Paper
Dalton Transactions
SAs/NHCSs achieved a remarkable conversion of 99% with a Foundation of Anhui province (1908085QB45, 2008085QB81,
selectivity to aminobenzene of 99%, which was higher than and 2008085QA33) and the Education Department of Anhui
those of Fe NPs/NHCSs (ESI, Table S5†) and comparable to Province Foundation (KJ2019A0503). The calculations in this
those of the reported catalysts (ESI, Table S6†). The kinetic paper have been done using the supercomputing system of the
analysis indicated that the hydrogenation of nitrobenzene over National Supercomputing Center in Changsha. The authors
Fe SAs/NHCSs obeyed the first order kinetics (ESI, Fig. S14†). thank BL1W1B in the Beijing Synchrotron Radiation Facility
Fig. 6b shows the stability of the Fe SAs/NHCSs for the catalytic (BSRF) for help with characterization.
hydrogenation of nitrobenzene. Both the conversion and the
selectivity of Fe SAs/NHCSs exhibited negligible decay after 5
cycles, demonstrating high stability. The Fe SAs/NHCSs after
the stability test were characterized by HRTEM, elemental
Notes and references
mapping, XRD and XPS (ESI, Fig. S15–17†). All results demon-
strated the absence of Fe nanoparticles or clusters, which indi-
cated that the Fe single atoms in Fe SAs/NHCSs hardly aggre-
gated during the reusability tests. Consequently, Fe SAs/
NHCSs served as robust catalysts for the highly efficient hydro-
genation of nitrobenzene to aniline. Moreover, we performed
the hydrogenation of nitroaromatic compounds with different
substituents to study the hydrogenation scope of Fe SAs/
NHCSs (Fig. 6c), and found that the Fe SAs/NHCS catalyst exhi-
bits high activity and selectivity in the hydrogenation of all of
the investigated nitroarenes. The results further confirm the
high catalytic performance of the as-obtained Fe SAs/NHCS
catalyst.
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Conclusions
In this study, DFT calculations were used to predict the cata-
lytic activity of the Fe SA catalyst in the hydrogenation of nitro-
benzene to aniline. The results revealed that the isolated Fe
atom on the support can weaken the adsorption of nitro-
benzene on the catalyst surface, thus ensuring the appropriate
adsorption energy of the reactants on the surface of the cata-
lysts needed for an efficient catalytic process. Moreover, com-
pared with the Fe NP catalyst, the activation barriers for the
hydrogenation reaction on the Fe SA catalyst were much lower,
which significantly increased the reaction rate. To validate the
theory, Fe SAs/NHCSs were synthesized and the catalytic per-
formance for the hydrogenation of nitrobenzene was per-
formed. The experimental results were in good agreement with
the theoretical calculations, since Fe SAs/NHCSs achieved a
conversion of 99% with a selectivity of 99%, performance
exceeding that of the Fe NPs/NHCSs. Our finding provides a
new insight for the rational design of catalytic systems at the
atomic level.
Conflicts of interest
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Y. Q. Lin, J. J. Mao and L. Q. Mao, Nat. Commun., 2020, 11,
3188.
The authors declare no conflict of interest.
17 J. J. Mao, J. S. Yin, J. J. Pei, D. S. Wang and Y. D. Li, Nano
Today, 2020, 34, 100917.
18 W. J. Wu, Y. Liu, D. Liu, W. X. Chen, Z. Y. Song,
X. M. Wang, Y. M. Zheng, N. Lu, C. X. Wang, J. J. Mao and
Y. D. Li, Nano Res., 2021, 14, 998–1003.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21971002), the Natural Science
8000 | Dalton Trans., 2021, 50, 7995–8001
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