10.1002/ange.202007297
Angewandte Chemie
COMMUNICATION
phenanthrenylmethylene)benzenamine, using PdCu@HCS as
the catalyst (Figure 5a). In the first step, the nitrobenzene can
quickly diffuse into the void space of PdCu@HCS (as inferred
from hydrogenation of styrene and phenylacetylene, Figure 3b,
4a), and convert into aniline through a reductive process. The
formed aniline will then condense with the phenanthrene-9-
carboxaldehyde outside of the hollow nanoreactor to generate the
target imine (experiment indicates that the condensation reaction
can proceed without catalysts). In fact, the molecular size of
phenanthrene-9-carboxaldehyde is similar to the molecules of 9-
vinylanthracene and 9-ethynylphenanthrene, which cannot
diffuse through the carbon shells of PdCu@HCS. Therefore, it
can be expected that the over-reduction of the target imine to
amine can be avoided through the molecular-sieving effect. As
shown in Figure 5b, the conversion of nitrobenzene over the
PdCu@HCS reached 100% after reaction for 3 h, and imine
selectivity was indeed higher than 99% (Figure S16). In contrast,
the imine was completely converted into amine when using
PdCu/HCS as the catalyst (Figure S17). These results indicate
that the specific imines as well as other organic compounds can
be efficiently and selectively produced by utilizing the unique
features of the hollow nanoreactors.
Keywords: heterogeneous catalysis • hollow nanoreactors •
void-confinement effects • shape-selective catalysis •
hydrogenation
[1]
a) H. Z. Yang, X. Wang, Adv. Mater. 2019, 31, 1800743; b) F. Schüth,
Chem. Mater. 2014, 26, 423-434; c) Z. G. Teng, W. Li, Y. X. Tang, A.
Elzatahry, G. M. Lu, D. Y. Zhao, Adv. Mater. 2019, 31, 1707612; d) L. S.
Lin, J. Song, H. H. Yang, X. Chen, Adv. Mater. 2018, 30, 1704639; e) X.
J. Wang, J. Feng, Y. C. Bai, Q. Zhang, Y. D. Yin, Chem. Rev. 2016, 116,
10983-11060; f) Y. S. Li, J. L. Shi, Adv. Mater. 2014, 26, 3176-3205; g)
H. Tian, J. Liang, J. Liu, Adv. Mater. 2019, 31, 1903886; h) T. N. Gao, T.
Wang, W. Wu, Y. L. Liu, Q. S. Huo, Z. A. Qiao, S. Dai, Adv. Mater. 2019,
31, 1806254; i) R. Bi, N. Xu, H. Ren, N. Yang, Y. Sun, A. Cao, R. Yu, D.
Wang, Angew. Chem. Int. Ed. 2020, 59, 4865-4868.
[2]
a) B. W. Li, H. C. Zeng, Adv. Mater. 2019, 31, 1801104; b) W. Zhu, Z.
Chen, Y. Pan, R. Dai, Y. Wu, Z. Zhuang, D. Wang, Q. Peng, C. Chen, Y.
Li, Adv. Mater. 2018, 31, 1800426; c) Z. A. Qiao, P. F. Zhang, S. H. Chai,
M. F. Chi, G. M. Veith, N. C. Gallego, M. Kidder, S. Dai, J. Am. Chem.
Soc. 2014, 136, 11260-11263; d) H. B. Zou, J. Y. Dai, R. W. Wang, Chem.
Commun. 2019, 55, 5898-5901; e) W. Liu, J. Huang, Q. Yang, S. Wang,
X. Sun, W. Zhang, J. Liu, F. Huo, Angew. Chem. Int. Ed. 2017, 56, 5512-
5516; f) D. Yao, Y. Wang, Y. Li, Y. Zhao, J. Lv, X. Ma, ACS Catal. 2018,
8, 1218-1226; g) J. Yang, F. Zhang, H. Lu, X. Hong, H. Jiang, Y. Wu, Y.
Li, Angew. Chem. Int. Ed. 2015, 54, 10889-10893; h) Y. Kuwahara, H.
Kango, H. Yamashita, ACS Catal. 2019, 12, 1993-2006; i) N. Wang, G.
Cheng, L. P. Guo, B. E. Tan, S. B. Jin, Adv. Funct. Mater. 2019, 29,
1904781; j) S. S. Ma, P. P. Su, W. J. Huang, S. Jiang, S. Y. Bai, J. Liu,
ChemCatChem 2019, 11, 6092-6098; k) J. Sheng, J. Kang, H. Ye, J. Xie,
B. Zhao, X. -Z. Fu, Y. Yu, R. Sun, C. -P. Wong, J. Mater. Chem. A 2018,
6, 3906-3912; l) H. R. Chen, K. Shen, Q. Mao, J. Y. Chen, Y. W. Li, ACS
Catal. 2018, 8, 1417-1426; m) K. Li, J. Wei, H. Yu, P. Xu, J. Wang, H.
Yin, M. A. Cohen Stuart, J. Wang, S. Zhou, Angew. Chem. Int. Ed. 2018,
57, 16458-16463; n) C. Galeano, J. C. Meier, M. Soorholtz, H. Bongard,
C. Baldizzone, K. J. J. Mayrhofer, F. Schüth, ACS Catal. 2014, 4, 3856-
3868; o) D. Yao, Y. Wang, K. Hassan-Legault, A. Li, Y. Zhao, J. Lv, S.
Huang, X. Ma, ACS Catal. 2019, 9, 2969-2976; p) R. P. Ye, X. Y. Wang,
C. A. H. Price, X. Y. Liu, Q. H. Yang, M. Jaroniec, J. Liu, Small 2020,
1906250; q) Q. Yang, C. C. Yang, C. H. Lin, H. L. Jiang, Angew. Chem.
Int. Ed. 2019, 58, 3511-3515; r) Q. Xia, Z. Lin, W. Lai, Y. Wang, C. Ma,
Z. Yan, Q. Gu, W. Wei, J. Z. Wang, Z. Zhang, H. K. Liu, S. X. Dou, S. L.
Chou, Angew. Chem. Int. Ed. 2019, 58, 14125-14128.
In conclusion, we have developed a general strategy to
synthesize a pair of hollow nanoreactors (PdCu@HCS and
PdCu/HCS). Based on the two comparative nanoreactors, the
void-confinement effects of hollow nanoreactors in liquid-phase
hydrogenation have been extensively investigated in the two-
chamber reactor. It has found that the PdCu@HCS can
accelerate the hydrogenation of styrene via an accumulation of
reactant molecules, decelerate the hydrogenation of 2-
vinylnaphthalene due to the mass transfer limitation and inhibit
the hydrogenation of 9-vinylanthracene because of the molecular-
sieving effect, respectively. In addition, the void space of the
PdCu@HCS can alter the hydrodynamics of the intermediate, and
correspondingly change the catalytic selectivity during
hydrogenation of small alkynes. Moreover, a specific imine has
been selectively produced over the PdCu@HCS by utilizing the
shape-selective catalysis principle. These studies provide
straightforward examples for clearly understanding and
estimating the void-confinement effects of the hollow
nanoreactors. It is expected that the synthesis strategy can be
extended to other metal systems, and meanwhile the HCS
structures (diameters, shell thicknesses and porous structures) as
well as the loading amount of metal nanoparticles can be tailored
by fine-tune synthetic parameters. Therefore, various pairs of
hollow nanoreactors can be designed and employed as ideal
models for study of catalytic mechanisms in various reactions,
and then guiding the design of efficient catalysts for specific
chemical transformations and the development of nanoreactor
reaction engineering.
[3]
[4]
J. Lee, S. M. Kim, I. S. Lee, Nano Today 2014, 9, 631-667.
H. Tian, X. Liu, L. Dong, X. Ren, H. Liu, C. A. H. Price, Y. Li, G. Wang,
Q. Yang, J. Liu, Adv. Sci. 2019, 6, 1900807.
[5]
[6]
G. Prieto, H. Tuysuz, N. Duyckaerts, J. Knossalla, G.-H. Wang, F. Schüth,
Chem. Rev. 2016, 116, 14056-14119.
a) K. Jiang, P. Wang, S. Guo, X. Zhang, X. Shen, G. Lu, D. Su, X. Huang,
Angew. Chem. Int. Ed. 2016, 55, 9030-9035; b) K. H. Park, Y. W. Lee, S.
W. Kang, S. W. Han, Chem. Asian J. 2011, 6, 1515-1519.
[7]
a) G.-H. Wang, K. Chen, J. Engelhardt, H. Tüysüz, H. -J. Bongard, W.
Schmidt, F. Schüth, Chem. Mater. 2018, 30, 2483-2487.b) G.-H. Wang,
J. Hilgert, F. H. Richter, F. Wang, H. -J. Bongard, B. Spliethoff, C.
Weidenthaler, F. Schuth, Nat. Mater. 2014, 13, 294-301.
[8]
[9]
Z. W. Guo, X. W. Kang, X. S. Zheng, J. Huang, S. W. Chen, J. Catal.
2019, 374, 101-109.
a) R. Roa, W. K. Kim, M. Kanduč, J. Dzubiella, S. Angioletti-Uberti, ACS
Catal. 2017, 7, 5604-5611; b) S. Angioletti-Uberti, Y. Lu, M. Ballauff, J.
Dzubiella, J. Phys. Chem. C 2015, 119, 15723-15730; c) S. Wu, J.
Dzubiella, J. Kaiser, M. Drechsler, X. Guo, M. Ballauff, Yan Lu, Angew.
Chem. Int. Ed. 2012, 51, 2229-2233.
Acknowledgements
[10] a) Y. Shiraishi, M. Ikeda, D. Tsukamoto, S. Tanaka, T. Hirai, Chem.
Commun. 2011, 47, 4811-4813; b) Z. Li, R. Yu, J. Huang, Y. Shi, D.
Zhang, X. Zhong, D. Wang, Y. Wu, Y. Li, Nat. Commun. 2015, 6, 8248;
c) S. Zavahir, H. Zhu, Molecules 2015, 20, 1941-1954.
This work was supported by the National Natural Science
Foundation of China (21872159), QIBEBT (QIBEBT
ZZBS201802) and the DNL Cooperation Fund, CAS
(DNL180402). The authors would like to thank Cameron Price for
proof reading. The authors are grateful to Prof. Can Li and Prof.
Qihua Yang for fruitful discussions.
5
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