ChemistrySelect
·
2024
·Vol. 9
·期 18
·e202304772
·
IF 1.9
Chenghao Tang,Chaoyang Song
Graphical Copper encapsulated N-rich carbon material derived from porous organic polymer was found to be highly active heterogeneous catalyst for solvent-free coupling of acyl chlorides with alkynes. Copper promoted Sonogashira coupling has recently emerged as an attractive route for synthesizing α, β-Acetylenic ketones (ynones). In this study, a porous organic polymer based on [2,6-Bis(1,2,3-triazol-4-yl)pyridine] (BTP) was prepared through oxidative coupling. By incorporating copper salt and subsequent pyrolysis, copper encapsulated N-doped carbon materials were obtained. The resulting copper/carbon materials exhibited excellent catalytic performance for the coupling of acyl chlorides and alkynes due to their large surface area, abundant mesopores, and uniformly distributed metal nanoparticles. The reaction proceeded efficiently, yielding ynones with good to excellent yields at room temperature within a short reaction time (4 h) using only 0.4 mol % catalyst. Compared to previously reported copper nanocatalysts, the N-doped carbon materials supported copper catalyst demonstrated higher catalytic activity and operated at lower reaction temperatures. Additionally, the catalyst displayed reliable recyclability without any significant loss in catalytic activity.
研究领域:
化学
·
材料科学
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产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 6
·1941-1949
·
IF 6.177
Yunhong Pi,Xiuting Wu,Zefeng Zheng,Liang Ma,Tiejun Wang
Methanol reforming in aqueous solution provides a significantly attractive and promising pathway to release hydrogen with mild H2 release conditions and high H2 storage capacity. Exploring non-noble metal-based catalysts with sufficiently high activity, stability, and selectivity for H2 remains a great challenge. We report here the construction of a chitosan–lignin (CS–LN) carbon framework bio-composite-encapsulated Cu catalyst (Cu@CS–LN) with high loading and dispersion for base-free hydrogen generation from aqueous-phase methanol reforming below 210 °C. With optimized conditions, the hydrogen generation rate of Cu@CS–LN (2.5 × 105 μmolH2 gCu−1 h−1) represents an approximately 2-fold enhancement compared with Cu@CS without lignin incorporation, and more than 3–5 times higher than commercial Cu-based catalysts such as Rainie Cu or CuO/ZnO. The catalyst underwent an intensified water gas shift reaction (WGSR), and it also exhibited extraordinary selectivity toward the CO byproduct. The unique carbon framework structure of CS–LN through electrostatic densification self-assembly not only enhanced the adsorption and dispersion of Cu species, but it also stabilized and further reduced the Cu particles to active phase Cu during the hydrogen generation reaction to promote catalytic activity and stability without obvious catalyst deactivation detected after running for 150 hours. This specific hydrogen production technology exhibits great potential for hydrogen-powered polymer electrolyte membrane (PEMFCs) fuel cells.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Yang Ruixin,Cai Yanming,Qi Yongbing,Tang Zhuodong,Zhu Jun-Jie,Li Jinxiang,Zhu Wenlei,Chen Zixuan
C–C coupling is of utmost importance in the electrocatalytic reduction of CO 2 , as it governs the selectivity of diverse product formation. Nevertheless, the difficulties to directly observe C–C coupling pathways at a specific nanocavity hinder the advances in catalysts and electrolyzer design for efficient high-value hydrocarbon production. Here we develop a nano-confined Raman technology to elucidate the influence of the local electric field on the evolution of C–C coupling intermediates. Through precise adjustments to the Debye length in nanocavities of a copper catalyst, the overlapping of electrical double layers drives a transition in the C–C coupling pathway at a specific nanocavity from *CHO–*CO coupling to the direct dimerization of *CO species. Experimental evidence and simulations validate that a reduced potential drop across the compact layer promotes a higher yield of CO and promotes the direct dimerization of *CO species. Our findings provide insights for the development of highly selective catalyst materials tailored to promote specific products.
研究领域:
催化化学
·
电化学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Zerui Su,Jian Zhang,Yang Li,Zheyu Qiao,Ziyuan Qiao,Lihang Wei,Xiaoyuan Qin,Xiaoxue Mu,Feng-Shou Xiao
Cu-based catalysts are crucial for the dehydrogenation of ethanol (EtOH) to acetaldehyde (AcH); however, their performance decreases at higher temperatures due to the low Tammann temperature of Cu species. In this study, we synthesized silica-supported Cu catalysts using microwave-assisted wet-kneading. Characterization revealed a typical core–shell structure (Cu@SiO 2 -WK), which demonstrated high activity, excellent selectivity, and superior stability for ethanol dehydrogenation. The Cu@SiO 2 -WK achieved 96.2 % EtOH conversion with 99.9 % selectivity to AcH at 260 °C. After 160 h of reaction, it maintained an EtOH conversion of 90.5 % and AcH selectivity of ∼99.9 %. Following simple calcination, the catalyst’s activity was fully regenerated to 96.1 %. Model catalysts and in situ FT-IR spectra indicate that the core–shell structure significantly enhances the catalyst’s performance in the dehydrogenation of EtOH to AcH.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Sustainable Chemistry and Pharmacy
·
2024
·
IF 5.5
Zhuoxi Li,Guangping Zhou,Shaoqu Xie,Xianwei Zheng,Chengshan Xie,Hao Huang,Wanli Zhang
The upgrading of acetone-butanol-ethanol (ABE) mixture from biomass to long-chain biofuels has aroused increasing attention since it is beneficial for alleviating energy crises and promoting high-value utilization of biomass. The main key to the ABE conversion is to find catalysts that are widely available and inexpensive. In this study, a simple way to prepare a low-cost highly dispersed Cu/MgO catalyst for ABE alkylation was proposed, resulting in C5–C11 molecules. The effects of experimental parameters such as reduction method, copper loading, reaction time, reaction temperature, and gas atmosphere on the production of long-chain products were also investigated. Compared to using hydrogen gas for reduction, the use of sodium borohydride in methanol results in the highest long-chain product yields. A copper loading of 2.5% or 5% is optimal, while an excessive copper load causes its aggregation. Within 18 h, the longer the reaction time, the higher the total yield and the higher the proportion of long-chain products. When the temperature increases from 250 °C to 300 °C, the total yield increases while the proportion of by-products decreases. The nitrogen atmosphere is conducive to increasing total production as hydrogen can cause the loss of acetone via hydrogenation.
研究领域:
生物化学
·
能源科学
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2016
·
IF 7.354
Junjie Su,Zhengpai Zhang,Donglong Fu,Da Liu,Xin-Chao Xu,Bianfang Shi,Xu Wang,Rui Si,Zheng Jiang,Jing Xu,Yi-Fan Han
A comparative study of higher alcohols synthesis directly from syngas has been performed over monometallic Co and bimetallic CoCu/SiO 2 catalysts. Particularly, the role of Cu on the origin of active sites and reaction mechanism were investigated thoroughly using multiple techniques such as ex situ X-rays diffraction (XRD), X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Reduction process of CoCu/SiO 2 catalysts was also determined using in situ XRD and in situ Raman spectroscopy while the surface structure of reduced catalysts was detected by CO-DRIFTS. CoCu bimetallic particles covered by Cu atoms are responsible for alcohols synthesis. The intrinsic kinetics was performed over both catalysts under realistic reaction conditions. By comparing the kinetic parameters, including apparent activation energies and reaction orders, the promotional effects of Cu have been identified as: (1) weakening the CO/HCO dissociation and reducing the formation of CH x species; (2) controlling surface Co ensemble size and inhibiting CH x insertion.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Chemistry
·
2021
·
IF 2.506
Renjie Zhou,Gui Chen,Yuejun Ouyang,Hairui Ni,Nonglin Zhou,Bailin Xiang
Using MOF-5 as a template, the porous carbon (MDPC-600) possessing high specific surface area was obtained after carbonization and acid washing. After MDPC-600 was loaded with Cu ions, the catalyst Cu/MDPC-600 was acquired by heat treatment under nitrogen atmosphere. The catalyst was characterized by X-ray powder diffraction (XRD), N2 physical adsorption (BET), field emission electron microscope (SEM), energy spectrum, and transmission electron microscope (TEM). The results show that the Cu/MDPC-600 catalyst prepared by using MOF-5 as the template has a very high specific surface area, and Cu is uniformly supported on the carrier. The catalytic hydrogen peroxide oxidation reaction of phenol hydroxylation was investigated and exhibits better catalytic activity and stability in the phenol hydroxylation reaction. The catalytic effect was best when the reaction temperature was 80°C, the reaction time was 2 h, and the amount of catalyst was 0.05 g. The conversion rate of phenol was 47.6%; the yield and selectivity of catechol were 37.8% and 79.4%, respectively. The activity of the catalyst changes little after three cycles of use.
研究领域:
材料科学
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催化化学
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产品关联
DOI
高影响因子
MOLECULES
·
2023
·Vol. 28
·期 15
·5683
·
IF 4.6
Yan Xiao,Nannan Zhan,Jie Li,Yuan Tan,Yunjie Ding
The catalytic upgrading of ethanol into butanol through the Guerbet coupling reaction has received increasing attention recently due to the sufficient supply of bioethanol and the versatile applications of butanol. In this work, four different supported Cu catalysts, i.e., Cu/Al2O3, Cu/NiO, Cu/Ni3AlOx, and Cu/Ni1AlOx(Ni2+/Al3+molar ratios of 3 and 1), were applied to investigate the catalytic performances for ethanol conversion. From the results, Ni-containing catalysts exhibit better reactivity; Al-containing catalysts exhibit better stability; but in terms of ethanol conversion, butanol selectivity, and catalyst stability, a corporative effect between Ni–Al catalytic systems can be clearly observed. Combined characterizations such as XRD, TEM, XPS, H2-TPR, and CO2/NH3-TPD were applied to analyze the properties of different catalysts. Based on the results, Cu species provide the active sites for ethanol dehydrogenation/hydrogenation, and the support derived from Ni–Al–LDH supplies appropriate acid–base sites for the aldol condensation, contributing to the high butanol selectivity. In addition, catalysts with strong reducibility (i.e., Cu/NiO) may be easily deconstructed during catalysis, leading to fast deactivation of the catalysts in the Guerbet coupling process.Keywords:copper catalyst;hydrotalcite;stability;ethanol;butanol
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
·
2025
·
IF 3.5
Zeng Fang,Zhang Shuyao,Lin Ting,Li Yiqun,Xiao Meng
A novel Cu catalyst immobilized on glycine-functionalized poly(vinyl chloride) (Cu@Gly-PVC) was synthesized conveniently. The as-prepared catalyst was fully characterized by FTIR, SEM, EDS, elemental mapping, XPS, TGA, ICP, and EA analysis. The Cu(II) ions were uniformly distributed on the as-prepared Gly-PVC matrix via coordinated by carboxylic groups in a bidentate bridging pattern. This catalyst can be used at ppm levels in water for alkyne–azide cycloadditions (CuAAC) reactions, producing high yields of 1,2,3-triazoles. The present methodology offers several merits such as low catalyst loading, high catalytic activity, excellent yields, short reaction times, environmentally friendly reactions, simple operations, and compatibility of wide range of substrates. Furthermore, the catalyst can be easily isolated from the reaction mixture through simple filtration and retains remarkable reusability and catalytic activity even after four consecutive reaction cycles. Graphical abstract
研究领域:
有机化学
·
材料科学
·
绿色化学
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产品关联
DOI
高影响因子
Journal of Cleaner Production
·
2023
·
IF 11.1
Lujie Zuo,Shufan Yu,Rongjun Zhang,Hongwei Li,Yu Wu,Rufat Abiev,Zhao Sun,Zhiqiang Sun
Methanol is a competitive candidate for in-situ hydrogen supply; however, the techniques of methanol-to-hydrogen production are suffered from high reforming temperatures and catalyst deactivation . In this work, the chemical looping oxidative reforming of methanol is conducted using a Pd–Cu-based catalytic oxygen carrier (PdO–CuO–CuMn 2 O 4 ). Synergistic enhancement of lattice oxygen induction and Pd–Cu alloy activation is confirmed, thereby achieving efficient methanol reforming at a temperature as low as 200 °C. Under such low temperatures, the hydrogen production rate can reach an average of 11.2 times higher than that of CuO/ZnO/Al 2 O 3 . Moreover, the catalytic oxygen carrier remains relatively satisfying redox durability after 30th cycle. SEM and AFM measurements reveal the high degree of roughness at the PdO–CuO–CuMn 2 O 4 surface, in which the methanol activation can be effectively promoted. XRD and XPS measurements verify the formation of Pd–Cu alloy, as proved by the charge transfer from Pd to Cu. During the redox looping, Pd–Cu alloy is formed and re-separated to be PdO and CuO, thus remaining homogenous distribution of the active phase on an atomic scale. Meanwhile, the lattice oxygen also plays a crucial role in methanol activation, synergistically enhancing the low-temperature reforming of methanol. This study provides a new implication for designing functionalized catalytic oxygen carrier materials , which will substantially promote in-situ hydrogen supply for proton exchange membrane fuel cells.
研究领域:
化学工程
·
催化材料科学
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DOI
高影响因子
JOURNAL OF CATALYSIS
·
2017
·
IF 6.844
Min Wang,Jianmin Lu,Lihua Li,Hongji Li,Huifang Liu,Feng Wang
Selective oxidative cleavage of C C bond is pivotal for producing functionalized molecules, useful for organic synthesis and biomass utilization. We herein report the oxidative C(OH) C bond cleavage of secondary alcohols to acids over a copper/1, 10-phenanthroline complex with molecular oxygen as the oxidant. A wide range of secondary alcohols are converted into acids with up to 98% yields. More interestingly, it is effective for breaking up lignin model systems into acids, which is rarely achieved in previous studies. Density functional theory (DFT) calculations indicate a copper-oxo-bridged oxygen dimer is the active species for the C H bond cleavage which is the rate-determining step for C C bond.
研究领域:
有机化学
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催化化学
✓ 已验证
DOI
高影响因子
Nanoscale
·
2024
·Vol. 16
·期 6
·3034-3042
·
IF 5.8
Haoyang Wu,Zhili Wang,Benqiang Tian,Yaping Li,Zheng Chang,Yun Kuang,Xiaoming Sun
Electrocatalytic CO2 reduction (ECR) to high value-added chemicals is an excellent method to attenuate the impact of greenhouse effect caused by CO2. At the same time, multicarbon products (C2+) get extensive attention in view of their relatively high energy density and market price. At present, Cu is an important metal electrocatalyst to convert CO2 into multicarbon products (e.g. ethylene, ethanol, and n-propanol); however, its poor selectivity impedes its practical application. It is well-known that the Cu(100) crystal facet can enhance the selectivity toward multicarbon products among different Cu crystal facets. Herein, the Cu nanoparticles were firstly prepared using the inductive effect of different gases (CO2, CO, Ar, N2, and air) during the Cu electrodeposition processes, in which the CO2-induced Cu catalyst (Cu-CO2) showed the largest normalized content of the Cu(100) crystal facet and the highest C2+ faradaic efficiency of 69% at a current density of 80 mA cm−2 in ECR. Subsequently, the different CO2 pressures during the Cu electrodepositions were studied to reveal the optimal CO2 pressure in the CO2-induced Cu synthesis for improved Cu(100) content as well as C2+ faradaic efficiency. Finally, density functional theory (DFT) calculations confirmed that CO2 molecules preferred to get adsorbed on the Cu(100) crystal facet, which resulted in not only the presence of dominant Cu(100) during the CO2-induced Cu synthesis but also the good electrocatalytic performance in ECR.
研究领域:
材料科学
·
环境科学
·
催化化学
✓ 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）