Aerobic Oxidation of 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid over Gold Stabilized on Zirconia-Based Supports

Abstract

A series with gold supported on monoclinic (m-), tetragonal (t-) ZrO2, and Mg-modified zirconia were prepared and used for the catalytic oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA). The Au stabilized on Mg-modified zirconia calcined at 600 °C (denoted as Au/MZ-600) exhibited a superior catalytic performance with 95% of FDCA yield after 4 h by adapting a two-temperature step reaction. The structure–activity relationship was investigated by using X-ray diffraction, temperature-programmed reduction by H2, X-ray absorption spectroscopy, temperature-programmed desorption of CO2, and N2 adsorption–desorption methods. The results clearly demonstrate that the addition of Mg ions in/on the zirconia support at appropriate calcination temperature plays an important role in optimizing the interaction between gold nanoparticles and the support by fine-tuning the surface base properties of the zirconia supports and creation of oxygen vacancies. Accordingly, tuning these gold–support interactions is essential to achieve high dispersion of small-sized gold nanoparticles with enhanced metallic character, which plays a significant role in enhancing the catalytic activity of the final catalyst.

Crystal Faces‐Tailored Oxygen Vacancy in Au/CeO2 Catalysts for Efficient Oxidation of HMF to FDCA

“…The catalysts show high activity for HMF conversion and low FDCA production. This phenomenon is attributed to pure CeO 2 possessing poor oxidation performance, along with low stability of HMF in strongly alkaline solution and easily occurring side‐reactions [38,39] . Among these CeO 2 catalysts, rod‐CeO 2 with (110) crystal face shows higher FDCA production than cube‐CeO 2 (100) and oct‐CeO 2 (111) for HMF oxidation.…”

“…This phenomenon is attributed to pure CeO 2 possessing poor oxidation performance, along with low stability of HMF in strongly alkaline solution and easily occurring side-reactions. [38,39] Among these CeO 2 catalysts, rod-CeO 2 with (110) crystal face shows higher FDCA production than cube-CeO 2 (100) and oct-CeO 2 (111) for HMF oxidation. This result indicates that the catalytic performance depends on the exposed crystal faces.…”

Current Advances in the Sustainable Conversion of 5‐Hydroxymethylfurfural into 2,5‐Furandicarboxylic Acid

“…Extensive work was also directed toward milder conditions in terms of pressure. Rabee et al, [29] for example, studied a series of gold-based catalysts supported on monoclinic tetragonal ZrO 2 and Mg-modified zirconia at atmospheric pressure and mild temperature, achieving FDCA with 95 % yield. Liu et al [16] reported the successful application of β-zeolite/encapsulated Pt nanoparticles, obtaining FDCA at 90 °C and 0.1 MPa with a yield up to 90 %.…”

Catalytic Conversion of 5‐Hydroxymethylfurfural to High‐Value Derivatives by Selective Activation of C−O, C=O, and C=C Bonds

“…They found that the addition of Mg ions in/on the zirconia support at appropriate calcination temperature plays an important role in optimizing the interaction between gold nanoparticles and the support by fine-tuning the surface base properties of the zirconia supports and creation of oxygen vacancies, and thus excellent results can be achieved. [83] Various morphology CeO 2supported Au catalysts were also applied for HMF oxidation, and the Au/CeO 2 -rod was more efficient for the oxidation reaction. In the catalytic system of Au/CeO 2 , oxygen vacancies on the AuÀ CeO 2 interface determined the catalytic activity by affecting the size, valence of Au, and the interfacial acidic properties, and the results demonstrated that the Au/CeO 2 -rod with the highest oxygen vacancies presented a higher proportion of cationic gold and more interfacial Lewis acidic sites between ceria and Au nanoparticles.…”