CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xiaolong Liu,Jiahe Sun,Shuo Li,Kaixuan Yang,Ting Su,Hongying Lü,Zhiguo Zhu
Sn-containing zeolite catalysts exhibit the unique feature of selectively activating carbonyl groups in organic compounds, which demonstrate relatively high activity and selectivity in the Baeyer-Villiger (B V) oxidation of aldehydes or ketones using H 2 O 2 as the oxidant. However, the influence of diffusion property and trace water on the ε-caprolactone selectivity as targeted product in the cyclohexanone's B V oxidation system with the green oxidant of aqueous H 2 O 2 remains unclear. To address this, three kinds of Sn-Beta zeolites are prepared by interzeolite transformation, structural reconstruction, and post-synthesis method to establish structure-property relationships. The physicochemical property and Sn coordinated state are investigated in detail. The existence of trace water in the reaction system negatively affects the conversion and product selectivity by competitive adsorption of water with reaction substrates and facilitated hydrolysis of ε-caprolactone, respectively. DFT calculation implies that kinetics dominates the conversion of cyclohexanone → ε-caprolactone → 6-hydroxycaproic acid. The structure-property relationship indicates that the cyclohexanone conversion and ε-caprolactone selectivity are closely related to the adsorption amounts of substrates and the diffusion performance of products, respectively, over Sn-Beta zeolite catalysts. Finally, the reusability and deactivation mechanism are analyzed. This study aims to provide guidance for designing efficient stannosilicate zeolite catalysts for B V oxidation through precisely modulating the zeolite's diffusion property.
研究领域:
催化化学
·
材料科学
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Zhihui Cai,Duo Liu,Jiangnan Huang,Jianning Feng,Hongjuan Wang,Guangxing Yang,Feng Peng,Yonghai Cao,Hao Yu
As an important raw material for the synthesis of polycaprolactone, a significant alternative for the nondegradable plastic, ε-caprolactone (ε-CL) monomer is typically produced through the Baeyer–Villiger oxidation of cyclohexanone (Cy═O). In this work, a solvent-free, highly efficient, and nonmetallic catalytic system was developed to produce the ε-CL monomer with dioxygen as the oxidant and benzaldehyde (BEA) as the co-oxidant. Nitrogen-doped carbon nanotubes (NCNTs) as the catalyst boost the catalytic activity (10.09% conversion, 10.06% yield of ε-CL), much higher than other carbon catalysts. The normalized specific activity of NCNTs reached 2964.80 mmol/g/h and 20.02 mmol/m2/h, which are 2–4 orders of magnitude higher than the state-of-the-art catalysts. The structure-dependent activity result shows that the ratio between pyridine nitrogen (NP) and graphite nitrogen (NG) on the surface of NCNTs positively affects the catalytic performance. Oxygen functionalities on the NCNT surface inhibit the activity by suppressing the auto-oxidation of BEA, which unexpectedly increases aldehyde efficiency. Finally, this process could be scaled up to a molar-scale reaction with a similar activity, which lays down the foundation of the industrial application of the solvent-free Baeyer–Villiger oxidation catalyzed by nanocarbons.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xiaolong Liu,Jiaxing Zhang,Xue Liu,Kaixuan Yang,Ting Su,Hongying Lü,Peng Wu,Zhiguo Zhu
Catalytic conversions of cyclic ketones into lactones by the Baeyer–Villiger oxidation are particularly attractive for practical applications because catalytic transformations minimize reactant use as well as waste production while simplify processing conditions. Understanding the unique behaviors of highly mesoporous Sn-Beta zeolite catalyst during Baeyer–Villiger oxidation is a challenging research topic. Herein, highly mesopore single-crystalline Sn-Beta zeolite (Sn-Beta-2s) is hydrothermally synthesized via our developed two-step interzeolite transformation strategy. The synthesis mechanism obeys dissolution–recrystallization process, where the degradation step is essential to prepare Sn-Beta-2s zeolite with abundant mesoporous and relatively high hydrophobicity. This single-crystalline Sn-Beta zeolite is adopted to the Baeyer-Villiger oxidation of cyclic ketones as heterogeneous Lewis acid catalyst. Structure-performance relationship reveals that the diffusion performance dominates the product selectivity over three Sn-Beta zeolites. Through the investigation of catalytic mechanism by in-situ FT-IR spectra and DFT calculations, it is found that carbonyl group is activated by zeolitic framework Sn. As for the bulky tert -butyl hydroperoxide oxidant, the reaction can be only triggered on the zeolite surface due to the severe steric constraints within zeolite channels, accounting for the excellent catalytic activity of Sn-Beta-2s zeolite with nanocrystalline nature.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Nano Materials
·
2024
·
IF 5.3
Jiwen Si,Ruifeng Guo,Fagui Qiu,Weikun Ning,Yanbin Sun,Wenqing Li,Qinglong Tao,Shiding Miao
The nanosize Beta-zeolites with hierarchical structures were time efficiently synthesized from natural diatomite and ball clays under 150 °C via a vapor-assisted method with the absence of solvents and F– anions. The Sn(IV) species were incorporated within frameworks of the presynthesized Beta-zeolite using a modified treatment of acid and tetraethylammonium hydroxide (TEAOH). The dealumination and reconstruction of zeolite frameworks were essential. A high atomic ratio of Si/Sn = 63.95 was obtained and the Sn(IV) species were in a tetrahedral coordination in the zeolite framework, as confirmed by various characterizations. The Sn-Beta zeolites show excellent performance in the Baeyer–Villiger oxidation reaction for the conversion of cyclohexanone to ε-caprolactone, with 63.3% conversion of cyclohexanone and superior selectivity for ε-caprolactone. The durability and stability of the catalyst was acceptable, as evidenced by a slight decrease in conversion of only 2.5% after 5 catalytic runs. These demonstrated a prototype practice in synthesizing Sn-Beta zeolites from natural ores and applicable catalysis in green chemistry.
研究领域:
材料科学
·
催化化学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2020
·
IF 2.627
Liqun Shen,Ran Cang,Guang Yang,Anqi Zeng,He Huang,Zhigang Zhang
The microbial production of either ester/lactones or enantio-enriched alcohols through Baeyer–Villiger oxidation or stereoselective reduction of ketones, respectively, is possible by using whole cells of A. subglaciale F134 as a bifunctional biocatalyst. The chemoselective pattern of acetophenone biotransformation catalyzed by these cells can be regulated through reaction temperature, directing the reaction either towards oxidation or reduction products. The Baeyer–Villiger oxidation activity of A. subglaciale F134 whole cells is particularly dependent on reaction temperature. Acetophenone was transformed efficiently to phenol via the primary Baeyer–Villiger product phenyl acetate at 20 °C after 48 h with 100% conversion. In contrast, at 35 °C, enantio-enriched ( S )-1-phenylethanol was obtained as the sole product with 64% conversion and 89% ee . In addition, A. subglaciale F134 cells also catalyze the selective reduction of various structurally different aldehydes and ketones to alcohols with 40% to 100% yield, indicating broad substrate spectrum and good enantioselectivity in relevant cases. Our study provides a bifunctional biocatalyst system that can be used in Baeyer–Villiger oxidation as well as in asymmetric carbonyl reduction, setting the stage for future work concerning the identification and isolation of the respective enzymes.
研究领域:
生物化学
·
微生物学
✓ 已验证
DOI
高影响因子
Science China-Chemistry
·
2024
·Vol. 67
·期 7
·2282-2291
·
IF 10.4
Jiao Meichen,Jia Chunmin,Xu Hao,Wu Peng,Zhang Xian-Ming
Ge-containing Lewis acidic zeolites are typically synthesized using a conventional hydrothermal strategy from amorphous silica sources, through a long time- and energy-consuming approach limiting their wide applications. This study reports a rapid synthesis strategy for a series of IWV aluminogermanosilicate zeolites ( T- x -Al ) with a wide range of Si/Ge molar ratios (5–15) by interzeolite transformation of dealuminated FAU (DA-FAU). Notably, Ge-rich IWV could be obtained with crystallization time as short as one day by the equimolecular Si/Ge ratio gel. The effect of synthetic parameters was investigated and the obtained T- x -Al samples were characterized by XRD, SEM, EDS, ICP, 29 Si and 27 Al MAS NMR, FTIR, and N 2 physisorption analyses. Compared with a previously reported IWV germanosilicate (H-3), T- x -Al displayed a better catalytic activity in Baeyer-Villiger (BV) oxidation, attributed to the presence of the active framework Ge sites with the assistance of the extra-framework Al species. The cyclic catalysis tests revealed that the presence of framework Al species contributed to the stability of the T- x -Al . Specifically, T- x -Al , with 14-membered ring (MR) supercages, outperformed the typical 12-MR Sn-beta catalyst in the BV oxidation of large ketone-like 2-admantanone, indicating a promising potential application in the macromolecular catalytic process.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Guiyi Zhao,Weiguang Wang,Kaixuan Yang,Ting Su,Zhiguo Zhu,Hongying Lü
A deep eutectic solvent (DES) comprising p-toluenesulfonic acid (PTSA) and polyethylene glycol 200 (PEG200) was synthesized and applied to the Baeyer-Villiger (B-V) oxidation reaction of 2-adamantanone, which exhibited good catalytic effect and cyclic stability under relatively mild conditions. It was found that the hydrogen bond of DESs not only governed their physical properties, such as viscosity and electrical conductivity, but also influenced their chemical behavior, including the catalytic effect in B-V oxidation reaction. By adjusting the composition, the hydrogen bond properties can be optimized. This study aims to elucidate the intricate relationship between composition, hydrogen bond strength, and physicochemical properties of DESs, thereby establishing a preliminary theoretical foundation for a comprehensive understanding and construction of DESs systems. This provides a novel and promising environmentally friendly approach for the B-V oxidation reaction.
研究领域:
化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2019
·
IF 4.182
Qingrun Meng,Jiaxu Liu,Guang Xiong,Xinyao Li,Liping Liu,Hongchen Guo
The Sn-Beta zeolite is an efficient Lewis acid catalyst for a wide range of chemical reactions. Here a seed-free aerosol-assisted hydrothermal strategy is used to synthesize plate-like Sn-Beta zeolite with higher tin content. A majority of Sn species were transformed into the framework of Beta zeolite as the desired tetrahedral coordination state, which creates strong Lewis acid sites. Moreover, the diffusion property of the Sn-Beta zeolite can be further improved by a mild base-surfactant (NH 3 ˙ H 2 O-CTAB) treatment. The addition of CTAB can not only narrow the mesopore distribution but also prevent the excessive loss of Sn species. The obtained hierarchical Sn-Beta zeolite exhibits an enhanced catalytic performance in the Baeyer–Villiger oxidation of bulky ketone.
研究领域:
催化材料
·
化学工程
·
纳米材料合成
✓ 已验证
DOI
高影响因子
Scientific Reports
·
2017
·Vol. 7
·期 1
·1-5
·
IF 4.259
Wang Xu-Ping,Zhou Peng-Fei,Li Zhi-Gang,Yang Bo,Hollmann Frank,Wang Yong-Hua
A Ser105Ala mutant of the lipase B from Candida antarctica enables ‘perhydrolase-only’ reactions. At the example of the chemoenzymatic Baeyer-Villiger oxidation of cyclohexanone, we demonstrate that with this mutant selective oxidation can be achieved in deep eutectic solvent while essentially eliminating the undesired hydrolysis reaction of the product.
研究领域:
生物化学
·
酶工程
·
绿色化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）