Catalysis Science & Technology
·
2024
·
IF 4.4
Peng Zhang,Liying An,Chunqiu Zhao,Qiang Chang,Fei Wang,Chenghua Zhang,Yulei Zhu,Yong Yang,Yongwang Li
For catalytic carbonylation reactions, the high-cost catalyst recovery process is a huge challenge in industrial applications. Herein, the “honeycomb catalytic strategy” based on the structural evolution of supported cobalt catalysts successfully implements a facile and efficient catalyst recovery in the methoxycarbonylation of propylene oxide. In this strategy, cobalt species mainly exist in the form of homogeneous cobalt carbonyl species and supported cobalt nanoparticles in the reaction and product/catalyst separation stage, respectively, for reconciling catalytic efficiency and metal recovery. Our results demonstrate that catalytic behaviors of supported cobalt catalysts strongly depend on the support materials and the in situ generated cobalt carbonyls. And higher CO partial pressure and lower temperature are conducive to the conversion of metallic cobalt into cobalt carbonyls, while additional post-treatment procedures (removing CO and introducing high temperature) can recover the dissolved cobalt species in the product mixture onto the support. ICP testing proved that the optimal post-treatment process can increase the Co retention ratio of the Co/C catalyst from 45.3% to 98.9%. After four honeycomb catalytic cycles, the Co retention ratio remained at 95.2% with a slight loss of productivity. Meanwhile, for the cobalt-based catalysts with different supports and higher loadings, the post-treatment process also significantly enhanced the Co retention ratio, thereby demonstrating the effectiveness and universality of the “honeycomb catalytic strategy”.
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Materials
·
2020
·Vol. 13
·期 18
·4026
·
IF 3.057
Shasha Zhang,Wenxin Ji,Ning Feng,Liping Lan,Yuanyuan Li,Yulong Ma
In this study, a Rh(I)/Ru(III) catalyst with a bimetallic space structure was designed and synthesized. The interaction between the metals of the bimetallic catalyst and the structure of the bridged dimer can effectively reduce the steric hindrance effect and help speed up the reaction rate while ensuring the stability of the catalyst. X-ray photoelectron spectroscopy (XPS) results show that rhodium accepts electrons from chlorine, thereby increasing the electron-rich nature of rhodium and improving the catalytic activity. This promotes the nucleophilic reaction of the catalyst with methyl iodide and reduces the reaction energy barrier. The methanol carbonylation performance of the Rh/Ru catalyst was evaluated, and the results show that the conversion rate of methyl acetate and the yield of acetic acid are 96.0% under certain conditions. Furthermore, during the catalysis, no precipitate is formed and the amount of water is greatly reduced. It can be seen that the catalyst has good stability and activity.Keywords:carbonylation;acetic acid;bimetallic catalyst
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2022
·
IF 4.198
Tianhao Xu,Xingyu Zhou,Xiong Xiao,Yan Yuan,Long Liu,Tianzeng Huang,Chunya Li,Zhi Tang,Tieqiao Chen
A nickel-catalyzed decarbonylative thioetherification of carboxylic acids with thiols was developed. Under the reaction conditions, benzoic acids, cinnamic acids, and benzyl carboxylic acids coupled with various thiols including both aromatic and aliphatic ones produce the corresponding thioethers in up to 99% yields. Moreover, this reaction was applicable to the modification of bioactive molecules such as 3-methylflavone-8-carboxylic acid, probenecid, and flufenamic acid, and the synthesis of acaricide chlorbenside. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
Foods
·
2023
·Vol. 12
·期 7
·1455
·
IF 5.2
Junting Yu,Zhilei Zhou,Xibiao Xu,Huan Ren,Min Gong,Zhongwei Ji,Shuangping Liu,Zhiming Hu,Jian Mao
Huangjiuis one of the oldest alcoholic beverages in the world. It is usually made by fermenting grains, and Qu is used as a saccharifying and fermenting agent. In this study, we identified differential carbonyl compounds inHuangjiuwith varying sugar contents from different regions. First, we developed and validated a detection method for volatile carbonyl compounds inHuangjiu, and for optimal extraction, 5 mL ofHuangjiuand 1.3 g/L of O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) were incubated at 45 °C for 5 min before extracting the volatile carbonyl compounds at 45 °C for 35 min. Second, the targeted quantitative analysis of 50 carbonyl compounds inHuangjiushowed high levels of Strecker aldehydes and furans. Finally, orthogonal projections to latent structures discriminant analysis (OPLS-DA) was used to differentiate betweenHuangjiuwith different sugar contents, raw materials, and region of origin. A total of 19 differential carbonyl compounds (VIP > 1,p< 0.05) were found inHuangjiuwith different sugar contents (semidry and semisweetHuangjiu), and 20 differential carbonyl compounds (VIP > 1,p< 0.05) were found in different raw materials forHuangjiuproduction (rice and nonriceHuangjiu). A total of twenty-two and eight differential carbonyl compounds, with VIP > 1 andp< 0.05, were identified in semidry and semisweetHuangjiufrom different regions (Zhejiang, Jiangsu, Shanghai, and Fujian), respectively.Keywords:Huangjiu;carbonyl compounds;PFBHA;targeted metabolomics;OPLS-DA
研究领域:
食品科学
·
分析化学
·
代谢组学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Jiayuan Sun,Shanshan Shao,Xinggang Hu,Xiaohua Li,Huiyan Zhang
The aqueous fraction of bio-oil from biomass fast pyrolysis mainly contains low-molecular-weight oxygenates such as carboxylic acids, ketones, aldehydes, phenols, and furans. In this study, the full components of aqueous bio-oil are directionally converted into carbonyl groups such as aldehydes and ketones, and then the oxygen-containing precursors of aviation fuel are prepared through coupling, focusing on exploring the mechanism of carbonylation and C–C coupling. Studies have revealed that propionic acid, furfural, and phenol can be directionally converted into ketones, in which reaction 3-pentanone, cyclopentanone, and cyclohexanone were formed via ketonization and hydrogenation in the aqueous phase. Then the two components of 3-pentanone, cyclopentanone, cyclohexanone, acetone, and acetaldehyde were subjected to aldol condensation to explore the C–C coupling mechanism in the preparation of the C7–C18 precursor of aviation fuel. The mechanism in the high-quality utilization of all components of the aqueous phase bio-oil fraction was explored, which was favorable for the synthesis of biomass-based aviation fuel.
研究领域:
化学工程
·
可再生能源
·
生物质转化
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF FOOD COMPOSITION AND ANALYSIS
·
2023
·
IF 4.3
Shouyin Wang,Shengjie Li,Wenhui Wang,Xiuxia Guo,Jinfeng Pan,Xiuping Dong
This paper aimed to develop a quantitative method based on high-performance liquid chromatography (HPLC) coupled with triple quadrupole tandem mass spectrometry (MS/MS) for the simultaneous determination of two protein carbonylation products derived from lysine residues in meat proteins, namely, α-aminoadipic semialdehyde (AAS) and lysinonorleucine (LNL). Mass spectrometry conditions and derivatization parameters were optimized and the linearity, repeatability, bias, the limit of detection (LOD), the lower limit of quantification (LLOQ), and recovery were validated. The developed method showed satisfactory linearity, repeatability, and sensitivity for both AAS and LNL. This method was applied to analyze the contents of these compounds in different meat products, and the formation of AAS was observed to be closely related to the severity of the manufacturing conditions. Moreover, AAS was demonstrated to be a reliable but more sensitive marker for protein carbonylation compared to the DNPH method, which could also provide information regarding the specific pathway of protein carbonylation.
研究领域:
食品科学
·
分析化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Qiang Chen,Yujun Wang,Guangsheng Luo
Photocatalytic direct decarboxylative carbonylation of ubiquitous carboxylic acids is a promising strategy to obtain highly versatile ketone building blocks, but metal-free and efficient conversions are still lacking. Here, density functional theory calculations are used to guide the experimental screening of catalysts, highlighting the potential influence of frontier molecular orbital energy levels on the catalytic process and revealing an acridine photocatalyst capable of realizing value-added conversion of carboxylic acid at room temperature under visible light with excellent performance. The possible mechanism for this conversion was elucidated in depth by combining study of the excited state behavior of the photosensitizer and the results of detection experiments for radicals. Theoretical calculations and mechanistic studies further disclose the kinetically rate-limiting role of oxygen, including its participation in the formation of superoxide radicals for carbonylation and as an electron trapping agent for catalyst cycling. Based on these findings, a flow microreactor platform was ingeniously built to achieve previously inaccessible photocatalytic decarboxylative carbonylation promoted by acridine in concert with oxygen. Interestingly, the gas–liquid segmented microflow is found to enable a significant acceleration (from 14 to 2 h) and higher yield compared to the batch counterpart, resulting in a high space–time yield of 137.4 g/L d -1 for this transformation, which far exceeds the reported values. This study underscores the feasibility of broadening the competence of acridine photocatalysis through the involvement of kinetically adapted oxygen, thus enabling substitution of metal-dependent photocatalysis and even more efficient and high-yield decarboxylative carbonylation of carboxylic acids.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 10
·1327
·
IF 3.9
Di Wang,Jiangang Lv
Methyl glycolate was synthesized as a precursor to ethylene glycol from the acid-catalyzed carbonylation of formaldehyde, followed by esterification with methanol. Homogeneous acids and different solid acids (e.g., resins and zeolites) were used as catalysts, and the effect of the solvent was examined. Afterward, a carboxylic acid protection strategy was proposed. With sulfolane and acetic acid as the mixed solvent, the solubility of CO increases, and the reaction rate can be accelerated. The rapid reaction between acetic acid and glycolic acid inhibits glycolic acid polymerization and pulls the reaction balance to promote the carbonylation reaction rate. Under the optimal solvent system (a molar ratio of acetic acid to sulfolane of 1:5) and the appropriate reaction conditions, the selectivity of the target product is higher than 85%. Solid acid catalysts with a −SO3H or −CF2SO3H functional group are supposed to be efficient in the carbonylation of formaldehyde, based on which a supported Nafion catalyst with a high surface area and total acid content was designed and synthesized. The novel supported Nafion catalyst presents a high total acid content and high Brönsted–Lewis acid ratio due to the characteristics of modified zeolite and, thus, leads to the high reactivity and very low selectivity of the by-product. A possible reaction mechanism is proposed to explain the product’s distribution by ascribing the formation of different products to different types of acid sites.Keywords:carbonylation;formaldehyde;methyl glycolate;ethylene glycol;acid catalyst
研究领域:
化学合成
·
催化化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Xiang Hui,Liguo Wang,Jianhui Shi,Tiping Wei,Fengqin Guo,Yan Cao,Peng He,Jiajun Zhang,Huiquan Li
The methoxycarbonylation of amines into carbamates via the construction of a C–N bond is an important reaction in pharmaceutical and fine chemical syntheses. However, the methoxycarbonylation of amines with dimethyl carbonate (DMC) without metal-based catalysts or other base catalysts has rarely been studied, and the reaction mechanisms remain underexplored. Herein, efficient methoxycarbonylation of biobased pentanediamine (PDA) with DMC promoted by water is proposed. The addition of water as a catalyst resulted in a 4-fold increase in yield. The conducted kinetic studies showed that proton transfer from PDA to methoxy occurs through the hydrogen bond between the zwitterionic intermediate and water. In situ analyses have shown that OH– and water form hydrogen bonds with the ether O atom of DMC and hydroxyl H atoms of PDA, synergistically promoting the elimination of the methoxy group. The addition of water reduced the energy barrier of the methoxy group elimination from 16.3 to 0.6 kcal/mol, confirming the results of theoretical computations. Furthermore, the methyl (5-aminophenyl)carbamate intermediate was recycled into dimethyl pentane-1,5-diyldicarbamate without the use of an additional catalyst, which was mediated by the hydrogen bond between PDA and methyl (5-aminophenyl)carbamate. The reported mild methoxycarbonylation of biobased PDA under metal-free conditions is a green and sustainable method of synthesizing biobased dicarbamate.
研究领域:
有机化学
·
绿色化学
✓ 已验证
产品关联
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
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
·
IF 17.7
Shaolei Gao,Peng Lu,Liang Qi,Yingli Wang,Hua Li,Mao Ye,Valentin Valtchev,Alexis T. Bell,Zhongmin Liu
Methyl methoxyacetate (MMAc) and methyl formate (MF) can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane (DMM), with near 100% selectivity for each process. Despite continuous research efforts, the insight into the reaction mechanism and kinetics theory are still in their nascent stage. In this study, ZEO-1 material, a zeolite with up to now the largest cages comprising 16×16-MRs, 16×12-MRs, and 12×12-MRs, was explored for DMM carbonylation and disproportionation reactions. The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1 (Si/Al = 21) relative to the previously investigated FAU (Si/Al = 15), indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity. A higher MF formation rate is also observed over ZEO-1 with lower activation energy (79.94 vs. 95.19 kJ/mol) compared with FAU (Si/Al = 30). Two types of active sites are proposed within ZEO-1 zeolite: Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs, which is active predominantly for MMAc formation, and Site 2 located in smaller cages for methyl formate/dimethyl ether formation. Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure. The DMM disproportionation is nearly first-order dependence on DMM partial pressure, while it reveals a strongly inverse dependence with increasing CO partial pressure. Furthermore, ZEO-1 exhibits good catalytic stability, and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%, due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.
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
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2014
·Vol. 2014
·期 6
·975-985
·
IF 2.965
Jing Zhang,Yongyong Wang,Xiaoli Zhao,Ye Liu
Graphical The ionic palladium complexes 1A – 4A ligated by imidazolium-based-phosphanes were prepared and shown, by single-crystal X-ray diffraction analyses, to be composed of Pd II -centered square-planar cations and OTf – counteranions. The complexes were tested as precatalysts for the homogeneous carbonylative Sonogashira coupling of aryl iodides with phenylacetylene. The stable ionic Pd II complexes 1A – 4A were synthesized through the complexation of PdCl 2 (MeCN) 2 with the phosphane-functionalized ionic liquids (FILs) 1 – 4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A – 4A were all composed of Pd II -centred square-planar cations and triflate (OTf – , CF 3 SO 3 – ) counteranions. The complex cations in 1A – 3A possessed structural similarity to trans -PdCl 2 (PPh 3 ) 2 . The cation in 4A was a new Pd II -centered planar complex ligated by the phosphane–carbon anion–carbene (PCC) pincer in a tripodal manner. The stabilities of 1A – 4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A – 4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A – 3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A . The recycling experiments of 3A in [Bpy]BF 4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）