JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
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2014
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IF 3.679
Tie Jun Lin,Xuan Meng,Li Shi
A non-petroleum route to produce acrylic acid was investigated through hydrocarboxylation of acetylene with CO and water in the presence of Ni 2 O 3 and cupric bromide as combined catalysts. The activity of Ni 2 O 3 was compared with various homogeneous catalysts; the effect of initial total pressure, reaction temperature, molar ratio of CO/C 2 H 2 , the volume ratio of solvent/water, the catalyst amount and the role of promoters have been studied in detail. It was found that the acrylic acid space-time-yield as high as 764.6 mol AA/(mol Ni h) was obtained under the optimal experimental conditions. The Ni 2 O 3 catalyst could be reused at least five times without obvious loss of activity. The characterization of recovered catalysts by XRD, XPS, SEM and TG–DTG revealed that the state of nickel remains unchanged during the reaction, and there are three types of soft coke deposited on the surface of the catalyst. The catalysts can be regenerated through calcination within 400 °C according to TG curve.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED SYNTHESIS & CATALYSIS
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2020
·Vol. 362
·期 12
·2337-2341
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IF 5.851
Wei Hang,Yaping Yi,Chanjuan Xi
Cobalt-catalyzed reductive carboxylation of aryl bromides with carbon dioxide has been developed. The reaction proceeded under one atm pressure of CO 2 at 40 °C in the presence of cobalt iodide/2,2′-bipyridine catalysts and zinc dust as a reducing reagent. Various aryl bromides could be converted to the corresponding carboxylic acids in good to high yields. Preliminary mechanistic experiments ruled out intervention of intermediate organozinc species for carboxylation with CO 2 , thus suggesting a direct CO 2 insertion into the corresponding ArCoBr species.
研究领域:
有机化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Asian Journal of Organic Chemistry
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2023
·Vol. 12
·期 7
·e202300216
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IF 2.7
Yi-Ying Zhuang,Xiao-Chao Chen,Kai-Chun Zhao,Guo-Sheng Zhang,Yu-Fen Xie,Yong Lu,Ye Liu
Graphical Pd-catalyzed anti -Markovnikov hydrocarboxylation of vinylarenes with formic acid free of auxiliary additive has been reported. This work was financially supported by the National Natural Science Foundation of China (Nos. 22172052 and 21972045), and the Research Funds of Happiness Flower ECNU (2022ST2203).
研究领域:
有机化学
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催化化学
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产品关联
DOI
高影响因子
CURRENT ORGANIC SYNTHESIS
·
2017
·Vol. 14
·期 8
·1185-1192
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IF 1.917
Zhou Zhi-Hua,Guo Chun-Xiang,Xie Jia-Ning,Liu Kai-Xuan,He Liang-Nian
Aim and Objective: The carboxylation of organoboronic esters with CO2 is an attractive way of preparing the functionalized carboxylic acid derivatives. For the silver-catalyzed carboxylation of arylboronic esters with CO2, sensibility of catalytic system to CO2 pressure resulted in
a high CO2 pressure required in the reaction. This work focuses on solving this problem and promoting this transformation under atmospheric CO2 pressure. Material and Method: Arylboronic esters were synthesized according to the published procedure. Arylorganic esters, silver compound,
base, PPh3 and solvent were introduced into a 25 mL Schlenk flask. Then, the gasexchanging operation via a “freeze-pump-thaw” method was conducted. After being enclosed with a CO2 balloon, the resulting mixture was stirred at 70oC for 12 h. Then, the reaction was quenched by 1
M HCl and extracted with ethyl acetate. The yields of the corresponding carboxylic acids were determined by GC. The structures of products were confirmed by NMR and GC-MS. Results: The carboxylation of arylboronic esters with ambient CO2 was achieved on the basis of the silver chloride/triphenylphosphine
system by using cesium carbonate as the base and dimethyl sulfoxide as the solvent. Through this protocol, various functionalized carboxylic acids were synthesized in 85-99% yields. Conclusion: The silver-catalyzed carboxylation of arylboronic esters with ambient CO2 was established.
This approach represents an alternative way to prepare carboxylic acids derivatives from the organoboron compounds with CO2 under mild reaction conditions.
研究领域:
有机化学
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环境化学
✓ 已验证
DOI
高影响因子
Carbohydrate Polymer Technologies and Applications
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2022
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IF 0
Xiwang Cao,Min Liu,Wentao Bi,Jun Lin,David Da Yong Chen
The surface of cellulose particles was carboxylated (2.44 mmol/g) in a deep eutectic solvent containing carboxylic acid. Based on the carboxyl content, the effects of key factors on cellulose carboxylation was systematically investigated. In addition, the reaction mechanism was studied by using liquid chromatography-mass spectrometry, and the influence of deep eutectic solvent containing carboxylic acid on the structure and physicochemical properties of cellulose during carboxylation was examined using different characterization techniques. The results showed that the type of carboxylic acid, cellulose particle size, and pretreatment methods significantly affect the carboxylation efficiency, degradation, and carbonization of cellulose. The internal crystal structure of cellulose did not change after the carboxylation reaction, while the surface crystal structure was destroyed by carboxylation, which greatly improved the dispersion and hydrophilicity properties of the product. The kinetics and thermodynamics of carboxyl cellulose adsorption were studied as well. Potential application of carboxyl cellulose in the adsorption of pollutants was demonstrated. This study provides a new method for the direct modification of cellulose in deep eutectic solvents, as well as a new sustainable strategy for modifying other materials.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
DOI
DALTON TRANSACTIONS
·
2024
·
IF 3.5
Peiyao Liu,Zhengzeng Yang,Mengyuan Zhang,Yufeng Liu,Dandan Han,Dan Wu,Charles Chunbao Xu,Jianshe Wang
C-H carboxylation of furoic acid (FA) with CO2 is an atom-efficient strategy to produce 2,5-furandicarboxylic acid (2,5-FDCA) from lignocellulose. The existing carbonate-promoted CO2 carboxylation processes rely on the use of large amounts of expensive Cs2CO3 as deprotonating reagent and molten salt. Substitution of Cs with other cheap and abundant alkali ions (such as K and Na) can reduce the use of Cs, but faces the problem of low yield of 2,5-FDCA. This study found that the addition of catalytic amounts of ZnCl2 as a Lewis acid can increase the yield of 2,5-FDCA in the CO2 carboxylation reaction of Na/K-FA in a molten salt reaction system. 1H NMR analysis and DFT calculations confirmed that ZnCl2 coordinates with the furan ring through electron transfer from the conjugated furan ring to Zn2+, thereby activating the H at the C5 position of Na/K-FA. This coordination lengthened the C5-H bond and lowered its heterolytic dissociation energy, making it more susceptible to being deprotonated by CO32- and subsequently carboxylated by CO2. The developed Lewis acid coordination strategy provides a new idea for the efficient construction of C-C bonds between CO2 and aromatics through carbonate-promoted C-H carboxylation.
研究领域:
化学工程
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可再生资源转化
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
·
IF 9.4
Ziyu Gao,Huidong Wang,Yuchen Hu,Jianmin Sun
Multi-functional MOF catalyst with oxidative- and acid- centers showed potential in olefins oxidative carboxylation to cyclic carbonates directly. In this work, a series of bimetallic MnZn-MOF-74 with different molar ratios of Mn and Zn were synthesized successfully through a one-pot facile method. Thoroughly characterization indicated that the existence of Zn regulated the valance state distribution of Mn in the obtained MnZn-MOF-74. Mn 99.3 Zn 0.7 -MOF-74 with the highest ratio of Mn III (61.3 %) performed the most efficient activity for olefin direct tandem oxidative carboxylation reaction using aqueous tert -butyl hydroperoxide oxidant under solvent-free condition of 90 °C, 1.0 MPa CO 2 and 4 h. Mn 99.3 Zn 0.7 -MOF-74 also showed satisfactory versatility and recyclability. Based on the experiments, a feasible mechanism was presented. Thanks to the high ratio of active Mn III as main oxidative center, the coordination unsaturated bimetal Mn and Zn as Lewis-acid sites, O 2– of metal − O as Lewis-base sites and combined effect with Bu 4 NBr cocatalyst, Mn 99.3 Zn 0.7 -MOF-74 presented efficient performance for the direct synthesis of cyclic carbonates from olefins. The metal Zn in MOF can regulate the valance state distribution of Mn and result in efficient catalytic property, presenting a potential avenue for direct oxidative carboxylation reaction of olefins to cyclic carbonates synthesis.
研究领域:
化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2019
·Vol. 25
·期 36
·8560-8569
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IF 5.16
Xingwang Lan,Yiming Li,Cheng Du,Tiantian She,Qing Li,Guoyi Bai
Graphical Carboxylation catalysts : Porous carbon nitride frameworks with uniform and rich nitrogen dopants and abundant porosity were successfully fabricated through the carbonization of the covalent triazine frameworks at different pyrolysis temperatures, and used as supports to immobilize and stabilize Ag nanoparticles for catalytic CO 2 conversion (see picture). Porous carbon nitride frameworks (PCNFs) with uniform and rich nitrogen dopants and abundant porosity were successfully fabricated through the direct carbonization of the covalent triazine frameworks (CTFs) at different pyrolysis temperatures and used as supports to anchor and stabilize Ag nanoparticles (NPs) for catalytic CO 2 conversion. Importantly, the pyrolysis temperature plays a crucial role in the properties of porous carbon nitride frameworks. The material carbonized at 700 °C showed the highest surface area and micro- and mesoporous structure with a certain interlayer distance. Taking advantage of their unique surface characteristics, PCNF-supported Ag NP catalysts (Ag/PCNF- T , T =pyrolysis temperature) were prepared by a simple chemical method. A series of characterizations revealed that Ag NPs are embedded in the porous carbon nitride frameworks and confined to a relatively small size with high dispersion owing to the assistance of the abundant surface groups and porous structures. The as-obtained Ag/PCNF- T catalysts, especially Ag/PCNF-700, showed excellent catalytic activity, selectivity, and stability for the carboxylation of CO 2 with terminal alkynes under mild conditions. This can be due to the existence of abundant nitrogen atoms and diverse porosity, which resulted in highly efficient catalytic activity and stability.
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
高影响因子
Journal of CO2 Utilization
·
2020
·
IF 5.993
Jian Fang,Kun Li,Zhiqiang Wang,Difan Li,Yuan Ma,Xueqing Gong,Zhenshan Hou
The direct synthesis of cyclic carbonate from carbon dioxide (CO 2 ) and olefins is attracting much interest in recent years. Herein, 1,5,7-triazabicyclo[4.4.0]dec-5-ene-functionalized phosphonate salts have been synthesized and characterized fully by Nuclear Magnetic Resonance (NMR), Electrospray Ionization Mass Spectrometry (ESI-MS) and Fourier Transform-infrared Spectroscopy (FT-IR) etc. The as-obtained salts have been employed as efficient catalysts for one-pot synthesis of cyclic carbonate from styrene and CO 2 through oxidative carboxylation reaction under very mild conditions (0.1 MPa CO 2 , 80 °C) without any other solvents. The yield of cyclic carbonate can reach up to ca. 70 % in the presence of ZnBr 2 under the mild reaction condition. Besides, the catalyst can be recycled at least five times without significantly losing its catalytic activity. This approach can be extended to various styrene derivatives and good yields of cyclic carbonates was achieved under ambient conditions. Based on activity evaluation, reaction kinetics and DFT calculation, the six-membered carboxyphosphate species was proposed as a crucial intermediate species and played a crucial role in CO 2 activation. Finally, the reaction mechanism is proposed accordingly.
研究领域:
化学
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环境科学
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2023
·
IF 3.8
Xiaochen Han,Chongyang Guo,Yugao Wang,Gang Liu,Jun Shen
Furan-2,5-dicarboxylic acid (FDCA) is an important biomass-derived diacid, and it is the most promising substitute for terephthalic acid. The common method of FDCA usually involves 5-hydroxymethylfurfural oxidation. Edible fructose is often used as the feedstock of 5-hydroxymethylfurfural, and the oxidation step would generate undesirable impurities. Herein, FDCA was novelty synthesized by carboxylation of formate and 2-furoic acid (FA) derived from unedible-biomass. This route is potentially advantageous because it is simple to operate and does not require any additional additives. The reaction mechanism has been elucidated by density functional theory (DFT) calculations. In the carboxylation process, the C(sp 2 )-H bond of formate (HCOOM) undergoes cleavage, generating the carbon dioxide radical anion (CO 2 •− ). Subsequently, CO 2 •− attacks the C 5 of FA, forming the C C bond and ultimately yielding FDCA. The conversion of HCOOM to CO 2 •− is an effective way to achieve carboxylation reaction. The rate-determining step of the carboxylation reaction is the cleavage of the C(sp 2 )-H bond of HCOO − with activation barrier of 159.11 kJ⋅mol −1 . The investigation would provide a new strategy for the mechanism of carboxylation reactions, and hold the potential to establish pathways for FDCA production.
研究领域:
化学
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材料科学
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生物化学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Yuanyuan Cui,Jianmin Sun
The direct oxidative carboxylation of olefins and CO 2 to synthesize cyclic carbonates involves a tandem process of epoxidation and CO 2 cycloaddition reactions. However, designing a multifunctional catalyst for this reaction remains challenging. Herein, a composite catalyst ImBr@UiO-66-Br(Co) was synthesized by post-metallization of Co 2+ and subsequent functionalization with an imidazole ionic liquid (IL), which was used effectively for this reaction. The effects of temperature, CO 2 pressure, catalyst dosage, and reaction time on the direct oxidative carboxylation of olefins to cyclic carbonates were investigated. The results showed that ImBr@UiO-66-Br(Co) exhibited optimal performance in the solvent-free reaction system with styrene (3 mmol), tert -butyl hydroperoxide (6 mmol), and tetrabutylammonium bromide (TBAB, 50 mg) at 80 ℃ under 1 MPa CO 2 for 24 h, achieving a styrene conversion of 90.3 % and styrene carbonate selectivity of 80.7 %. The excellent catalytic activity of ImBr@UiO-66-Br(Co) was attributed to the synergistic interactions of the Lewis acidity Zr 4+ sites, the strong nucleophilicity provided by Br - , the weak base sites from tertiary amine and quaternary ammonium groups in imidazole IL, and the redox-active Co 2+ sites. Additionally, the catalyst was easy to separate and maintained stable activity and selectivity over at least five cycles. Finally, the potential catalytic mechanism for the direct oxidative carboxylation of olefins to cyclic carbonates was proposed.
研究领域:
材料化学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2023
·
IF 3.6
Yunying Yan,Jianjun Hao,Fenfen Xie,Fen Han,Linhai Jing,Pan Han
Magnesium-mediated reductive carboxylation of p-QMs with CO2 via an Umpolung strategy has been developed, which can be used for the preparation of various aryl acetic acids. This protocol featured high atom economy, mild conditions, and operational simplicity. The creation of this Umpolung carboxylation of p-QMs will unprecedentedly extend the application of p-QMs to nucleophilic reagents.
研究领域:
有机化学
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环境化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）