Chemoselective oxidation of 5-hydroxymethylfurfural (HMF) over non-noble metals to produce a bioplastic monomer, 2,5-furandicarboxylic acid (FDCA), under alkaline-free conditions is challenging and worthy of investigation. HMF oxidation into FDCA involves the concurrent oxidation of primary alcohol and an aldehyde functional group into carboxylic groups, which therefore demand a bifunctional catalyst containing dual active sites and chemoselective oxidation of HMF. The present work demonstrated the formation of new selective active sites in a composite porous material (Cu-BTC_PMA) that consists of Cu-BTC (metal–organic framework (MOF)) and polyoxometalate (POM). The porous framework provides (Cu-BTC_PMA) the desired chemoselectivity, while a selective Cu metal center in Cu-BTC (MOF) and Cu–O–Mo sites functions as active sites for the concurrent oxidation of HMF into FDCA. This catalyst exhibited a HMF conversion of 89% and an FDCA selectivity of 92.3% under base-free and mild reaction conditions. In detail, X-ray absorption spectroscopy analysis demonstrated the chemical bond tuning, as well as electronic structural modulations of MOF and POM at the molecular level, which directs the formation of new synergistic interfacial active sites and charge transfer states. This phenomenon causes the generation of the unique redox environment of copper and the multiple oxidation states along with the oxygen vacancy in the Cu-BTC_PMA catalyst, which most likely behaves as active sites for base-free oxidation. A kinetics study of this reaction was followed using in situ attenuated total reflection-infrared spectroscopy, demonstrating the stabilization of the specific intermediates that lead to the formation of FDCA. Moreover, we made comparative density functional theory and quantum theory of atoms in molecules investigations on the surface interaction between the reactant (HMF) and two catalyst models of Cu-BTC and Cu-BTC_PMA to interpret quantitatively the higher catalytic activity of the Cu-BTC_PMA catalyst. The kinetics study also evaluates the rate-determining step and activation energy for the multistep oxidation reactions. 

Elucidation of Active Sites and Mechanistic Pathways of a Heteropolyacid/Cu-Metal–Organic Framework Catalyst for Selective Oxidation of 5-Hydroxymethylfurfural via Ex Situ X-ray Absorption Spectroscopy and In Situ Attenuated Total Reflection-Infrared Studies

Advances in enzymatic conversion of biomassderived furfural and 5-hydroxymethylfurfural to value-added chemicals and solvents.

Abstract Biomass assumes an increasingly vital role in the realm of renewable energy and sustainable development due to its abundant availability, renewability, and minimal environmental impact. Within this context, 5‐hydroxymethylfurfural (HMF), derived from sugar dehydration, stands out as a critical bio‐derived product. It serves as a pivotal multifunctional platform compound, integral in synthesizing various vital chemicals, including furan‐based polymers, fine chemicals, and biofuels. The high reactivity of HMF, attributed to its highly active aldehyde, hydroxyl, and furan ring, underscores the challenge of selectively regulating its conversion to obtain the desired products. This review highlights the research progress on efficient catalytic systems for HMF synthesis, oxidation, reduction, and etherification. Additionally, it outlines the techno‐economic analysis (TEA) and prospective research directions for the production of furan‐based chemicals. Despite significant progress in catalysis research, and certain process routes demonstrating substantial economics, with key indicators surpassing petroleum‐based products, a gap persists between fundamental research and large‐scale industrialization. This is due to the lack of comprehensive engineering research on bio‐based chemicals, making the commercialization process a distant goal. These findings provide valuable insights for further development of this field. This article is protected by copyright. All rights reserved 

5‐hydroxymethylfurfural and its Downstream Chemicals: A Review of Catalytic Routes

The production of hydrogen through water electrolysis has garnered significant interest and extensive research as a sustainable and environmentally friendly method. However, the process of water splitting is thermodynamically unfavorable, and the slow oxygen evolution reaction (OER) with four-electron transfer significantly hinders overall efficiency. In order to overcome this limitation, researchers have conducted comprehensive analyses of the OER mechanism and have made remarkable progress on the development of superior catalysts. However, the reaction rate of OER remains limited due to the significant theoretical overpotential. Consequently, an alternative approach involving the substitution of OER with other low-energy anodic reactions has emerged as a promising avenue for reducing the potential required for hydrogen production and overall energy consumption. This review aims to provide a comprehensive summary of the advancements in hybrid water electrolysis as well as analyze the characteristics, advantages, and disadvantages of prevalent small molecule oxidation methods, with a particular focus on catalyst design and modification mechanisms. Additionally, strategies for enhancing high current performance are discussed. This review concludes by addressing the challenges and future prospects of hybrid water electrolysis, offering guidance for the systematic development of catalysts with enhanced efficiency. 

Recent advances in hydrogen production coupled with alternative oxidation reactions

In this study, the CuCoFe-LDH catalyst was synthesized by hydrothermal method and applied to degrade levofloxacin (LFX) by peroxymonosulfate (PMS) activation. The physicochemical properties of the synthesized samples were analyzed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The influence of various factors such as catalyst system, pH, catalyst content, PMS, pH, and coexisting ions on the degradation of LFX was systematically investigated. The results showed that after 10 min, 94.57 % of LFX was decomposed under the conditions of 200 mg/L of catalyst, 500 mg/L of PMS, 10 mg/L of LFX, and pH 7.0. Besides, the CuCoFe-LDH/PMS system can effectively remove LFX over a wide pH range from 3.5 to 9.0. Both radical superoxide (O2•-) and non-radical singlet oxygen (1O2) were major reactive oxygen species in the CuCoFe-LDH/PMS system. Mass spectrometry identified 16 major degradation products of LFX, and 38.43 % of LFX was mineralized after 30 min of reaction. Besides, the CuCoFe-LDH/PMS system had the ability to effectively degrade different groups of antibiotics (e.g., fluoroquinolone, tetracycline, and sulfonamide). The mechanism of PMS activation by CuCoFe-LDH and the LFX degradation pathway were proposed. Finally, testing the reusability of CuCoFe-LDH in LFX degradation showed that a decrease of nearly 7 % occurred after five consecutive cycles, suggesting its stability for practical applications. 

Hydrothermal synthesis of CuCoFe layered double hydroxide and its performance in the degradation of antibiotics: Influencing factors, degradation pathways, and reaction mechanism

A highly efficient iron phthalocyanine-intercalated CuFe-LDH catalyst for the selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furanic acid

The development of new strategies to improve reaction efficiency and light utilization is one of the biggest challenges in photosynthetic chemistry. Dynamics control, in particular, tuning the adsorption/desorption of reactants and products is an ideal way to improve the conversion and selectivity in a catalytic reaction, but it is rarely studied in photocatalytic organic synthesis. Here, we designed an amorphous FeOOH coating to decorate the CdS photocatalyst to control the adsorption/desorption of reactants and products to improve reaction efficiency. The best conversion of the core-shell photocatalyst reaches up to 74.1% in 2 h together with >99.9% selectivity, and the photocatalyst responses above 600 nm, which is the longest active wavelength reported for the reaction. Further data illustrate that amorphous FeOOH coating enables selective sorption of BA/BAD molecules by H-bonding induced interaction, which may result in the excellent performance. Construction of amorphous coating layers and understanding the selective permeability may provide a new strategy for design more efficient photocatalytic system for organic synthesis.

Selectively Permeable FeOOH Amorphous Layer Coating CdS for Enhanced Oxidation of Benzyl Alcohol to Benzaldehyde.

Porous nitrogen-doped carbons supporting Fe-porphyrins for the highly efficient catalytic oxidation of HMF to HMFCA

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A highly efficient iron phthalocyanine-intercalated CuFe-LDH catalyst for the selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furanic acid

Selectively Permeable FeOOH Amorphous Layer Coating CdS for Enhanced Oxidation of Benzyl Alcohol to Benzaldehyde.

Porous nitrogen-doped carbons supporting Fe-porphyrins for the highly efficient catalytic oxidation of HMF to HMFCA