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Title: Hybrid nanomaterials with single-site catalysts by spatially controllable immobilization of nickel complexes via photoclick chemistry for alkene epoxidation
Authors: Ghosh, Dwaipayan
Febriansyah, Benny
Gupta, Disha
Ng, Leonard Kia-Sheun
Xi, Shibo
Du, Yonghua
Baikie, Tom
Dong, ZhiLi
Soo, Han Sen
Keywords: DRNTU::Science::Chemistry
Hybrid Nanomaterials
Single-site Heterogeneous Catalysts
Issue Date: 2018
Source: Ghosh, D., Febriansyah, B., Gupta, D., Ng, L. K. S., Xi, S., Du, Y., Baikie, T., Dong, Z., & Soo, H. S. (2018). Hybrid nanomaterials with single-site catalysts by spatially controllable immobilization of nickel complexes via photoclick chemistry for alkene epoxidation . ACS Nano, 12(6), 5903-5912. doi:10.1021/acsnano.8b02118
Series/Report no.: ACS Nano
Abstract: Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide (e.g. titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy (UV-DRS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes, and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.
ISSN: 1936-0851
DOI: 10.1021/acsnano.8b02118
Rights: © 2018 American Chemical Society (ACS). This is the author created version of a work that has been peer reviewed and accepted for publication by ACS Nano, American Chemical Society (ACS). It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [].
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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