Insights into the effect of substrate adsorption behavior over heme-like Fe1/AC single-atom catalyst
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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.
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Insights into the effect of substrate adsorption behavior over heme-like Fe1/AC single-atom catalyst
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.
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Acknowledgements
The authors wish to acknowledge the support of National Natural Science Foundation of China (NSFC, Nos. 21802094, 22002118, 22172119, and 22102167), Postdoctoral Research Foundation of China (Nos. 2020TQ0245 and 2021M693060) and Natural Science Basic Research Plan in Shaanxi Province of China (No. 2021JM-047). We also thank the BL 14W beamline at the SSRF and MCD-A beamline at NSRL. The calculations were performed on the Supercomputing Center of the University of Science and Technology of China.
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