Fang Lai

Copper(II)-containing aluminum phosphate material (CuAPO-5) was synthesized hydrothermally and used as a multiphase catalyst for the oxidation of α-pinene to verbenone. The catalysts were analyzed using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area techniques, X-ray photoelectron spectroscopy (XPS), and ammonia temperature programmed reduction (NH₃-TPD). Scanning electron microscopy (SEM), X-ray energy spectrometry (EDS), inductively coupled plasma emission spectroscopy (ICP-OES), Fourier infrared spectroscopy (FT-IR), and ultraviolet-visible spectroscopy (UV-vis) were performed to characterize the material. The effects of reaction temperature, reaction time, n(α-pinene)/n(TBHP), and solvent on the catalytic performance of CuAPO-5 were investigated. The results show that all the prepared catalysts have AFI topology and a large specific surface area. Copper is evenly distributed in the skeleton in a bivalent form. The introduction of copper increases the acid content of the catalyst. Under the optimized reaction conditions, 96.8% conversion of α-pinene and 46.4% selectivity to verbenone were achieved by CuAPO-5(0.06) molecular sieve within a reaction time of 12 h. CuAPO-5(0.06) can be recycled for five cycles without losing the conversion of α-pinene and the selectivity to verbenone.

It has been a challenge to synthesize macrolide musk in excellent yields with high purity. KF-La/γ-Al ₂ O ₃ catalyst was prepared from a highly basic mesoporous framework using a mild method. The prepared KF-La/γ-Al ₂ O ₃ catalyst was employed for the synthesis of cyclopentadecanolide from methyl 15-hydroxypentadecanoate. The morphology and structure of prepared catalysts were characterized using XRD, TG-DTG, SEM, EDX, TEM, BET and CO ₂ -TPD. The results revealed that the K ₃ AlF ₆ and LaOF are produced on the surface of KF-La/γ-Al ₂ O ₃ , and LaO can promote the dispersion of KF on the surface of Al ₂ O ₃ . Catalysts pore size main distribution ranges between 10 and 30 nm, the maximum CO ₂ desorption temperature is 715°C when the La loading is 25%. Because F ⁻ ion has a higher electronegativity than O ²⁻ ion, the KF-promoted metal oxide (Al ₂ O ₃ or/and La ₂ O ₃ ) contained more strong basic sites, compared with that of the corresponding metal oxide. The yield of cyclopentadecanolide obtained at 0.5 g KF-25La/γ-Al ₂ O ₃ catalyst and a reaction temperature of 190°C for 7 h were 58.50%, and the content after reactive distillation is 98.8%. The KF-La/γ-Al ₂ O ₃ catalyst has a larger pore size and basic strength, which is more conducive to the macrolactonization of long-chain hydroxy ester.

The synthesis costs of macrolide musks are higher than those of other commercial musks. To make this process less expensive, eggshell waste was calcined at a low temperature to obtain a catalyst for the cyclopentadecanolide production via reactive distillation using a glycerol entrainer. X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses of the original and recovered catalysts revealed that the main catalytic ingredient was calcium glycerolate (CaG) and not calcium diglyceroxide (CaDG). The basic strengths of CaG and CaDG obtained by Hammett indicators were 7.2 < H_≤ 15.0 and 9.8 < H_≤15.0, while the corresponding base amounts were 1.9 and 7.3 mmol/ g, respectively. Because CaG was soluble in glycerine, the catalyst was efficiently reused. The reaction product containing over 95.0% cyclopentadecanolide with a yield of 49.8% was obtained at a temperature of 190°C and catalyst amount of 12 wt% after 7 h of reaction. Thus, eggshell waste may be directly placed into the reaction mixture after calcination at 600°C to synthesise a large amount of cyclopentadecanolide within a relatively short time. The results of this work indicate that eggshell waste can serve as a potential eco-friendly and affordable catalyst source for the production of macrolide musks.

A self-designed reaction device was used as a promising equipment to investigate the oxidation characteristics and kinetics of rosin pentaerythritol ester (RPE) under UV irradiation. Photo-oxidation kinetics and the initial quantum yield (Φ) of RPE were calculated. The initial oxidation product of the photo-oxidation reaction—peroxide was analyzed by iodimetry. The peroxide concentration is related to the light intensity (I) and the temperature (T), and the increasing T and I would destabilize the RPE by accelerating peroxide forming. Photo-oxidation of RPE follows the pseudo first-order reaction kinetics. The relationship between activation energy and logarithm of light intensity (ln I) is linear, and it is expressed as Ea = −4.937ln I + 45.565. Φ was calculated by the photo-oxidation kinetics, and the average value of Φ was 7.19% in the light intensity range of 200–800 μW cm⁻². This research can provide fundamental information for application of RPE, and help obtain a better understanding of the stability of rosin esters.