Oxygenase mimicking immobilised iron complex catalysts for alkane hydroxylation with H<sub>2</sub>O<sub>2</sub>

Sakakura, Seiya; Kitamoto, Ryunosuke; Goto, Kazuki; Miura, Seito; Takeda, Takamasa; Okamura, Masaya; Fukatsu, Arisa; Itoh, Shinobu; Hikichi, Shiro

doi:10.1039/d3cy00698k

Cited by 4 publications

(1 citation statement)

References 35 publications

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“…The partial oxidation of propane to valuable liquid oxygenates represents a novel strategy to utilize this class of light alkane 34 . Among the several current strategies, such as electrocatalysis 35 , photocatalysis 36 , 37 , thermal-derived homogeneous 38 , and thermal-derived heterogeneous catalysis, the exploitation of heterogeneous catalyst shows the greatest application potential 39 – 41 . However, the consumption of costly oxidants poses an obstacle to it.…”

Section: Resultsmentioning

confidence: 99%

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

Wang,

Li,

Han

et al. 2024

Nat Commun

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Catalyst systems populated by high-density single atoms are crucial for improving catalytic activity and selectivity, which can potentially maximize the industrial prospects of heterogeneous single-atom catalysts (SACs). However, achieving high-loading SACs with metal contents above 10 wt% remains challenging. Here we describe a general negative pressure annealing strategy to fabricate ultrahigh-loading SACs with metal contents up to 27.3–44.8 wt% for 13 different metals on a typical carbon nitride matrix. Furthermore, our approach enables the synthesis of high-entropy single-atom catalysts (HESACs) that exhibit the coexistence of multiple metal single atoms with high metal contents. In-situ aberration-corrected HAADF-STEM (AC-STEM) combined with ex-situ X-ray absorption fine structure (XAFS) demonstrate that the negative pressure annealing treatment accelerates the removal of anionic ligand in metal precursors and boosts the bonding of metal species with N defective sites, enabling the formation of dense N-coordinated metal sites. Increasing metal loading on a platinum (Pt) SAC to 41.8 wt% significantly enhances the activity of propane oxidation towards liquid products, including acetone, methanol, and acetic acid et al. This work presents a straightforward and universal approach for achieving many low-cost and high-density SACs for efficient catalytic transformations.

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Section: Resultsmentioning

confidence: 99%

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

Wang,

Li,

Han

et al. 2024

Nat Commun

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Ni(II)‐Complex Anchored Over Functionalized Mesoporous SBA‐15: A Nanocatalyst for the Synthesis of Aminophenoxazinone Derivatives

Ghanta,

Mondal,

Chowdhury

et al. 2024

ChemCatChem

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Immobilization of the reactive metal sites over high surface area porous nanomaterial is a very demanding route in designing novel nanocatalysts for the synthesis of valuable fine chemicals. Here we report an efficient, eco‐friendly and sustainable route for the synthesis of aminophenoxazinone derivatives via oxidative coupling of o‐aminophenols catalysed by a novel mesoporous highly ordered Ni(II)‐complex functionalized mesoporous heterogeneous organosilica catalyst. A novel structurally characterized Ni(II)‐complex derived from 2‐(I‐(2‐(piperizin‐1‐yl)ethylimino)methyl)‐5‐methylphenol ligand has been immobilised over a 2D‐hexagonally ordered functionalized mesoporous SBA‐15 synthesized via surface functionalization of SBA‐15 material with 3‐aminopropyltriethoxysilane (APTES) to obtain the Ni(II)‐nanocatalyst SANI. Its catalytic activity has been explored for three different substrates like o‐aminophenol (OAP), 3‐amino‐4‐hydroxybenzoic acid (CAP) and 2‐amino‐4‐methylphenol (MAP) that produces corresponding phenoxazinone derivatives having the yields of 92, 81 and 85%, respectively. suggesting wide scope of this supported mesoporous nanocatalyst.

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Switching Product Selectivity in Immobilized Tungstate Catalysts by Control of Hydrophobicity of Mesoporous Silicate Supports

Kuwamoto,

Okamura,

Hikichi

2024

ChemistryEurope

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Novel mesoporous silicates modified with imidazolium cation were applied as the support for peroxotungstate. Stepwise introduction of multiple functional groups to SBA‐15 was achieved by the combination of the direct and post‐synthesis procedures. The co‐condensation of tetraethoxysilane and 3‐(imidazolyl‐1‐yl)‐propyltriethoxysilane in the presence of the micelles of an amphiphilic surfactant yields the hydrophilic SBA‐15 type silicate support with the imidazole modifier locating into the mesopores. The hydrophobic environment of the supports was imparted by capping the residual silanols on the silicate surface with trimethylsilyl groups. The fluoroalkyl‐ or alkyl‐imidazolium cation‐anchored supports were derived from the corresponding imidazole‐functionalized precursors. The anion‐exchanging reaction between peroxytungstate and the imidazolium cation‐anchored supports yielded the corresponding tungstate‐immobilized catalysts. The hydrophilic catalyst with the fluoroalkyl‐imidazolium mediated alkene epoxidation with H2O2 in less polar solvents. The hydrophobic one, in contrast, produced diol through the epoxidation and following hydration in an aqueous solvent by the action of the highly Lewis acidic tungsten. The hydrophobic catalysts had the advantage of being more tolerant than hydrophilic catalysts, as evidenced by reusability tests. The activities of the alkyl‐imidazolium catalysts were lower than those of the corresponding fluoroalkyl‐imidazolium catalysts, indicating that the local structures surrounding the tungstate site affected the catalytic performance.

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Oxygenase mimicking immobilised iron complex catalysts for alkane hydroxylation with H₂O₂

Abstract: Immobilised iron complex catalysts with hydrophobic reaction fields that mimic the active sites of alkane hydroxylating enzymes were constructed into the mesopore of the SBA-15 type silicate support. The reaction...

Cited by 4 publications

References 35 publications

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

Ni(II)‐Complex Anchored Over Functionalized Mesoporous SBA‐15: A Nanocatalyst for the Synthesis of Aminophenoxazinone Derivatives

Switching Product Selectivity in Immobilized Tungstate Catalysts by Control of Hydrophobicity of Mesoporous Silicate Supports

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Oxygenase mimicking immobilised iron complex catalysts for alkane hydroxylation with H2O2

Abstract: Immobilised iron complex catalysts with hydrophobic reaction fields that mimic the active sites of alkane hydroxylating enzymes were constructed into the mesopore of the SBA-15 type silicate support. The reaction...

Cited by 4 publications

References 35 publications

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

Ni(II)‐Complex Anchored Over Functionalized Mesoporous SBA‐15: A Nanocatalyst for the Synthesis of Aminophenoxazinone Derivatives

Switching Product Selectivity in Immobilized Tungstate Catalysts by Control of Hydrophobicity of Mesoporous Silicate Supports

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Oxygenase mimicking immobilised iron complex catalysts for alkane hydroxylation with H₂O₂