Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Hammond-Pereira, Ellis; Bryant, Kristin; Graham, Trent R.; Yang, Chen; Mergelsberg, Sebastian T.; Wu, Di; Saunders, Sam C.

doi:10.1039/d0re00198h

Cited by 6 publications

(5 citation statements)

References 50 publications

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“…This specific band appears due to the mixed vibrational mode consisting of ring COH stretching (ν(ph-COH)), aldehydic CH bending (δ(C–H) ald ), CH bending of the ring (δ(C–H) ring ), and C=C stretching of the ring (ν(C–C) ring ), commensurate with a surface-bound BnCHO. 44 − 47 Similarly, for bare Bi, a band appears at 1718 cm –1 , which is also attributed to the −C=O stretch of aldehyde according to previous literature reports 40 , 48 ( Figure S22a ). On the contrary, for Bi-UiO-66, such BnCHO adsorption IR features do not appear under the same experimental conditions ( Figure 7 b and Figure S22b ), thus hinting at the fact that the MOF membrane weakens the surface binding affinity of BnCHO.…”

Section: Resultssupporting

confidence: 83%

Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde

Shanker,

Ghatak,

Binyamin

et al. 2024

ACS Catal.

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Electrocatalytic alcohol oxidation in acid offers a promising alternative to the kinetically sluggish water oxidation reaction toward low-energy H 2 generation. However, electrocatalysts driving active and selective acidic alcohol electrochemical transformation are still scarce. In this work, we demonstrate efficient alcohol-to-aldehyde conversion achieved by reticular chemistry-based modification of the catalyst's immediate environment. Specifically, coating a Bi-based electrocatalyst with a thin layer of metal−organic framework (MOF) substantially improves its performance toward benzyl alcohol electro-oxidation to benzaldehyde in a 0.1 M H 2 SO 4 electrolyte. Detailed analysis reveals that the MOF adlayer influences catalysis by increasing the reactivity of surface hydroxides as well as weakening the catalyst-benzaldehyde binding strength. In turn, low-potential (0.65 V) cathodic H 2 evolution was obtained through coupling it with anodic benzyl alcohol electro-oxidation. Consequently, the presented approach could be implemented in a wide range of electrocatalytic oxidation reactions for energy-conversion application.

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Section: Resultssupporting

confidence: 83%

Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde

Shanker,

Ghatak,

Binyamin

et al. 2024

ACS Catal.

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“…It is possible that because the pores are in the microporous range, the available space restricted the formation of a seed and the subsequent nanoparticle. Some studies have shown the formation of gold nanoparticles inside the pores of MSN, such as MCM-41 …”

Section: Resultsmentioning

confidence: 99%

“…Some studies have shown the formation of gold nanoparticles inside the pores of MSN, such as MCM-41. 41 The internalization of FeCl 3 and NaBH 4 and the formation of Fe(0) both inside and on the particle could be explained as follows. (i) When the calcined PHSN was immersed in the FeCl 3 solution, some of the Fe and Cl ions infiltrated the pores and filled the hollow core.…”

Section: ■ Introductionmentioning

confidence: 99%

Self-Assembled Surfactant-Templated Synthesis of Porous Hollow Silica Nanoparticles: Mechanism of Formation and Feasibility of Post-Synthesis Nanoencapsulation

Bueno

Ghoshal

2020

Langmuir

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SiO2 is bioinert and highly functionalizable, thus making it a very attractive material for nanotechnology applications such as drug delivery and nanoencapsulation of pesticides. Herein, we synthesized porous hollow SiO2 nanoparticles (PHSNs) by using cetyltrimethylammonium bromide (CTAB) and Pluronic P123 as the structure-directing agents. The porosity and hollowness of the SiO2 structure allow for the protective and high-density loading of molecules of interest inside the nanoshell. We demonstrate here that loading can be achieved post-synthesis through the pores of the PHSNs. The PHSNs are monodisperse with a mean diameter of 258 nm and a specific surface area of 287 m2 g–1. The mechanism of formation of the PHSNs was investigated using 1-D and 2-D solid-state nuclear magnetic resonance (SS-NMR) and Fourier-transform infrared spectroscopy (FTIR). The data suggest that CTAB and Pluronic P123 interact, forming a hydrophobic spherical hollow cage that serves as a template for the porous hollow structure. After synthesis, the surfactants were removed by calcination at 550 °C and the PHSNs were added to an Fe3+ solution followed by addition of the reductant NaBH4 to the suspension, which led to the formation of Fe(0) NPs both on the PHSNs and inside the hollow shell, as confirmed by transmission electron microscopy imaging. The imaging of the formation of Fe(0) NPs inside the hollow shell provides direct evidence of transport of solute molecules across the shell and their reactions within the PHSNs, making it a versatile nanocarrier and nanoreactor.

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“…At the same time, Hammond-Pereira et al aerobically oxidized benzyl alcohol in the presence of silica-encapsulated gold core@shell nanoparticles, Au@m-SiO 2 , under alkaline conditions using K 2 CO 3 . The substrate conversion of 60.4% was obtained after 1 h of reaction under solvent-free conditions, and a TOF value of 1.28 × 10 4 h −1 was registered, indicating a rather high activity [34]. The selectivity for aldehyde (ca.…”

Section: Benzylic Alcoholsmentioning

confidence: 97%

“…75%) (entry 3, Table 1) is attributed to the mesoporous shell of the AuNPs which seems to inhibit the formation of larger species. The addition of potassium carbonate has a distinct effect on the conversion and selectivity of the reaction, i.e., it favors the substrate conversion from 17.3 to 60.4% but decreases the selectivity from 98.7 to 75.0% [34]. PS@PNIPA/Au ->99…”

Section: Benzylic Alcoholsmentioning

confidence: 99%

Core–Shell Catalysts for Conventional Oxidation of Alcohols: A Brief Review

2023

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This review highlights recent research on the application of core–shell structured materials as catalysts in the oxidation of alcohols to value-added products, such as benzaldehyde, acetophenone, benzophenone, cinnamaldehyde, and vanillin, among others. While the application of various unconventional energy inputs (such as microwave and ultrasound irradiation) was reported, this paper focuses on conventional heating. The oxidation of homocyclic aromatic, heterocyclic aromatic, aliphatic, and alicyclic alcohols catalyzed by core–shell composite catalysts is addressed. This work also highlights some unique advantages of core–shell nanomaterial catalysis, namely the flexibility of combining individual functions for specific purposes as well as the effect of various parameters on the catalytic performance of these materials.

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Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Abstract: Silica-encapsulated gold core@shell nanoparticles (Au@SiO2 CSNPs) were synthesized via a tunable bottom-up procedure to catalyze the aerobic oxidation of benzyl alcohol. The nanoparticles exhibit a mesoporous shell which enhances selectivity...

Cited by 6 publications

References 50 publications

Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde

Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde

Self-Assembled Surfactant-Templated Synthesis of Porous Hollow Silica Nanoparticles: Mechanism of Formation and Feasibility of Post-Synthesis Nanoencapsulation

Core–Shell Catalysts for Conventional Oxidation of Alcohols: A Brief Review

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