Strain enhances the activity of molecular electrocatalysts via carbon nanotube supports

Su, Jianjun; Musgrave, Charles B.; Song, Yun; Huang, Libei; Liu, Yong; Li, Geng; Xin, Yinger; Xiong, Pei; Li, Molly Meng-Jung; Wu, Haoran; Zhu, Minghui; Chen, Hao Ming; Zhang, Jianyu; Shen, Hanchen; Tang, Ben Zhong; Robert, Marc; Goddard, William A.; Ye, Ruquan

doi:10.1038/s41929-023-01005-3

Strain enhances the activity of molecular electrocatalysts via carbon nanotube supports

Journal Article · Mon Aug 14 04:00:00 EDT 2023 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-023-01005-3· OSTI ID:2421863

Su, Jianjun ^[1]; Musgrave, Charles B.; Song, Yun; Huang, Libei; Liu, Yong; Li, Geng; Xin, Yinger; Xiong, Pei; ; Wu, Haoran; ; ; ; Shen, Hanchen; Tang, Ben Zhong; ; ;

OSTI

Abstract

Support-induced strain engineering is useful for modulating the properties of two-dimensional materials. However, controlling strain of planar molecules is technically challenging due to their sub-2 nm lateral size. Additionally, the effect of strain on molecular properties remains poorly understood. Here we show that carbon nanotubes (CNTs) are ideal substrates for inducing optimum properties through molecular curvature. In a tandem-flow electrolyser with monodispersed cobalt phthalocyanine (CoPc) on single-walled CNTs (CoPc/SWCNTs) for CO₂reduction, we achieve a methanol partial current density of >90 mA cm⁻²with >60% selectivity, surpassing wide multiwalled CNTs at 16.6%. We report vibronic and X-ray spectroscopies to unravel the distinct local geometries and electronic structures induced by the strong molecule–support interactions. Grand canonical density functional theory confirms that curved CoPc/SWCNTs improve *CO binding to enable subsequent reduction, whereas wide multiwalled CNTs favour CO desorption. Our results show the important role of SWCNTs beyond catalyst dispersion and electron conduction.

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: SC0021266

OSTI ID:: 2421863

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 9 Vol. 6; ISSN 2520-1158

Publisher:: Springer Nature

Country of Publication:: United States

Language:: English

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