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. 2019 Nov 1;5(11):eaax6976.
doi: 10.1126/sciadv.aax6976. eCollection 2019 Nov.

Cyclodextrin polymer networks decorated with subnanometer metal nanoparticles for high-performance low-temperature catalysis

Tiefan Huang  1 , Guan Sheng  2 , Priyanka Manchanda  1 , Abdul H Emwas  3 , Zhiping Lai  2 , Suzana Pereira Nunes  1 , Klaus-Viktor Peinemann  2
Affiliations

Cyclodextrin polymer networks decorated with subnanometer metal nanoparticles for high-performance low-temperature catalysis

Tiefan Huang et al. Sci Adv. .

Abstract

The synthesis of support materials with suitable coordination sites and confined structures for the controlled growth of ultrasmall metal nanoparticles is of great importance in heterogeneous catalysis. Here, by rational design of a cross-linked β-cyclodextrin polymer network (CPN), various metal nanoparticles (palladium, silver, platinum, gold, and rhodium) of subnanometer size (<1 nm) and narrow size distribution are formed via a mild and facile procedure. The presence of the metal coordination sites and the network structure are key to the successful synthesis and stabilization of the ultrasmall metal nanoparticles. The as-prepared CPN, loaded with palladium nanoparticles, is used as a heterogeneous catalyst and shows outstanding catalytic performance in the hydrogenation of nitro compounds and Suzuki-Miyaura coupling reaction under mild conditions. The CPN support works synergistically with the metal nanoparticles, achieving high catalytic activity and selectivity. In addition, the catalytic activity of the formed catalyst is controllable.

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Figures

Fig. 1
Fig. 1. CPN synthesized by a click reaction.
(A) Synthesis of the CPN from per-(6-azido-6-deoxy)-β-cyclodextrins with 1,4-diethynylbenzene. (B) TEM images of the CPN. Inset: Selected area electron diffraction of the dashed black square. (C) Scanning electron microscopy image of the CPN. (D) Photo of the as-prepared CPN powder (photo credit: Tiefan Huang, KAUST).
Fig. 2
Fig. 2. Synthesis and characterizations of PdNPs@CPN.
(A) Wet chemistry procedure of metal NPs@CPN synthesis. (B) SEM image. (C and D) TEM images at different magnifications. Inset: Selected area electron diffraction of the dashed black square. (E and F) HAADF-STEM images at different magnifications. Inset: Size distribution of PdNPs in PdNPs@CPN. (G) EDS of PdNPs@CPN. (H) EDS mapping of composition elements Pd, C, N, and O, respectively.
Fig. 3
Fig. 3. Morphology characterizations of various metal NPs@CPN.
HAADF-STEM images of (A) AgNPs@CPN, (B) PtNPs@CPN, (C) AuNPs@CPN, and (D) RhNPs@CPN.
Fig. 4
Fig. 4. Catalytic performance of PdNPs@CPN for 4-nitrophenol reduction.
(A) UV-Vis spectra of 0.1 mM 4-nitrophenol (4-NP) aqueous solution before and after addition of NaBH4. Time-dependent UV-Vis spectra of the reduction of 4-NP (0.1 mM) in NaBH4 (10 mM) aqueous solution catalyzed by (B) CPN, (C) Pd black, and (D) PdNPs@CPN. Inset: Optical images of reaction mixtures at 0 and 3 min. (E) Recyclability of the PdNPs@CPN for seven cycles of 4-NP reduction reactions. (F) Time-dependent UV-Vis spectra of the reduction of 4-NP (0.1 mM) catalyzed by PdNPs@CPN with the addition of 1-adamantane-carboxylate sodium salt (ACNa).
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