Journal of Energy Chemistry
·
2014
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IF 0
Hongyan Li,Hong Ma,Xinhong Wang,Jin Gao,Chen Chen,Song Shi,Minjie Qu,Na Feng,Jie Xu
Efficient catalytic oxidation of ethylbenzene to acetophenone was realized using the catalytic system of cobalt zeolitic imidazolate framework ZIF-67/N-hydroxyphthalimide (NHPI) under mild conditions. 95.2% conversion of ethylbenzene with 90.3% selectivity to acetophenone could be obtained at 373 K under 0.3 MPa O 2 for 9 h. The results show that there exists synergetic effect between ZIF-67 and NHPI. 1-Phenylethyl hydroperoxide (PEHP) was generated via a radical process involving the hydrogen abstraction from ethylbenzene by phthalimide N-oxyl, and subsequently effectively decomposed to acetophenone by ZIF-67.
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
APPLIED CATALYSIS A-GENERAL
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2024
·
IF 4.7
Lihong Ding,Xiuliang Sun,Chongpin Huang,Jianwei Li,Biaohua Chen
Cumyl hydroperoxide (CHP) is an important intermediate in phenol/acetone production; however, its long reaction time and low yield remain industrial challenges. In this study, an active and promising catalyst combination—NHPI + BmimBr ionic liquid (IL)—was developed for cumene oxidation under solvent-, transition-metal-salt-, and CHP-initiator-free conditions, which exhibited a synergistic catalytic effect and excellent catalytic performance. The cumene oxidation rate was accelerated by 33.3 %, leading to the rapid synthesis of a significant amount of the target product, CHP. DFT calculations demonstrated that NHPI undergoes hydrogen atom abstraction reaction through its interaction with BmimBr, forming PINO and carbene-Br radicals that can extract hydrogen. Additionally, EPR analysis demonstrated that both radicals are involved in the reaction. The nature of the synergistic effect was confirmed using theoretical and experimental approaches. The proposed catalyst eliminates the requirement of an initiator for IL and NHPI application, paving the way for the efficient production of CHP without solvents or initiators.
研究领域:
化学工程
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催化化学
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
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2015
·
IF 3.615
Qiming Zhao,Kexian Chen,Wensong Zhang,Jia Yao,Haoran Li
A metal- and initiator-free catalytic system comprising N -hydroxyquinolinimide (NHQI) and 4-carboxyl- N -hydroxyphthalimide (Car-NHPI) was developed for the oxidation of ethylbenzene using molecular oxygen as the terminal oxidant. The catalytic activity of Car-NHPI/NHQI catalytic system was higher than that of Car-NHPI or NHQI alone. The high catalytic performance of Car-NHPI/NHQI catalytic system could be attributed to the dual interactions of radical exchange and acid-base neutralization, which resulted in the increment of the conversion of ethylbenzene up to 70% and the selectivity of acetophenone up to 66% at 120 °C under 1 atm O 2 for 15 h.
研究领域:
化学工程
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环境科学
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Yuxi Li,Zhuwei Zhu,Ximai Zhang,Fengkuan Ma,Qiaohong Zhang,Chen Chen,Hongying Lü
Selective oxidation of hydrocarbon under mild conditions is one of scientific challenges. In the present work, facet effect was utilized to design an efficient catalytic system of N -hydroxyphthalimide (NHPI) and specific α-Fe 2 O 3 with different preferential crystal facets. Higher ratio of crystalline facet {110}/{104} was identified as a key factor to facilitate the interaction between NHPI molecules and surface of α-Fe 2 O 3 , then realize a higher catalytic activity. Being photo-irradiated with the blue light (455 nm, 3 W) at ambient temperature for 4 h, conversion of 92.2% was obtained for the selective oxidation of ethylbenzene with α-Fe 2 O 3 -T100 that owns more preferential crystalline facets {110}, which is about 1.8 times as high as that (51.0%) being obtained with commercial C-α-Fe 2 O 3 -{104}. The present efficient catalytic system also exhibited good universality for the selective oxidation of a series of other hydrocarbons.
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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物理化学
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产品关联
DOI
高影响因子
Molecular Catalysis
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2020
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IF 3.687
Sihao Xu,Guojun Shi,Ya Feng,Chong Chen,Lijun Ji
Acetophenone is an important industrial intermediate and generally produced by the Friedel-Crafts acylation reaction, suffering from a low reactivity and serious equipment corrosion. Direct oxidation of ethylbenzene to acetophenone by molecular oxygen will be benign and cost-effective. The catalytic performance of NHPI/Co(II) herein was investigated by selective oxidation of ethylbenzene to acetophenone in different solvents at room temperature. The solvent hexafluoropropan-2-ol (HFIP) was found to markedly enhance the transformation efficiency from ethylbenzene to acetophenone in comparison with acetic acid, pyridine and ethanol, and the ethylbenzene conversion and the selectivity to acetophenone was high up to 87.9 % and 61.2 %, respectively. A higher concentration of phthalimide -N- oxyl (PINO) radicals was observed by an in situ electron paramagnetic resonance spectrometer (EPR) in HFIP with respect to other solvents, suggesting that HFIP may facilitate the generation of the N-oxyl radical and thus promote the selective oxidation of ethylbenzene to acetophenone. Furthermore, the benzylic carbon radical (PhCHCH 3 ) from ethylbenzene was trapped by tetramethylpiperidine N-oxyl radical (TEMPO) and observed by a high resolution mass spectrometer. The findings of both PINO and PhCHCH 3 under reaction conditions indicated that the selective oxidation of ethylbenzene to acetophenone catalyzed by NHPI/Co(II) should proceed via a radical mode. The selective oxidation of ethylbenzene to acetophenone using molecular oxygen by NHPI/Co(II) in HFIP exhibited an important industrial application prospect.
研究领域:
化学工程
·
有机化学
✓ 已验证
DOI
高影响因子
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
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2025
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IF 1.9
Guanwen Chen,Bo Yuan,Ruolin Wang,Min Yang,Zhanke Wang,Guangxu Zhang
As an important monomer material for synthesizing polycaprolactone, ε-caprolactone (ε-CL), is currently produced through the Baeyer–Villiger oxidation of cyclohexanone. As a green and promising process to produce ε-CL, oxidizing cyclohexanone with air in the presence of sacrificial agents has attracted extensive attention from academia and industry. However, the slow reaction kinetic and the weak oxidation capacity of air limits the application of this green technology. Herein, we used N-hydroxyphthalimide (NHPI) as a higdhly efficient homogeneous catalyst for the air oxidation of cyclohexanone. Through investigating the influence of reaction conditions such as temperature, gas velocity, aldehyde-ketone ratio, and solvent ratio on the conversion rate of cyclohexanone and selectivity of ε-CL, an optimum reaction condition was obtained and the ε-caprolactone production rate is as high as 3.43 mmol/gcat/min with a selectivity of 90%. The reaction mechanism is investigated through in-situ UV–visible spectra, electron paramagnetic resonance (EPR) spectra, and starch/KI experiment, and a plausible mechanistic mode involving three pivotal reactions was proposed. The dynamic model was constructed to validate the proposed mechanism and provide good predictions for the actual reaction rate. This work provides meaningful insights into NHPI-catalyzed air oxidation of cyclohexanone, and the constructed kinetic model provides theoretical guidance for scale-up processes.
研究领域:
化学工程
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催化化学
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绿色化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Dongmei Hao,Yanbin Sun,Dezhong Xie,Fuhao Chu,Weiguang Wang,Anran Zhou,Chen Chen,Yong Wang,Hongying Lü
The oxidation of 5-hydroxymethylfurfural (HMF) to produce high value-added 5-formyl-2-furancarboxylic acid (FFCA) represents a promising biomass conversion reaction that holds potential for biomass-based material for the drug synthesis and polyester industry. The present study presents a metal-free and alkali-free catalytic system consisting of N-hydroxyphthalimide (NHPI) as an organic molecule and a deep eutectic solvent (DES). This system was successfully employed for the aerobic oxidation process of HMF to FFCA, demonstrating exceptional catalytic activity with 100% conversion and 96% FFCA yield in the absence of any alkali. Multiple hydrogen bond interactions were found to be indispensable and play a crucial role in promoting the catalytic process. These H-bond interactions serve three essential purposes: facilitating the formation of deep eutectic solvents (DESs) between polyethylene glycol and tetrabutylammonium chloride, accelerating the dissolution and activation of HMF, and aiding in the generation of active free radicals for NHPI. This work demonstrated the predominant oxidation ability of the NHPI-DESs system for the oxidation of HMF to FFCA through hydrogen bond interaction, thereby offering invaluable insights into the aerobic oxidation processes involving hydrocarbons or alcohols.
研究领域:
有机化学
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生物质转化
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催化化学
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产品关联
DOI
高影响因子
EUROPEAN POLYMER JOURNAL
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2023
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IF 6
Huizi Zhang,Xu Zhao,Xiyue Wang,Yuchao Li,Shuangshuang Wang
Developing polyolefin microporous membranes with good antifouling ability and high separation efficiency is an important and urgent work. Herein, polypropylene microporous membranes (PP (mm)) containing zwitterionic polymer was prepared by grafting poly (sulfobetaine methacrylate) (PSBMA) onto the membrane via N-hydroxyphthalimide(NHPI) catalysis and activators regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP) for the first time. The structure, morphology, hydrophilicity and antifouling ability of PP (mm)-g-PSBMA was systematically studied. Water contact angle of the modified membrane could be sharply reduced at a proper grafting degree (GD), and it exhibited extraordinary hydrophilicity. The PP (mm)-g-PSBMA membrane also showed excellent protein antifouling ability and higher water flux compared to that of pristine PP membrane. Flux recovery ratio (FRR) of PP (mm)-g-PSBMA was increased to 93.1 % and relative flux reduction ratio (RFR) was decreased to 25.3%. This work presents a controllable and high efficiency strategy to polyolefin separation membrane for high value products.
研究领域:
材料科学
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膜技术
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高分子化学
✓ 已验证
产品关联
DOI
高影响因子
Environmental Science and Ecotechnology
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2024
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IF 14
Honglong Zhang,Qiaoqiao Zhao,Kangbao Zhong,Ruopeng Bai,Jiaojiao Dong,Jun Ma,Jing Zhang,Timothy J. Strathmann
Research efforts on permanganate (Mn(VII)) combined with redox-mediator (RM), have received increasing attention due to their significant performance for bisphenol-A (BPA) removal. However, the mechanisms underpinning BPA degradation remain underexplored. Here we show the overlooked interactions between RM and BPA during permanganate oxidation by introducing an RM—N-hydroxyphthalimide (NHPI). We discovered that the concurrent generation of MnO 2 and phthalimide- N -oxyl (PINO) radical significantly enhances BPA oxidation within the pH range of 5.0–6.0. The detection of radical cross-coupling products between PINO radicals and BPA or its derivatives corroborates the pivotal role of radical cross-coupling in BPA oxidation. Intriguingly, we observed the formation of an NHPI-BPA complex, which undergoes preferential oxidation by Mn(VII), marked by the emergence of an electron-rich domain in NHPI. These findings unveil the underlying mechanisms in the Mn(VII)/RM system and bridge the knowledge gap concerning BPA transformation via complexation. This research paves the way for further exploration into optimizing complexation sites and RM dosage, significantly enhancing the system's efficiency in water treatment applications.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2020
·
IF 3.807
Yuan Li,Yuyang Wei,Wenbin Zhang
The effect of proton acceptor on the electrochemistry of proton-coupled electron transfer reagents is always worthy of attention. Formal potentials of NHPI with different proton acceptors have been measured by cyclic voltammetry and were used to discriminate hydrogen bonding and deprotonation engaging in the oxidation of NHPI. With the negative shifting of formal potentials, the formation of hydrogen bonding complex was suggested when adding water into NHPI acetonitrile solution, a new wave caused by the addition of one pyridine base may be caused by a deprotonation process followed by a single electron transfer step. In addition, electrooxidation reactions of benzyl alcohol mediated by hydrogen bonding or deprotonation modified NHPI have been addressed and significant findings have been reported.
研究领域:
电化学
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有机化学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2026
·Vol. 18
·期 18
·e71062
·
IF 4.1
Zheng Yang,Yin-Bo Yang,Chong Zhang,Yu-Le Wang,Zi-Yang Zhu,Song-Hai Wu,Yong Liu,Han Xu
Oxidation of alcohols to acids is a key transformation in the chemical industry; however, one-pot oxidation to acids via the environment-friendly and cost-effective method remains challenging. In this study, a series of ZIF-67-derived CoO x catalysts were synthesized, and ZIF-CoO x -2 exhibits a high conversion of 95.2% 2-methyl-1-butanol and selectivity of 99% toward 2-methyl-1-butanic acid by O 2 in the presence of NHPI. In addition, this protocol is also efficient in the one-pot oxidation of a variety of alcohols to acids. The gram-scaled reaction can also be conducted using O 2 or even air as the oxidant. EPR analysis indicates that the NHPI-PINO cycle plays an important role in this process. Quenching experiments and Raman analysis indicate that Co-superoxo on the surface of ZIF-CoO x -2 is an important oxidizing species facilitating the NHPI-PINO cycle. DFT calculations further reveal that the NHPI-PINO cycle facilitates H-abstraction from alcohols by PINO, as well as H-abstraction from NHPI by ROO•, thus apparently enhancing the conversion and selectivity. This study offers a sustainable method to directly oxidize alcohols to acids with high conversion and selectivity, enriching our understanding on the importance of synergistic interactions between the surface superoxo species and the NHPI-PINO cycle in the selective oxidation of organic substrates. Graphical Co-superoxo (≡Co—OO•) species on the surface of the recyclable ZIF-CoO x -2 catalyst facilitate the NHPI-PINO cycle, efficiently promoting the selective aerobic oxidation of alcohols to carboxylic acids via hydrogen abstraction. This catalytic system delivers up to 98% conversion and 99% selectivity with broad substrate scope and gram-scale applicability.
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·
IF 3.9
Chong Zhang,Yu-Dong Shan,Yi-Ying Lin,Yu-Le Wang,Zheng Yang,Yong Liu,Song-Hai Wu,Xu Han
Diacetyl (2,3-butanedione) is an important ingredient used in the food and perfume industries, whose synthesis is largely constrained by environmental pollution and low selectivity. In this study, Fe-MIL-88B_NH2 has been successfully synthesized via the microwave-assisted solvothermal method, which exhibits high reactivity in acetoin oxidation, affording 81.3% conversion and 95.8% selectivity toward diacetyl under mild conditions in the presence of NHPI (N-hydroxyphthalimide). Raman and a series of characterizations reveal that O2 is activated by surface Fe(II) on Fe-MIL-88B_NH2 with the generation of ≡Fe-OO• superoxo, which then abstracts H from acetoin with the formation of diacetyl and H2O2. Quenching experiments indicate that ≡Fe-OO• superoxo on Fe-MIL-88B_NH2 is the primary oxidizing species in the oxidation of acetoin. EPR and DPD analyses further reveal that the NHPI/PINO cycle effectively shuttles H from the acetoin to ≡Fe-OO• superoxo, thus enhancing the oxidation efficiency of acetoin. This study enriches our understanding on the importance of surface superoxo species and the H-shuttle in the selective oxidation of alcohols toward ketones.
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DOI
高影响因子
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