PHYSICAL CHEMISTRY CHEMICAL PHYSICS
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2022
·Vol. 24
·期 20
·12550-12562
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IF 3.945
Xue Fu,Xiaochen Tang,Tingting Chen,Yingjie Xu,Xiang Luo,Yueqing Lu,Xuming Wang,Dandan Qin,Lin Zhang
The interactions between azole-anion-based ionic liquids (AILs) and 2-methyl-3-butyn-2-ol (MBY) play an important role in AIL-promoted carboxylative cyclization of MBY with CO2. To better understand the interactions between AILs ([P66614][Im], [P66614][4-MeIm], and [P66614][4-BrIm]) and MBY, a detailed investigation from the experimental perspective has been carried out in this study. The results show that the derivative of viscosity (η) with the mole fraction of AIL (xAIL) of AIL + MBY mixtures appears to have the maximum value when xAIL ≈ 0.3, while 1H NMR chemical shifts of P-CH2 of [P66614]+ reach the minimum value at xAIL ≈ 0.3, indicating that [P66614]+ of AILs tend to self-aggregate. The interaction parameters (gji–gii) of the systems obtained from η by the Eyring-UNIQUAC equation are positive, and the difference between the bulk and local composition (xi–xii) is always negative, indicating that AILs can interact with MBY. Moreover, excess molar volumes and isentropic compressibility deviations are all negative deviations and become more negative as the temperature increases, reaching a minimum value at xAIL ≈ 0.30, indicating that azole-based anions can form H-bonds with MBY, and MBY molecules tend to enter the aggregates formed by AILs. Consequently, the cage effect is proposed to describe the interactions between AILs and MBY: MBY first enters the cage formed by the aggregation of [P66614]+, and then forms H-bonds with azole-based anions. Finally, the sizes of the particles of the [P66614][Im] + MBY mixture from dynamic light scattering increase first and then decrease with xAIL, with the maximum of 122 nm at xAIL ≈ 0.25, which confirms the rationality of the cage effect.
研究领域:
化学
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材料科学
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DOI
PubMed
高影响因子
JOURNAL OF CHEMICAL SCIENCES
·
2020
·Vol. 132
·期 1
·1-7
·
IF 1.406
DU ZHONGLIN,LI FENRUI,LI LI,LI RAN
Abstract Microwave-assisted one-pot quick synthesis to 1-monosubstituted 1,2,3-triazoles was achieved with good to excellent yields using the widely available arylboronic acids, sodium azide and 3-butyn-2-ols within 15 min. This method features high efficient and facile as organic azides, acetylene gas and harsh conditions were avoided. Graphic abstract Microwave-assisted one-pot quick synthesis to 1-monosubstituted 1,2,3-triazoles was achieved with good to excellent yields using the widely available arylboronic acids, sodium azide and 3-butyn-2-ols within 15 min.
研究领域:
有机化学
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药物化学
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合成方法学
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绿色化学
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杂环化学
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DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Wenxin Wang,Ruidong Yang,Qiqi Mao,Xu Mu,Hongjie Yu,Kai Deng,Jianguo Wang,Liang Wang,Hongjing Wang
The utilization of green hydrogen sources in H 2 O for alkynols electrocatalytic semihydrogenation reaction (ESHR) at ambient temperature provides a promising pathway toward the sustainable conversion of alkynols. However, it is still a great challenge to construct specific interfacial structure to adjust the electronic structure of Pd for the purpose of altering the strong adsorption of Pd with active hydrogen to enhance the production of alkenols. Here, the atomically dispersed GaO x -PdMo bimetallene nanoribbons (GaO x -PdMo BNRs) via oxygen bridging Ga atoms is designed to the surface of PdMo BNRs for 2-methyl-3-butyn-2-ol (MBY) ESHR to the synthesis of 2-methyl-3-buten-2-ol (MBE). The GaO x -PdMo BNRs achieve the excellent MBE selectivity (≈97.4%), Faraday efficiency (≈96.1%), and maintain long-term stability. Density functional theory demonstrates that the top electron-enriched Ga atoms and the bottom electron-deficient Pd atoms construct a “pyramidal” interface via the oxygen bridge. The unique surface can effectively activate H 2 O and weaken interaction between catalyst and MBE, thus promoting MBE generation. Moreover, the electron bridge effect between Ga-O-PdMo can induce p-d orbital hybridization to achieve lower the d -band center of surface Pd thus modulating the reactants adsorption. This work provides a strategy to improve ESHR performance by electron bridge effect to modulate interfacial electron distribution.
研究领域:
材料科学
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催化化学
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理论计算
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DOI
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 15
·4143-4151
·
IF 9.405
Shanjun Mao,Bowen Zhao,Zhe Wang,Yutong Gong,Guofeng Lü,Xiao Ma,Lili Yu,Yong Wang
Semi-hydrogenation of alkynols to alkenols with Pd-based catalysts is of great significance in fine chemical industries. Industrial Lindlar catalysts, employing Pb to modify the Pd nanoparticles for higher selectivity toward alkenols, however, generally suffer from both a severe activity decrease and environment pollution caused by using heavy metal Pb and additives. Therefore, how to overcome the selectivity–activity paradox remains a great challenge in industry. Here, we report a controllable strategy for the synthesis of semi-hydrogenation catalysts, which successfully improves the catalytic performance through selectively poisoning the edge and corner sites of Pd nanoparticles. When the integrity of the crystal face is reserved, both higher activity (∼1340 h−1) and selectivity (∼95% at 99% conversion) are achieved in the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY) in ethanol, an industrially important intermediate product for the synthesis of vitamin E, without adding any toxic additives. What's more, the yield could exceed 98% at 99% conversion under no solvent and organic adsorbate conditions, which had never been achieved before. This work provides a different perspective to design and develop high performance catalysts for semi-hydrogenation of alkenols or even substituted alkynes.
研究领域:
催化
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化学工程
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精细化工
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2021
·
IF 5.706
Yankai Liu,Ruinian Zhou,Jianyu Qu,Feng Han,Shuai Zhang,Xingliang Xu
Upgrading carbon dioxide (CO 2 ) into valuable products is a highly promising strategy of artificial carbon cycle. In this study, a series of in situ reduced CuMgAl layered double hydroxides (R-CuMgAl-LDHs) composites were synthesized, in which Cu nanoparticles were effectively dispersed and anchored on MgAl-LDHs with formation of Cu + and Cu 0 species. The optimized R-Cu 1.5 Mg 1.5 Al 1 -LDH exhibited excellent catalytic performance for the carboxylative cyclization of 2-methyl-3-butyn-2-ol with CO 2 (turnover number of 243) under mild conditions. The layered structure of LDH stabilized the active Cu species with high dispersion, enhancing the catalytic efficiency of this carboxylative cyclization reaction. Simultaneously, the dual-activation of both CO 2 and propargylic alcohol by Cu 0 /Cu + species generated on the surface of LDH contributed significantly to the catalytic efficiency enhancement. Furthermore, R-Cu 1.5 Mg 1.5 Al 1 -LDH catalyzed the reaction of a wide range of terminal or internal propargyl alcohols with CO 2 , yielding various functionalized α-alkylene cyclic carbonates. Finally, a reasonable reaction mechanism was put forward according to the comprehensive analysis.
研究领域:
催化
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材料科学
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化学工程
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环境化学
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DOI
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-10
·
IF 17.694
Yang Yang,Zhu Xiaojuan,Wang Lili,Lang Junyu,Yao Guohua,Qin Tian,Ren Zhouhong,Chen Liwei,Liu Xi,Li Wei,Wan Ying
Pd catalysts are widely used in alkynol semi-hydrogenation. However, due to the existence of scaling relationships of adsorption energies between the key adsorbed species, the increase in conversion is frequently accompanied by side reactions, thereby reducing the selectivity to alkenols. We report that the simultaneous increase in alkenol selectivity and alkynol conversion is achieved by manipulating interstitial atoms including B, P, C, S and N in Pd catalysts. A negative linear relationship is observed between the activation entropies of 2-methyl-3-butyn-2-ol and 2-methyl-3-buten-2-ol which is highly related to the filling of d -orbital of Pd catalysts by the modification of p -block elements. A catalyst co-modified by B and C atoms has the maximum d charge of Pd that achieves a 17-fold increase in the turn-over frequency values compared to the Lindlar catalysts in the semi-hydrogenation of 2-methyl-3-butyn-2-ol. When the conversion is close to 100%, the selectivity can be as high as 95%.
研究领域:
催化
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化学工程
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材料科学
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DOI
高影响因子
ACS Catalysis
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2019
·
IF 12.221
Zhongzhe Wei,Zihao Yao,Qiang Zhou,Guilin Zhuang,Xing Zhong,Shengwei Deng,Xiaonian Li,Jianguo Wang
The reaction/diffusion kinetics are fundamentally determined by the electronic properties of supported Pd catalysts and further govern the catalytic activity and selectivity in the partial hydrogenation of alkynes. However, how the electronic metal–support interactions and the tradeoff between reaction and diffusion affect the catalytic performance still remain elusive. Here, the optimized catalyst Pd supported on carbon decorated with oxygen-deficient TiO2(Pd/TiO2-VO@C) features a remarkable enhancement in performance for semihydrogenation of 2-methyl-3-butyn-2-ol with a TOF 31-fold higher than that of Lindlar catalyst. The improved performance of Pd/TiO2-VO@C benefits from the fact that TiO2-VO@C subtly modulates the electronic properties of Pd, and an appropriate amount of TiO2-VO allows a decrease in the reaction barrier and C promotes the diffusion ability of the catalyst, achieving the balance between reaction and diffusion. By using microkinetic modeling, the reactivity difference of various catalysts is quantitatively predicted and the calculated turnover frequency volcano curve is rationalized as a function of reaction barrier and diffusion ability, which agrees well with the experimental results. The quantitative regulation of catalytic performance by tuning the support properties is a general strategy, which provides a basis to design robust catalysts for diverse reactions.
研究领域:
催化
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化学工程
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材料科学
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物理化学
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DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
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2026
·
IF 3.1
Zhengyuan Zhang,Peng Tang,Jiao Chen,Hongyu Yan,Yuechuang Wang,Ming Xiao
Ethynyl-functionalized polymethacrylates are promising precursors for diverse click reactions, yet their direct preparation from corresponding monomers is often hindered by gelation, low conversion, and low molecular weight. This work reports a novel and straightforward strategy to prepare soluble, high-molecular-weight ethynyl-functionalized polymers via conventional free radical polymerization of disubstituted ethynyl methacrylates. We reveal the α-methyl group selectively suppress 1,2- and 1,3-migrations and prevent the formation of stable low-reactivity allylic radicals, increasing both the monomer conversion and molecular weight. Specifically, with the α-methyl group, the monomer conversion reaches up to 86.2%, and number-average molecular weight ( M n ) exceeds 14,000 Da, whereas the corresponding ethynyl acrylates yielded only 14.8%–17.8% conversion and M n = 3,900–4,200 Da. The α-methyl effect mechanism is further supported by ab initio calculations, 13 C-NMR, and ESR spectroscopy. The resulting polymers retain reactive ethynyl groups and undergo efficient thiol-yne click reactions with approximately 80% conversion of C≡C bonds within 6 s under UV irradiation. This work establishes the α-methyl effect in controlling polymerization pathways of acetylenic (meth)acrylates and offers a new routine toward polymerization of functional (meth)acrylate monomers with high conversion and molecular weight.
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高影响因子
VACUUM
·
2025
·
IF 3.9
Xiaoli Ji,Fan Chen,Jian Liu,Qianqian Ma,Zhihao Xu,Ruochen Qiao
In this paper, MWCNTs/Si 3 N 4 binary composites were synthesized using a chemical click method, establishing a foundation for the in situ polymerization of MWCNTs/Si 3 N 4 /PPy ternary composites. The morphology, electrical conductivity, and electromagnetic parameters of the composites were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and infrared analysis. The wave-absorbing properties of the composites were assessed with a vector network analyzer. The impact of varying feeding ratios on the absorption properties of the composites was investigated. The results indicated that as the amount of PPy increased, the minimum reflection loss of the nano-hybrid materials initially decreased before subsequently increasing. When the feeding ratio of MWCNTs: Si 3 N 4 : PPy was set at 2:1:4 and the thickness of the absorption layer was 2.5 mm, the minimum reflection loss (RL min ) reached −40.14 dB, while the maximum absorption bandwidth (EAB max ) attained 6.88 GHz (d = 2.0 mm). Compared to MWCNTs/Si 3 N 4 binary materials, the ternary materials demonstrated enhanced electromagnetic absorption capabilities. The numerous heterogeneous interface formed by MWCNTs, Si 3 N 4 , and PPy facilitates charge accumulation, creating a structure similar to a capacitor that induces interface polarization and attenuates electromagnetic waves (EMWs) by aligning polar bonds or charges in response to an alternating electric field. Additionally, the MWCNTs/Si 3 N 4 binary nanohybrid materials exhibit a larger surface area following PPy coating, which further enhances impedance matching, extends the propagation distance of EMWs, and improves their dissipation. These research results are of great significance for the production of absorbent composite materials and provide new ideas for the design of absorbent materials.
研究领域:
材料科学
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纳米技术
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电磁学
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高分子化学
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DOI
高影响因子
BULLETIN OF MATERIALS SCIENCE
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2024
·Vol. 47
·期 3
·1-13
·
IF 1.9
Ji Xiaoli,Ma Qianqian,Liu Jian,Yuan Haoze,Ma Xukai
Titanium dioxide/multi-walled carbon nanotubes (TiO 2 /MWCNTs) are nanocomposites (NCs) prepared via click reaction of TiO 2 nanoparticles (TiO 2 NPs) with azide groups (TiO 2 –N 3 ) on the surface and MWCNTs with alkynyl groups (MWCNTs–ALK) on the surface. The phase structure, graphitization degree, structure, elemental composition, the microstructure of TiO 2 /MWCNTs NCs were characterized by XRD, Raman, IR, XPS and SEM, and their electromagnetic (EM) parameters were determined by the vector network analyser. For TiO 2 /MWCNTs NCs with click reaction, the minimum reflection loss (RL min ) is up to −47.87 dB at 12.02 GHz, the matching thickness is 2.0 mm, and the bandwidth is lower than −10 dB in the range of 7.7–12.48 GHz. Compared with the physically mixed TiO 2 /MWCNTs composites, TiO 2 /MWCNTs NCs prepared by click reaction show more excellent EM absorption properties, which is mainly due to the binding of covalent bonds between the two kinds of materials that lead to the enhancement of interfacial effects, the improvement of impedance matching and the increase of electron migration.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF ELECTRONIC MATERIALS
·
2024
·
IF 2.2
Ji Xiaoli,Chen Fan,Liu Jian,Ma Qianqian,Qiao Ruochen,Xu Zhihao
This study details microwave-absorbing materials made of multi-walled carbon nanotubes (MWCNTs) and silicon nitride (Si 3 N 4 ). The synthesis of MWCNTs/Si 3 N 4 nanocomposites (NCs) involves combining alkyne-functionalized multi-walled carbon nanotube (MWCNTs-ALK) nanoparticles (NPs) with azide-functionalized silicon nitride (Si 3 N 4 –N 3 ) NPs through a click reaction. In order to analyze the morphology and structure of the MWCNTs/Si 3 N 4 NCs, scanning electron microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, and infrared analysis techniques are employed. The electromagnetic properties of the NCs are evaluated using a vector network analyzer. The results indicate when this feeding ratio of MWCNTs-ALK and Si 3 N 4 –N 3 was 1:2 and a matching thickness of 3.0 mm at 6.82 GHz, the minimum reflection loss reaches − 30.7 dB. Additionally, with a feeding ratio of 1:1 and a matching thickness of 1.5 mm, the bandwidth below − 10 dB ranges from 11.6 to 15.8 GHz. The compositions of MWCNTs/Si 3 N 4 synthesized by click reactions indicate that, compared to physical mixed samples, our material has superior wave-absorbing properties. This improvement can be attributed to the covalent bonding between MWCNTs and Si 3 N 4 facilitated by the click reaction, resulting in enhanced dielectric loss and impedance matching. The results of this study have significant implications for the processing of composite microwave-absorbing materials and offer novel insights into the design of multifunctional microwave-absorbing materials. Graphical
研究领域:
材料科学
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化学工程
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yun Fang,Yong Yan,Xiayan Wang,Guangsheng Guo
The selective semi‑hydrogenation of alkynols to alkenols is crucial in pharmaceutical and fine chemical industries, yet hindered by inefficient thermocatalytic processes and over‑hydrogenation on Pd-based catalysts. Herein, we report a palladium‑copper bimetallic nanohybrid sheet catalyst (PdCu NHSs/NF) that enables efficient electrocatalytic alkynol semi‑hydrogenation (ECSH) using water as the proton source. For 1,4-butynediol (BYD), PdCu NHSs/NF achieves 99.8 % conversion within only 1 h, and 96.4 % selectivity, 95.2 % Faradaic efficiency at a low potential of −0.2 V vs. RHE, while maintaining stability over 10 cycles and broad substrate applicability. In situ EIS and spectroscopic studies revealed that the PdCu bimetallic interface enhances mass transport and reaction kinetics, enabling selective BED formation without over‑hydrogenation. DFT calculations demonstrated the cooperative effect between Pd and Cu active sites optimized the adsorption/desorption energetics, balancing the competition between HER and ECSH. This work provides critical mechanistic insights for designing advanced bimetallic catalysts in selective semi‑hydrogenation.
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高影响因子
危险品化学品经营许可证（带存储）