Selective hydrogenation of phenol to cyclohexanone over Pd nanoparticles encaged hollow mesoporous silica catalytic nanoreactors

Yang, Caoping; Li, Kaijie; Wang, Junyou; Zhou, Shenghu

doi:10.1016/j.apcata.2020.117961

Cited by 20 publications

(8 citation statements)

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“…Figure S6 presents H 2 -TPR studies of the mentioned (PdO) 1 –(Fe x O y ) 1/ x @HMSNs. As shown in Figure S6, the peak at 94 °C is due to the reduction of PdO and is slightly higher than that (70 °C) of PdO@HMSNs reported in our previous work, suggesting the presence of PdO and Fe x O y interaction. The two peaks centered at 427 and 518 °C are due to the reduction of Fe x O y , where the former can be assigned to the reduction of Fe 2 O 3 to Fe 3 O 4 and the latter is ascribed to the reduction of Fe 3 O 4 to metallic Fe. , Although literatures and our TPR studies reported the complete reduction of Fe x O y to metallic Fe at 500–600 °C, , we cannot exclude the possibility of complete reduction of a small amount of Fe x O y at 350 °C in the presence of metallic Pd.…”

Section: Resultscontrasting

confidence: 50%

Pd–Fe_xO_y Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Chen

Yan

et al. 2021

J. Phys. Chem. C

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In this work, Pd−Fe x O y hybrid nanoparticles encaged hollow mesoporous silica nanoreactors (Pd−Fe x O y @HMSNs) are synthesized, which features ∼3−4 nm Pd−Fe x O y hybrid nanoparticles inside ∼17 nm hollow cavities of ∼32 nm mesoporous silica nanoreactors. By employing Pd and Fe ions containing polymer micelles as templates for silica deposition, hollow mesoporous silica nanoreactors and the residence of functional nanoparticles inside hollow cavities are simultaneously obtained. Through adjusting the ratios of Pd 2+ /Fe 3+ in micelles, various Pd−Fe x O y @HMSNs with different Pd/Fe ratios are synthesized and tested for reduction of nitroarenes with NaBH 4 . Relative to Pd@HMSNs, Fe x O y @HMSNs and their physical mixtures, Pd 1 −(Fe x O y ) 1/x @HMSNs illustrate a greatly enhanced catalytic performance for reductions of a series of substituted nitroarenes with NaBH 4 to aminoarenes. The catalytic enhancement of Pd−Fe x O y @HMSNs is ascribed to the synergistic effect of Pd and Fe x O y as well as the confinement effect of functional nanoparticles inside hollow cavities.

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Section: Resultscontrasting

confidence: 50%

Pd–Fe_xO_y Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Chen

Yan

et al. 2021

J. Phys. Chem. C

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“…The spherical morphology of COF-280 is conducive to the formation of Pd with higher Pd 0 proportion on the catalyst surface (Figures and , Table ), which is in favor of the contact between the reactants and Pd NPs. The current studies suggest that Pd 0 is the active site for the phenol hydrogenation. ,− Furthermore, the abundant mesopores in COF-280 (Figure , Table ) can enhance the mass transfer during the phenol hydrogenation. These aspects together lead to the superior catalytic activity of Pd@COF-280 for the phenol hydrogenation.…”

Section: Results and Discussionmentioning

confidence: 68%

Palladium Nanoparticles Anchored on COFs Prepared by Simple Calcination for Phenol Hydrogenation

Jiang

Shen

Wang

et al. 2021

Ind. Eng. Chem. Res.

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Covalent organic frameworks (COFs) used as supports for metal nanoparticles (MNPs) show high efficiency in heterogeneous catalysis. Developing a green and efficient way to synthesize COFs remains a great challenge. Herein, an imine COF (TpPa-1) was prepared via a green and convenient calcination method under low temperature, and then Pd nanoparticles (NPs) were loaded to prepare Pd@COFs catalysts for the selective phenol hydrogenation to cyclohexanone. XRD and FTIR results confirm the successful synthesis of TpPa-1 by a simple calcination method. A suitable calcination temperature (280 °C) is conducive to the synthesis of TpPa-1 (COF-280) with higher crystallinity, larger BET surface area, higher mesoporous proportion, and uniform spherical morphology. These characteristics of COF-280 increase the Pd loading, promote the formation of Pd with higher Pd0 proportion on the catalyst surface, and enhance the mass transfer, thereby improving the catalytic properties of Pd@COF-280 for the phenol hydrogenation, with a catalytic activity increased by 2 times compared to Pd@COF-220. The addition of p-toluenesulfonamide during the synthesis can affect the crystallinity and morphology of TpPa-1 and the corresponding catalytic performance. Furthermore, Pd@COF-280 shows good reusability during four reaction cycles. The work provides a green approach for preparing imine-COFs and their efficient applications in heterogeneous catalysis.

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“…For instance, Pd/C gives the phenol conversion of 96% and the cyclohexanone selectivity of 95% at 80°C and 0.1 MPa H 2 with hexane as solvent [9] . Pd@HMSNs e ciently catalyze hydrogenation of phenol and m-cresol to cyclohexanone derivatives with ≥ 98.3% selectivity at ≥ 99.0% conversions at 55 o C, ambient H 2 pressure and water media [10] . A nearly full conversion of phenol with high selectivity (> 99.0%) to cyclohexanone can be achieved on TiO 2 nanowires supported Pd at 50°C and 5.0 bar H 2 in water [11] Although noble metal catalysts possess high activity, the high-cost limits the wide industrial application.…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation of phenol to cyclohexanone in aqueous phase on WO3 modified Ni/ZrO2 catalyst

Han

Shi

Wang

et al. 2023

Preprint

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Ni/ZrO2 (Ni/Zr) and Ni/WO3-ZrO2 (Ni/xWZr, x denotes WO3/ZrO2 mass ratios) were prepared by the impregnation-direct reduction method and tested for the aqueous phase hydrogenation of phenol to cyclohexanone in an autoclave reactor. It has been found that the Ni-W alloy forms in Ni/xWZr, and a charge transfer occurs from Ni to W. The presence of W species promotes the Ni dispersion and increases the amounts of acid sites and spilt-over hydrogen species. This leads to higher hydrogenation and direct deoxygenation activity of Ni/xWZr than that of Ni/Zr. In addition, the W6+ and W4+ species, acted as Lewis acidic sites, may stabilize cyclohexanone and the hydrogenation of cyclohexanone to cyclohexanol is inhibited. Under suitable condition, the phenol conversion and the cyclohexanone selectivity reach 93.1% and 90.6% on Ni/0.8WZr, respectively.

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Selective hydrogenation of phenol to cyclohexanone over Pd nanoparticles encaged hollow mesoporous silica catalytic nanoreactors

Cited by 20 publications

References 61 publications

Pd–Fe_xO_y Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Pd–Fe_xO_y Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Palladium Nanoparticles Anchored on COFs Prepared by Simple Calcination for Phenol Hydrogenation

Hydrogenation of phenol to cyclohexanone in aqueous phase on WO3 modified Ni/ZrO2 catalyst

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Selective hydrogenation of phenol to cyclohexanone over Pd nanoparticles encaged hollow mesoporous silica catalytic nanoreactors

Cited by 20 publications

References 61 publications

Pd–FexOy Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Pd–FexOy Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Palladium Nanoparticles Anchored on COFs Prepared by Simple Calcination for Phenol Hydrogenation

Hydrogenation of phenol to cyclohexanone in aqueous phase on WO3 modified Ni/ZrO2 catalyst

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Pd–Fe_xO_y Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes

Pd–Fe_xO_y Hybrid Nanoparticles Encaged Hollow Mesoporous Silica Nanoreactors for Reduction of Nitroarenes to Aminoarenes