Stabilization of Ni⁰/Ni^II Heterojunctions inside Robust Porous Metal Silicate Materials for High-Performance Catalysis

Abstract

Heterostructural nanomaterials demonstrate great potential to replace noble metal-based catalysts because heterojunctions could induce relocalization of electrons and facilitate the migration of electrons and charge carriers at the heterostructural boundary between electron-rich and electrondeficient metal sites; however, the instability of heterojunctions greatly hinders their practical applications. We report herein an effective strategy for the fabrication and stabilization of Ni 0 /Ni II heterojunctions inside a porous metal silicate (PMS) material PMS-22 using a nickel coordination complex as the bifunctional template. The synergistic activity between metallic nickel and nickel silicate in PMS-22 highly boosts the catalytic activity in the hydrogenation of phenol, which could activate phenol at a very low temperature of 50 °C. Most importantly, PMS-22 demonstrates robust stability in catalysis, attributed to the strong interaction and charge transfer between metallic Ni and nickel silicate at the heterointerfaces inside the confined pores. Therefore, this work paves a new pathway to improve the stability and activity of heterostructural nanomaterials for catalytic applications.

Decarboxylation-Induced Defects in MOF-Derived Ni@C Catalysts for Efficient Chemoselective Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime

“…Additionally, the binding energy of Ni 0 for Ni@DC-0.03, Ni@DC-0.04, Ni@DC-0.05, and Ni@DC-0.06 is 852.1, 852.4, 852.7, and 853.2 eV, respectively. The upward shift indicates that the electronic environment of Ni is regulated by the electron shift from Ni to the defective carbon species. − Furthermore, as seen in Figure b, the C 1s peaks at 285.7 and 289.8 eV are related to C–O and CO 3 2– groups, respectively, , indicating that the carbon layer surface is rich in oxygen-containing functional groups. It is noteworthy that the strongest signal peaks are all around the binding energy (BE) of 284.0 eV, demonstrating that the carbon layer of the Ni@DC- x is always dominated by sp 2 , and the carbon layer is rich in defects. , In detail, the binding energies of sp 2 C for Ni@DC-0.03, Ni@DC-0.04, Ni@DC-0.05, and Ni@DC-0.06 are 284.2, 283.9, 283.6, and 283.2 eV, respectively, suggesting that the binding energy of sp 2 C decreases with the increment of carbon defects.…”

Stabilization of transition metal heterojunctions inside porous materials for high-performance catalysis

“…16). 139 The composition of the Ni 0 /Ni II heterojunction could be easily adjusted by tuning the ratio of the nickel complex template to tetraethyl silicate. Attributable to the pore confinement effect and the synergistic work between metallic Ni and nickel silicate in PMS-22, activation of phenol could be easily realized at a very low temperature of 50 °C under 1.0 MPa H 2 , while phenol could be almost fully converted into cyclohexanol at 80 °C.…”

Immunosensor with Enhanced Electrochemiluminescence Signal Using Platinum Nanoparticles Confined within Nanochannels for Highly Sensitive Detection of Carcinoembryonic Antigen

“…However, Pt nanomaterials prepared by traditional chemical synthesis methods tend to aggregate. In situ growth of noble metal nanomaterials within confined nanospaces allows for the production of high-performance nanocatalysts [ 31 , 32 ]. Specifically, confined spaces can restrict the diffusion and aggregation of reactants, allowing reactions to occur in very small areas.…”