Base-free oxidative esterification of 5-hydroxymethylfurfural to furan-2,5-dimethylcarboxylate over n-doped carbon-supported Co/Fe bimetallic catalyst under batch-operation or continuous-flow conditions

Xie, Weizhen; Chen, Binglin; Jia, Wenlong; Liu, Huai; Li, Zheng; Yang, Shuliang; Tang, Xing; Zeng, Xianhai; Sun, Yong; Ke, Xixian; Li, Tianyuan; Fang, Huayu; Lin, Lu

doi:10.1016/j.jechem.2022.07.018

Cited by 19 publications

(6 citation statements)

References 56 publications

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“…The NiFeS catalyst possessed a strong basic site resulting in a CO 2 desorption signal at 492 °C, while NiFeP-400 showed two less basic sites (giving CO 2 -TPD signals at 281 and 352 °C). The basic sites in NiFeS and NiFeP-400 were expected to be useful for promoting the dehydrogenation of HMF and its semi-acetal intermediate . The surface base concentrations of the NiFeS and NiFeP-400 catalysts were calculated to be 7.047 mmol/g and 4.065 mmol/g, respectively, which are significantly higher than that of NiFe-LDH (0.776 mmol/g) (Table S2).…”

Section: Resultsmentioning

confidence: 99%

“…The basic sites in NiFeS and NiFeP-400 were expected to be useful for promoting the dehydrogenation of HMF and its semi-acetal intermediate. 40 The surface base concentrations of the NiFeS and NiFeP-400 catalysts were calculated to be 7.047 mmol/g and 4.065 mmol/g, respectively, which are significantly higher than that of NiFe-LDH (0.776 mmol/g) (Table S2). Catalysts rich in basic sites show high activity for HMF oxidation.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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NiFe Layered Double Hydroxide-Derived Catalysts with Remarkable Selectivity for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Furanedicarboxylic Acid under Base-Free Conditions

Gao

Han

Waterhouse

et al. 2023

ACS Sustainable Chem. Eng.

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In this work, we report the exciting discovery of inexpensive and durable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furanedicarboxylic acid (FDCA) under base-free conditions. A nickel-iron layered double hydroxide (NiFe-LDH) precursor was first prepared then subjected to hydrothermal sulfidation with thioacetamide at 120 °C or thermal phosphidation with sodium hypophosphite at 400 °C to produce NiFeS and NiFeP-400 catalysts, respectively. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) showed these catalysts to contain FeNi2S4 and FeNi2P, respectively, as the dominant phases. The catalytic activity of each catalyst was optimized by studying the effect of the solvent, reaction temperature, oxidant, and reaction time on HMF conversions and product distributions. Under optimized conditions (acetonitrile solvent, 120 °C, tert-butanol peroxide as an oxidant, 12 h, respectively), the NiFeS catalyst afforded 100% HMF conversion with an 83.2% FDCA selectivity with the performance of the NiFeP-400 catalyst being almost identical (HMF conversion of 100%; FDCA selectivity of 82.7%). Both catalysts showed excellent stability over five cycles of catalyst tests with the catalysts able to be easily collected after use with a magnet. Based on the experimental findings, the similar reaction mechanisms used are to be proposed for HMF oxidation to FDCA over the two catalysts. Results show that metal sulfide-based and metal phosphide-based catalysts are promising alternatives to traditional noble metal-based catalyst for the valorization of bio-derived HMF.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

NiFe Layered Double Hydroxide-Derived Catalysts with Remarkable Selectivity for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Furanedicarboxylic Acid under Base-Free Conditions

Gao

Han

Waterhouse

et al. 2023

ACS Sustainable Chem. Eng.

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“…Xie et al [72] developed a facile strategy for the synthesis of N-doped carbon-supported Co/Fe bimetallic catalysts (CoFeÀ NC) attaining an FDMC yield of 93 % in an intermittent reactor. Interestingly, CoFeÀ NC also produced a high FDMC yield of 91 % under continuous flow conditions for 80 hours (5 bar O 2 , 80 °C, and no base).…”

Section: Co-based Loaded Non-metallic (Carbonà Nitrogen-based) Catalystsmentioning

confidence: 99%

Research progress of Co and Mn‐based catalysts for the oxidation of 5‐hydroxymethylfurfural

Tang,

Lv,

Wang

et al. 2024

ChemCatChem

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Biomass is a renewable energy source abundantly available in nature. Their degradation by chemical or biological means produces various transition compounds. These transition compounds can be further transformed into valuable chemicals and biofuels that exhibit a wide range of applications and benefits. Recently, there has been a significant focus on this research area. Among the transition compounds, 5‐hydroxymethylfurfural (HMF), derived from the degradation of hexose, is an important biomass‐based platform compound that has hydroxymethyl and aldehyde functional groups in its molecular structure. This study reviews the recent progress in the transition metal‐catalysed conversion of HMF using Co and Mn to generate high‐value‐added downstream products. Furthermore, the active components, the carbon supporter, the reaction mechanism, the oxidants and the reaction conditions of the catalysts are discussed in detail. The oxidation of HMF deserves further research as an important and complete value‐added process for generating biomass‐based valuable chemicals.

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“…For instance, Fu et al reported a system containing Co x O y –N@C and K-OMS-2 with the base of K 2 CO 3 , resulting in DMFD and monomethyl-2,5-furan dicarboxylate (MMFD) yields of 50 and 40%, respectively . Catalyst combinations such as CoO x -N/C + MnO 2 and Co x O y -N/C + Ru/C have also been reported to achieve high DMFD yields (>95%). , Lin et al investigated Co x Cu y -NC and CoFe-NC catalysts, which exhibited excellent DMFD yields (>90%) under base-free conditions. , Gold catalysts, known for their outstanding ability to convert alcohols and aldehydes to esters, − have also been applied in the conversion of HMF. Corma et al utilized Au-CeO 2 , achieving a remarkable 99% yield of DMFD, where alcohols were oxidized to aldehydes and subsequently converted to ester via the formation of a hemiacetal intermediate .…”

Section: Introductionmentioning

confidence: 99%

“…8,9 Lin et al investigated Co x Cu y -NC and CoFe-NC catalysts, which exhibited excellent DMFD yields (>90%) under base-free conditions. 10,11 Gold catalysts, known for their outstanding ability to convert alcohols and aldehydes to esters, 12−15 have also been applied in the conversion of HMF. Corma et al utilized Au-CeO 2 , achieving a remarkable 99% yield of DMFD, where alcohols were oxidized to aldehydes and subsequently converted to ester via the formation of a hemiacetal intermediate.…”

Section: Introductionmentioning

confidence: 99%

Base-Free Oxidative Esterification of HMF Using Mg–Al Hydrotalcite-Supported Gold Catalyst

Guo,

Si,

Huang

et al. 2023

Ind. Eng. Chem. Res.

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Gold-catalyzed oxidative esterification of 5-hydroxymethylfurfural (HMF) under basic conditions is a promising process to produce dimethyl-2,5-furan dicarboxylate (DMFD). However, it has been overlooked that the DMFD readily hydrolyzes in the presence of soluble bases. Herein, we report solid basesupported gold catalysts for the base-free conversion of HMF. The catalysts' basic sites (BSs) were found to facilitate the esterification of aldehydes and oxidation of alcohols to aldehydes. Moreover, the properties of the BSs strongly influenced the catalyst performance, as excessive and insufficient BS strengths resulted in extensive hydrolysis of the DMFD and low catalytic activity, respectively. A larger quantity of BSs is beneficial for complete conversion of the reaction intermediate. The hydrotalcite (HT)-supported catalyst of Au/HT-0.2 possesses a large quantity and moderate strength of BSs, therefore providing an excellent DMFD yield of 94.5%. Our results reveal for the first time the issue of DMFD hydrolysis in gold-catalyzed oxidative esterification of HMF. Replacement of a soluble base by a solid base-supported catalyst to enhance product stability provides insights for similar reactions.

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Base-free oxidative esterification of 5-hydroxymethylfurfural to furan-2,5-dimethylcarboxylate over n-doped carbon-supported Co/Fe bimetallic catalyst under batch-operation or continuous-flow conditions

Cited by 19 publications

References 56 publications

NiFe Layered Double Hydroxide-Derived Catalysts with Remarkable Selectivity for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Furanedicarboxylic Acid under Base-Free Conditions

NiFe Layered Double Hydroxide-Derived Catalysts with Remarkable Selectivity for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Furanedicarboxylic Acid under Base-Free Conditions

Research progress of Co and Mn‐based catalysts for the oxidation of 5‐hydroxymethylfurfural

Base-Free Oxidative Esterification of HMF Using Mg–Al Hydrotalcite-Supported Gold Catalyst

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