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Research Article

Insights into the effect of substrate adsorption behavior over heme-like Fe1/AC single-atom catalyst

Jianglin Duan1,§, Yanan Zhou2,§, Yujing Ren1,§( ), Dan Feng3, Jinlong Shang1, Huibin Ge1, Jie Gao1, Jinlong Yang2( ), Yong Qin1,4( )
Interdisciplinary Research Center of Biology & Catalysis, School of Life Sciences, Northwestern Polytechnical University, Xi’an 710072, China
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Analytical & Testing Center, Northwestern Polytechnical University, Xi’an 710072, China
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

§ Jianglin Duan, Yanan Zhou, and Yujing Ren contributed equally to this work.

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Graphical Abstract

The effect of substrate adsorption behavior has been for the first time uncovered over M1/C single-atom catalysts (M1/C SACs), that is, for heme-like Fe1/activated carbon (AC)-n SAC, the more surface carboxyl/C quantity ratio, the more substrate molecular adsorption and the higher peroxidase-like activity.

Abstract

Unraveling the substrate adsorption structure–performance relationship is pivotal for heterogeneous carbon supported metal single-atom catalysts (M1/C SACs). However, due to the complexity of the functional groups on carbon material surface, it is still a great challenge. Herein, inspired by structure of enzymes, we used activated carbon (AC), which has adjustable surface oxygen functional groups (OFGs), supported atomically dispersed Fe-N4 sites as heme-like catalyst. And based on a combination of scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy, Fourier transform infrared (FT-IR) characterizations, kinetics experiments and density functional theory (DFT) calculations, we revealed the effect of substrate adsorption behavior on AC support surface, that is, with the increase of carboxyl group in OFGs, the adsorbed 3,3',5,5'-tetramethylbenzidine (TMB) molecular increased, and consequently the substrate enriched on AC surface. Such carboxyl group as well as Fe-N4 active sites synergistically realized high-efficiency peroxidase-like activity, just like the heme. This work suggests that simultaneously constructing metal single-atom active sites and specific functional groups on carbon support surface may open an avenue for engineering metal-support synergistic catalysis in M1/C SACs, which can further improve catalytic performance.

Keywords

single-atom catalystsheme-likecarboxyl groupsubstrate adsorption behaviorperoxidase-like activity

Electronic Supplementary Material

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Nano Research
Volume 15 Issue 7,
July 2022
Pages 5970-5976
DOI: 10.1007/s12274-022-4274-x
Cite this article:
Duan J, Zhou Y, Ren Y, et al. Insights into the effect of substrate adsorption behavior over heme-like Fe1/AC single-atom catalyst. Nano Research, 2022, 15(7): 5970-5976. https://doi.org/10.1007/s12274-022-4274-x
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Received: 28 December 2021
Revised: 16 February 2022
Accepted: 27 February 2022
Published: 04 May 2022
© Tsinghua University Press 2022
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