Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions

doi:10.1016/S1872-2067(21)63968-2

Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (4): 1058-1065.DOI: 10.1016/S1872-2067(21)63968-2

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Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions

Hehe Wei^a^,^d^,^†, Xiaoyang Li^b^,^†, Bohan Deng^a^,^†, Jialiang Lang^a, Ya Huang^a, Xingyu Hua^b, Yida Qiao^b, Binghui Ge^c^,^$(), Jun Ge^b^,^#(), Hui Wu^a^,^*()

^aState Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
^bKey Lab for Industrial Biocatalysis, Ministry of Education, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
^cInstitutes of Physical Science and Information Technology, Anhui University, Hefei 230601, Anhui, China
^dKey Laboratory for Advanced Materials, Center for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China

Received:2021-08-23 Accepted:2021-08-23 Online:2022-03-05 Published:2022-03-01
Contact: Binghui Ge, Jun Ge, Hui Wu
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(51788104);National Natural Science Foundation of China(51661135025);National Natural Science Foundation of China(21878174);National Key Research and Development Plan of China(2016YFA0204300);Beijing Natural Science Foundation(JQ19005);Shanghai Sailing Program(21YF1409400)

Abstract

Abstract:

Palladium (Pd)-based catalysts are essential to drive high-performance Suzuki coupling reactions, which are powerful tools for the synthesis of functional organic compounds. Herein, we developed a solution-rapid-annealing process to stabilize nitrogen-mesoporous carbon supported Pd single-atom/cluster (Pd/NMC) material, which provided a catalyst with superior performance for Suzuki coupling reactions. In comparison with commercial palladium/carbon (Pd/C) catalysts, the Pd/NMC catalyst exhibited significantly boosted activity (100% selectivity and 95% yield) and excellent stability (almost no decay in activity after 10 reuse cycles) for the Suzuki coupling reactions of chlorobenzenes, together with superior yield and excellent selectivity in the fields of the board scope of the reactants. Moreover, our newly developed rapid annealing process of precursor solutions is applied as a generalized method to stabilize metal clusters (e.g. Pd, Pt, Ru), opening new possibilities in the construction of efficient highly dispersed metal atom and sub-nanometer cluster catalysts with high performance.

Key words: Pd single-atom/cluster catalyst, Suzuki coupling reactions, Solution rapid annealing, Energy barrier, High yield

Hehe Wei, Xiaoyang Li, Bohan Deng, Jialiang Lang, Ya Huang, Xingyu Hua, Yida Qiao, Binghui Ge, Jun Ge, Hui Wu. Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions[J]. Chinese Journal of Catalysis, 2022, 43(4): 1058-1065.

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Figures/Tables 6

Fig. 1. Schematic diagram of the structure of Pd/NMC. (a) Schematic diagram of the solution-rapid-annealing process; (b,c) TEM and HRTEM images of Pd/NMC; (d?g) HAADF STEM images of Pd/NMC. Selected area electron diffraction (SAED) image of Pd/NMC were inset in (b).

Fig. 2. Characterization of Pd/NMC, commercial Pd/C, and NMC. (a) XRD results of Pd/NMC, Pd NP/NMC, and commercial Pd/C; (b) Raman spectra of Pd/NMC and NMC; (c) N 1s XPS spectra of Pd/NMC and NMC; (d) Pd 3d XPS spectra of Pd/NMC and Pd/C.

Fig. 3. Performance of the Suzuki coupling reaction over Pd/NMC, Pd NP/NMC, and commercial Pd/C catalysts. (a) Evaluation of aryl chlorides in the Suzuki coupling reaction of chlorobenzene over Pd/NMC, Pd NP/NMC and commercial Pd/C catalysts under mild conditions; (b) Yields of the Suzuki coupling reaction of chlorobenzene over Pd/NMC, Pd NP/NMC, NMC and commercial Pd/C catalysts after 30 min; (c) Kinetic studies of the Suzuki coupling reaction of chlorobenzene over Pd/NMC, Pd NP/NMC and commercial Pd/C catalysts; (d) STEM images of Pd/NMC after the Suzuki coupling reaction of chlorobenzene; (e) Pd 3d XPS spectra of Pd/NMC after catalytic reactions. (f) Recyclability and stability of Pd/NMC and commercial Pd/C; (g) Comparative scope of Pd/NMC (red) and commercial Pd/C (blue) catalysts. Yield (bars) and selectivity (circles) of the Suzuki coupling reactions using different substrates were shown. The detailed reactants are provided in Table 1.

Table 1 Suzuki coupling reactions catalyzed by Pd/NMC.

Fig. 4. Reaction path for the Suzuki coupling of chlorobenzenes. (a) Energy profiles and structure of different processes over Pd1/NMC; (b) Energy profiles and structure of different processes over Pd13/NMC; (c) Relative Gibbs free energy evolution of Pd1/NMC, Pd13/NMC and Pd(111) during the processes of the Suzuki coupling reaction. The x axis showed the reaction intermediates and transition states. N, Pd, C, H, and Cl was shown in blue, green, grey, white, and cyan, respectively. In order to make a distinction, the adsorption state was presented as *. R and P are the reactant and product, respectively.

Table 2 Energy barrier for the Suzuki coupling reaction of chlorobenzene over various catalysts.

Catalyst	E_a (eV)
Catalyst	PhCl* → Ph* + Cl*	Ph-B(OH)₃^-* + Ph* → 2Ph* + B(OH)₃*	2Ph* → Ph-Ph*
Pd₁/NMC	0.67	0.13	0.60
Pd₁₃/NMC	0.64	0.46	0.31
Pd(111)	0.72	0.90	0.39

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Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions

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