Huayin Li

The synthesis of ester compounds is one of the most important chemical processes. In this work, Zn-Mg-Al mixed oxides with different Zn²⁺/Mg²⁺ molar ratios were prepared via co-precipitation method and supported gold nanoclusters to study the direct oxidative esterification of aldehyde and alcohol in the presence of molecular oxygen. Various characterization techniques such as N₂-physical adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and CO₂ temperature programmed desorption (TPD) were utilized to analyze the structural and electronic properties. Based on the results, the presence of small amounts of Zn²⁺ ions (~5 wt.%) provoked a remarkable modification of the binary Mg-Al system, which enhanced the interaction between gold with the support and reduced the particle size of gold. For oxidative esterification reaction, the Au₂₅/Zn_0.05MgAl-400 catalyst showed the best performance, with the highest turnover frequency (TOF) of 1933 h⁻¹. The active center was believed to be located at the interface between metallic gold with the support, where basic sites contribute a lot to transformation of the substrate.

Methyl methacrylate (MMA) is an important monomer in fine chemicals. The synthesis of MMA by one-step oxidative esterification from methacrolein with methanol over a heterogeneous catalyst with high activity, selectivity and stability is highly desirable. Herein, Zn-Al-hydrotalcites (HTs)-supported atomically precise Au₂₅ nanoclusters with different molar ratios of Zn²⁺/Al³⁺ were prepared and used as the precursors for this reaction. They exhibited good performances in comparison with the gold catalysts prepared by the deposition precipitation method. The structural and electronic properties were evaluated by various characterization technologies, including X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) of CO adsorption, X-ray photoelectron spectroscopy (XPS), and CO₂ temperature-programmed desorption (TPD). The combined characterization results suggested that the adsorption property of gold and the basicity of the catalyst contributes to their high activities. Substrates extended experiments and stability tests implied the potential application of Zn-Al-mixed oxides supported gold catalysts, which paves a new way for supported gold catalyst in the one-step oxidation esterification reaction.

Gold catalysts have been reported to exhibit good performance in aerobic oxidation of alcohols, but the intrinsic origin of the catalytic reactivity is still illusive. The catalyst preparation method, the morphology of the gold particles, and even the support might be key factors that determine the activity. Here, we prepared a series of gold catalysts with different supports, i.e., the hydrotalcite (HT), ZnO, MgO, Al₂O₃, and SiO₂, by using the atomically controlled Au₂₅ nanoclusters (NCs) as the gold precursor. The characterization results of the X-ray diffraction (XRD), UV-vis and transmission electron microscopy (TEM) show that the gold particles were mostly uniformly distributed on the supports, with a mean particle size within 3 nm. In aerobic oxidation of benzyl alcohol, the MgAl-HT- and Al₂O₃-supported Au₂₅ NCs display good performances, with turnover frequency (TOF) values of ~2927 and 2892 h⁻¹, respectively, whereas the SiO₂-, MgO-, and ZnO-supported analogues show much inferior activity. The high resolution TEM and X-ray photoelectron spectra (XPS) results suggest that the interactions between gold and the supports in different samples are differing, which influences the morphology and the nature of gold. Our results further point to the importance of acid-base property of the support and the metal-support synergy rather than the gold particle size alone in achieving high-performance in selective alcohol oxidation. Moreover, this work provided a good way to design gold catalysts with controllable sizes that is crucial for understanding the reaction process in aerobic oxidation of alcohol.