Design of bifunctional single-atom catalysts NiSA/ZIF-300 for CO2 conversion by ligand regulation strategy

• Published in: Nano research Vol. 17; no. 5; pp. 3827 - 3834
• Main Authors: Fu, Wengang, Yun, Yapei, Sheng, Hongting, Liu, Xiaokang, Ding, Tao, Hu, Shuxian, Yao, Tao, Ge, Binghui, Du, Yuanxin, Astruc, Didier, Zhu, Manzhou
• Format: Journal Article
• Language: English
• Published: Beijing Tsinghua University Press 01.05.2024; Springer Nature B.V
• Subjects: Atomic/Molecular Structure and Spectra; Biomedicine; Biotechnology; Carbon dioxide; Catalysts; Chemical bonds; Chemistry and Materials Science; Condensed Matter Physics; Controllability; Cycloaddition; Fabrication; Green chemistry; Ligands; Materials Science; Metal-organic frameworks; Nanocomposites; Nanotechnology; Nickel; Noble metals; Pyrolysis; Research Article; Single atom catalysts; Styrene; Styrenes; bifunctional; cycloaddition; CO; catalyst; single atom; conversion
• ISSN: 1998-0124; 1998-0000
• DOI: 10.1007/s12274-023-6334-2

Carbon-supported noble-metal-free single-atom catalysts (SACs) have aroused widespread interest due to their green chemistry aspects and excellent performances. Herein, we propose a “ligand regulation strategy” and achieve the successful fabrication of bifunctional SAC/MOF (MOF = metal–organic framework) nanocomposite (abbreviated NiSA/ZIF-300; ZIF = ZIF-8) with exceptional catalytic performance and robustness. The designed NiSA/ZIF-300 has a planar interfacial structure with the Ni atom, involving one S and three N atoms bonded to Ni(II), fabricated by controllable pyrolysis of volatile Ni-S fragments. For CO 2 cycloaddition to styrene epoxide, NiSA/ZIF-300 exhibits ultrahigh activity (turnover number (TON) = 1.18 × 10 5 ; turnover frequency (TOF) = 9830 mol SC ·mol Ni −1 ·h −1 ; SC = styrene carbonate) and durability at 70 °C under 1 atm CO 2 pressure, which is much superior to Ni complex/ZIF, NiNP/ZIF-300, and most reported catalysts. This study offers a simple method of bifunctional SAC/MOF nanocomposite fabrication and usage, and provides guidance for the precise design of additional original SACs with unique catalytic properties.