Oxidative esterification of furfural by Au nanoparticles supported CMK-3 mesoporous catalysts

Furfural (FF) is a strategic product for the development of highly valued chemicals from biomass. The oxidation product of FF, furoic acid (FA), is an important precursor for the synthesis of green esters, such as methyl furoate. Taking into account issues with the direct furfural oxidation, furfural derivatives, such as alkyl furoates, can be easily prepared via oxidative esterification. Here, Au nanoparticles that were immobilized on alkaline-earth metal oxide supports were studied for the oxidative esterification of furfural while using alcohol as both reactant and solvent. The formation of esters is favored by the presence of basic sites on catalyst surface, resulting in high selectivity, preventing the formation of the acetal as a by-product. The Au/MgO sample provided up to 95% methyl furoate (MF) yield, a fast reaction rate, and high performance for furfural:Au molar ratios between 50 and 300. Furthermore, this catalyst was stable during reuse, since both the selectivity and the activity were maintained after four cycles. Oxidative esterification products were achieved in the presence of other alcohols, leading to the formation of esters of up to C5 (isopentyl furoate) with high selectivity (>99%). Linear and branched esters were formed, but the long-chain linear alcohols resulted in higher yields, such as n-butyl furoate in 94% yield.

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A Multifunctional Au/CeO2-Mg(OH)2 Catalyst for One-Pot Aerobic Oxidative Esterification of Aldehydes with Alcohols to Alkyl Esters

Nanomaterials ◽

10.3390/nano11061536 ◽

2021 ◽

Vol 11 (6) ◽

pp. 1536

Author(s):

Seulgi Lim ◽

Seungdon Kwon ◽

Nagyeong Kim ◽

Kyungsu Na

Keyword(s):

Methyl Methacrylate ◽

Heterogeneous Catalysts ◽

Au Nanoparticles ◽

Alkyl Esters ◽

One Pot ◽

Oxidative Esterification ◽

Highly Active ◽

Metal Support Interaction ◽

Metal Support ◽

Supported Metal Nanoparticles

Au nanoparticles bound to crystalline CeO2 nanograins that were dispersed on the nanoplate-like Mg(OH)2, denoted as Au/CeO2-Mg(OH)2, were developed as the highly active and selective multifunctional heterogeneous catalyst for direct oxidative esterification of aldehydes with alcohols to produce alkyl esters under base-free aerobic conditions using oxygen or air as the green oxidants. Au/CeO2-Mg(OH)2 converted 93.3% of methacrylaldehyde (MACR) to methyl methacrylate (MMA, monomer of poly(methyl methacrylate)) with 98.2% selectivity within 1 h, and was repeatedly used over eight recycle runs without regeneration. The catalyst was extensively applied to other aldehydes and alcohols to produce desirable alkyl esters. Comprehensive characterization analyses revealed that the strong metal–support interaction (SMSI) among the three catalytic components (Au, CeO2, and Mg(OH)2), and the proximity and strong contact between Au/CeO2 and the Mg(OH)2 surface were prominent factors that accelerated the reaction toward a desirable oxidative esterification pathway. During the reaction, MACR was adsorbed on the surface of CeO2-Mg(OH)2, upon which methanol was simultaneously activated for esterifying the adsorbed MACR. Hemiacetal-form intermediate species were subsequently produced and oxidized to MMA on the surface of the electron-rich Au nanoparticles bound to partially reduced CeO2−x with electron-donating properties. The present study provides new insights into the design of SMSI-induced supported-metal-nanoparticles for the development of novel, multifunctional, and heterogeneous catalysts.

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Sol-immobilized vs deposited-precipitated Au nanoparticles supported on CeO2 for furfural oxidative esterification

Journal of Chemical Technology & Biotechnology ◽

10.1002/jctb.5240 ◽

2017 ◽

Vol 92 (9) ◽

pp. 2196-2205 ◽

Cited By ~ 6

Author(s):

Federica Menegazzo ◽

Michela Signoretto ◽

Tania Fantinel ◽

Maela Manzoli

Keyword(s):

Au Nanoparticles ◽

Oxidative Esterification

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Modification of Au nanoparticles electronic state by MOFs defect engineering to realize highly active photocatalytic oxidative esterification of benzyl alcohol with methanol

Catalysis Communications ◽

10.1016/j.catcom.2020.106002 ◽

2020 ◽

Vol 140 ◽

pp. 106002 ◽

Cited By ~ 2

Author(s):

Chaoyang Fan ◽

Ruiyi Wang ◽

Peng Kong ◽

Xiaoyu Wang ◽

Jie Wang ◽

...

Keyword(s):

Benzyl Alcohol ◽

Electronic State ◽

Au Nanoparticles ◽

Defect Engineering ◽

Oxidative Esterification ◽

Highly Active

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Controlled Synthesis of Au Nanoparticles in the Nanocages of SBA-16: Improved Activity and Enhanced Recyclability for the Oxidative Esterification of Alcohols

The Journal of Physical Chemistry C ◽

10.1021/jp2093252 ◽

2012 ◽

Vol 116 (11) ◽

pp. 6512-6519 ◽

Cited By ~ 63

Author(s):

Yajuan Hao ◽

Yanzhu Chong ◽

Shuru Li ◽

Hengquan Yang

Keyword(s):

Au Nanoparticles ◽

Controlled Synthesis ◽

Oxidative Esterification

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Machine Learning Accelerated Genetic Algorithms for Computational Materials Search

10.26434/chemrxiv.7411172 ◽

2018 ◽

Author(s):

Steen Lysgaard ◽

Paul C. Jennings ◽

Jens Strabo Hummelshøj ◽

Thomas Bligaard ◽

Tejs Vegge

Keyword(s):

Machine Learning ◽

Genetic Algorithm ◽

Genetic Algorithms ◽

Au Nanoparticles ◽

Learning Model ◽

Energy Calculations ◽

Atomic Distribution ◽

Machine Learning Model ◽

Fold Reduction ◽

Computational Materials

A machine learning model is used as a surrogate fitness evaluator in a genetic algorithm (GA) optimization of the atomic distribution of Pt-Au nanoparticles. The machine learning accelerated genetic algorithm (MLaGA) yields a 50-fold reduction of required energy calculations compared to a traditional GA.

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Electrochemical Oxidative Esterification of Thiophenols: Efficient Access to Sulfinic Esters

Current Organic Synthesis ◽

10.2174/1570179417666200620215704 ◽

2020 ◽

Vol 17 (7) ◽

pp. 540-547

Author(s):

Chun-Hui Yang ◽

Cheng Wu ◽

Jun-Ming Zhang ◽

Xiang-Zhang Tao ◽

Jun Xu ◽

...

Keyword(s):

Organic Synthesis ◽

Efficient Method ◽

High Efficiency ◽

Building Blocks ◽

Constant Current ◽

Good Efficiency ◽

Oxidative Esterification ◽

Efficient Access ◽

New Applications ◽

Sulfinic Esters

Background: The sulfinic esters are important and useful building blocks in organic synthesis. Objective: The aim of this study was to develop a simple and efficient method for the synthesis of sulfinic esters. Materials and Methods: Constant current electrolysis from thiols and alcohols was selected as the method for the synthesis of sulfinic esters. Results and Discussion: A novel electrochemical method for the synthesis of sulfinic esters from thiophenols and alcohols has been developed. Up to 27 examples of sulfinic esters have been synthesized using the current methods. This protocol shows good functional group tolerance as well as high efficiency. In addition, this protocol can be easily scaled up with good efficiency. Notably, heterocycle-containing substrates, including pyridine, thiophene, and benzothiazole, gave the desired products in good yields. A plausible reaction mechanism is proposed. Conclusion: This research not only provides a green and efficient method for the synthesis of sulfinic esters but also shows new applications of electrochemistry in organic synthesis. It is considered that this green and efficient synthetic protocol used to prepare sulfinic esters will have good applications in the future.

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