Zhenshan Hou

Find an error

Name: 侯震山; Hou, ZhenShan
Organization: East China University of Science and Technology , China
Department: Research Institute of Industrial Catalysis
Title: Professor(PhD)

TOPICS

Co-reporter:Yunxiang Qiao, Wenbao Ma, Nils Theyssen, Chen Chen, and Zhenshan Hou
Chemical Reviews May 24, 2017 Volume 117(Issue 10) pp:6881-6881
Publication Date(Web):March 30, 2017
DOI:10.1021/acs.chemrev.6b00652
Temperature-responsive ionic liquids (ILs), their fundanmental behaviors, and catalytic applications were introduced, especially the concepts of upper critical solution temperature (UCST) and lower critical solution temperature (LCST). It is described that, during a catalytic reaction, they form a homogeneous mixture with the reactants and products at reaction temperature but separate from them afterward at ambient conditions. It is shown that this behavior offers an effective alternative approach to overcome gas/liquid–solid interface mass transfer limitations in many catalytic transformations. It should be noted that IL-based thermomorphic systems are rarely elaborated until now, especially in the field of catalytic applications. The aim of this article is to provide a comprehensive review about thermomorphic mixtures of an IL with H2O and/or organic compounds. Special focus is laid on their temperature dependence concerning UCST and LCST behavior, including systems with conventional ILs, metal-containing ILs, polymerized ILs, as well as the thermomorphic behavior induced via host–guest complexation. A wide range of applications using thermoregulated IL systems in chemical catalytic reactions as well as enzymatic catalysis were also demonstrated in detail. The conclusion is drawn that, due to their highly attractive behavior, thermoregulated ILs have already and will find more applications, not only in catalysis but also in other areas.
Co-reporter:Kun Li;Xiaohui Wu;Qingwen Gu;Xiuge Zhao;Mingming Yuan;Wenbao Ma;Wenxiu Ni
RSC Advances (2011-Present) 2017 vol. 7(Issue 24) pp:14721-14732
Publication Date(Web):2017/03/03
DOI:10.1039/C7RA00416H
The inclusion complexes between β-cyclodextrin (β-CD) and the organic bases 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU)-based phenolates have been prepared by a simple method and also characterized by FT-IR, 1H NMR, 19F NMR, TGA etc. Among these inclusion complexes, DBU-based 2,3,4,5,6-pentafluorophenolate as a guest compound bound by β-CD ([DBUH][PFPhO]/β-CD) has been employed as an easily-separable organocatalyst for the cycloaddition of CO2 into cyclic carbonate and exhibited the best catalytic performance. High conversion of epoxides and excellent selectivity to carbonates could be achieved at 130 °C and under the 3.0 MPa CO2 without additional organic solvents or additives. Additionally, the organocatalyst [DBUH][PFPhO]/β-CD exhibited the better recycability in consecutive catalytic recycles, as compared with that of corresponding DBU-based phenolates. The β-CD played a crucial role in immobilizing catalytically active species and thus improving the recyclability of the present organocatalysts. The detailed characterization indicated that phenolate anions had been bound inside the cavity of β-CD, while the [DBUH]+ cation was located outside of β-CD. More interestingly, it was observed that phenolate anions could dissociate from the β-CD cavity under the reaction temperature, but the inclusion compound could form on cooling the reaction mixture after reaction, which was extremely attractive for separation and recycling of the supramolecular organocatalysts. Finally, on the basis of the characterization above, a reaction mechanism for the present organocatalysts has been proposed.
Co-reporter:Chen Chen, Haiyang Yuan, Haifeng Wang, Yefeng Yao, Wenbao Ma, Jizhong Chen, and Zhenshan Hou
ACS Catalysis 2016 Volume 6(Issue 5) pp:3354
Publication Date(Web):April 12, 2016
DOI:10.1021/acscatal.6b00786
This work reports new kinds of monomeric peroxoniobate anion functionalized ionic liquids (ILs) designated as [A+][Nb═O(O-O)(OH)2] (A+ = tetrapropylammonium, tetrabutylammonium, or tetrahexylammonium cation), which have been prepared and characterized by elemental analysis, HRMS, NMR, IR, TGA, etc. With hydrogen peroxide as an oxidant, these ILs exhibited excellent catalytic activity and recyclability in the epoxidation of various allylic alcohols under solvent-free and ice bath conditions. Interestingly, subsequent activity tests and catalyst characterization together with first-principles calculations indicated that the parent [Nb═O(O-O)(OH)2]− anion has been oxidized into the anion [Nb(O-O)2(OOH)2]− in the presence of H2O2, which constitutes the real catalytically active species during the reaction; this anion has higher activity in comparison to the analogous peroxotungstate anion. Moreover, the epoxidation process of the substrate (allylic alcohol) catalyzed by [Nb(O-O)2(OOH)2]− was explored at the atomic level by virtue of DFT (density functional theory) calculations, identifying that it is more favorable to occur through a hydrogen bond mechanism, in which the peroxo group of [Nb(O-O)2(OOH)2]− serves as the adsorption site to anchor the substrate OH group by forming a hydrogen bond, while OOH as the active oxygen species attacks the C═C bond in substrates to produce the corresponding epoxide. This is the first example of the highly efficient epoxidation of allylic alcohols using a peroxoniobate anion as a catalyst.Keywords: allylic alcohols; DFT; epoxidation; ionic liquid; peroxoniobate anion
Co-reporter:Mengpan Wang, Hanmin Yang, Yinzheng Xie, Xiaohui Wu, Chen Chen, Wenbo Ma, Qifeng Dong and Zhenshan Hou  
RSC Advances 2016 vol. 6(Issue 35) pp:29769-29778
Publication Date(Web):16 Mar 2016
DOI:10.1039/C6RA02682F
The one-pot hydrogenolysis of biomass-derived glycerol to 1-propanol has been investigated over sequential two-layer catalysts in a continuous-flow fixed-bed reactor. The zirconium phosphate layer was packed in the upper layer for dehydration of glycerol into acrolein and the supported Ru catalysts were in the second layer for the sequential hydrogenation of acrolein to 1-propanol. It was observed that the second layer catalyst with the strong acid sites would cause the formation of glycerol degradation products such as methanol, ethanol, methane and carbon dioxide etc., while 2%Ru/SiO2 with weak acid sites afforded the highest selectivity for 1-propanol. The sequential packing of zirconium phosphate and the 2%Ru/SiO2 catalytic system can give full glycerol conversions at 77% selectivity of 1-propanol, as well as exhibiting long-term stability (80 h). Carbonaceous deposits were a main reason for deactivation and the deactivated catalysts can be regenerated conveniently by calcinations in air. The present approach afforded an effective one-pot hydrogenolysis of glycerol to biopropanol, which could bring about the benign development of the biodiesel industry.
Co-reporter:Li Guo, Xiuge Zhao, Ran Zhang, Chen Chen, Jizhong Chen, Angjun Chen, Xuerui Liu, Zhenshan Hou
The Journal of Supercritical Fluids 2016 Volume 107() pp:715-722
Publication Date(Web):January 2016
DOI:10.1016/j.supflu.2015.07.036
•The compressed CO2 can induce to form a microemulsion.•The mesoporous spherical silica was synthesized by CO2-induced microemulsion.•The morphology of mesoporous silica can be tuned by changing CO2 pressure.•The Pd NPs can be encapsulated inside the spherical silica.•The core–shell structure Pd catalyst was effective for Suzuki coupling reaction.The CO2-in-water (C/W) microemulsion was formed when the pressure of CO2 was above 4.0 MPa and has been investigated in-situ via high-pressure UV/vis spectra. The spherical mesoporous silica was successfully synthesized in CO2-induced microemulsion. Uniform spherical silica with a diameter of 102 ± 15 nm can be obtained by using C/W microemulsion as a template. It was observed that the BET area and pore volume of the spherical silica were enlarged with increasing the pressure of CO2. Moreover, Pd nanoparticles (Pd NPs) were encapsulated inside the spherical mesoporous silica through one-pot approach. Owing to the particular core–shell structure, this catalyst showed excellent recyclability in the Suzuki coupling reaction when compared with conventional Pd/SiO2 and Pd/C catalysts. The new strategy can be extended as a general approach to prepare other metal nanoparticles encapsulated in spherical mesoporous silica.
Co-reporter:Mei Qu, Shuai Chen, Wenbao Ma, Jiangang Chen, Kang Kong, Fengwei Zhang, Huan LiZhenshan Hou, Xian-Ming Zhang
Langmuir 2016 Volume 32(Issue 51) pp:13746-13751
Publication Date(Web):November 29, 2016
DOI:10.1021/acs.langmuir.6b03742
The phase transfer of nanoparticles (NPs) from water to organic solvents by an amphiphilic room-temperature ionic liquid (IL) was reported. The geminal IL modified with Pluronic P123 stabilizes a variety of NPs of different size and nature, such as Pd, Au, Ag, and SiO2 NPs. Their phase transfer into a hydrophobic environment was realized by raising the temperature and adding salts (such as NaCl and KBr), both of which have a common effect of breaking the hydrogen bonds of the IL with H2O. A more straightforward method of using an organic solvent working as a hydrogen bond donor (such as butyl alcohol) was then proposed. In this case, NaCl was no longer required. To further apply this strategy to the organic solvents that are generally incapable of forming hydrogen bonds (e.g., toluene), a small quantity of benzoic acid was added to the organic phase. By forming hydrogen bonds from benzoic acid to the IL, an even more facile approach was provided. FT-IR confirmed the hydrogen bonding between them. The phase-transfer protocol does not rely on coordination bonding of ligands with a specific metal and is capable of the phase transfer of objects with large sizes and different natures. Thus, it has the potential for wide application.
Co-reporter:Yinzheng Xie;Mengpan Wang;Xiaohui Wu;Chen Chen;Wenbo Ma;Qifeng Dong;Mingming Yuan ; Zhenshan Hou
ChemPlusChem 2016 Volume 81( Issue 6) pp:541-549
Publication Date(Web):
DOI:10.1002/cplu.201600062

Abstract

A pH-responsive polymer has been synthesized successfully by means of copolymerization of dimethyl aminopropyl acrylamide (DMAPA) and N-p-styrenesulfonyl-1,2-diphenylethylenediamine (V-TsDPEN). The pH-responsive polymer coordination ruthenium complex was thus prepared and employed as an efficient catalyst for the asymmetric transfer hydrogenation (ATH) of various ketones. The polymer catalyst exhibited an attractive pH-induced phase-separable behavior in water: it could be dissolved in water when the pH of the solution was lower than 6.5 at the beginning of the reaction, but was precipitated completely from water when the pH of the solution was above 8.5 after reaction. Additionally, the catalysts were highly efficient for the ATH of a wide range of substrates that bore different functional groups and could be recycled easily from the aqueous solution by means of self-separation. They could be recycled eight times without significant changes in catalytic activity and enantioselectivity.

Co-reporter:Angjun Chen, Chen Chen, Yuhe Xiu, Xuerui Liu, Jizhong Chen, Li Guo, Ran Zhang and Zhenshan Hou  
Green Chemistry 2015 vol. 17(Issue 3) pp:1842-1852
Publication Date(Web):16 Jan 2015
DOI:10.1039/C4GC02244K
A series of peroxoniobate salts of amidine and guanidine were prepared successfully and utilized as halogen-free catalysts for the synthesis of cyclic carbonates from epoxides and CO2 under solvent-free and halide-free conditions. The reaction could be performed with high activity and selectivity with the assistance of the environmentally benign catalysts. CO2 could be chemically activated through an organic base dissociated from the parent catalyst during the reaction, while niobate anions played a crucial role in immobilizing catalytically active organic cations and thus improving the recyclability of the catalyst. The structural characterization of the catalysts indicated that peroxoniobate anions had undergone structural changes and were transformed into more stable niobate anions in the consecutive recycles. It was shown that the catalyst could be reused with high conversion and selectivity by a really straightforward process. Furthermore, this protocol was found to be applicable to a variety of epoxides producing the corresponding cyclic carbonates in high conversion and selectivity. The process herein represents a simple, ecologically friendly and efficient route for CO2 chemical fixation into high value chemicals.
Co-reporter:Ran Zhang, Li Guo, Chen Chen, Jizhong Chen, Angjun Chen, Xiuge Zhao, Xuerui Liu, Yuhe Xiu and Zhenshan Hou  
Catalysis Science & Technology 2015 vol. 5(Issue 5) pp:2959-2972
Publication Date(Web):26 Mar 2015
DOI:10.1039/C5CY00166H
A novel highly active Mn-doping ceria heterogeneous catalyst (MnOx–CeO2) was prepared and dedicated to the catalytic synthesis of aliphatic carbamates from CO2, aliphatic amines and methanol in one step. The as-obtained catalyst can attain a high yield of carbamate up to 82%, and can also be recycled at least four times through a simple procedure. It was observed that the Mn doping to ceria can alleviate the catalyst deactivation in consecutive catalytic recycles. In this regard, the role of Mn doping in the ceria in the synthesis of the aliphatic carbamates was investigated by means of X-ray diffraction (XRD), Raman spectra, specific surface areas (BET), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), CO2-temperature programmed desorption (CO2-TPD) and in situ diffuse reflectance infrared Fourier transform (DRIFT). The characterization demonstrated that the presence of MnOx in the ceria can not only inhibit the formation of stable carbonate species on the surface of the catalyst but also promote the decomposition/consuming of the carbonaceous species during the synthesis of aliphatic carbamates so as to allow improvement of the recyclability of the catalyst.
Co-reporter:Li Guo, Ran Zhang, Chen Chen, Jizhong Chen, Xiuge Zhao, Angjun Chen, Xuerui Liu, Yuhe Xiu and Zhenshan Hou  
Physical Chemistry Chemical Physics 2015 vol. 17(Issue 9) pp:6406-6414
Publication Date(Web):30 Jan 2015
DOI:10.1039/C4CP05733C
Metal nanoparticles embedded in hollow materials are important due to their wide applications in catalysis. In this work, we disclosed a nontraditional synthetic pathway to prepare silica hollow nanospheres by hydrothermal treatment in the presence of compressed CO2. Especially, the silica hollow nanospheres with an outer diameter of about 16 nm and an inner pore size of 7 nm were obtained using 1.0 MPa CO2. The formation mechanism of silica hollow nanospheres induced by CO2 was investigated by high-pressured UV/Vis spectroscopy. Moreover, gold nanoparticles (2.5 nm) embedded in the silica hollow nanospheres were prepared by a one-pot synthesis using HAuCl4 as a precursor. The current synthetic route of nano-catalysts was simple and facile, in which no etching agent was needed in the process of the hollow material preparation. Besides, this nano-catalyst showed an excellent catalytic performance in epoxidation of styrene with high conversion (82.2%) and selectivity (90.2%) toward styrene oxide, as well as in the selective oxidation of ethylbenzene with good conversion (26.6%) and selectivity (87.8%) toward acetophenone. Moreover, the Au nanoparticles (AuNPs) embedded in silica hollow nanospheres exhibited an excellent recyclability in both the oxidation reactions.
Co-reporter:Yuhe Xiu, Angjun Chen, Xuerui Liu, Chen Chen, Jizhong Chen, Li Guo, Ran Zhang and Zhenshan Hou  
RSC Advances 2015 vol. 5(Issue 36) pp:28233-28241
Publication Date(Web):16 Mar 2015
DOI:10.1039/C5RA01371B
Novel polymer-supported Brønsted acid polymer catalysts have been successfully synthesized by radical polymerization, followed by a simple solvothermal route and ion exchange step. The as-synthesized co-polymers were characterized by Elemental Analysis, FT-IR spectroscopy, thermogravimetric analysis and scanning electron microscopy and then were employed as a heterogeneous catalyst for dehydration of sorbitol. Especially, the polymer catalysts have a unique advantage of adjustable Brønsted acidity, and the polymer with 1.82 mmol g−1 of Brønsted acidity was a very efficient catalyst for highly selective dehydration of sorbitol into 1,4-anhydro-D-sorbitol. The dehydration reaction can be completed within 4 h and the selectivity of 1,4-anhydro-D-sorbitol achieved 90%. Moreover, the present catalysts resisted acid-leaching and can be recycled in five consecutive cycles without obvious loss of activity.
Co-reporter:Jizhong Chen, Chen Chen, Ran Zhang, Li Guo, Li Hua, Angjun Chen, Yuhe Xiu, Xuerui Liu and Zhenshan Hou  
RSC Advances 2015 vol. 5(Issue 33) pp:25904-25910
Publication Date(Web):02 Mar 2015
DOI:10.1039/C5RA00136F
New peroxotungsten anion-based ionic liquid-type catalysts were synthesized and characterized using NMR, IR, TG, etc. Then, these salts were used as catalysts for the deep desulfurization of model oil containing dibenzothiophene (DBT) with H2O2 as an oxidant. The effects of the temperature, H2O2/DBT molar ratio, and catalyst loading on the desulfurization activity have been investigated in detail. The present catalysts showed excellent desulfurization activity under solvent-free and mild reaction conditions. Moreover, this catalyst could be recycled at least ten times without any decrease in activity. It was found that the H-bonding interaction between the H2-proton in imidazolium and the basic S atom in the DBT molecule played a very important role in enhancing the catalytic activity. On the basis of the activity measurements and characterization of the catalyst, the reaction mechanism for the oxidative desulfurization process has been suggested.
Co-reporter:Jizhong Chen;Dr. Li Hua;Chen Chen;Li Guo;Ran Zhang;Angjun Chen;Yuhe Xiu;Xuerui Liu ; Zhenshan Hou
ChemPlusChem 2015 Volume 80( Issue 6) pp:1029-1037
Publication Date(Web):
DOI:10.1002/cplu.201402456

Abstract

A tungsten peroxo complex stabilized by the bidentate picolinato ligand has been synthesized and then immobilized successfully on imidazole-functionalized silica. The immobilized tungsten-based catalyst was employed as an efficient catalyst for the one-pot synthesis of β-alkoxy alcohols from olefins and methanol with H2O2. Regarding the catalyst evaluation and the results of characterization by the various methods, it was demonstrated that the immobilization of tungsten peroxo complex was highly temperature-dependent. The tungsten peroxo complex can dissociate and diffuse into the liquid phase at reaction temperature, resulting in a homogeneous reaction. Nevertheless, the catalytically active species was anchored on the imidazole-functionalized silica by hydrogen bonding as the temperature was lowered to 0 °C after the reaction, which thus offered a highly effective approach for recycling the catalyst for consecutive cycles. In addition, various olefins can be converted to the corresponding β-alkoxy alcohols with good conversion and selectivity under relative mild conditions by H2O2.

Co-reporter:Wenwen Zhu, Hanmin Yang, Jizhong Chen, Chen Chen, Li Guo, Huimei Gan, Xiuge Zhao and Zhenshan Hou  
Green Chemistry 2014 vol. 16(Issue 3) pp:1534-1542
Publication Date(Web):09 Dec 2013
DOI:10.1039/C3GC41917G
A sulfonic acid-functionalized silica-supported ruthenium catalyst (Ru/SiO2–SO3H) was employed for the hydrogenolysis of cellulose in one pot in neutral water medium. Ru/SiO2–SO3H is a bifunctional catalyst containing both a Brønsted acidic site and a metal site (Ru). Compared with the mechanical mixture of a silica-supported Brønsted acid (SiO2–SO3H) and a silica-supported Ru catalyst (Ru/SiO2), the bifunctional catalyst showed much higher yield of sorbitol, which could reach up to 61.2% when the reaction was performed for 10 h at 150 °C. Through the characterization by XPS and pyridine-adsorbed FT-IR, the existence of the interaction between sulfonic groups and Ru nanoparticles in the Ru/SiO2–SO3H catalyst was observed. The sulfonic acid groups and metal sites in the adjacent position were important for enhancing the yield of sorbitol. In addition, the present catalyst can be reused five times with only a slight decrease in yield of sorbitol in the consecutive recycles.
Co-reporter:Zhenhong He, Zhenshan Hou, Yanping Luo, Yierxiati Dilixiati and Wumanjiang Eli  
Catalysis Science & Technology 2014 vol. 4(Issue 4) pp:1092-1103
Publication Date(Web):13 Jan 2014
DOI:10.1039/C3CY00842H
Pd–TPPTS–OTPPTS (denoted as Pd–P–OP, where TPPTS was the sodium salt of tri(m-sulfophenyl)phosphine and OTPPTS was the oxidized form of TPPTS) complexes supported on acidic resins (denoted as Pd–P–OP/resin) were prepared and employed as versatile heterogeneous catalysts for the hydroesterification of vinyl-aromatics with alcohols. The catalysts were characterized by the methods of FT-IR, XPS, N2 physisorption, XRD, TGA, SEM and 31P NMR. According to the 31P NMR results, there was a weak coordination between OTPPTS and the Pd sites. Consequently, OTPPTS was a weak ligand to the Pd sites and thus dissociated easily, acting as a protective agent of the vacant coordination site of the Pd metal sites, which allowed the substrates more access to the metal sites. In the hydroesterification of styrene, the distribution of the branched and linear esters was remarkably impacted by adding an appropriate amount of OTPPTS and the acidic resin supports. A high yield and excellent selectivity towards the branched ester were obtained when OTPPTS and TPPTS were used in equimolar amounts under optimized reaction conditions. The generality and recyclability of the catalyst for the hydroesterification of vinyl-aromatics were also examined. In addition, the poisoning and hot filtration tests indicated that Pd(0) acted as the active species in a truly heterogeneous way. A Pd–hydride mechanism was proposed for the hydroesterification over the Pd–P–OP/LSI-600 catalyst.
Co-reporter:Ran Zhang, Li Guo, Jizhong Chen, Huimei Gan, Baoning Song, Wenwen Zhu, Li Hua, and Zhenshan Hou
ACS Sustainable Chemistry & Engineering 2014 Volume 2(Issue 5) pp:1147
Publication Date(Web):March 20, 2014
DOI:10.1021/sc400511u
The process of urea transamidation with amine to urea derivative has been developed in the presence of both carbon dioxide and water. Through the present reaction route, not only can the urea derivatives be obtained in high yield, but also inorganic salt ammonium bicarbonate (ABic) can be successfully isolated simultaneously from the reaction mixture. The phase behavior observed in situ by high pressure visual autoclave illustrated that the reaction occurred in biphasic conditions during the reaction. A number of verifying tests were conducted to investigate the role of carbon dioxide and water in the system. It was found that reaction temperature, total pressure, reaction time, and water played a crucial role in producing urea derivatives. The further investigation showed that the transamidation reaction between various amines and urea occurred successfully without the addition of any other catalysts in the presence of CO2 and water. The acidity resulting from reaction of CO2 with water facilitated the transamidation reaction.Keywords: Ammonia scrubbing; Carbon dioxide; Green chemistry; Transamidation of urea; Urea derivatives
Co-reporter:Yinyin Yu, Wenwen Zhu, Li Hua, Hanmin Yang, Yunxiang Qiao, Ran Zhang, Li Guo, Xiuge Zhao, Zhenshan Hou
Journal of Colloid and Interface Science 2014 Volume 415() pp:117-126
Publication Date(Web):1 February 2014
DOI:10.1016/j.jcis.2013.10.023
•The addition of ionic liquid affects the micelle structure of triblock copolymer P123 solutions.•These mixed micelles can stabilize water-soluble Ni nanoparticles (Ni NPs) effectively.•The Ni NPs catalyzed selective hydrogenation in aqueous phases.•The basic IL ([BMMIm]OAc) gave rise to enhanced catalytic activity.•The Ni NPs were stable enough for eight consecutive catalytic recycles.Ionic liquid (1-butyl-2,3-dimethylimidazolium acetate, [BMMIm]OAc)-Pluronic P123 mixed micelle stabilized water-soluble Ni nanoparticles were characterized by UV–vis, XRD, XPS and TEM and then employed for catalytic hydrogenation. It was demonstrated that the mixed-micelle stabilized Ni NPs showed excellent catalytic performance for the selective hydrogenation of CC and nitro compounds in the aqueous phase under very mild reaction conditions, and also the Ni NPs catalysts can be recycled at least for eight times without significant decrease in catalytic activity. The results of characterization revealed that the mixed micelle-stabilized Ni NPs catalysts were highly dispersed in aqueous phases even after five catalytic recycles. In addition, adding ionic liquid ([BMMIm]OAc) can affect the micelle structure of P123 solutions and thus afford an additional steric protection from aggregation of Ni NPs, resulting in enhancing stability and catalytic activity of Ni NPs.
Co-reporter:Li Hua, Jizhong Chen, Chen Chen, Wenwen Zhu, Yinyin Yu, Ran Zhang, Li Guo, Baoning Song, Huimei Gan and Zhenshan Hou  
New Journal of Chemistry 2014 vol. 38(Issue 8) pp:3953-3959
Publication Date(Web):15 May 2014
DOI:10.1039/C4NJ00270A
A novel ionic liquid consisting of a PEG-functionalized ammonium cation and a lacunary-type phosphotungstate anion was synthesized and characterized structurally. The ionic liquid was then immobilized onto environmentally benign polymer-carboxymethyl cellulose by two different routes: the impregnation method and the co-precipitation method. The immobilized ionic liquid can be used as a catalyst for olefin epoxidation with aqueous hydrogen peroxide in ethyl acetate. It was found that both of the immobilized ionic liquid catalysts showed better catalytic activities and stability than the homogeneous analogue in consecutive runs. In particular, the ionic liquid catalyst immobilized by the co-precipitation method afforded a higher catalytic stability than the catalyst immobilized by the impregnation method. It is suggested that the crucial factor influencing the catalytic performance is the difference in the interactions between the heteropoly anions and the polymer supports.
Co-reporter:Letao Zhang;Yanping Luo
Journal of the American Oil Chemists' Society 2014 Volume 91( Issue 1) pp:143-150
Publication Date(Web):2014 January
DOI:10.1007/s11746-013-2358-1
Epoxidized cotton seed oil (ECSO) was conveniently synthesized from cotton seed oil (CSO) in the presence of hydrogen peroxide, formic acid, and phosphoric acid. Then the ECSO was converted into carbonated cotton seed oil (CCSO) by reacting with CO2 using tetrabutylammonium bromide as a catalyst. The reaction conditions including reaction temperature, pressure, reaction time and the amount of catalyst were examined. In addition, the final product (CCSO) from cyclic addition reaction was characterized by FT-IR, 1H NMR and TGA. Compared with CSO and ECSO, CCSO showed excellent thermal and oxidation stability. Additionally, the CCSO’s properties of extreme pressure, anti-wear and friction reduction were tested and analyzed. The results indicated that it could be used as potential lubricating base oil.
Co-reporter:Chen Chen;Xiuge Zhao;Jizhong Chen;Li Hua;Ran Zhang;Li Guo;Baoning Song;Huimei Gan ;Dr. Zhenshan Hou
ChemCatChem 2014 Volume 6( Issue 11) pp:3231-3238
Publication Date(Web):
DOI:10.1002/cctc.201402545

Abstract

Modified niobium peroxides were prepared and used for catalyzing the epoxidation of allylic alcohols with hydrogen peroxide in the absence of any other solvent under ice bath conditions. Niobium peroxides modified with ionic liquid-type 1-dodecyl-3-methylimidazolium hydroxide or conventional tetradecyl trimethyl ammonium hydroxide surfactants demonstrated excellent yields (80–99 %) for the epoxidation of allylic alcohols to their epoxides even if the reaction was performed without any other solvent at 0 °C for 0.5 h. The catalyst characterization demonstrated that the surfactant molecules were anchored on the surface of the niobium catalyst by weak noncovalent interactions. Compared with niobium peroxides, the modified amphiphilic catalysts allowed easier accessibility to hydrophobic substrates and thus demonstrated high reaction rate and excellent recyclability for the epoxidation under mild conditions.

Co-reporter:Ran Zhang;Li Hua;Li Guo;Baoning Song;Jizhong Chen
Chinese Journal of Chemistry 2013 Volume 31( Issue 3) pp:381-387
Publication Date(Web):
DOI:10.1002/cjoc.201201143

Abstract

The calcined Mg-Al layered double hydroxides (LDHs) with a Mg/Al molar ratio of 3:1 were synthesized and characterized thoroughly by X-ray diffraction (XRD), temperature-programmed desorption (TPD) of CO2, and thermogravimetric analysis (TGA). Thus the calcined Mg-Al LDHs were used as catalyst for the catalytic synthesis of disubstituted ureas from amines and CO2. The effects of reaction time, reaction temperature, pressure, solvent and calcined temperature on activity have been investigated. The results indicated that aliphatic amines, cyclohexylamine and benzylamine can be converted to the corresponding ureas selectively over the calcined Mg-Al LDHs catalysts with N-methyl-2-pyrrolidone (NMP) as solvent without using any dehydrating regent. The catalyst can be recycled several times with only slight loss of activity.

Co-reporter:Yunxiang Qiao, Li Hua, Jizhong Chen, Nils Theyssen, Walter Leitner, Zhenshan Hou
Journal of Molecular Catalysis A: Chemical 2013 380() pp: 43-48
Publication Date(Web):
DOI:10.1016/j.molcata.2013.09.020
Co-reporter:Wenwen Zhu;Yinyin Yu;Dr. Hanmin Yang;Li Hua;Yunxiang Qiao;Xiuge Zhao;Dr. Zhenshan Hou
Chemistry - A European Journal 2013 Volume 19( Issue 6) pp:2059-2066
Publication Date(Web):
DOI:10.1002/chem.201202707

Abstract

The use of transition-metal nanoparticles/ionic liquid (IL) as a thermoregulated and recyclable catalytic system for hydrogenation has been investigated under mild conditions. The functionalized ionic liquid was composed of poly(ethylene glycol)-functionalized alkylimidazolium as the cation and tris(meta-sulfonatophenyl)phosphine ([P(C6H4-m-SO3)3]3−) as the anion. Ethyl acetate was chosen as the thermomorphic solvent to avoid the use of toxic organic solvents. Due to a cooperative effect regulated by both the cation and anion of the ionic liquid, the nanocatalysts displayed distinguished temperature-dependent phase behavior and excellent catalytic activity and selectivity, coupled with high stability. In the hydrogenation of α,β-unsaturated aldehydes, the ionic-liquid-stabilized palladium and rhodium nanoparticles exhibited higher selectivity for the hydrogenation of the CC bonds than commercially available catalysts (Pd/C and Rh/C). We believe that the anion of the ionic liquid, [P(C6H4-m-SO3)3]3−, plays a role in changing the surrounding electronic characteristics of the nanoparticles through its coordination capacity, whereas the poly(ethylene glycol)-functionalized alkylimidazolium cation is responsible for the thermomorphic properties of the nanocatalyst in ethyl acetate. The present catalytic systems can be employed for the hydrogenation of a wide range of substrates bearing different functional groups. The catalysts could be easily separated from the products by thermoregulated phase separation and efficiently recycled ten times without significant changes in their catalytic activity.

Co-reporter:Zhenhong He;Yanping Luo;Liang Zhou;Yuanfeng Liu
Catalysis Letters 2013 Volume 143( Issue 3) pp:289-297
Publication Date(Web):2013 March
DOI:10.1007/s10562-013-0961-2
Hydrocarboxylation of styrene catalyzed by water-soluble Pd-TPPTS complexes was investigated. The reaction conditions, including reaction pressure, temperature, time and etc. have a significant influence on the catalytic performance. It was found that the yield of total acids and the selectivity towards 3-phenylpropionic acid were enhanced by adding a suitable amount of alkali metal halide salts. In addition, the reaction mechanism and the role of alkali metal halide salts in the reaction were discussed on the basis of the characterization of 1H NMR and 31P NMR.
Co-reporter:Bo Feng;Chen Chen;Hanmin Yang;Xiuge Zhao;Li Hua;Yinyin Yu;Ting Cao;Yu Shi
Advanced Synthesis & Catalysis 2012 Volume 354( Issue 8) pp:1559-1565
Publication Date(Web):
DOI:10.1002/adsc.201100908

Abstract

An oxidant-free dehydrogenation of alcohols in the aqueous phase was developed for the first time using water-soluble poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium nanoparticles with an ionic liquid as a promoter. The present catalytic system was highly efficient and stable for the catalytic dehydrogenation of various alcohols. It was found that the basic ionic liquid 1-n-butyl-2,3-dimethylimidazolium acetate ([BMMIM] OAc) additive played a crucial role in enhancing the catalytic activity and stability of ruthenium(0) nanoparticles. A reaction kinetics study and 1H NMR analysis demonstrated that the basic ionic liquid and ruthenium nanoparticles exerted a synergetic effect for the dehydrogenation reaction.

Co-reporter:Yunxiang Qiao;Dr. Huan Li;Li Hua;Dr. Lars Orzechowski;Dr. Kai Yan;Dr. Bo Feng;Zhenyan Pan;Dr. Nils Theyssen; Walter Leitner; Zhenshan Hou
ChemPlusChem 2012 Volume 77( Issue 12) pp:1128-1138
Publication Date(Web):
DOI:10.1002/cplu.201200246

Abstract

Magnetically separable catalysts were prepared and employed for the epoxidation of olefins with hydrogen peroxide. In all cases the magnetic core was firstly covered with a silica layer to prevent iron ion-initiated decomposition of hydrogen peroxide. The catalytic active species, an ionic liquid-type peroxotungstate, was then immobilized either by hydrogen bonding (catalyst 1) or by covalent SiO linkage (catalyst 2). In addition to a thorough characterization by FT-IR, XRD, NMR, DRIFT, XPS, and TEM, the catalytic potential was evaluated in the epoxidation of a variety of olefins as well as allylic alcohols. Both catalysts showed essentially a constant activity after at least ten consecutive cycles. On the basis of the research above, a new type of magnetically separable catalyst was constructed by immobilization of lacunary-type phosphotungstate by hydrogen bonding between the sulfonate anion and silanol group on the surface of the core–shell magnetic nanoparticles. After the detailed characterization, the catalyst was used in the epoxidation of a variety of olefins and allylic alcohols and was found to possess high activity, selectivity towards epoxides, and a constant activity after at least ten catalytic recycles without solvent.

Co-reporter:Wenwen Zhu, Hanming Yang, Yinyin Yu, Li Hua, Huan Li, Bo Feng and Zhenshan Hou  
Physical Chemistry Chemical Physics 2011 vol. 13(Issue 30) pp:13492-13500
Publication Date(Web):13 May 2011
DOI:10.1039/C1CP20255C
The highly water-soluble palladium nanoparticles (NPs) were synthesized by using the amphiphilic poly(ethylene glycol)-functionalized dicationic imidazolium-based ionic liquid (C12Im-PEG IL) as a stabilizing agent. The aqueous dispersed palladium NPs in the range of 1.9 ± 0.3 nm were observed by transmission electron microscopy (TEM). The physicochemical properties of C12Im-PEG IL in aqueous phase have been characterized by electrical conductivity, surface tension and dynamic light scattering (DLS) measurements. It was demonstrated that the amphiphilic ionic liquid can form micelles above its critical micelle concentration (CMC) in aqueous solution and the micelles played a crucial role in stabilizing the palladium NPs and thus promoted catalytic hydrogenation. Furthermore, the dicationic ionic liquid can also act as a gemini surfactant and generated emulsion between hydrophobic substrates and the catalytic aqueous phase during the reaction. The aqueous dispersed palladium NPs showed efficient activity for the catalytic hydrogenation of various substrates under very mild conditions and the stabilizing Pd(0) nanoparticles (NPs) can be reused at least eight times with complete conservation of activity.
Co-reporter:Li Hua, Yunxiang Qiao, Yinyin Yu, Wenwen Zhu, Ting Cao, Yu Shi, Huan Li, Bo Feng and Zhenshan Hou  
New Journal of Chemistry 2011 vol. 35(Issue 9) pp:1836-1841
Publication Date(Web):01 Jul 2011
DOI:10.1039/C1NJ20312F
The Ti-substituted polyoxometalates ([C12mim]5PTiW11O40, [CTA]5PTiW11O40 and [TBA]5PTiW11O40) were prepared and characterized by FT-IR, NMR, UV-vis and ICP-AES. Then the polyoxometalates (POM) were used as catalysts for the epoxidation of various olefins. It was found that the organic countercations had a considerable effect on the catalytic performance. In addition, UV-vis and the FT-IR spectroscopy indicated that the peroxo structure regarded as the active site for oxygen transfer was present even after the reaction, which led to the increasing reaction rate in the second run due to the disappearance of the induction period, as compared with that in the first run. A heterogeneous reaction mechanism has been suggested in olefin epoxidation catalyzed by a Ti-substituted polyoxometalate ([C12mim]5PTiW11O40) with aqueous hydrogen peroxide in ethyl acetate. The heterogeneous POM catalyst can be easily separated and recycled eight times without decreasing the catalytic activities.
Co-reporter:Li Hua;YunXiang Qiao;Huan Li;Bo Feng;ZhenYan Pan;YinYin Yu
Science China Chemistry 2011 Volume 54( Issue 5) pp:
Publication Date(Web):2011 May
DOI:10.1007/s11426-011-4251-9
Olefins and allylic alcohols have been epoxidized with commercially available hydrogen peroxide (30% H2O2) using a phase transfer catalyst, composed of cetyltrimethylammonium cations and a lacunary-type phosphotungstate anion [PW11O39]7− or the complete Keggin-type heteropolyanion [PW12O40]3−, under two-phase conditions using ethyl acetate as the solvent. It was found that the lacunary-type catalyst showed higher activity and better recyclability than the complete Keggin-type catalyst under the same reaction conditions. 31P NMR spectroscopy and solubility measurements for the two catalysts revealed that the [PW11O39]7− anion had a much faster degradation rate than the [PW12O40]3− anion in an excess of H2O2, which resulted in the formation of more catalytically active species. As a result, the lacunary-type phosphotungstate anion-based catalyst gave a better catalytic performance than the complete Keggin-type anion in ethyl acetate.
Co-reporter:Yu Hu;YinYin Yu;XiuGe Zhao;HanMing Yang;Bo Feng;Huan Li
Science China Chemistry 2010 Volume 53( Issue 7) pp:1541-1548
Publication Date(Web):2010 July
DOI:10.1007/s11426-010-4003-2
Two kinds of nickel nanoparticles (NPs) well-dispersed in aqueous phase have been conveniently prepared by reducing nickel(II) salt with hydrazine in the presence of amino group (−NH2) functionalized ionic liquids: 1-(3-aminopropyl)-2,3-dimethylimidazolium bromide ([AMMIM][Br]) and 1-(3-aminopropyl)-2,3-dimethylimidazolium acetate ([AMMIM][AcO]). The Ni(0) particles are composed of smaller ones which assemble in a blackberry-like shape. The Ni nanoparticles stabilized with [AMMIM][AcO] are much larger than those stabilized with [AMMIM][Br], and the former unexpectedly give much higher activity in the selective hydrogenation of citral and nitrobenzene (NB) in aqueous phase. The Ni(0) nanocatalysts dispersed in aqueous phase are stable enough to be reused at least five times without significant loss of catalytic activity and selectivity during the catalytic recycles.
Co-reporter:Huan Li;Yunxiang Qiao;Li Hua;Dr. Zhenshan Hou;Bo Feng;Zhenyan Pan;Yu Hu;Xiangrui Wang;Xiuge Zhao ;Yinyin Yu
ChemCatChem 2010 Volume 2( Issue 9) pp:1165-1170
Publication Date(Web):
DOI:10.1002/cctc.201000021

Abstract

A new family of polyoxometalate-based ionic liquids (POM-IL) is synthesized, characterized, and employed as catalysts in the esterification of various alcohols with acetic acid. The ionic liquid catalyst shows high activity and gives excellent yields of esters. An emulsion forms between the IL catalyst and substrates during the reaction and promotes the catalytic process. After reaction, the emulsion can conveniently be broken by the addition of a weakly polar organic solvent to facilitate the separation of the catalyst. On the basis of the above results, a direct transformation of benzaldehyde to methyl ester under relatively mild conditions is also developed in the absence of any cocatalyst. Finally, the scope of the substrates and recyclability of the catalyst are also investigated.

Co-reporter:Yu Hu;Yinyin Yu Dr.;Hanming Yang Dr.;Bo Feng;Huan Li;Yunxiang Qiao;Xiangrui Wang;Li Hua;Zhenyan Pan;Xiuge Zhao
Chemistry – An Asian Journal 2010 Volume 5( Issue 5) pp:1178-1184
Publication Date(Web):
DOI:10.1002/asia.200900628

Abstract

Nickel nanoparticles (NPs) well-dispersed in the aqueous phase were conveniently prepared by reducing nickel(II) salt with hydrazine in the presence of the functionalized ionic liquid 1-(3-aminopropyl)-2,3-dimethylimidazolium bromide. UV/Vis spectroscopy, elemental analysis, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) show the presence of a weak interaction of the functionalized ionic liquid with NiII and Ni0 complexes. The face-centered cubic structure of the Ni0 NPs was confirmed by X-ray diffraction (XRD) characterization. Transmission electron microscopy (TEM) images reveal that smaller Ni0 particles of approximately 6–7 nm average diameter assemble to give larger, blackberry-shaped particles with an average diameter of around 35 nm. The Ni NPs were employed as highly efficient catalysts for the selective hydrogenation of CC double bonds in the aqueous phase under mild reaction conditions (40–90 °C at 1.0–3.0 MPa), and the Ni0 nanocatalysts in the aqueous phase are stable enough to be reused at least seven times without significant loss of catalytic activity during subsequent reuse cycles.

Co-reporter:Yunxiang Qiao, Zhenshan Hou, Huan Li, Yu Hu, Bo Feng, Xiangrui Wang, Li Hua and Qingfa Huang  
Green Chemistry 2009 vol. 11(Issue 12) pp:1955-1960
Publication Date(Web):14 Sep 2009
DOI:10.1039/B916766H
Two protic alkylimidazolium polyoxometalates, together with two corresponding aprotic N-methyl-alkylimidazolium polyoxometalates were synthesized and characterized by the methods of NMR, IR and TGAetc. Then, these salts were employed as catalysts for the epoxidation of cyclooctene in different media. The novel protic N-dodecylimidazolium peroxotungstate [HDIm]2[{WO(O2)2}2(μ–O)] was found to be a room temperature liquid molten salt (ionic liquid) and the most effective catalyst for the epoxidation of cyclooctene among these salts. The ionic liquid catalyst [HDIm]2[{WO(O2)2}2(μ–O)] can also be extended to the epoxidation of some other substrates. On the basis of this experimental observation, an efficient reaction-induced phase-separation catalyst system has been developed in this work. The reaction system can switch from tri-phase to emulsion and then to biphase and finally to all the catalyst self-precipitating at the end of the reaction, which made the recovery and reuse of the present catalyst very convenient.
Co-reporter:Bo Feng, Zhenshan Hou, Xiangrui Wang, Yu Hu, Huan Li and Yunxiang Qiao  
Green Chemistry 2009 vol. 11(Issue 9) pp:1446-1452
Publication Date(Web):09 Jul 2009
DOI:10.1039/B900807A
Selective oxidation of styrene to benzaldehyde has been carried out for the first time in aqueous phase by using a green and water-soluble palladium(II) complex as a catalyst under neutral, chloride and base-free conditions. The influences of reaction temperature, reaction time, palladium concentration and O2 pressure on the conversion of styrene and the selectivity to benzaldehyde have been discussed. The reaction products, benzaldehyde, benzoic acid, acetophenone are readily isolated by ether extraction at room temperature. The water-soluble catalyst immobilized in aqueous phase can be reused for eight catalytic runs with an almost constant catalytic activity for the styrene oxidation. The influence of substituting groups in the aromatic ring of styrene on the reactivity was also discussed. Spectroscopic studies revealed that the hydrophilic dipyridyl-based ligand (L) with Pd(OAc)2 formed a water-soluble Pd(II) complex. The UV/Vis spectra analysis further showed that the Pd(II)-L complex could serve as the catalytically active species in the present catalytic system.
Co-reporter:Xiangrui Wang;Hanmin Yang;Bo Feng;Yu Hu
Catalysis Letters 2009 Volume 132( Issue 1-2) pp:34-40
Publication Date(Web):2009 September
DOI:10.1007/s10562-009-0038-4
The functionalized Poly(ethylene glycol) (PEG)-stabilized Pd(0) nanoparticles have been utilized to selectively oxidize alcohols to the corresponding aldehydes or ketones in supercritical carbon dioxide (scCO2)/PEG (PEG-2000) biphasic system. It was demonstrated that the Pd(0) nanocatalyst was more active and selective, in comparison with the commercially available Pd/C catalyst, PVP-stabilized Pd nanocatalyst and Pd(0) catalyst without stabilization. The effects of CO2 pressure, reaction time and temperature on activity and selectivity were also further investigated in detail. The scCO2/PEG biphasic system was proved to be not only cheap and clean, but also recyclable for the aerobic oxidation of alcohols.
Co-reporter:Yu Hu;Yinyin Yu, ;Huan Li;Xiuge Zhao ;Bo Feng
Advanced Synthesis & Catalysis 2008 Volume 350( Issue 13) pp:2077-2085
Publication Date(Web):
DOI:10.1002/adsc.200800290

Abstract

Palladium nanoparticles in the size range of 5–6 nm were prepared conveniently by reducing palladium(II) with atmospheric pressure hydrogen and stabilized by 2,2′-dipyridylamine-functionalized imidazolium cations according to our approach. The efficient catalytic conversion of cyclohexene into cyclohexane by the functionalized ionic liquid-stabilized palladium nanoparticles has been performed under very mild hydrogen pressure (0.1 MPa) and at 35 °C. It was found that the concentration of palladium and the reaction temperature considerably affected the size and degree of aggregation of Pd nanoparticles in ionic liquid, which further changed the performance of the catalyst activity. The synthesized nanocatalysts can be recycled at least five times without any loss of the activity. Finally, the scope of substrates was also investigated. The excellent catalytic activity of the present system can be attributed to good stabilization and high dispersion of palladium nanoparticles.

Co-reporter:Baoning Song, Li Guo, Ran Zhang, Xiuge Zhao, Huimei Gan, Chen Chen, Jizhong Chen, Wenwen Zhu, Zhenshan Hou
Journal of CO2 Utilization (June 2014) Volume 6() pp:62-68
Publication Date(Web):1 June 2014
DOI:10.1016/j.jcou.2014.03.005
•Polydiallyldimethylammonium bromide was supported on silica gel as a catalyst.•The addition of Lewis acid would improve the catalytic activity significantly.•The catalyst was highly efficient for the catalytic synthesis of cyclic carbonate.•The catalyst was highly leaching-resistant.•The catalyst could be reused at least 10 times without any loss of activity.A polymeric quaternary ammonium salt, polydiallyldimethylammonium bromide (PDDA-Br), was supported on silica gel and employed as a recyclable heterogeneous catalyst for the catalytic synthesis of cyclic carbonate. The supported catalysts had been characterized by FT-IR, XRD, TGA and SEM methods. It was observed that PDDA-Br, silica and Lewis acid exhibited strong synergistic effect for the cycloaddition reaction. The addition of Lewis acid like ZnBr2, ZnCl2 and FeCl3 AlCl3 would improve the catalytic activity significantly. Especially, the combination of PDDA-Br with ZnBr2 afforded the most efficient catalyst for the cycloaddition reaction. Silica gel has high BET surface area and allowed good dispersion of PDDA-Br and ZnBr2. Moreover, the as-prepared catalyst was highly stable and leaching-resistance. It could be reused at least 10 times without any loss of activity.Download high-res image (345KB)Download full-size image
Co-reporter:Xiaohui Wu, Mengpan Wang, Yinzheng Xie, Chen Chen, Kun Li, Mingming Yuan, Xiuge Zhao, Zhenshan Hou
Applied Catalysis A: General (5 June 2016) Volume 519() pp:146-154
Publication Date(Web):5 June 2016
DOI:10.1016/j.apcata.2016.04.002
Co-reporter:Xuerui Liu, Chen Chen, Yuhe Xiu, Angjun Chen, Li Guo, Ran Zhang, Jizhong Chen, Zhenshan Hou
Catalysis Communications (5 July 2015) Volume 67() pp:90-94
Publication Date(Web):5 July 2015
DOI:10.1016/j.catcom.2015.04.013
•Ru(II) complexes of sulfonic-acid functionalised TsDPEN derivatives were prepared.•The Ru(II) complexes showed thermoregulated phase-separation behavior.•The Ru(II) complexes were used as efficient catalysts for ATH of various ketones.•The catalyst showed excellent enantioselectivity and recyclability.A sulfonated chiral diamine ligand anion-based functionalized ionic liquid has been synthesized. Then the new ionic liquid-regulating ruthenium complexes were prepared successfully and employed as efficient catalysts for the asymmetric transfer hydrogenation of various ketones. The catalysts were highly efficient for the hydrogenation of a wide range of substrates bearing different functional groups and could be separated easily from the reaction mixture by thermoregulated phase separation, which can be efficiently recycled five times without significant changes in catalytic activity and enantioselectivity.Download full-size image
Co-reporter:Zhenhong He, Zhenshan Hou, Yanping Luo, Yierxiati Dilixiati and Wumanjiang Eli
Catalysis Science & Technology (2011-Present) 2014 - vol. 4(Issue 4) pp:NaN1103-1103
Publication Date(Web):2014/01/13
DOI:10.1039/C3CY00842H
Pd–TPPTS–OTPPTS (denoted as Pd–P–OP, where TPPTS was the sodium salt of tri(m-sulfophenyl)phosphine and OTPPTS was the oxidized form of TPPTS) complexes supported on acidic resins (denoted as Pd–P–OP/resin) were prepared and employed as versatile heterogeneous catalysts for the hydroesterification of vinyl-aromatics with alcohols. The catalysts were characterized by the methods of FT-IR, XPS, N2 physisorption, XRD, TGA, SEM and 31P NMR. According to the 31P NMR results, there was a weak coordination between OTPPTS and the Pd sites. Consequently, OTPPTS was a weak ligand to the Pd sites and thus dissociated easily, acting as a protective agent of the vacant coordination site of the Pd metal sites, which allowed the substrates more access to the metal sites. In the hydroesterification of styrene, the distribution of the branched and linear esters was remarkably impacted by adding an appropriate amount of OTPPTS and the acidic resin supports. A high yield and excellent selectivity towards the branched ester were obtained when OTPPTS and TPPTS were used in equimolar amounts under optimized reaction conditions. The generality and recyclability of the catalyst for the hydroesterification of vinyl-aromatics were also examined. In addition, the poisoning and hot filtration tests indicated that Pd(0) acted as the active species in a truly heterogeneous way. A Pd–hydride mechanism was proposed for the hydroesterification over the Pd–P–OP/LSI-600 catalyst.
Co-reporter:Ran Zhang, Li Guo, Chen Chen, Jizhong Chen, Angjun Chen, Xiuge Zhao, Xuerui Liu, Yuhe Xiu and Zhenshan Hou
Catalysis Science & Technology (2011-Present) 2015 - vol. 5(Issue 5) pp:NaN2972-2972
Publication Date(Web):2015/03/26
DOI:10.1039/C5CY00166H
A novel highly active Mn-doping ceria heterogeneous catalyst (MnOx–CeO2) was prepared and dedicated to the catalytic synthesis of aliphatic carbamates from CO2, aliphatic amines and methanol in one step. The as-obtained catalyst can attain a high yield of carbamate up to 82%, and can also be recycled at least four times through a simple procedure. It was observed that the Mn doping to ceria can alleviate the catalyst deactivation in consecutive catalytic recycles. In this regard, the role of Mn doping in the ceria in the synthesis of the aliphatic carbamates was investigated by means of X-ray diffraction (XRD), Raman spectra, specific surface areas (BET), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), CO2-temperature programmed desorption (CO2-TPD) and in situ diffuse reflectance infrared Fourier transform (DRIFT). The characterization demonstrated that the presence of MnOx in the ceria can not only inhibit the formation of stable carbonate species on the surface of the catalyst but also promote the decomposition/consuming of the carbonaceous species during the synthesis of aliphatic carbamates so as to allow improvement of the recyclability of the catalyst.
Co-reporter:Wenwen Zhu, Hanming Yang, Yinyin Yu, Li Hua, Huan Li, Bo Feng and Zhenshan Hou
Physical Chemistry Chemical Physics 2011 - vol. 13(Issue 30) pp:NaN13500-13500
Publication Date(Web):2011/05/13
DOI:10.1039/C1CP20255C
The highly water-soluble palladium nanoparticles (NPs) were synthesized by using the amphiphilic poly(ethylene glycol)-functionalized dicationic imidazolium-based ionic liquid (C12Im-PEG IL) as a stabilizing agent. The aqueous dispersed palladium NPs in the range of 1.9 ± 0.3 nm were observed by transmission electron microscopy (TEM). The physicochemical properties of C12Im-PEG IL in aqueous phase have been characterized by electrical conductivity, surface tension and dynamic light scattering (DLS) measurements. It was demonstrated that the amphiphilic ionic liquid can form micelles above its critical micelle concentration (CMC) in aqueous solution and the micelles played a crucial role in stabilizing the palladium NPs and thus promoted catalytic hydrogenation. Furthermore, the dicationic ionic liquid can also act as a gemini surfactant and generated emulsion between hydrophobic substrates and the catalytic aqueous phase during the reaction. The aqueous dispersed palladium NPs showed efficient activity for the catalytic hydrogenation of various substrates under very mild conditions and the stabilizing Pd(0) nanoparticles (NPs) can be reused at least eight times with complete conservation of activity.
Co-reporter:Li Guo, Ran Zhang, Chen Chen, Jizhong Chen, Xiuge Zhao, Angjun Chen, Xuerui Liu, Yuhe Xiu and Zhenshan Hou
Physical Chemistry Chemical Physics 2015 - vol. 17(Issue 9) pp:NaN6414-6414
Publication Date(Web):2015/01/30
DOI:10.1039/C4CP05733C
Metal nanoparticles embedded in hollow materials are important due to their wide applications in catalysis. In this work, we disclosed a nontraditional synthetic pathway to prepare silica hollow nanospheres by hydrothermal treatment in the presence of compressed CO2. Especially, the silica hollow nanospheres with an outer diameter of about 16 nm and an inner pore size of 7 nm were obtained using 1.0 MPa CO2. The formation mechanism of silica hollow nanospheres induced by CO2 was investigated by high-pressured UV/Vis spectroscopy. Moreover, gold nanoparticles (2.5 nm) embedded in the silica hollow nanospheres were prepared by a one-pot synthesis using HAuCl4 as a precursor. The current synthetic route of nano-catalysts was simple and facile, in which no etching agent was needed in the process of the hollow material preparation. Besides, this nano-catalyst showed an excellent catalytic performance in epoxidation of styrene with high conversion (82.2%) and selectivity (90.2%) toward styrene oxide, as well as in the selective oxidation of ethylbenzene with good conversion (26.6%) and selectivity (87.8%) toward acetophenone. Moreover, the Au nanoparticles (AuNPs) embedded in silica hollow nanospheres exhibited an excellent recyclability in both the oxidation reactions.
Phosphoric acid,zirconium salt (8CI,9CI)
1-Hexanol, 2-methoxy-
2-Hexanol, 1-methoxy-
Oxiranemethanol, 2-methyl-3-phenyl-, (2R,3R)-rel-
Oxirane, 2-phenoxy-
N-(TRIMETHOXYSILYLPROPYL)IMIDAZOLE
1-phenylglycerol
Oxiranemethanol, 3-methyl-3-(4-methyl-3-pentenyl)-, (2R,3R)-rel-
1,2,3-Butanetriol, 3-methyl-
(1r)-1-(4-nitrophenyl)ethanol