Chem Catalysis
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2022
·
IF 0
Xianhao Zhang,Huijuan Jing,Shiming Chen,Bing Liu,Liang Yu,Jianping Xiao,Dehui Deng
Summary Cyclohexanone oxime (CHO), a key C=N organic compound in the manufacture of nylon 6, is conventionally synthesized via a multistep process that consumes expensive NH 3 and H 2 under harsh conditions. Herein, we report the direct electro-synthesis of CHO from low-cost NO, H 2 O, and cyclohexanone over a carbon catalyst under ambient conditions. A high Faradaic efficiency of 44.8% and a formation rate of 10.7 mg cm −2 h −1 for CHO were achieved at −0.4 V versus the reversible hydrogen electrode through optimizing the surface hydrophobicity of the catalyst to facilitate diffusion of reactants. Controlled experiments and 15 N-labeling tests verified that the nitrogen in the CHO product originates from NO. Density functional theory calculations showed that the armchair edge of carbon could be the active site with a reaction mechanism following NO → NO∗ → HNO∗ → HNOH∗ → NH 2 OH → CHO. This work suggests a direct, green, and low-cost synthesis strategy for high-value CHO from pollutant NO.
研究领域:
化学工程
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环境科学
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DOI
RSC Advances
·
2015
·Vol. 5
·期 32
·25365-25371
·
IF 3.84
Yang Li,Kai Wang,Kang Qin,Tao Wang
As an important green synthesis technology of caprolactam, the Beckmann rearrangement reaction of cyclohexanone oxime using high temperature and pressure water as the reaction media was carefully studied with a microreactor. An important byproduct – acetamide was confirmed with a selectivity higher than 40% in the subcritical water, which was more serious than the reported cyclohexanone. The effects of phase state and operating conditions, such as reaction temperature, pressure, flow rate ratio and reactant residence time, on the cyclohexanone oxime conversion and caprolactam selectivity were carefully analyzed, and the results showed that keeping the reaction close to the supercritical state was critical for the preparation of caprolactam.
研究领域:
化学工程
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绿色化学
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DOI
高影响因子
Green Chemical Engineering
·
2023
·
IF 0
Xin Guo,Zhiyuan Wang,Ye Yang,Jiahui Zhang,Yanduo Liu,Zhiyuan Mu,Siqi Jiang,Chunxiao Ren,Dan Lv,Yufeng Hu,Zhichang Liu
A production technique with the high yield and environmentally friendly process need be developed for ε-Caprolactam (CPL) in the chemical industry. This technology is highly desired to design and synthesize high−performance catalysts for liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) to CPL. In this work, 3-methyl-1-(propyl-4-sulfonyl) imidazolium methanesulfonate ([PHSO 3 MIM][MSA]) with highly efficient and excellent yield is synthesized successfully. When the optimum molar ratio of ZnCl 2 over [PHSO 3 MIM][MSA] was 0.02, it exhibits the high selectivity (94%) of CPL at 90 °C for 1 h. Interestingly, Fourier-transform infrared (FT-IR) investigations show that the functional Brønsted−Lewis acidic types of ionic liquids (ILs) are formed by the uniformly distributed ZnCl 2 and [PHSO 3 MIM][MSA]. In addition, the hydrogen bond (H-bond) is formed between CHO and ILs. After ten reaction cycles, no significant structure changes are observed in the recovered [PHSO 3 MIM][MSA]·ZnCl 2 . The solubilities of ILs are predicted by using COSMO-RS model, the results show that [PHSO 3 MIM][MSA] is a promising candidate for the liquid phase Beckmann rearrangement of CHO into CPL. Finally, a theoretical model of the H-bond interactions between ILs and CHO is further confirmed to support the advance of reaction mechanism. A feasible way is provided for the CPL production technique in the liquid phase Beckmann rearrangement reaction.
研究领域:
化学工程
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催化化学
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DOI
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2012
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IF 2.237
Yi-Qiang Deng,Shuang-Feng Yin,Chak-Tong Au
Series of silicalite-1 catalysts with particle size varying from 50 to 450 nm were synthesized by hydrothermal method using tetrapropylammonium hydroxide as a template and l-lysine as an additive. The crystal size of silicalite-1 could be easily controlled by regulating the amount of l-lysine. The series of silicalite-1 and their NaOH-modified derivatives were examined as catalysts for vapor-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam in the 330–390 °C range. It was found that the crystal size of silicalite-1 has an effect on catalytic activity, ε-caprolactam selectivity, and catalyst stability. With a decline in crystal size, there was improvement of catalytic activity and catalyst stability. It is deduced that silicalite-1, of a smaller crystal size, is less inclined to pore blocking by coke and hence has better resistance to deactivation.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2015
·
IF 3.942
Difan Li,Dan Mao,Jing Li,Yu Zhou,Jun Wang
Exploring environmentally friendly, efficient and recyclable heterogeneous catalysts for low-temperature liquid-phase organic reactions are important for the development of green and sustainable processes. In this work, we applied an in situ sulfonated polymeric solid acid H-PDVB-SO 3 H for catalyzing liquid-phase Beckmann rearrangements for the first time, with post-sulfonated sample and other various counterparts as control catalysts. H-PDVB-SO 3 H was prepared by copolymerization of divinylbenzene with sodium p -styrene sulfonate under solvothermal condition, followed by ion-exchanging to convert the polymer into proton form. It possessed a large surface area, plenty of mesopores and high sulfur content, and exhibited the high yield to ε-caprolactam (75%) with quite steady reusability in the heterogeneous Beckmann rearrangement of cyclohexanone oxime. The catalyst also showed good substrate compatibility with such a high reaction rate that the reaction time was as short as 1 h. No any co-catalysts or metals were used in the catalytic system, making the catalyst an environmentally friendly and efficient candidate for Beckmann rearrangements.
研究领域:
绿色化学
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催化化学
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DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 6
·978
·
IF 3.9
Chunxiao Ren,Zhiyuan Wang,Qingwei Gao,Jisheng Li,Siqi Jiang,Qizhong Huang,Ye Yang,Jiahui Zhang,Yajing Wang,Yufeng Hu,Zhichang Liu,Xin Guo
Exploring environmentally friendly, efficient, cheap and recyclable catalysts are essential for the development of green, sustainable and mild processes for the liquid-phase Beckmann rearrangement. Herein, a novel caprolactam-based Brønsted acidic ionic liquid ([CPL][2MSA]) was developed for the conversion of cyclohexanone oxime (CHO) to caprolactam (CPL), not only as a catalyst, but also as a mild reaction medium. Under the reaction conditions for the reaction temperature (90 °C), reaction time (2 h) and mole ratio ([CPL][2MSA]: CHO = 3:1), [CPL][2MSA] possesses plenty of high sulfonate groups, which exhibit high conversion (100%) and selectivity (95%) without any other co-catalysts or metals. Based on the thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses, the decomposition and glass transition temperatures are gradually increased with the increase in MSA mole content, revealing the existence of hydrogen-bonded clusters. Interestingly, the occurrent route of the liquid-phase Beckmann rearrangement for CHO in [CPL][2MSA] is revealed by in situ FT-Raman. In addition, the dominating H-bond combination between CHO and [CPL][2MSA] is further confirmed by COSMO-RS model. The activation energy (Ea) of the reaction is calculated by the first-order reaction kinetics. Thus, the [CPL][2MSA] with plenty of acidic catalytic active species is an environmentally friendly and efficient candidate for the liquid-phase Beckmann rearrangement.
研究领域:
绿色化学
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催化化学
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DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-10
·
IF 14.7
Tang Yirong,Jiang Zhan,Yuan Yubo,Xu Li,Jin Chuyao,Chen Bulin,Lin Zhichao,Zao Jie,Du Jianwei,Zhang Xiao,Gao Xiang,Liang Yongye
The electrocatalytic reduction of nitrogenous waste offers a sustainable approach to producing nitrogen-containing chemicals. The selective synthesis of high-value hydroxylamine (NH 2 OH) is challenging due to the instability of NH 2 OH as an intermediate. Here, we present a rational electrocatalyst design strategy for promoting NH 2 OH electrosynthesis by suppressing the competing pathways of further reduction. We screen zinc phthalocyanines (ZnPc) with a high energy barrier for NH 2 OH reduction by regulating their intrinsic activity. Additionally, we discover that carbon nanotube substrates exhibit significant NH 3 -producing activity, which can be effectively inhibited by the high coverage of ZnPc molecules. In-situ characterizations reveal that NH 2 OH and HNO are generated as intermediates in nitrate reduction to NH 3 , and NH 2 OH can be enriched in the ZnPc electrode. In the H-cell, the optimized ZnPc catalyst demonstrates a Faradaic efficiency (FE) of 53 ± 1.7% for NH 2 OH with a partial current density exceeding 270 mA cm −2 and a turnover frequency of 7.5 ± 0.2 s −1 . It also enables the rapid electrosynthesis of cyclohexanone oxime from nitrite with a FE of 64 ± 1.0%.
研究领域:
电化学
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催化
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环境科学
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材料科学
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产品关联
DOI
PubMed
高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
·
2025
·
IF 3.5
Yan Jiaqi,Chen Wenkai,Ni Wenjin,Li Lu,Fu Jinfeng,Yang Qian,Yang Zhiyong
N -cyclohexylcyclohexanimine (N-CCA), a by-product of cyclohexylamine (CHA) oxidation to cyclohexanone oxime (CHO), was used as the starting reactant for the efficient conversion to CHO under an oxygen atmosphere, utilizing the constructed surface hydroxyl-rich Ti-based catalysts. Of these, the 20% TiO 2 /Hβ catalyst exhibited unique catalytic activity and stability, achieving 45.9% N-CCA conversion and 82.1% CHO selectivity, with the content of high-boiling by-products not exceeding 1.0%. The superior catalytic performance, as evidenced by characterization results, stems primarily from: (i) the combination of TiO 2 and Hβ, which promotes the formation of a high specific surface area with fine TiO 2 nanoparticles and high-density Ti δ+ active sites, which facilitate the adsorption and activation of N-CCA; (ii) the construction of rich hydroxyl groups, which enhances the Brønsted acid sites, thereby improving the generation of active oxygen species; (iii) the intercrystalline embedding of TiO 2 and Hβ, which forms Ti–O–Si bonds, effectively inhibiting Ti leaching and ensuring excellent catalyst stability. The conversion of N-CCA, the main by-product of CHA oxidation, to the desired CHO using an efficient and robust 20% TiO 2 /Hβ catalyst represents an attractive pathway.
研究领域:
催化
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材料科学
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化学反应工程
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表面化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2026
·
IF 6
Fuhua Zhang,Yuxin Zhang,Pengpeng Wen,Yuhao Nie,Yanyuan Song,Qing Zhu,Wenbo Gong,Yufei Liu,Jingyi Lao,Jialuo Yin,Huihui Wang,Yue Liu,Sai Geng,Shiwei Liu
The intrinsic tension among strong Brønsted acidity, Lewis acid assistance, and catalyst stability in homogeneous systems fundamentally constrains the efficiency and recyclability of Beckmann rearrangement catalysis. In conventional dual-acid systems, static Brønsted–Lewis interactions inevitably lead to active-site passivation, acid accumulation, and irreversible deactivation, thereby severely compromising catalytic activity and reusability. Here, we report an intelligent, thermo-responsive Brønsted–Lewis dual-acid deep eutectic solvent, RDES[PEG600][CF 3 COOH] 3 [InCl 3 ] 0.1 , constructed on a dynamic coordination-switching strategy. By enabling reversible switching of coordination sites and autonomous regeneration of active centers, this system successfully overcomes the above-mentioned limitations. Trace amounts of In 3+ not only introduce spatially well-dispersed Lewis acid sites but also induce a controllable perturbation of the hydrogen-bonding network, thereby promoting reversible oxygen-to-nitrogen (O → N) coordination switching during the catalytic cycle. This dynamic synergy effectively prevents acid-site saturation and enables a temperature-driven homogeneous reaction/heterogeneous separation process. Experimentally, under reaction conditions of 100 °C, cyclohexanone oxime conversion reaches 99.7% with an ε-caprolactam selectivity of 99.3%, accompanied by a pronounced reduction in the apparent activation energy to 21.0 kJ·mol −1 . Combined density functional theory calculations, molecular dynamics simulations, and electronic structure analyses reveal a previously unrecognized catalytic state-evolution mechanism, in which Lewis acid coordination switching is precisely synchronized with proton transfer, rearrangement chemistry, and catalyst self-repair. Beyond providing a new paradigm for the design of stimuli-responsive polyacid catalytic systems, this work establishes a theoretical foundation for the development of multifunctional liquid-phase catalysis extending well beyond the Beckmann rearrangement.
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产品关联
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Huanyu Zeng,Cheng Xu,Xiaoping Wang,Jianhua Song,Dianzi Zhang,Benbin Li,Hongqin Hu,Dianhua Liu,Baowei Yu
The development of efficient and stable solid acid catalysts for the Beckmann Rearrangement is critical to advancing sustainable chemical synthesis. However, challenges persist in balancing active site density, structural stability, and mass transfer efficiency. To address these limitations, nanosphere sulfonic acid resins were synthesized through soap-free emulsion polymerization and evaluated in the liquid-phase Beckmann Rearrangement, achieving exceptional performance with 86.96 % conversion and 96.12 % selectivity. Density Functional Theory (DFT) calculations revealed distinct catalytic performance of terminal sulfonate groups versus paired sulfonate groups, with the latter found to be the dominant active sites. Three distinct reaction pathways for cyclohexanone oxime (COX) were proposed based on the spatially constrained distribution of the two different active sites within the catalyst architecture, supported by subsequent DFT calculations providing mechanistic insights into the differential characteristics. Characterization of the catalysts through BET, SEM, TEM, FT-IR, TG, and acid-base titration indicated that 20 % divinylbenzene (DVB) content yielded the highest acidic sites density, while 10 % DVB content produced the most uniform nanosphere morphology. Notably, turnover number (TON) analysis demonstrated that the catalyst with 10 % DVB content exhibited a TON 1.7 times higher than that of commercial resin, underscoring its superior efficiency.
研究领域:
催化化学
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材料科学
·
计算化学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2024
·
IF 2.7
Yufen Wang,Yantao Wang,Yongqing Ma,Asma Mohmmad Elsharif,Chen Zhang,Weiran Yang,Christophe Len
A new transition-metal-free catalytic system which uses sodium iodide as the catalyst with formic acid as the hydrogen donor in a biphasic medium was reported for the reduction of the hydroxyl group and various unsaturated groups such as CC, CC, CN and CO. Using the same catalytic system, reductive N-formylation of nitroarenes with formic acid was explored to produce the corresponding amide in high selectivity. Moreover, the catalyst stability was evaluated and reaction mechanisms were studied and proposed for the three model reactions.
研究领域:
有机化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
MINERALS ENGINEERING
·
2024
·
IF 4.9
Kangjing Wu,Yuxi Lu,Shuai Wang,Xin Ma,Hong Zhong
The weak collection ability of conventional benzohydroxamic acid (BHA) impedes its widespread application in the direct flotation of copper oxide minerals. Conversely, octyl hydroxamic acid (OHA) with enhanced hydrophobicity demonstrated superior collecting ability while exhibiting weak selectivity in malachite flotation. In order to achieve a balance between collecting ability and selectivity, we synthesized a novel N -cyclohexyl- N -hydroxyacetamide collector (ECHA) that featured similar structure of hydroxamate compounds and improved selectivity for the direct flotation of malachite. The bench-scale flotation results demonstrated that ECHA exhibited stronger collecting ability and excellent selectivity, 14.66% and 15.17% of copper recoveries increased than sodium butyl xanthate (SBX) and BHA, respectively. Contact angle tests, Zeta potential tests and solution chemistry analysis revealed that the interaction intensity of ECHA with malachite was significantly stronger than that of calcite and quartz. FTIR and XPS analysis showed that the reaction sites of ECHA were primarily located on the [–N(OH)CO–] group, suggesting possible chemisorption on the malachite surface. Additionally, DFT calculations indicated that the ECHA anion could potentially form a five-membered structure chelate complex with a Cu atom on the malachite surface through its [–N(OH)CO–] functional group. ECHA proved to be promising as an attractive collector in the direct flotation of malachite.
研究领域:
矿物加工工程
·
化学工程
·
理论计算
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）