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    Chinese Journal of Catalysis
    2015, Vol. 36, No. 4
    Online: 23 March 2015

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    Prof. Kannan and his coworkers in their Review on pages 458–472 analyzed the current status of nanocatalysts for proton exchange membrane fuel cells and alkaline membrane fuel cells. The review covers several synthesis methods of noble and non-noble metal catalysts and numerous ex situ and in situ characterization methods for these catalyst materials are discussed.

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    Table of Contents
    Table of Contents for VOL.36 No.4
    2015, 36 (4):  0-0. 
    Abstract ( 114 )   PDF (2546KB) ( 492 )  
    Special Column on Electrocatalysis for Fuel Cells
    Preface to Special Column on Electrocatalysis for Fuel Cells
    Panagiotis Tsiakaras, Shuqin Song
    2015, 36 (4):  457-457.  DOI: 10.1016/S1872-2067(15)60832-4
    Abstract ( 250 )   [Full Text(HTML)] () PDF (241KB) ( 472 )  
    Nano-electrocatalyst materials for low temperature fuel cells: A review
    K. Vignarooban, J. Lin, A. Arvay, S. Kolli, I. Kruusenberg, K. Tammeveski, L. Munukutla, A. M. Kannan
    2015, 36 (4):  458-472.  DOI: 10.1016/S1872-2067(14)60175-3
    Abstract ( 306 )   [Full Text(HTML)] () PDF (3549KB) ( 1058 )  

    Low temperature fuel cells are an attractive technology for transportation and residential applications due to their quick start up and shut down capabilities. This review analyzed the current status of nanocatalysts for proton exchange membrane fuel cells and alkaline membrane fuel cells. The preparation process influences the performance of the nanocatalyst. Several synthesis methods are covered for noble and non-noble metal catalysts on various catalyst supports including carbon nanotubes, carbon nanofibers, nanowires, and graphenes. Ex situ and in situ characterization methods like scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and fuel cell testing of the nanocatalysts on various supports for both proton exchange and alkaline membrane fuel cells are discussed. The accelerated durability estimate of the nanocatalysts, predicted by measuring changes in the electrochemically active surface area using a voltage cycling method, is considered one of the most reliable and valuable method for establishing durability.

    A review of the development of high temperature proton exchange membrane fuel cells
    Suthida Authayanun, Karittha Im-orb, Amornchai Arpornwichanop
    2015, 36 (4):  473-483.  DOI: 10.1016/S1872-2067(14)60272-2
    Abstract ( 321 )   [Full Text(HTML)] () PDF (529KB) ( 1364 )  

    Due to the need for clean energy, the development of an efficient fuel cell technology for electricity generation has received considerable attention. Much of the current research efforts have investigated the materials for and process development of fuel cells, including the optimization and simplification of the fuel cell components, and the modeling of the fuel cell systems to reduce their cost and improve their performance, durability and reliability to enable them to compete with the conventional combustion engine. A high temperature proton exchange membrane fuel cell (HT-PEMFC) is an interesting alternative to conventional PEMFCs as it is able to mitigate CO poisoning and water management problems. Although the HT-PEMFC has many attractive features, it also possesses many limitations and presents several challenges to its widespread commercialization. In this review, the trends of HT-PEMFC research and development with respect to electrochemistry, membrane, modeling, fuel options, and system design were presented.

    Facile synthesis of Zr- and Ta-based catalysts for the oxygen reduction reaction
    David Sebastián, Vincenzo Baglio, Shuhui Sun, Ana C. Tavares, Antonino S. Aricò
    2015, 36 (4):  484-489.  DOI: 10.1016/S1872-2067(14)60253-9
    Abstract ( 209 )   [Full Text(HTML)] () PDF (792KB) ( 554 )  

    Cathode catalysts for direct alcohol fuel cells (DAFCs) must have high catalytic activity for the oxygen reduction reaction (ORR), low cost, and high tolerance to the presence of methanol or ethanol. Pt is the benchmark catalyst for this application owing to its excellent electrocatalytic activity, but its high cost and low tolerance to the organic fuel permeating through the membrane have hindered the commercialization of DAFCs. Herein we present a facile synthesis route to obtain organic fuel-tolerant Zr- and Ta-based catalysts supported on carbon. This method consists of a simple precipitation of metal precursors followed by a heat treatment. X-ray diffraction analyses confirmed that the obtained samples were crystalline ZrO2-x and Na2Ta8O21-x having crystallite sizes of 26 and 32 nm, respectively. The thermal treatment effectively increased the activity of the catalysts towards the ORR, although further optimization is necessary. Both catalysts exhibited a high tolerance to the presence of methanol with only a moderate reduction in ORR activity even at high methanol concentration (0.5 mol/L).

    Core-shell graphene@amorphous carbon composites supported platinum catalysts for oxygen reduction reaction
    Hui Wu, Tao Peng, Zongkui Kou, Jian Zhang, Kun Cheng, Daping He, Mu Pan, Shichun Mu
    2015, 36 (4):  490-495.  DOI: 10.1016/S1872-2067(14)60211-4
    Abstract ( 375 )   [Full Text(HTML)] () PDF (1122KB) ( 720 )  

    A core-shell graphene nanosheets (GNS) and amorphous carbon composite (GNS@a-C) was prepared by a chlorination method and used as a highly efficient catalyst support for oxygen reduction reaction. Herein, GNS as a shell, with excellent conductivity, high surface area, and corrosion resistance, served as a protecting coating to alleviate the degradation of amorphous carbon core. Platinum nanoparticles were homogeneously deposited on the carbon support (Pt/GNS@a-C) and showed a good catalytic activity and a higher electrochemical stability when compared with a commercial Pt/C catalyst. The mass activity of Pt/GNS@a-C catalyst was 0.121 A/mg, which was almost twice as high as that of Pt/C (0.064 A/mg). Moreover, Pt/GNS@a-C retained 51% of its initial electrochemical specific area after 4000 operating cycles when compared with Pt/C (33%). Thus, the prepared catalyst featured excellent electrochemical stability, showing promise for application in polymer electrolyte membrane fuel cells.

    Improving the efficiency of a direct ethanol fuel cell by a periodic load change
    Andrzej Jablonski, Adam Lewera
    2015, 36 (4):  496-501.  DOI: 10.1016/S1872-2067(14)60226-6
    Abstract ( 271 )   [Full Text(HTML)] () PDF (675KB) ( 676 )  

    We present a simple method to increase the efficiency of a direct ethanol fuel cell by a periodic modulation of the load (pulsed mode). The fuel cell was periodically short circuited with a resistor (1 Ω) for a few seconds (high load period) followed by a low load period of up to 100 s when the resistor was disconnected. The open circuit voltage (OCV) values before and after the short circuit of the cell showed an increase of up to 70 mV. The higher OCV was due to the oxidation and removal of strongly adsorbed CO during the electric short circuit when the electric potential of the anode was increased to be close to the cathode potential. The depoisoned anode surface was much more active directly after the short circuit. The slow decrease of the OCV observed after the short circuit was caused by the subsequent poisoning of the anode surface, which can be neutralized by another short circuit. In general, a stable increase in cell performance was obtained by repetition of the electric short circuit. The data showed that the pulse mode gave an increase in the power generated by the direct ethanol fuel cell by up to 51% and was 6% on average. It is anticipated that this mode of operation can be used also in different types of polymer electrolyte membrane fuel cells where CO poisoning is a problem, and after optimization of the parameters, a much higher gain in efficiency can be obtained.

    TiO2-modified La0.6Sr0.4Co0.2Fe0.8O3-δ cathode for intermediate temperature solid oxide fuel cells
    Weixing Liu, Zhe Zhao, Baofeng Tu, Daan Cui, Dingrong Ou, Mojie Cheng
    2015, 36 (4):  502-508.  DOI: 10.1016/S1872-2067(14)60235-7
    Abstract ( 386 )   [Full Text(HTML)] () PDF (901KB) ( 713 )  

    A La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode modified using nanosized TiO2 was direct prepared on the yttria stabilized zirconia (YSZ) electrolyte in an intermediate temperature solid oxide fuel cell. TiO2 prevents reaction between LSCF and YSZ, which would have formed a SrZrO3 phase. The cell with a LSCF-0.25 wt% TiO2 cathode exhibited a current density that was 1.6 times larger than that with a pure LSCF cathode at 0.7 V and 600 ℃. Electrochemical impedance spectra showed the accelerated incorporation of oxygen anions into the YSZ electrolyte with the TiO2-modified LSCF cathode. The improvement was attributed to the suppressed formation of a non-conductive SrZrO3 layer at the cathode/electrolyte interface.

    Carbon to electricity in a solid oxide fuel cell combined with an internal catalytic gasification process
    M. Konsolakis, G. E. Marnellos, A. Al-Musa, N. Kaklidis, I. Garagounis, V. Kyriakou
    2015, 36 (4):  509-516.  DOI: 10.1016/S1872-2067(14)60262-X
    Abstract ( 254 )   [Full Text(HTML)] () PDF (867KB) ( 802 )  

    This study explores strategies to develop highly efficient direct carbon fuel cells (DCFCs) by combining a solid-oxide fuel cell (SOFC) with a catalyst-aided carbon-gasification process. This system employs Cu/CeO2 composites as both anodic electrodes and carbon additives in a cell of the type: carbon|Cu-CeO2/YSZ/Ag|air. The study investigates the impact on in situ carbon-gasification and DCFC performance characteristics of catalyst addition and variation in the carrier gas used (inert He versus reactive CO2). The results indicate that cell performance is significantly improved by infusing the catalyst into the carbon feedstock and by employing CO2 as the carrier gas. At 800 ℃, the maximum power output is enhanced by approximately 40% and 230% for carbon/CO2 and carbon/catalyst/CO2 systems, respectively, compared with that of the carbon/He configuration. The increase observed when employing the catalyst and CO2 as the carrier gas can be primarily attributed to the pronounced effect of the catalyst on carbon-gasification through the reverse-Boudouard reaction, and the subsequent in situ electro-oxidation of CO at the anode three-phase boundary.

    Highlight
    Catalysis on a metal surface with a graphitic cover
    Qiang Fu, Xinhe Bao
    2015, 36 (4):  517-519.  DOI: 10.1016/S1872-2067(15)60828-2
    Abstract ( 299 )   [Full Text(HTML)] () PDF (495KB) ( 778 )  
    Review
    Silica supported Brönsted acids as catalyst in organic transformations: A comprehensive review
    Manpreet Kaur, Sahil Sharma, Preet M. S. Bedi
    2015, 36 (4):  520-549.  DOI: 10.1016/S1872-2067(14)60299-0
    Abstract ( 320 )   [Full Text(HTML)] () PDF (1040KB) ( 2105 )  

    Brönsted acid catalysts have been used in a number of organic transformations. To overcome limitations, such as toxicity, volatility, high price and hazardous nature of the conventional methods, the catalysts are adsorbed on silica gel to give the benefits and advantages of ready availability, simple work-up procedure, long catalytic life, environment-friendliness, good to excellent yields and recyclability. The uses of such catalysts have gained importance worldwide. This article describes some of the important silicated catalysts, namely, heteropolyacids, polyphosphoric acid, perchloric acid, fluoroboric acid, and silicated sulphuric acid. These catalysts have been used in a number of organic reactions to yield compounds that are important in the chemical and pharmaceutical industries. We summarize the beneficial effects of these catalysts and the reports that have been published on them in the past several years. In the present review, the description of the catalysts are introduced followed by a recent research history, and a comparison between the silica supported catalysts and other (polymer) supported catalysts. The article ends up giving the advantages of these catalytic systems over the conventional catalyst.

    Articles
    A TiN0.3/CeO2 photo-anode and its photo-electrocatalytic performance
    Huanan Cui, Deng Li, Guantao Liu, Zhenxing Liang, Jianying Shi
    2015, 36 (4):  550-554.  DOI: 10.1016/S1872-2067(14)60295-3
    Abstract ( 320 )   [Full Text(HTML)] () PDF (716KB) ( 657 )  

    A TiN0.3/CeO2 photo-anode was synthesized by the electro-deposition of CeO2 on TiN0.3 supported on a Ti substrate. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study its structure and morphology. The crystalline nature of TiN0.3 and CeO2 was confirmed by XRD, and SEM images showed that CeO2 spheres uniformly distributed on the TiN0.3 surface. In addition to visible light absorption by TiN0.3, UV light was also harvested by the outer CeO2 component on the TiN0.3/CeO2 combined photo-anode. In the photo-electrochemical measurement, TiN0.3/CeO2 showed four times higher photo-current density than TiN0.3 or CeO2, and the photo-current stabilization was also significantly improved compared to TiN0.3 or CeO2. The specific double-layer structure of TiN0.3/CeO2 contributed to its improved photo-electrocatalytic performance. Electron transfer from CeO2 to TiN0.3 driven by the hetero-junction and hole consumption by Ce3+ at the TiN0.3/CeO2 interface promoted the separation of electron and hole in the CeO2 layer, which improved the photo-current generation. Ce3+ that existed in CeO2 acted as the adsorption and activation site for H2O and accelerated the oxidation of H2O on the CeO2 surface, which further led to the high and stable photo-current density generated in TiN0.3/CeO2. This finding is useful for the design and synthesis of an effective photo-electrocatalysis material for solar energy conversion.

    Pd-isatin Schiff base complex immobilized on γ-Fe2O3 as a magnetically recyclable catalyst for the Heck and Suzuki cross-coupling reactions
    Sara Sobhani, Farzaneh Zarifi
    2015, 36 (4):  555-563.  DOI: 10.1016/S1872-2067(14)60291-6
    Abstract ( 251 )   [Full Text(HTML)] () PDF (600KB) ( 636 )  

    A Pd-isatin Schiff base complex immobilized on γ-Fe2O3 (Pd-isatin Schiff base-γ-Fe2O3) was synthesized and characterized by Fourier transform infrared, scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, thermogravimetric gravimetric analysis, inductively-coupled plasma, X-ray photoelectron spectroscopy, and elemental analysis. It was used as a magnetically reusable Pd catalyst for the Heck and Suzuki cross-coupling reactions.

    A stable and active AgxS crystal preparation and its performance as photocatalyst
    Pingjing Chang, Haiyang Cheng, Weiwei Lin, Xiaoru Li, Fengyu Zhao
    2015, 36 (4):  564-571.  DOI: 10.1016/S1872-2067(14)60288-6
    Abstract ( 248 )   [Full Text(HTML)] () PDF (790KB) ( 559 )  

    AgxS crystals were synthesized via hydrothermal (AgxS-H) and in situ ion-exchange (AgxS-IE) methods. The samples were characterized by scanning electron microscopy, X-ray diffraction, ultraviolet-visible-near infrared absorption spectroscopy, N2 adsorption-desorption, X-ray photoelectron spectroscopy and surface photovoltage measurements. The photocatalytic performance was investigated for the decomposition of methyl blue (MB) under visible light irradiation (λ ≥ 420 nm). The AgxS-H had smaller particles, wider band gap and weaker recombination of photoinduced charges than AgxS-IE, resulting in a higher photocatalytic activity. Moreover, AgxS-H was stable, and could be reused five times without loss of photocatalytic activity. Additionally, a possible pathway for the photocatalytic degradation of MB over AgxS has been proposed, that MB was oxidized mainly by hydroxyl radicals and partly via electron holes generated in the AgxS. AgxS-H is an efficient photocatalyst and has great potential for the degradation of harmful organic dyes in wastewater.

    Fe3O4@MCM-48-SO3H: An efficient magnetically separable nanocatalyst for the synthesis of benzo[f]chromeno[2, 3-d]pyrimidinones
    Hassan Kefayati, Mostafa Golshekan, Shahab Shariati, Mahsa Bagheri
    2015, 36 (4):  572-578.  DOI: 10.1016/S1872-2067(14)60286-2
    Abstract ( 273 )   [Full Text(HTML)] () PDF (663KB) ( 1028 )  

    Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM-48. The sulfonic acid-functionalized nanoparticles were evaluated as catalysts for the synthesis of 5-aryl-1H-benzo[f]chromeno[2,3-d]pyrimidine- 2,4(3H,5H)-dione derivatives in terms of activity and recyclability. Their catalytic activities were compared with that of the homogeneous acid catalyst 1-methylimidazolium hydrogen sulfate ([HMIm][HSO4]). The activity of Fe3O4@MCM-48-SO3H was comparable to those of the other heterogeneous and homogeneous catalysts.

    Catalytic abatement of CO and volatile organic compounds in waste gases by gold catalysts supported on ceria-modified mesoporous titania and zirconia
    Vasko Idakiev, Dimitar Dimitrov, Tatyana Tabakova, Krasimir Ivanov, Zhong-Yong Yuan, Bao-Lian Su
    2015, 36 (4):  579-587.  DOI: 10.1016/S1872-2067(14)60283-7
    Abstract ( 189 )   [Full Text(HTML)] () PDF (683KB) ( 723 )  

    Mesoporous oxides TiO2 and ZrO2, synthesized by surfactant templating via a neutral C13(EO)6-Zr(OC3H7)4 assembly pathway, and ceria-modified TiO2 and ZrO2, prepared by a deposition-precipitation (DP) method, featuring high surface areas and uniform pore size distributions were used as supports for gold catalysts. The supported gold catalysts were assessed for the catalytic abatement of air pollutants, i.e., CO, CH3OH, and (CH3)2O. The gold was supported on the mesoporous oxides by a DP method. The supports and catalysts were characterized by powder X-ray diffraction, high-resolution transmission electron microscopy, N2 adsorption-desorption analysis, and temperature-programmed reduction technique. A high degree of synergistic interaction between ceria and mesoporous ZrO2 and TiO2 as well as a positive modification of the structural and catalytic properties by ceria was observed. The ceria additive interacts with the mesoporous oxides and induces a strong effect on the reducibility of the supports. The catalytic behavior of the catalysts was discussed to determine the role of the ceria modifying additive and possible interaction between the gold nanoparticles and ceria-mesoporous oxide supports. The gold catalysts supported on ceria-modified mesoporous ZrO2 displayed superior catalytic activity (~100% conversion of CO at 10 ℃ and CH3OH at 60 ℃). The high catalytic activity can be attributed to the ability of the support to assist oxygen vacancies formation. The studies indicate that the ceria-modified mesoporous oxide supports have potential as supports for gold-based catalysts.

    Chemical vapor deposition of Pd(C3H5)(C5H5) for the synthesis of reusable Pd@ZIF-8 catalysts for the Suzuki coupling reaction
    Mingming Zhang, Ya Gao, Chuang Li, Changhai Liang
    2015, 36 (4):  588-594.  DOI: 10.1016/S1872-2067(14)60292-8
    Abstract ( 344 )   [Full Text(HTML)] () PDF (1028KB) ( 846 )  

    A zeolite-imidazolium-framework-supported Pd-based heterogeneous catalyst (Pd@ZIF-8) was prepared by a metal-organic chemical vapor deposition method under mild conditions using Pd(C3H5)(C5H5) as the Pd precursor. N2 adsorption and pore size distribution data showed that ZIF-8 and Pd@ZIF-8 both possessed high surface areas. Transmission electron microscopy images showed that Pd nanoparticles with sizes of about 1.5-3.5 nm were homogeneously dispersed on the ZIF-8 support in Pd@ZIF-8. The Pd@ZIF-8 catalyst showed good activity in Suzuki coupling reactions with several different kinds of aryl halides. It could be reused at least six times without dramatic loss of activity or decomposition of the ZIF-8 structure.

    Acetylation of alcohols and phenols under solvent-free conditions using iron zirconium phosphate
    Abdol R. Hajipour, Hirbod Karimi, Amir Masti
    2015, 36 (4):  595-602.  DOI: 10.1016/S1872-2067(14)60280-1
    Abstract ( 299 )   [Full Text(HTML)] () PDF (762KB) ( 792 )  

    Iron zirconium phosphate (ZPFe) nanoparticles were found to function as an efficient catalyst for the acetylation of a wide range of alcohols and phenols using acetic anhydride, generating good to excellent yields under solvent-free conditions. The steric and electronic properties of various substrates had a significant influence on the reaction conditions required to achieve the acetylation. The catalyst used in the current study was characterized by inductively coupled plasma-optical emission spectrometry, X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and transmission electron microscopy. These analyses revealed that the interlayer distance in the catalyst increased from 7.5 to 9.3 Å when Fe3+ was intercalated between the layers, whereas the crystallinity of the material was reduced. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity. This new method for the acetylation of alcohols and phenols has several important advantages, including mild and environmentally friendly reaction conditions, as well as good to excellent yields and a facile work-up.

    Modified hydrothermal synthesis and characterization of reduced graphene oxide-silver selenide nanocomposites with enhanced reactive oxygen species generation
    Lei Zhu, Shu Ye, Asghar Ali, Kefayat Ulla, Kwang Youn Cho, Won-Chun Oh
    2015, 36 (4):  603-611.  DOI: 10.1016/S1872-2067(14)60275-8
    Abstract ( 188 )   [Full Text(HTML)] () PDF (1433KB) ( 1023 )  

    A visible-light photocatalyst containing Ag2Se and reduced graphene oxide (RGO) was synthesized by a facile sonochemical-assisted hydrothermal method. X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analysis, and ultraviolet-visible diffuse reflectance spectroscopy results indicated that the RGO-Ag2Se nanocomposite contained small crystalline Ag2Se nanoparticles dispersed over graphene nanosheets and absorbed visible light. The high crystallinity of the nanoparticles increased photocatalytic activity by facilitating charge transport. N2 adsorption-desorption measurements revealed that the RGO-Ag2Se nanocomposite contained numerous pores with an average diameter of 9 nm, which should allow reactant molecules to readily access the Ag2Se nanoparticles. The RGO-Ag2Se nanocomposite exhibited higher photocatalytic activity than bulk Ag2Se nanoparticles to degrade organic pollutant rhodamine B and industrial dye Texbrite BA-L under visible-light irradiation (λ > 420 nm). The generation of reactive oxygen species in RGO-Ag2Se was evaluated through its ability to oxidize 1,5-diphenylcarbazide to 1,5-diphenylcarbazone. The small size of the Ag2Se nanoparticles in RGO-Ag2Se was related to the use of ultrasonication during their formation, revealing that this approach is attractive to form porous RGO-Ag2Se materials with high photocatalytic activity under visible light.

    Uniformly dispersed Pd nanoparticles on nitrogen-doped carbon nanospheres for aerobic benzyl alcohol oxidation
    Yan Hao, Shuai Wang, Qiang Sun, Lei Shi, An-Hui Lu
    2015, 36 (4):  612-619.  DOI: 10.1016/S1872-2067(14)60274-6
    Abstract ( 271 )   [Full Text(HTML)] () PDF (833KB) ( 798 )  

    Maintaining the dispersion and stability of supported metals is still an important issue for solid catalysts that suffer from aggregation or leaching. We report an easy procedure for the preparation of Pd nanoparticles supported on carbon nanospheres by the direct pyrolysis of the metal precursor impregnated on polybenzoxazine-based polymer nanospheres. The complexation interaction between the metal and support was beneficial for the dispersion and stability of the Pd nanoparticles. Pd nanoparticles with an average size of 3 nm were uniformly dispersed on the carbon nanospheres after a thermal treatment at 500 ℃ under argon flow. The catalyst was evaluated for aerobic benzyl alcohol oxidation under mild conditions without using a base additive. In order to get mostly outer surface Pd nanoparticles, the catalyst preparation conditions were investigated by varying the metal loading and loading time. The highest catalytic activity reached a TOF of 690 h-1 when the catalyst was prepared under the optimized conditions. The catalyst also showed good recyclability and can be easily regenerated by calcination at 200 ℃.

    Nano-sized silica supported FeCl3 as an efficient heterogeneous catalyst for the synthesis of 1, 2, 4-triazine derivatives
    Davood Habibi, Somayyeh Vakili
    2015, 36 (4):  620-625.  DOI: 10.1016/S1872-2067(15)60829-4
    Abstract ( 204 )   [Full Text(HTML)] () PDF (648KB) ( 724 )  

    The one-pot synthesis of a series of 1,2,4-triazines from the reactions of semicarbazide or thiosemicarbazide with various α,β-dicarbonyl compounds under reflux conditions in a EtOH-H2O (9:1) mixture as solvent and catalyzed by nano-sized silica supported FeCl3 (FeCl3@SiO2) was investigated. The FeCl3 content of the catalyst was measured by atomic absorption to get the adsorption capacity. The reactions gave high yields of the product and the catalyst was easily separated and reused for successive reaction runs without significant loss of activity.

    Tin sulfide nanoparticles supported on activated carbon as an efficient and reusable Lewis acid catalyst for three-component one-pot synthesis of 4H-pyrano[2, 3-c]pyrazole derivatives
    Nasir Iravani, Mosadegh Keshavarz, Hossein Ali Shojaeian Kish, Rasool Parandvar
    2015, 36 (4):  626-633.  DOI: 10.1016/S1872-2067(14)60284-9
    Abstract ( 248 )   [Full Text(HTML)] () PDF (664KB) ( 662 )  

    Tin sulfide nanoparticles (SnS-NPs) were prepared in aqueous solution at room temperature on the surface of activated carbon (AC) and were investigated using field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction, reflective ultraviolet-visible spectrophotometry, and spectrofluorimetry. Calculations based on the SEM and TEM images showed that the sizes of the SnS-NPs immobilized on the AC were 30-70 nm. The prepared nanocomposite was used as a heterogeneous Lewis acid catalyst for the three-components one-pot synthesis of 4H-pyrano[2,3-c]pyrazole derivatives in ethanol at 80 ℃. The reactions were efficiently performed in the presence of the prepared catalyst in short reaction times, and gave the desired products in high yields. This catalyst can be easily recovered by simple filtration and recycled up to eight consecutive times without significant loss of its efficiency.

    High enantioselectivity in the asymmetric hydrogenation of ketones by a supported Pt nanocatalyst on a mesoporous modified MCM-41 support
    Susmit Basu
    2015, 36 (4):  634-638.  DOI: 10.1016/S1872-2067(14)60279-5
    Abstract ( 169 )   [Full Text(HTML)] () PDF (654KB) ( 560 )  

    Catalysts containing metal nanotubes were prepared by the adsorption of platinum metal nanotubes onto functionalized and modified silica surfaces (MCM-41 and fumed silica). (3- Chloropropyl)trimethoxysilane and cinchonidine were used for functionalization and modification, respectively. Potassium chloroplatinate was used as the metal precursor to impregnate platinum metal nanotubes on the pretreated functionalized and modified silica surfaces. The solid catalysts were characterized by ESEM, TEM, EDAX, and XPS. The MCM-41 supported platinum nanotube catalyst showed >98% to ~100% enantioselectivity towards the hydrogenation of a range of pharmaceutically important chemicals such as methyl pyruvate, ethyl pyruvate, and acetophenone with nearly full conversion.

    The effect of Pd precursor on Pd/Ce0.67Zr0.33O2 catalysts for automotive emission control
    Siyu Lin, Linyan Yang, Xue Yang, Renxian Zhou
    2015, 36 (4):  639-648.  DOI: 10.1016/S1872-2067(14)60264-3
    Abstract ( 280 )   [Full Text(HTML)] () PDF (1136KB) ( 696 )  

    A Pd/CZ(NO) catalyst prepared with Pd(NO3)2 as the metal precursor exhibited the best catalytic performance for HC and CO elimination because of a higher oxygen storage capacity, abundant small Pdn clusters and a strong Pd-support interaction that facilitated electron transfer from PdOx particles to the CZ support. A Pd/CZ(NH) catalyst prepared with Pd(NH3)4(NO3)2 as the metal precursor exhibited good performance for NO and NO2 elimination due to a higher Pd dispersion, abundant bigger Pdn clusters and oxidized/metallic Pd coexistence. A Pd/CZ(Cl) catalyst prepared with H2PdCl4 as the metal precursor exhibited low catalytic activity due to a low Pd dispersion, weak Pd-support interaction, and the trace amount of CeOCl which inhibited oxygen vacancy creation. However, it showed good thermal stability, and benefited when an aging treatment removed the residual chlorine species and also promoted the interaction between PdOx and the support.

    The effect of Fe species distribution and acidity of Fe-ZSM-5 on the hydrothermal stability and SO2 and hydrocarbons durability in NH3-SCR reaction
    Xiaoyan Shi, Hong He, Lijuan Xie
    2015, 36 (4):  649-656.  DOI: 10.1016/S1872-2067(14)60268-0
    Abstract ( 276 )   [Full Text(HTML)] () PDF (654KB) ( 901 )  

    Fe-exchanged ZSM-5 catalysts prepared from Na+ and H+ forms of ZSM-5 were evaluated for the selective catalytic reduction of NOx by NH3 (NH3-SCR). Fe-H-ZSM-5 showed higher SCR activity than Fe-Na-ZSM-5 both when fresh and after hydrothermal aging at 750 ℃ in 5% H2O/air. The Fe species distribution and acidity of Fe-H-ZSM-5 and Fe-Na-ZSM-5 were found to be different. The dealumination of the zeolite framework of Fe-H-ZSM-5 during hydrothermal aging was found to be more severe compared with that of Fe-Na-ZSM-5. The durability of Fe-H-ZSM-5 and Fe-Na-ZSM-5 in NH3-SCR was compared using SO2 tolerance and hydrocarbon resistance experiments. The effect of water and SO2 on the activity of the two catalysts was similar, such that their activity decreased at low temperatures and increased at high temperatures. Fe-Na-ZSM-5 showed better propene resistance than Fe-H-ZSM-5. The SO2 and propene poisoning of the two Fe-ZSM-5 catalysts were found to be reversible.

    Theoretical investigation of the mechanism of ethylene polymerization with salicylaldiminato vanadium(Ⅲ) complexes
    Yongxia Wang, Minghui Zuo, Yuesheng Li
    2015, 36 (4):  657-666.  DOI: 10.1016/S1872-2067(14)60271-0
    Abstract ( 338 )   [Full Text(HTML)] () PDF (1073KB) ( 731 )  

    The use of vanadium-based catalysts allows the preparation of high molecular mass polymers with uniform molecular mass distributions, polypropylene and ethylene/α-olefin copolymers with high α-olefin incorporation. However, the design of ligand systems with vanadium catalysts would face difficulties, because it is difficult to experimentally determine the structures of the active species of vanadium catalysts. In this paper, possible structural candidates for the active species in ethylene polymerization catalyzed by the salicylaldiminato vanadium complex combined with AlEt2Cl were investigated using density functional theory. By comparing theoretical simulation results with previous experimental investigations, especially regarding the crucial role of the diethyaluminum chloride (AlEt2Cl) cocatalyst, it was concluded that a neutral bimetallic species containing two Al-Cl-V bridging bonds is the most favorable structure model for the active vanadium species. A notable effect of Al co-catalysts was clarified in the theoretical investigation. During the formation of the active species, AlEt2Cl act as an assistant for the alkylation and alkyl abstract processes of precursors. More importantly, AlEt2Cl is necessary for the formation of the bis(chlorine-bridged) structure in the active species, which showed a notable effect on the structural stability of the active species and its catalytic activity. Additionally, we investigated the chain termination mechanism in this system.

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