Catalysis Science & Technology
·
2015
·Vol. 6
·期 11
·3854-3861
·
IF 5.426
Peng Wang,Huan Liu,Yong-Qi Li,Xiao-Li Zhao,Yong Lu,Ye Liu
A series of ionic phosphonium-based aminophosphines L1–L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1–L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3–Rh(acac)(CO)2 system also exhibited good generality to hydroformylation–acetalization of a wide range of olefins in different alcohols.
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
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Li Bai,Mei Wu,Huazhong Yu,Shima Liu,Ke Song,Xianwu Zhou,Jie Guo,Jian He
Acetalization is a promising method for upgrading biomass-derived molecules into valuable chemicals, and acetal products are considered excellent oxygenated fuel additives. Herein, a catalyst-free, facile, and effective protocol for the acetalization of furfural and ethylene glycol is established, affording a 78.6% yield of 2-(furan-2-yl)-1,3-dioxolane with a furfural/ethylene glycol molar ratio of 1:15 in cyclohexane at 160 °C after 2 h. Moreover, the lower activation energy (15.8 kJ/mol) corroborates that the established system is efficient, and the thermodynamic studies demonstrate that catalyst-free acetalization is an endothermic, nonspontaneous, and endergonic reaction. A plausible mechanism including two pathways for catalyst-free acetalization of furfural and ethylene glycol is proposed, wherein the formed water from the acetalization process can render the ethylene glycol to be hydrolyzed, which plays a positive role in facilitating the acetalization of furfural and ethylene glycol. In addition, the excess ethylene glycol in the reaction mixture can be easily recovered and almost shows the same activity as fresh ethylene glycol in catalyst-free acetalization. Furthermore, the established catalyst-free protocol is viable for various biobased furanic compounds and alcohols, enabling broad access to various acetals. Finally, catalyst-free acetalization of furfural and ethylene glycol can be magnified to 10 times, showing the promising potential of large-scale production.
研究领域:
生物化学
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可再生资源
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 21
·7246
·
IF 4.927
Lifang Chen,Xiangzhu Ye,Ting Zhang,Hao Qin,Hongye Cheng,Zhiwen Qi
Zirconium-based metal-organic frameworks (MOFs) have attracted extensive attention owing to their robust stability and facile functionalization. However, they are generally prepared in common volatile solvents within a long reaction time. Here, we introduced environmentally friendly, cheap, and acid-based tunable deep eutectic solvents (DESs) formed from 2-methyl imidazole (MIm) and p-toluenesulfonic acid (PTSA) which significantly accelerated the assembly of zirconium-based MOF (UiO-66) without any aggressive additives. PTSA in acidic DES and ZrOCl2preliminarily formed Zr(IV) oxo organic acid framework, whereas basic DES completely dissolved the ligand of UiO-66. The strong hydrogen bond effect of PTSA and MIm efficiently accelerated the linker exchange between zirconium oxo organic coordination in acidic DES and benzenedicarboxylate linker in weak basic DES within a reaction time of 2 h at 50 °C. Thus, UiO-66 was quickly assembled with small particle sizes and used as an excellent catalyst for the acetalization of benzaldehyde and methanol. Therefore, the developed synthesis approach provides a new green strategy to quickly prepare and design various structures of metal-based compounds under mild reaction conditions.Keywords:deep eutectic solvent;metal organic framework;UiO-66;acid-base;acetalization
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2022
·
IF 9.965
Yaran Cheng,Jing Chen,Tong Wang,Qin Wu,Daxin Shi,Yaoyuan Zhang,Kangcheng Chen,Hansheng Li
Novel reusable acid-resistant magnetic polymer nanospheres-immobilized MIL-100 (CoFe 2 O 4 @Polymer@MIL-100) catalyst was prepared by a layer-by-layer method to achieve a controllable structure. The obtained core-shell catalyst consisted of modified magnetic nanoparticles as the core, a carboxylic-functionalized polymer as the protective layer, and an MIL-100 shell as the active catalytic layer by chemical bonds on the polymer. The catalysts showed good stability, good magnetic saturation, and acid corrosion resistance. The thickness of the MIL-100 shell could be adjusted by controlling the metal salt concentration and the number of layer-by-layer cycles. Nano-sized MIL-100 showed better mass transfer efficiency and catalytic activity. A conversion of 97.7% after 10 min was observed during acetalization when using CoFe 2 O 4 @Polymer@MIL-100 as the catalyst. CoFe 2 O 4 @Polymer@MIL-100 could be reused at least five times. The use of a polymer layer on CoFe 2 O 4 @Polymer@MIL-100 prevented acidic ligands from corroding the magnetic core. Chemical bonds between MIL-100 and functional magnetic polymer cores improved the catalyst’s stability. CoFe 2 O 4 @Polymer@MIL-100 exhibited high activity, excellent stability, and easy magnetic separation.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2018
·Vol. 8
·期 13
·7179-7185
·
IF 2.936
Ruiyun Li,Heyuan Song,Guoqin Wang,Jing Chen
Ketalization of cyclohexanone with glycol has been carried out using molecular sieve SBA-15 immobilized Brønsted acidic ionic liquid catalyst. The properties of the heterogeneous catalysts were characterized by elemental analysis, Fourier transform infrared (FT-IR) spectra, scanning electron microscopy (SEM), thermogravimetry/differential scanning calorimetry (TG/DSC), and N2 adsorption–desorption (BET). The results suggested that Brønsted acidic ionic liquid [BSmim][HSO4] had been successfully immobilized on the surface of SBA-15 and the catalytic performance evaluation demonstrated that the catalyst BAIL@SBA-15 exhibited excellent catalytic activities in the ketalization of cyclohexanone with glycol. In addition, the effects of reaction temperature, catalyst loading, reaction time, and reactant molar ratio have also been investigated in detail, and a general reaction mechanism for the ketalization of cyclohexanone with glycol was given. The SBA-15 immobilized ionic liquid can be recovered easily and after reusing for 5 times in the ketalization reaction, the catalyst could still give satisfactory catalytic activity.
研究领域:
化学工程
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 47
·41404-41409
·
IF 3.289
Wei-Hong Zhang,Shan-Shan Liu,Ping Liu,Jie Xu,Bing Xue,Xian-Yong Wei,Yong-Xin Li
Chitosan immobilized with an acidic ionic liquid (CS–VImPS–PW) was fabricated via a radical addition reaction of N-vinylimidazoliumpropane sulfonate and chitosan, followed by acidification with a heteropolyacid. It was characterized by a Fourier transform infrared spectrometer, solid-state 13C nuclear magnetic resonance spectrometer, thermogravimetric analyzer, elemental analyzer, and Hammett indicator. Some acetalization reactions were investigated to evaluate the catalytic activity of CS–VImPS–PW. The results show that CS–VImPS–PW is highly active for the acetalization reactions in high acetal yields ranging from 83.2 to 96.2% and can be reused 8 times without noticeable loss of activity.
研究领域:
化学工程
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材料科学
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有机化学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
·
2020
·Vol. 5
·期 3
·539-546
·
IF 3.441
Guangcai Zhang,Lu Zhang,Xuesong Wang,Aicheng Chen,Qinhui Zhang
This work presented microfluidic processing of zeolite films in a capillary microreactor and its potential application for biomass conversion. Uniform and continuous HZSM-5 zeolite films were fabricated under a continuous flow hydrothermal system in which the film thickness could be precisely tuned by flow rate and synthesis time. The catalytic performance of this acidic HZSM-5 film capillary microreactor was evaluated by the continuous flow acetalisation reaction of glycerol with acetone, affording ∼62.61% solketal yield under mild and solvent free conditions. No deactivation was observed even after 100 h, indicating the excellent stability of this HZSM-5 film capillary microreactor. This microfluidic processing strategy provided an extended applicability in the fabrication of zeolite film-based capillary microchannels with a high length-to-diameter ratio or other chip-based microchannel devices.
研究领域:
化学工程
·
生物质转化
·
微流控技术
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Zhichao Miao,Zhenbin Li,Manfen Liang,Jian Meng,Yuzhen Zhao,Leilei Xu,Jinglin Mu,Jin Zhou,Shuping Zhuo,Weijiang Si
In the present work, a series of ordered mesoporous titanium phosphate (M-TiPO) materials with controllable composition are prepared by a simple one-pot method. The introduced Ti and P species are homogeneously dispersed in the skeleton of M-TiPO. Moreover, the influence of P content in mesoporous structure and existing states of Ti species is detailedly discussed. The result shows that the mesoporous structure is successfully improved by the introduction of P species. The M-TiPO-0.5 material (P/Ti = 0.5) exhibits outstanding textural properties (specific surface area (215 m 2 ·g −1 ), pore size (6.6 nm) and volume (0.34 cm 3 ·g −1 )). Also, with the increasing of P species, the crystalline structure of mesoporous skeleton gradually changes from anatase TiO 2 to amorphous phase, and the bonds in the materials transfer from Ti–O–Ti to Ti–O–P. The electron density of Ti decreases, and the acidic property is gradually enhanced. The gotten M-TiPO samples are utilized as catalyst for acetalization of glycerol with acetone. The M-TiPO-0.75 with excellent textural and acidic properties exhibits the best catalytic effect (the glycerol conversion is 91.3% and the acetal selectivity is 94.7%). More importantly, the M-TiPO-0.75 solid acid catalyst shows attractive reusability, and there is no decline in catalytic activity even after ten cycles. Consequently, M-TiPO material is a promising catalyst for the acetalization of glycerol.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
CATALYSIS LETTERS
·
2019
·Vol. 150
·期 4
·1204-1217
·
IF 2.372
Feng Caiting,Li Qinlong,Wu Panfeng,Liu Bin,Hu Huaiming,Xue Ganglin
Abstract In this study, magnetically-recoverable core–shell catalysts with different amount of H 3 PW 12 O 40 loading [Fe 3 O 4 @C@mTa 2 O 5 -NH 2 -PW 12 (w%)] were prepared by the application of phosphotungstic acid supported on amino group functionalized magnetic core–shell mesoporous tantalum pentoxide microspheres. The prepared samples were characterized by FT-IR, N 2 -adsorption–desorption isotherms, TEM, SEM, Pyridine-IR analysis, XRD and magnetism. Fe 3 O 4 @C@mTa 2 O 5 -NH 2 -PW 12 samples present both Brönsted and Lewis acidity, large BET surface area and high magnetization. The catalytic activity was evaluated by the acetalization of different aldehydes with diols, and the results show that Fe 3 O 4 @C@mTa 2 O 5 -NH 2 -PW 12 (14.47%) catalyst exhibits the highest catalytic activity for acetalization of aldehydes with glycols with 94.5% conversion of benzaldehyde and 99% selectivity to benzaldehyde glycol acetal at 80 °C. The catalytic activity of the catalyst for acetalization is related to its total acidity and Brönsted–Lewis acid synergy. The catalyst Fe 3 O 4 @C@mTa 2 O 5 -NH 2 -PW 12 can be easily recovered and reused for at least 5 times without obvious decrease of catalytic activity. Graphic Abstract
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2015
·Vol. 18
·期 6
·1798-1806
·
IF 8.02
Yong-Qi Li,Peng Wang,Huan Liu,Yong Lu,Xiao-Li Zhao,Ye Liu
A novel ionic bi-functional ligand of L2 containing a phosphine and a Lewis acidic phosphonium with I− as the counter-anion was prepared and fully characterized. The molecular structure indicated that the bi-functionalities in L2 were well retained without the incompatibility problem for quenching of the acidity of the phosphonium cation by the Lewis basic phosphine fragment or the anionic I− when the incorporated phosphine fragment and the Lewis acidic phosphonium were strictly located in the confined cis-positions. The co-catalysis over L2–Rh(acac)(CO)2 in the ways of synergetic catalysis and sequential catalysis was successfully fulfilled for one-pot hydroformylation–acetalization, which proved not to be the result of the simple mixture of the mono-phosphine (L4) and the phosphonium salt (L4′). In L2, the phosphonium not only acted as a Lewis acid organocatalyst to drive the sequential acetalization of aldehydes, but also contributed to the synergetic catalysis for the preceding hydroformylation through stabilizing the Rh-acyl intermediate with the phosphine cooperatively. The L2-Rh(acac)(CO)2 system is also generally applied to hydroformylation–acetalization of a wide range of olefins in different alcohols. Advantageously, as an ionic phosphonium-based ligand, L2 could be recycled for 7 runs with Rh(acac)(CO)2 together in RTIL of [Bmim]BF4 without obvious activity loss or metal leaching.
研究领域:
催化化学
·
有机合成
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Huan Liu,Lei Liu,Wen-Di Guo,Yong Lu,Xiao-Li Zhao,Ye Liu
The complexation of IrCl 3 ⋅3H 2 O with the electron-deficient phosphines ( L1 - L6 ) respectively afforded a bi-functional catalyst possessing the dual functions of transition metal complex (Ir III -P) and Ir III -Lewis acid for tandem hydroformylation-acetalization of olefins. The best result was obtained over L5 -based IrCl 3 ⋅3H 2 O catalytic system which corresponded to 97% conversion of 1-hexene along with 92% selectivity to the target acetals free of any additive. The crystal structure of the novel Ir III -complex of Ir III -L4 indicated that the electron-deficient nature of the involved phosphine warranted Ir-center in +3 valence state without reduction, which served as the Lewis acid catalyst for the subsequent acetalization of the aldehydes as well. Moreover, as an ionic phosphine, L6 -based IrCl 3 ⋅3H 2 O system immobilized in RTIL of [Bmim]PF 6 could be recycled for 6 runs without the obvious activity loss or metal leaching.
研究领域:
化学
·
催化化学
·
有机合成
✓ 已验证
产品关联
DOI
高影响因子
Green Energy & Environment
·
2017
·
IF 0
Peng Wang,Xia Chen,Dong-Liang Wang,Yong-Qi Li,Ye Liu
The phosphine-functionalized phosphonium-based ionic liquids ( dppm-Q , dppe-Q , dppp-Q and dppb-Q ) as the bi-functional ligands enable the efficient one-pot tandem hydroformylation–acetalization. It was found that, in dppm-Q , dppe-Q , dppp-Q and dppb-Q , the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/ dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.
研究领域:
化学
·
催化科学
✓ 已验证
DOI
危险品化学品经营许可证（带存储）