CHINESE JOURNAL OF CHEMISTRY
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2023
·Vol. 41
·期 24
·3618-3624
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IF 5.4
Sanyin Yang,Jun Bu,Rui Bai,Jin Lin,Siying An,Yafei Wu,Ying Guo,Jie Gao,Jian Zhang
Comprehensive Summary Alkenols are important intermediates for the industrial manufacture of various commodities and fine chemicals. At present, alkenols are produced via thermocatalytic semihydrogenation of corresponding alkynols using precious metal Pd-based catalysts in pressurized hydrogen atmosphere. In this work, we highlight an efficient electrocatalytic strategy for selectively reducing alkynols to alkenols under ambient conditions. Using 2-methyl-3-butyn-2-ol as a model alkynol, Cu 3 P nanoarrays anchored on Cu foam remarkably deliver an industrial-level partial current density of 0.79 A·cm –2 and a specific selectivity of 98% for 2-methyl-3-buten-2-ol in acidic solution. Over a 40-runs stability test, Cu 3 P nanoarrays maintain 90% alkynol conversion and 90% alkenol selectivity. Even in a large two-electrode flow electrolyser, the single-pass alkynol conversion and alkenol selectivity of Cu 3 P nanoarrays exceed 90%. Moreover, this selective electrocatalytic hydrogenation approach is broadly feasible for the production of various water-soluble alkenols. Electrochemical analyses, theoretical simulation and electrochemical in-situ infrared investigations together reveal that exothermic alkynol hydrogenation, facile alkenol desorption and formation of active H on Cu 3 P surfaces account for the excellent electrocatalytic performance.
研究领域:
化学工程
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电化学
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DOI
高影响因子
Nature Communications
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2023
·Vol. 14
·期 1
·1-9
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IF 16.6
Bu Jun,Chang Siyu,Li Jinjin,Yang Sanyin,Ma Wenxiu,Liu Zhenpeng,An Siying,Wang Yanan,Li Zhen,Zhang Jian
Alkynols semi-hydrogenation is a critical industrial process as the product, alkenols, have extensive applications in chemistry and life sciences. However, this class of reactions is plagued by the use of high-pressure hydrogen, Pd-based catalysts, and low efficiency of the contemporary thermocatalytic process. Here, we report an electrocatalytic approach for selectively hydrogenating alkynols to alkenols under ambient conditions. For representative 2-methyl-3-butene-2-ol, Cu nanoarrays derived electrochemically from CuO, achieve a high partial current density of 750 mA cm − 2 and specific selectivity of 97% at −0.88 V vs. reversible hydrogen electrode in alkaline solution. Even in a large two-electrode flow electrolyser, the Cu nanoarrays deliver a single-pass alkynol conversion of 93% with continuous production of 2-methyl-3-butene-2-ol at a rate of ~169 g g Cu − 1 h − 1 . Theoretical and in situ electrochemical infrared investigations reveal that the semi-hydrogenation performance is enhanced by exothermic alkynol adsorption and alkenol desorption on the Cu surfaces. Furthermore, this electrocatalytic semi-hydrogenation strategy is shown to be applicable to a variety of alkynol substrates.
研究领域:
化学
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材料科学
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催化反应
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DOI
PubMed
高影响因子
Catalysis Science & Technology
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2019
·Vol. 10
·期 3
·736-741
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IF 5.726
Shaorui Yan,Ruinian Zhou,Feng Han,Mengmeng Feng,Chengxia Miao,Shuai Zhang,Shiyun Ai
A CO2-induced ROCO2Na/ROCO2H buffer solution is developed and employed in the carboxylative cyclization of propargyl alcohol to generate α-alkylene cyclic carbonates. The introduction of CO2 into the propargyl alcohol/sodium tertiary pentoxide system can provide the ROCO2Na/ROCO2H buffer solution with both basic and acidic species. The basic and acidic species can simultaneously promote the generation of a carbonate anion intermediate and the interaction between the alkyne moieties of propargyl alcohol and protons (H+), facilitating carboxylative cyclization. Furthermore, the bulky (n-C4H9)4N+ cation of tetrabutylammonium bromide as an additive plays a crucial role in enhancing the nucleophilicity of the carbonate anion intermediate. Various α-alkylene cyclic carbonates are obtained in this catalytic system with relatively good yields at 80 °C.
研究领域:
化学
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环境科学
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DOI
高影响因子
PHYTOMEDICINE
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2023
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IF 7.9
Mingli Li,Wenya Gao,Huijun Wang,Jiaying Yang,Yong Zhang,Shengya Guo,Baolin Bian,Hongjie Wang,Xiaolu Wei,Yanyan Zhou,Bo Gao,Chuan Luo,Mengxiao Wang,Nan Si,Xianchun Chen,Haiyu Zhao
ABSTRACT Background Panax notoginseng (PN) was an edible Chinese herbal medicine . PN's current quality control standard cannot precisely match the traditional grading experience. Purpose In this study, under the guidance of the traditional grading experience, the combined metabolomics and biological effect evaluation were used to reveal the distinct chemical quality of PN. Methods The quality of PN was evaluated by traditional experience and characterized by the electronic tongue . A zebrafish myocardial ischemia model was developed to verify the grading experience. The untargeted metabolomics method was used to identify and validate the grading markers of PN. Results The taste was the critical indicator for classifying the quality. Based on the experience sensory scores (ranged from 47.0 to 87.8), PNs could be divided into two grades. The experience scores were significantly associated with umami and richness of the electronic tongue( p <0.01). Besides, superior PN showed substantially stronger anti-myocardial ischemia activity( p <0.001). Thirty-nine differential components were found using UHPLC-LTQ-Orbitrap MS, of which 22 were identified. A new kind of grading quality markers alkynols in PN-associated efficacy was identified, which revealed stronger anti-myocardial ischemia activities than saponin . Conclusion This study evaluated PN through untargeted metabolomics and anti-myocardial ischemia evaluation of zebrafish and proposed the critical role of alkynols in PN's quality classification.
研究领域:
中药学
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代谢组学
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药理学
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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IF 24.319
Yongxing Zhang,Jia Hu,Yong Xu,Xiangyu Yan,Siqi Zhang,Kang Duan,Cheng Chen,Ye Yuan,Francis Verpoort
An unexpected CO 2 -induced dissolution of ZnO into ionic liquids was discovered. This process exhibited high dissolution speed and the dissociated mixture was applied as an efficient Zn-based catalytic system for the CO 2 -promoted hydration of propargylic alcohols under atmospheric pressure with broad substrate scope. Moreover, this system could be recycled and reused for at least 16 times with excellent yields continuously obtained, which is an unprecedented record for this reaction. Significantly, this system could employ waste pigments as the ZnO source and work even under flue gas atmosphere. In the mechanistic investigations, the interaction between ZnO, CO 2 and ionic liquids to give N-heterocyclic carbene/CO 2 adducts proved to be the key factor for this specific dissolution. These adducts were further identified to exhibit better reactivity than the normal CO 2 by experimental data and density functional theory (DFT) calculations, which might be responsible for the excellent performance of the abovementioned catalytic system.
研究领域:
化学
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催化科学
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材料科学
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产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2024
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IF 18.5
Qiqi Mao,Wenxin Wang,Yueji Wu,Ruidong Yang,Kai Deng,Hongjie Yu,Ziqiang Wang,Liang Wang,Hongjing Wang
Electrocatalytic alkynol semi-hydrogenation for the high-value chemicals alkenol with mild conditions and carbon-free emission is a potentially green and sustainable alternative to conventional thermocatalytic routes, which generally involves the design of electrocatalysts with high activity and high selectivity. Here, the rare-earth single-atom (Ln = La, Nd, Pr) coordinated Pd metallene (Ln 1 Pdene) is reported for electrocatalytic 2-methyl-3-butyn-2-ol (MBY) semi-hydrogenation reaction (MBY ESHR) to synthesis of 2-methyl-3-buten-2-ol (MBE). Typically, in alkaline medium containing 0.1 m MBY, MBY conversion and MBE selectivity of La 1 Pdene are as high as ≈97% and ≈95%, respectively, with excellent electrocatalytic stability. Meanwhile, in situ infrared spectra reveal the conversion of MBY to MBE during the dynamic electrocatalytic process. Theoretical calculations reveal that the interaction between La single-atom and Pd host triggers an unconventional transformation of the intermediate MBE* adsorption configuration during electrocatalytic hydrogenation, achieving the optimal desorption energy between La 1 Pd and target product and optimizing the reaction energy barriers to inhibit the over-hydrogenation of MBE. Moreover, La single-atom as the adsorption active site of the hydrogen supplier H 2 O effectively reduces the competition adsorption between the reactants MBY and H 2 O, rendering La single-atom and Pd host as the synergistic co-catalytic active sites to promote the electrocatalytic MBY semi-hydrogenation reaction.
研究领域:
材料科学
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电化学
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催化化学
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DOI
高影响因子
ChemCatChem
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2025
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IF 3.9
Cheng-Long Li,Rui-Ping Zhang,Lu Hou,An-Hui Lu
Pd-catalyzed semihydrogenation of alkynols to enols is a pivotal industrial process for synthesizing fine chemicals like fragrances and vitamins. The selection of carbon-based supports is crucial due to their advantages in good chemical and thermal stability, tunable surface properties, and facile metal recovery via combustion. Herein, we constructed the wood-based monolithic carbon support with a sulfur-doped mesoporous carbon layer to anchor high-dispersed Pd nanoparticles. This mesoporous carbon layer was fabricated via co-polymerization of 2-thiophenemethanol and tetraethoxysilane monomers formed by decomposition of the tetrakis(2-thiophenemethoxy)silane on wood substrates, followed by pyrolysis, and removal of silica. The resultant Pd/C catalyst exhibited high catalytic activity (4323 mol mol Pd −1 h −1 ) and selectivity (93% at 99% conversion) under mild conditions (298 K, 2 bar H 2 ) in 2-methyl-3-butyn-2-ol (MBY) semihydrogenation. The thiophene-like sulfur and mesoporous framework synergistically promoted Pd dispersion, thereby boosting catalytic activity. Meanwhile, the electron-rich Pd 0 sites, which originated from electron donation of thiophene-like sulfur species, significantly enhanced catalytic selectivity. Additionally, the sulfur-modified monolithic catalyst presented good stability over five cycles and facile separation from the solution. It also displayed broad applicability in diverse alkynol semihydrogenation reactions, demonstrating high potential for liquid-phase catalytic applications. Graphical Surface sulfur-doped monolithic carbon with mesoporous structures is constructed to anchor high-dispersed Pd nanoparticles. Thiophene-like sulfur synergizes with mesopores to enhance Pd dispersions and donates electrons to form electron-enriched Pd sites, thereby boosting catalytic activity and selectivity. This monolithic design facilitates separation, demonstrating high potential for liquid-phase reactions.
研究领域:
催化化学
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材料科学
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有机合成
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纳米催化
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多相催化
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产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
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2023
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IF 3.9
Cheng Zhang,Yi Zheng,Jianfeng Li,Hongzhang Cao,Yanhui Xu,Weisheng Liu,Zhengping Dong
Selective hydrogenation of alkynol compounds to produce high value-added enols is an important reaction in the fine chemical industry. The construction of selective hydrogenation catalysts for alkynols is challenging because the alkynyl group is prone to over hydrogenation and the selectivity in the hydrogenation is always low. Herein, a simple sacrificial template strategy was designed to prepare mesoporous CeO2, on which ultrafine and highly-dispersed bimetallic PdCu nanoparticles were anchored, obtaining the PdCu@CeO2 catalyst. Introducing non-precious metallic Cu can improve the selectivity of precious metal Pd catalysts for the selective hydrogenation of alkynols through electronic and geometric modulation. The obtained PdCu@CeO2 catalyst showed high selectivity (99%) and good recyclability for the selective hydrogenation of the probe compound propynol ethoxylate under mild conditions. The PdCu@CeO2 catalyst also exhibited excellent performance in the catalytic selective hydrogenation of various substituted alkynols. Therefore, this research work provides a feasible strategy for the effective regulation of catalytic performance, which has potential application for the efficient catalytic selective hydrogenation of alkynols in the fine chemical industry.
研究领域:
催化化学
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材料科学
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精细化工
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2021
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IF 9.229
Jian Zhao,Zhuo-Hao Jiao,Sheng-Li Hou,Yue Ma,Bin Zhao
Carboxylative cyclization of propargylic alcohols with CO2 is significant in synthetic chemistry, but harsh conditions are often needed according to reported results. Herein, a new stable nitro-functionalized metal–organic framework (MOF) of {[Co3(L)2(bpy)4(H2O)2]·DMF·H2O·bpy}n (1) was fabricated through the solvothermal reaction, which exhibited excellent stability in acid and basic solutions. Owing to the porous structure, unsaturated metal sites, and uncoordinated 4,4′-bpy ligands, 1 can serve as an excellent platform for catalytic applications. Hence, Ag(I) ions were incorporated in 1 through a postsynthetic method, and the as-synthesized Ag-1 catalyst with low metal loading (0.64 mol %) displayed excellent catalytic performance in the chemical fixation of CO2 with alkynols under room temperature and atmospheric pressure. The results of 1H NMR analyses further confirmed that Ag-1 can efficiently activate hydroxyl groups and promote the reaction. Moreover, the turnover frequency (TOF) of the Ag-1 catalyst can reach 262 h–1 in a short period of time, which is a high TOF value among the state-of-the-art MOF-based catalysts for catalyzing cycloaddition of CO2 with propargylic alcohols.
研究领域:
化学
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材料科学
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催化领域
✓ 已验证
DOI
PubMed
高影响因子
GREEN CHEMISTRY
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2019
·Vol. 21
·期 15
·4143-4151
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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
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2021
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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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产品关联
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
✓ 已验证
DOI
高影响因子
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