Catalysts
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2026
·Vol. 16
·期 1
·49
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IF 4
Ziqi Zhang,Hui Xu,Haojie Chu,Hong Meng,Hongwei Fan,Yingzhou Lu,Chunxi Li
Methylbutynol (MB) is a typical propargylic alcohol with both alkynyl and hydroxyl groups, featuring excellent modifiability and broad applications. Currently, it is produced through the reaction of alkaline metallic acetylides and acetone, requiring expensive raw material and harsh reaction conditions. Herein, a novel method was proposed by replacing the metallic acetylide with calcium carbide (CaC2) as a low-cost industrial acetylide reagent. The effects of solvent, activator, and proton donor on the ball mill reaction, and the defoaming performance of the resultant MB and its oxidative coupling product (2,7-dimethyl-3,5-octadiyn-2,7-diol), were studied. Nucleophilic reactivity of CaC2with acetone can be regulated by the activating effect of the ball mill, an appropriate activator, and a proton donor. High yield of MB (~94%) was obtained under synergistic action of TBAF·3H2O and acetylene, which represents a facile synthesis process of MB under mild conditions. MB exhibits good defoaming performance, and 2,7-dimethyl-3,5-octadiyn-2,7-diol is more promising, being an excellent non-ionic defoamer. The result is of great significance for exploring new chemical reactions of CaC2and its high-value utilizations.
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Nature Communications
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2026
·Vol. 17
·期 1
·2500
·
IF 18.1
Li Minghang,Fu Zhaoyuan,Luo Qian,Lu Bing,Zhang Liwei,Liang Shipan,Liu Ting,Wang Yong,Mao Shanjun
The entangled electronic and geometric effects in heterogeneous catalysis have long obscured precise attribution of their individual roles. By employing a thermal-induced surface reconstruction strategy to progressively enhance metal-support interactions, we achieve continuous tuning of Pd’s electronic and geometric structures. Using alkyne semi-hydrogenation as a prototypical structure-sensitive probe reaction, we demonstrate that despite the linear coupling of electronic and geometric structures during Pd reconstruction, the turnover frequency scales solely with the geometric descriptor W (quantifying Pd particle flattening), while selectivity regulation bifurcates into two distinct regimes: Below a critical W, electron-deficient Pd sites offset geometric constraints, yielding a non-structure-sensitive selectivity plateau; whereas above this threshold, electron-rich surfaces establish unequivocal geometric control. Moreover, surface reconstruction drastically shrinks the electronic-geometric space of Pd sites for over-hydrogenation side reaction. These insights provide a blueprint for metal catalysts regulation in hydrogenation and may open avenues for quantifying electronic-geometric interplay in other structure-sensitive reactions.
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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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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2026
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IF 5.4
Jianan Song,Feng Wei,Beibei Chen,Guangxing Huang,Jiajia Meng,Kan Zhang
Line-plane CNT@MXene hybrids are constructed via electrostatic assembly. • CNTs effectively suppress MXene restacking and improve dispersion. • In-situ cross-linking drives filler rearrangement and network densification. • The composites exhibit high electrical and thermal conductivity with flexibility. • The composites enable strain sensing and thermal management capabilities. Flexible electronics require elastomeric composites that integrate efficient thermal management, electrical conductivity, mechanical compliance, and stable sensing capability. However, MXene-based composites are often limited by nanosheet restacking, filler aggregation, and poor network stability in elastomer matrices. Herein, a line-plane CNT@MXene hybrid filler was constructed by electrostatic self-assembly and incorporated into solution-cross-linked PDMS (S-PDMS) through a solution-driven in-situ cross-linking strategy. The CNTs bridged adjacent MXene nanosheets and suppressed their restacking, while solvent-evaporation-induced polymer chain shrinkage promoted filler rearrangement and network densification. As a result, the CNT@MXene/S-PDMS composite achieved an electrical conductivity of 0.126 S/cm and a thermal conductivity of 1.57 W·m −1 ·K −1 at 14.0 wt% filler content, while maintaining good stretchability and resilience. The composite also exhibited stable conductivity under repeated deformation, sensitive strain-sensing behavior, and effective heat-dissipation performance in LED thermal management. This work provides an effective strategy for constructing stable hybrid conductive networks in flexible polymer composites for integrated thermal management and strain sensing. Download: Download high-res image (168KB) Download: Download full-size image
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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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PROGRESS IN ORGANIC COATINGS
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2022
·
IF 6.206
Yuan Wang,Liwei Yan,Youquan Ling,Ying Ge,Congshu Huang,Shengtai Zhou,Shuang Xia,Mei Liang,Huawei Zou
A uniformly dispersed epoxy/polydimethylsiloxane (PDMS) hybrid system was prepared through hydrosilylation and in-situ polymerization reaction. The obtained epoxy/PDMS coating possessed enhanced mechanical and adhesive properties. The hybrid structure of epoxy/PDMS was confirmed by FTIR, 1 H NMR, GPC and SEM, respectively. Results indicated that the tensile strength , elongation at break and shear strength of the epoxy-containing polydimethylsiloxane (EPS) modified PDMS (EPS-PDMS) were increased by 187 %, 185 % and 137 %, respectively, when compared to the pure PDMS. Besides, TGA analysis indicated that the initial degradation temperature of EPS-PDMS was well maintained when compared to that of pure PDMS. Therefore, the convenient strategy of in-situ formation of epoxy reinforcing phase with flexible long-chain siloxane into PDMS effectively integrated the advantages of two incompatible polymers. The prepared EPS-PDMS coatings with enhanced mechanical and adhesive properties show great potential applications in the aerospace and industrial fields as flexible thermal protection coatings.
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POLYMER
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2021
·
IF 4.43
Zhengyuan Zhang,Hongyu Yan,Zejun Yin,Yuechuan Wang
The acetylene functional groups on polymer chains provide a photochemical access to modulate or actuate the properties of the polymer. We report here a photochemical way to actuate a polyacrylate to elastomers . High molecular weight acetylene functionalized homo- and copolymers of are prepared with a novel monomer , 2-(dimethylpropargyloxy)ethyl methacrylate , DMPOEMA, by photo-initiated free-radical polymerization (FRP) in solution at room temperature . The acetylene groups are tolerant of the solution photo FRP at 50 wt% concentration, but not tolerant to thermal FRP and photo FRP at 80 wt% concentration. Copolymers P(DMPOEMA- co -EA) with‾M n in 12,500–15,100 g/mol were prepared with conversion up to 90% at 50% concentration and three monomer feed ratios. The feed ratio of DMPOEMA had slight effects on the polymerization rate, but effects on PDI at higher monomer conversion with prolonged photo-irradiation. The acetylene functionalized polyacrylates become photo-sensitive and are photo cross-linkable or photo clickable after solvent is removed. Real-time FT-IR study reveals that the photo cross-linking with a tri-thiol compound follows the normal thiol-yne photochemistry , and the photo cross-linking catalyzed with only photoinitiator results in diene units in the cross-linked polymer networks . These photo-treated polyacrylate exhibited designable elastomer properties: with T g in −24 to −11 °C, more than 10 times increase of relative cross-linking density and resistant to solvents, improved stress, strain and elongation properties. This work paves a way for the acetylene functionalized (meth)acrylates as advanced photo-reactive material.
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POLYMER
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2021
·
IF 4.43
Yuan Wang,Yuanbo Cai,Hao Zhang,Ji Zhou,Shengtai Zhou,Yang Chen,Mei Liang,Huawei Zou
In this study, the high-performance PDMS elastomer was successfully prepared by constructing epoxy/silicone hybrid network through hydrosilylation and epoxide-opening reaction. The tensile strength , elongation at break and shear strength of the prepared hybrid material were increased by 200.0%, 59.6%, 140.6% respectively when compared with the pure PDMS. The thermal residual weight of the hybrid material at 800 °C in N 2 was kept at 56.9%. The thermal degradation mechanism of hybrid material was investigated through TG-IR analysis. Friedman technique was used to compute the kinetic parameters of degradation reaction. Meanwhile, the composition and structure of residual char of hybrid material after thermal degradation at 800 °C was systematically characterized. Results indicated that the high-performance PDMS elastomer with excellent thermal and mechanical properties was expected to be applied in many prospects such as thermal protective coating, high temperature resistant adhesive and ablative material matrix.
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ACS Sustainable Chemistry & Engineering
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2021
·
IF 8.198
Jiajia Liu,Xiaochen Tang,Huiling Lu,Yingjie Xu
To reveal the interactions between azole-anion-based ionic liquids (AILs) and propargyl alcohol (PA) and their effect on the carboxylative cyclization reaction of PA with CO2, three AILs, namely, [P66614][Im], [P66614][4-MeIm], and [P66614][4-BrIm], were synthesized and characterized. The interactions between the AILs with 2-methyl-3-butyn-2-ol (MBY) were investigated through IR and 1H NMR spectra and DFT calculations. The results indicate that azole-based anions can form H-bonds with the hydroxyl (O–H) and the alkynyl hydrogen atoms (C≡C–H) of MBY simultaneously, with the former much stronger than the latter, which is supported by the interaction energy and the distance of the H-bond from DFT calculations. Interestingly, the strength of the former always increases with the mole fraction of AIL (xAIL), while that of the latter first decreases and then increases, reaching a minimum at xAIL ≈ 0.4. Furthermore, the order of the strength of the two H-bonds is as follows: [P66614][Im] > [P66614][4-MeIm] > [P66614][4-BrIm], which is in good agreement with their basicity. According to the interactions between the AILs with MBY and combined with the reaction mechanism of MBY with CO2 promoted by AILs, it is evident that the increase in the basicity of the AILs enhances the H-bond between the AILs with O–H, thereby enhancing the activation of MBY and the subsequent CO2 conversion. However, this will also increase the interaction between AILs and C≡C–H, resulting in the deprotonation of C≡C–H and hindering the activation of MBY. Therefore, choosing a suitable basic AIL and controlling its ratio are the keys to the reaction of PA and CO2.
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Molecular Catalysis
·
2021
·
IF 5.062
Lingqi Huang,Kecheng Hu,Ganggang Ye,Zhibin Ye
Soluble small molecular/polymeric ligands are often used in Pd-catalyzed semi-hydrogenation of alkynes as an efficient strategy to improve the selectivity of targeted alkene products. The use of soluble ligands requires their thorough removal from the reaction products, which adds significant extra costs. In the paper, commercially available, inexpensive, metallic sulfide-based solid-phase ligands (SPL8-4 and SPL8-6) are demonstrated as simple yet high-performance insoluble ligands for a heterogeneous Pd nanocatalyst (Pd@CaCO 3 ) toward the semi-hydrogenation of alkynes. Based on the reactions with a range of terminal and internal alkyne substrates, the use of the solid-phase ligands has been shown to markedly enhance the selectivity of the desired alkene products by efficiently suppressing over-hydrogenation and isomerization side reactions, even during the long extension of the reactions following full substrate conversion. A proper increase in the dosage or a reduction in the average size of the solid-phase ligands enhances such effects. With their insoluble nature, the solid-phase ligands have the distinct advantage in their simple, convenient recycling and reuse while without contaminating the products. A ten-cycle reusability test with the SPL8-4/Pd@CaCO 3 catalyst system confirms its well-maintained activity and selectivity over repeated uses. A mechanistic study with x-ray photoelectron spectroscopy indicates that the solid-phase ligands have electronic interactions with Pd in the supported catalyst, contributing to inhibit the binding and further reaction of the alkene products. This is the first demonstration of solid-phase ligands for highly selective semi-hydrogenation of alkynes, which show strong promise for commercial applications.
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POLYMER
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2021
·
IF 4.43
Zhengyuan Zhang,Yu Liu,Xiaochuan Shui,Youqing Yu,Chunyan Zheng,Yuechuan Wang
It is still a challenge to directly, without any control means, synthesize polymers bearing acetylene groups by normal free radical polymerization (FRP) of acetylenyl vinyl monomers , such as propargyl (meth)acrylates, because the reactive acetylene groups result in chain branching and gelation . Some propargyl acrylates with alkyl substitutes, however, can afford linear and soluble polymers. To clarify the substitute effects the FRP behaviours of a series of acrylates bearing acetylene groups with or without substitutes are studied. Homopolymerizations of acetylenyl acrylates without or with mono-substitute on propargyl led to branched polymers at early reaction stage, and became gelled after 0.5 h with monomer conversion over 12% and gel content over 50%. The acetylenyl acrylates with di-substitutes on propargyl can afford linear and soluble homo- and copolymers with‾M n up to over 10,000 and with 45–75% monomer conversion, except for monomer 2-(2-methylbut-3-yn-2-yloxy)ethyl acrylate (DMPOEA) which has di-substitutes and a spacer connecting to the propargyl. Reactivities of vinyl and acetylene groups were found within 20 times difference by laser flash photolysis (LFP) experiments. The substitute effects of acetylenyl acrylates on FRP are explained by the intramolecular cycloaddition between C C and C C to form lactone from the s-cis conformers of the di-alkyl substituted acetylenyl acrylates. Propagating radicals can transform to stable allyl radicals by α-H atom transfer and thus the chain propagations stop. Both real-time FT-IR monitoring of photo-polymerization and high resolution 13 C NMR spectra of the polymer confirmed the existence of lactone units on polymer chains. The hypothesis is also accordance with facts obsorved in the FRP. Finally postpolymerization modification through acetylene groups on polymer chains by photo thiol-yne click reaction is exemplified.
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GREEN CHEMISTRY
·
2020
·Vol. 23
·期 1
·592-596
·
IF 9.48
Guiling Shi,Ran Zhai,Haoran Li,Congmin Wang
A highly efficient catalytic system was developed for the reaction between CO2 and propargylic alcohols for alkylidene cyclic carbonates. Ionic liquids (ILs) with different anions and cations were designed as cocatalysts, in order to find out the effect of the cation and the anion on this reaction. The results indicated that the effect of the cation was significant, especially the hydroxyl group on the cation played an important role due to the presence of a hydrogen bond. It was also found that the basicity of the anion was important for its catalytic activity, where the anion with moderate basicity gave the best activity. Moreover, this hydroxyl and azolate dual functionalized catalytic system showed excellent reusability and generality. It is worth mentioning that at a low concentration of CO2, this dual functionalized catalytic system showed excellent catalytic activity even in a gram-scale reaction, indicating its potential in carbon capture and utilization processes.
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