found that nanoparticle (NP) surface ligands can actively participate in creating a favorable catalytic microenvironment, as part of the nanoparticle/ordered-ligand interlayer (NOLI), for selective CO₂ conversion. However, much of the ligand–ligand interactions presumed essential to the formation of such a catalytic interlayer remains to be understood. In this study, by varying the initial size of NPs and utilizing spectroscopic and electrochemical techniques, we show that the assembly of NPs leads to the necessary ligand interactions for the NOLI formation. The large surface curvature of small NPs promotes strong noncovalent interactions between ligands of adjacent NPs through ligand interdigitation. This ensures their collective behavior in electrochemical conditions and gives rise to the structurally ordered ligand layer of the NOLI. Thus, the use of smaller NPs was shown to result in a greater catalytically effective NOLI area associated with desolvated cations and electrostatic stabilization of intermediates, leading to the enhancement of intrinsic CO₂-to-CO turnover. Our findings highlight the potential use of tailored microenvironments for NP catalysis by controlling its surface ligand interactions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1833365

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 47 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Nanoparticle Assembly Induced Ligand Interactions for Enhanced Electrocatalytic CO2 Conversion

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Nanoparticle Assembly Induced Ligand Interactions for Enhanced Electrocatalytic CO₂ Conversion