INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Tiping Wei,Liguo Wang,Jiajun Zhang,Yan Cao,Xiang Hui,Jianhui Shi,Shuang Xu,Liyan Zhao,Peng He,Huiquan Li
Bio-based pentamethylene dicarbamate (PDC) belongs to N-substituted carbamates, which are important fine chemicals and organic intermediates. In this work, well-defined CeO2 rods, cubes, and octahedrons were successfully prepared to catalyze the synthesis of PDC by carbonylation of 1,5-pentanediamine (PDA) with methyl carbamate (MC). Among them, CeO2 rods with higher amounts of acid–base sites and abundant oxygen vacancies showed superior intrinsic activity in the PDA carbonylation reaction. In situ FTIR results showed that intermediate polyureas were readily formed in the reaction, and then, CeO2 rods promoted the alcoholysis of polyureas to PDC. In situ DRIFTS results indicated that the surface of CeO2 rods is more favorable for the adsorption and activation of the reactants. CeO2 rods can also be used for the efficient synthesis of a series of N-substituted carbamates. We believe that this work will contribute to the efficient, green, and sustainable production of N-substituted carbamates.
研究领域:
催化
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化学工程
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绿色化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Green Energy & Environment
·
2020
·
IF 6.395
Chenhao Jiang,Hongye Cheng,Zexian Qin,Ruizhuan Wang,Lifang Chen,Chen Yang,Zhiwen Qi,Xiucai Liu
1,5-Pentanediamine (PDA) produced by biological fermentation becomes popular, but the separation of PDA from the broth is a typical difficult problem. In this work, the performance of 200 ionic liquids (ILs), formed by combining 25 cations and 8 anions, in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model. The extraction mechanism was investigated with the help of σ-profile and interaction energy analyses. Both the cation and anion have impacts on the extraction efficiency, where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL. The IL composed of long alkyl-chain in cation and the anion of [PF 6 ] - or [TF 2 N] - , which has the σ-profile more likely distributed in the nonpolar region but less distributed in the polar region, is favorable for extraction. The experimental liquid–liquid equilibrium demonstrated the effects of cation and anion on extraction performance, which validated the reliability of COSMO-RS model in IL screening for PDA extraction. The IL [IM-1,8][PF 6 ] could serve as a promising extractant for the downstream separation process of the biological production of PDA.
研究领域:
化学工程
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生物技术
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分离科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Xiang Hui,Liguo Wang,Jianhui Shi,Tiping Wei,Fengqin Guo,Yan Cao,Peng He,Jiajun Zhang,Huiquan Li
The methoxycarbonylation of amines into carbamates via the construction of a C–N bond is an important reaction in pharmaceutical and fine chemical syntheses. However, the methoxycarbonylation of amines with dimethyl carbonate (DMC) without metal-based catalysts or other base catalysts has rarely been studied, and the reaction mechanisms remain underexplored. Herein, efficient methoxycarbonylation of biobased pentanediamine (PDA) with DMC promoted by water is proposed. The addition of water as a catalyst resulted in a 4-fold increase in yield. The conducted kinetic studies showed that proton transfer from PDA to methoxy occurs through the hydrogen bond between the zwitterionic intermediate and water. In situ analyses have shown that OH– and water form hydrogen bonds with the ether O atom of DMC and hydroxyl H atoms of PDA, synergistically promoting the elimination of the methoxy group. The addition of water reduced the energy barrier of the methoxy group elimination from 16.3 to 0.6 kcal/mol, confirming the results of theoretical computations. Furthermore, the methyl (5-aminophenyl)carbamate intermediate was recycled into dimethyl pentane-1,5-diyldicarbamate without the use of an additional catalyst, which was mediated by the hydrogen bond between PDA and methyl (5-aminophenyl)carbamate. The reported mild methoxycarbonylation of biobased PDA under metal-free conditions is a green and sustainable method of synthesizing biobased dicarbamate.
研究领域:
有机化学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
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IF 7.2
Xiaojie Zhao,Huazong Liu,Lu Wang,Wenxi Ji,Qixu Hu,Yue Yang,Jiao Feng,Xin Wang,Ganlu Li,Hui Li,Kequan Chen
Impurity sulfate produced in upstream process of nylon 54 salt (cadaverine succinate) are significantly impacting the product quality. In the present study, we elucidated the mechanism underlying the crystallization of the nylon 54 salt; using sulfate ions as the only inorganic impurity before crystallized nylon 54 salt, we revealed the principles underlying their impact. Specifically, sulfate ions profoundly affect the thermodynamics and kinetics of nylon 54 salt crystallization. The solubility of the monomer salt decreased. At 288.15 K, the solid-liquid interfacial energy, critical nucleation radius, and Gibbs free energy increased 0.104 mJ . m −2 , 2.890 × 10 −10 m, and 9.668 × 10 −22 J respectively. The increased nucleation barrier further hinders the crystallization of nylon 54 salt. Molecular dynamics simulations reveal that sulfate impurities reduce molecular diffusion, enhance hydrogen bond formation, increase intermolecular and overall interaction energy. Thus, our study provides valuable insights into the one-step separation of bio-based cadaverine and succinic acid in a coproduction system.
研究领域:
生物化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
INORGANICA CHIMICA ACTA
·
2023
·
IF 2.8
Zhi-Nian Liu,Jian-Hang Hu,Yu Xiong,Jia-Yi Zhang,Run-Xin Hou,Chun-Rong Li,Tie-Hong Meng,Timothy J. Prior,Carl Redshaw,Xin Xiao
In this study, single crystal X-ray diffraction and 1 H NMR spectroscopy were used to examine the interaction of the guest 1,5-pentanediamine with inverted cucurbit[6]uril ( i Q[6]) in the presence of [ZnCl 4 ] 2− anion. The results show that [ZnCl 4 ] 2− and [Zn(H 2 O)Cl 3 ] − anions form a honeycomb framework structure, and i Q[6] forms a 1:1 complex with 1,5-pentanediamine. Inverted cucurbit[6]uril forms molecular chains via outer surface interactions, which in turn fill in the honeycomb framework structure. The amino groups at both ends of the 1,5-pentanediamine guest are situated at the entrance of the central cavity, while the alkyl chain part resides in the central cavity of the i Q[6].
研究领域:
化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Kejian Yang,Qi Guo,Yanlin Liu,Jinping Ni,Zhaobin Tang,Xudong Chen
The long-ignored discoloration behavior of polyamide during polymerization has a significant impact on its properties and applications. Here, we innovatively analyzed the discoloration behavior of pentamethylenediamine-derived bio-based copolyamide (PA5T/56) and proposed a possible discoloration mechanism. Pentamethylenediamine performed cyclization reactions at high temperature to generate piperidine, which was then combined with terephthalic acid to form dipiperidine terephthalate. After being oxidized, dipiperidine terephthalate was converted to terephthalic acid bis(2-carbonyl substituted piperidine), which was believed to be responsible for the discoloration of polyamide during polymerization. Moreover, it was demonstrated that the discoloration behavior led to poor spinnability and dyeability of ultrafine polyamide fibers. This work will help to optimize the polymerization process of pentamethylenediamine-derived polyamide and expand its applications in high-performance fibers and other fields.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 7
·2315-2327
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IF 6.177
Xiang Hui,Liguo Wang,Yan Cao,Shuang Xu,Peng He,Huiquan Li
Carbonylation of pentanediamine (PDA) is a green and effective route for the synthesis of pentamethylene dicarbamate (PDC), an important intermediate compound for the preparation of polyurethanes (PUs) and other chemicals. In this work, TiO2-101 and TiO2-110 catalysts with preferential exposure of (101) and (110) facets, respectively, were prepared and studied for the carbonylation of PDA with ethyl carbamate (EC). The catalysts were characterized by various techniques, including XRD, BET, SEM, TEM, XPS, NH3-TPD, and in situ FTIR. The characterization results indicated that TiO2 catalysts with exposed (110) and (101) facets were synthesized successfully. The overall results suggested that the (101) facets on the TiO2 surface provide high amounts of surface Lewis acid sites that played a pivotal role in PDC formation, which gave a conversion and yield both up to 99% under optimized conditions. In situ FTIR spectroscopy clearly revealed that polyurea as an intermediate was formed in the reaction and subsequently converted to PDC catalyzed by the TiO2 catalyst. Furthermore, the DFT results showed that the conversion of polyurea to PDC over the (101) facets was more prone to occur than the (110) facets due to the lower reaction energy barrier. In addition, the TiO2-101 catalyst displayed excellent stability without an obvious activity decline after five cycles. Furthermore, this strategy also could be successfully expanded to the efficient syntheses of a series of N-substituted carbamates.
研究领域:
化学工程
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材料科学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
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IF 15.1
Chenxin Hou,Yan Chu,Jinlei Zeng,Yitong Wang,Ganlu Li,Kequan Chen,Hui Li
Global output of bio-based products continues to increase, but the release of carbon dioxide (CO 2 ) has exacerbated the environmental crisis. The simultaneous conversion of CO 2 released by bioprocesses into high-value products is increasingly gaining attention. With this in mind, a compartmentalized photocoupling multi-enzyme nanoreactor consisting of two nanocompartments was created. This nanoreactor uses a ferric tannin-gelatin (TA-Gel) coacervate to synchronously wrap nanocompartment I, which quickly sequesters the CO 2 released by biodecarboxylation to prevent its loss, and nanocompartment II, which converts the sequestered CO 2 into formic acid. The results indicate that nanocompartment I and II were encapsulated in the nanoreactor with high catalytic efficiency. Under the optimal conditions, the yields of pentanediamine and formic acid reached 15.7 ± 1.06 and 8.4 ± 0.07 mM, respectively. Yields of pentanediamine and formic acid by the photocoupling multi-enzyme nanoreactor were highest. The conversion efficiency of formic acid from CO 2 released by biodecarboxylation by the photocoupling multi-enzyme nanoreactor, mixed nanocompartments, and free one-pot multi-enzyme system was 54.5 %, 43.8 %, and 10.0 %, respectively. The proximity effect significantly promotes the catalytic efficiency of formic acid synthesis from CO 2 released by biodecarboxylation. The novel photocoupling multi-enzyme nanoreactor has important capabilites for upgrading multi-enzyme programmed catalysis.
研究领域:
生物技术
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Bioengineering and Biotechnology
·
2023
·
IF 5.7
Li Hui,Chen Xu,Tang Yibo,Yang Yue,He Feng,Wang Xin,Li Ganlu,Chen Kequan,Ouyang Pingkai,Yang Yuning
1,5-Pentanediamine hydrochloride (PDAH) was an important raw material for the preparation of bio-based pentamethylene diisocyanate (PDI). PDI has shown excellent properties in the application of adhesives and thermosetting polyurethane. In this study, PDAH was recovered from 1,5-pentanediamine (PDA) fermentation broth using a cation exchange resin and purified by crystallization. D152 was selected as the most suitable resin for purifying PDAH. The effects of solution pH, initial temperature, concentration of PDA, and adsorption time were studied by the static adsorption method. The equilibrium adsorption data were well fitted to Langmiur, Freundlich, and Temkin-Pyzhev adsorption isotherms. The adsorption free energy, enthalpy, and entropy were calculated. The experimental data were well described by the pseudo first-order kinetics model. The dynamic experiment in the fixed bed column showed that under optimal conditions, the adsorption capacity reached 96.45 mg g−1, and the recovery proportion of the effective section reached 80.16%. In addition, the crystallization of the PDAH solution obtained by elution proved that the crystal product quality of resin eluting solution was highest. Thus, our research will contribute to the industrial scale-up of the separation of PDAH.
研究领域:
化学工程
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生化工程
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）