CATALYSIS LETTERS
·
2019
·Vol. 149
·期 3
·699-712
·
IF 2.372
Dai Weili,Mao Jie,Liu Ying,Mao Pei,Luo Xubiao,Zou Jianping
Development of efficient, cheap and recyclable catalysts for the synthesis of cyclic carbonates from CO 2 and epoxides is still a very attractive topic. Herein, the polymer grafted TBD-based ionic liquids (ILs) were fabricated from commercially available polystyrene (PS) and ingredients of the ILs, and used as heterogeneous catalysts for the conversion of CO 2 into cyclic carbonates in the absence of solvent and co-catalyst. To improve the catalytic performance, various substitutes (such as –COOH, –OH and –NH 2 ) were functionalized on the TBD cation. Among the as-obtained catalysts, carboxyl-containing catalyst (PS–[CETBD]Br) showed superior activity than others, which may be attributed to the stronger polarization capability of –COOH on the C–O bond of epoxide through the formed hydrogen bonding. Additionally, the combined synergistic effect of the nucleophilic attack by the halide anions also account for the facile ring-opening of epoxide. It is noted that CO 2 can be activated by the formation of carbamate between CO 2 and alkaline nitrogen of the TBD cations, thus facilitating the formation of cyclic carbonates. Moreover, the catalyst shows good chemical stability and catalytic reusability, which is very important for the practical conversion of CO 2 in chemical industry. Graphical Abstract
研究领域:
化学工程
·
材料科学
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DOI
高影响因子
Green Energy & Environment
·
2025
·
IF 14.6
Xiang Hui,Jianhui Shi,Jiajun Zhang,Yan Cao,Huiquan Li,Peng He,Liguo Wang
The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy. However, conventional catalysts exhibit limited catalytic efficiency, and the underlying proton transfer mechanism remains elusive. Herein, we reported a metal-free, room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a dual hydrogen bond catalyst to synergistically activate propylamine (PA) and dimethyl carbonate (DMC). This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions. This is enabled by dual hydrogen bonding of TBD with PA and DMC, which facilitates rapid proton transfer and stabilizes tetrahedral intermediates. Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs. Furthermore, it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate. This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.
研究领域:
化学
·
催化科学
·
有机合成
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·
IF 3.9
Zhu Jianxiang,Li Jiahui,Shen Runqiu,Song Yuwei,Xie Yuanyuan,Duan Hongliang,Su An
The development of efficient and sustainable amide-bond-forming
processes, together with their quantitative kinetic characterization,
is of major significance to the fine chemical and pharmaceutical industries.
In this study, the aminolysis of d -(−)-pantolactone
(DPL) with pyrrolidine (Pyr), catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene
(TBD), was investigated in a continuous-flow microreactor equipped
with inline Fourier transform infrared (FTIR) spectroscopy. For the
first time, a flow-rate-ramp transient kinetic method was applied
to an organobase-catalyzed aminolysis system. A multiresponse FTIR–PLS
quantitative model was developed using Latin hypercube sampling (LHS)
for calibration-set design, thereby effectively reducing the collinearity
inherent in conventional calibration samples distributed along the
reaction stoichiometric line. An analytical mapping between experimental
time and the actual residence time of fluid elements under dynamic
flow conditions was established, making it possible to extract continuous
kinetic data over a residence-time range of 2–40 min from just
one 83.1 min flow-rate-ramp experiment. The reaction orders with respect
to DPL, Pyr, and TBD were determined to be 1, 1, and 0.85, respectively,
via the isolation and initial-rate methods. An explicit analytical
expression for DPL conversion was derived based on a plug-flow reactor
model. Arrhenius analysis yielded an activation energy of 26.26 kJ·mol –1 and a pre-exponential factor of 2.96 × 10 5 L 1.85 ·mol –1.85 ·min –1 . The resulting model demonstrated good predictive
accuracy when applied to temperatures and initial concentrations outside
the fitting range. This work provides a reliable kinetic basis for
the design and scale-up of continuous DPL aminolysis processes and
offers a rapid and resource-efficient strategy for kinetically characterizing
related metal-free organocatalytic systems.
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高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Renlong Min,Chenyu Zhang,Haijuan Kong,Shuo Liu,Ziyao Peng
Carbon fiber-reinforced polymers (CFRPs) are widely applied due to their outstanding mechanical properties. However, the intrinsic difficulty in recycling their thermoset resin matrix has led to serious environmental pollution and resource waste, becoming a major bottleneck hindering the sustainable development of CFRPs. In this study, a green and efficient chemical recycling strategy was developed by constructing a synergistic catalytic system composed of β-phenylethanol and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), enabling the rapid degradation of anhydride-cured epoxy-based CFRPs under mild conditions (190 °C, atmospheric pressure). By optimizing the mass ratio of the catalyst to the composite material [TBD : CFRP (wt : wt) = 1 : 3.27], nearly complete resin degradation (>99%) was achieved within 2 hours. The reclaimed carbon fibers retained up to 93.2% of their original single-fiber tensile strength. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses confirmed that no significant deterioration occurred in the surface chemical functionalities or the degree of graphitization of the reclaimed fibers compared to the pristine ones. This work offers a simple, efficient, and environmentally friendly solution for the closed-loop recycling of thermoset-based CFRPs.
研究领域:
材料科学
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化学工程
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高分子科学
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环境科学
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机械工程
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DOI
高影响因子
RSC Sustainability
·
2025
·
IF 4.9
ZIXIAN JIA,JIE ZHANG,LIN GAO,LIJIAO QIN,HAOCHENG SUN,JIAXING CHEN,Jian-Zhong Yin
The chemical recycling of polyethylene terephthalate (PET) via glycolysis is a promising route for recovering the monomer bis(2-hydroxyethyl) terephthalate (BHET), which can be used for virgin-grade PET production. However, the influence of water—an inevitable impurity and potential byproduct—on this process is complex and not fully elucidated. This study systematically investigates the effect of water content (0–22.2 vol%) on PET glycolysis using selected heterogeneous catalysts (ZnO, Mn₂O₃) and homogeneous catalysts (zinc acetate (ZnAc₂), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)). Product distribution and reaction kinetics were quantified by HPLC and in-situ IR spectroscopy, respectively.The heterogeneous catalysts (ZnO, Mn₂O₃) and homogeneous ZnAc₂ maintained high PET conversion (>95%) even at elevated water concentrations. Nevertheless, the BHET yield and selectivity for these systems decreased significantly due to a competing hydrolytic side reaction, promoted by water, which yields terephthalic acid (TPA). Notably, ZnAc₂ exhibited a more rapid decline in BHET selectivity compared to ZnO. Conversely, the organic base catalysts TBD and DBU experienced complete deactivation in the presence of water, resulting in a drastic reduction in both PET conversion and BHET yield, with DBU showing greater susceptibility. In-situ IR experiments corroborated that the deactivation mechanism for TBD involves protonation by water. These results emphasize that water's influence is a function of the catalyst's chemical nature, modulating product selectivity for metal-based systems while causing the deactivation of organic bases. Understanding these divergent effects is critical for the optimization of industrial PET glycolysis and the rational design of water-tolerant catalytic systems.
研究领域:
高分子化学
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催化化学
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化学回收
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反应工程
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环境化学
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材料科学
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DOI
高影响因子
Polymers
·
2025
·Vol. 17
·期 14
·1991
·
IF 4.9
Xiaojuan Shi,Hui Zhang,Hongjiu Hu
Traditional covalently cross-linked solid-state electrolytes exhibit desirable mechanical durability but suffer from limited processability and recyclability due to their permanent network structures. Incorporating dynamic covalent bonds offers a promising solution to these challenges. In this study, we report a reprocessable and recyclable polymer electrolyte based on a dynamic ester bond network, synthesized from commercially available materials. Polyethylene glycol diglycidyl ether (PEGDE) and glutaric anhydride (GA) were cross-linked and cured in the presence of benzyl dimethylamine (BDMA), forming an ester-rich polymer backbone. Subsequently, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was introduced as a transesterification catalyst to facilitate network rearrangement. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated to establish efficient ion transport pathways. By tuning the cross-linking density and catalyst ratio, the electrolyte achieved an ionic conductivity of 1.89 × 10−5S/cm at room temperature along with excellent reprocessability.
研究领域:
材料科学
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高分子化学
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储能技术
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固态电解质
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可持续材料
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DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）