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Chinese Journal of Catalysis
2016, Vol. 37, No. 9
Online: 21 September 2016


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Liu and coworkers in their Article on pages 1451–1460 reported a kind of Fe catalyst supported on mesoporous carbon (FeO_x/HCMK-3). It shows high activity and recyclability in imine synthesis from oxidative coupling of alcohol and amine with air as oxygen source. The highly dispersed FeO_x species give FeOx/HCMK-3 high reducibility and are responsible for the high catalytic performance.

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Table of Contents for VOL.37 No.9 2016, 37 (9):  0-0.  Abstract ( 217 )   PDF (8903KB) ( 528 )

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Ultrastable nanogold catalyst-on the way going to practical application Masatake Haruta 2016, 37 (9):  1441-1442.  DOI: 10.1016/S1872-2067(16)62526-3 Abstract ( 2218 )   [Full Text(HTML)] () PDF (611KB) ( 1016 )

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Single Co atom catalyst stabilized in C/N containing matrix Can Li 2016, 37 (9):  1443-1445.  DOI: 10.1016/S1872-2067(16)62520-2 Abstract ( 679 )   [Full Text(HTML)] () PDF (4527KB) ( 2081 )

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Highly active binuclear Cu(Ⅱ) catalyst bearing an unsymmetrical bipyridine-pyrazole-amine ligand for the azide-alkyne cycloaddition reaction Baofeng Han, Xiao Xiao, Lan Wang, Wenjing Ye, Xiaoping Liu 2016, 37 (9):  1446-1450.  DOI: 10.1016/S1872-2067(15)61121-4 Abstract ( 471 )   [Full Text(HTML)] () PDF (678KB) ( 949 )   Ligands containing NH groups often show special characteristics. In this paper, a well-defined dinuclear Cu(Ⅱ) complex bearing an unsymmetrical bipyridine-pyrazole-amine ligand was synthesized by the condensation of N-H to release H2O. Using sodium L-ascorbate as a reductant, the binuclear complex showed excellent activity in 1,3-dipolar cycloaddition reactions between alkynes and azides to obtain 1,4-disubstituted triazoles in 95%-99% isolated yields.

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Aerobic oxidative coupling of alcohols and amines to imines over iron catalysts supported on mesoporous carbon Longlong Geng, Jinling Song, Bin Zheng, Shujie Wu, Wenxiang Zhang, Mingjun Jia, Gang Liu 2016, 37 (9):  1451-1460.  DOI: 10.1016/S1872-2067(16)62506-8 Abstract ( 612 )   [Full Text(HTML)] () PDF (955KB) ( 896 )   Direct oxidative coupling of an alcohol and amine, with air or molecular oxygen as the oxygen source, is an environmentally friendly method for imine synthesis. We developed an Fe catalyst supported on mesoporous carbon(denoted by FeOx/HCMK-3) for this reaction with excellent activity and recyclability. FeOx/HCMK-3 was prepared by impregnating HNO3-treated mesoporous carbon(CMK-3) with iron nitrate solution. The highly dispersed FeOx species give FeOx/HCMK-3 high reducibility and are responsible for the high catalytic performance. Imine synthesis over FeOx/HCMK-3 follows a redox mechanism. The oxygen species in FeOx/HCMK-3 participate in the reaction and are then regenerated by oxidation with molecular O2. The reaction involves two consecutive steps: oxidative dehydrogenation of an alcohol to an aldehyde and coupling of the aldehyde with an amine to give an imine. Oxidative dehydrogenation of the alcohol is the rate-determining step in the reaction.

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Bovine serum albumin: An efficient and green biocatalyst for the one-pot four-component synthesis of pyrano[2,3-c]pyrazoles Xingtian Huang, Zhipeng Li, Dongyang Wang, Yiqun Li 2016, 37 (9):  1461-1468.  DOI: 10.1016/S1872-2067(15)61088-9 Abstract ( 564 )   [Full Text(HTML)] () PDF (593KB) ( 953 )   The use of biocatalysts is attracting an increasing amount of attention in chemical catalysis. Here, we have shown that bovine serum albumin(BSA), a ubiquitous, inexpensive, non-enzymatic transport protein, can serve as an efficient, retrievable catalyst in the one-pot four-component reaction of aryl aldehydes, malononitrile, hydrazine hydrate, and ethyl acetoacetate for the synthesis of pyrano[2,3-c]pyrazoles under mild reaction conditions. The BSA biocatalyst also displayed a high catalytic affinity for acyclic/cyclic ketones to yield the corresponding pyrano[2,3-c]pyrazoles or their spirocyclic variants. The BSA could be used for at least five cycles without serious loss of catalytic activity. This novel, efficient protocol has the merits of high yield, operational simplicity, and a relatively benign environmental impact. Moreover, the method extends the promiscuity of BSA as a biocatalyst.

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A new solid acid SO42-/TiO2 catalyst modified with tin to synthesize 1,6-hexanediol diacrylate Xiaxia Bai, Liuyi Pan, Peng Zhao, Daidi Fan, Wenhong Li 2016, 37 (9):  1469-1476.  DOI: 10.1016/S1872-2067(16)62474-9 Abstract ( 486 )   [Full Text(HTML)] () PDF (1484KB) ( 952 )   A new solid acid catalyst, SO42-/TiO2 modified with tin, was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption, X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, infrared spectroscopy of adsorbed pyridine, temperature-programmed desorption of ammonia and thermal gravimetric analysis. The structure, acidity and thermal stability of the SO42-/TiO2-SnO2 catalyst were studied. Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO42-/TiO2 catalyst. The total acid sites of the modified catalyst increased and Brönsted acid strength remarkably increased with increasing tin content. The decomposition temperature of sulfate radical in the modified catalyst was 100℃ greater and its mass loss was more than twice that of the SO42-/TiO2 catalyst. The SO42-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid. The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions: crylic acid to 1,6-hexanediol molar ratio=3.5, catalyst loading=7%, reaction temperature=130℃ and reaction time=3 h. The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.

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Experimental and kinetic study of n-heptane isomerization on nanoporous Pt-(Re,Sn)/HZSM5-HMS catalysts N. Parsafard, M. H. Peyrovi, M. Rashidzadeh 2016, 37 (9):  1477-1486.  DOI: 10.1016/S1872-2067(15)61114-7 Abstract ( 530 )   [Full Text(HTML)] () PDF (894KB) ( 1012 )   Pt-(Sn,Re)/HZSM5-HMS catalysts were evaluated for n-heptane isomerization at 200-350℃. To characterize the catalyst, X-ray diffraction, X-ray fluorescene, Fourier transform infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, temperature-programmed reduction of H2, temperature-programmed desorption of NH3, infrared spectroscopy of adsorbed pyridine, H2 chemisorption, nitrogen adsorption-desorption, scanning electron microscopy and thermogravimetric analysis were performed. Kinetics of n-C7 isomerization were investigated under various hydrogen and n-C7 pressures, and the effects of reaction conditions on catalytic performance were studied. The results showed that biand trimetallic catalysts exhibit better performance than monometallic catalysts for this reaction. For example, a maximum i-C7 selectivity(> 74%) and multibranched isomer selectivity(40%) were observed for Pt-Sn/HZSM5-HMS at 200℃.

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CoFe2O4/CdS nanocomposite: Preparation, characterisation, and application in sonocatalytic degradation of organic dye pollutants Saeed Farhadi, Firouzeh Siadatnasab 2016, 37 (9):  1487-1495.  DOI: 10.1016/S1872-2067(16)62473-7 Abstract ( 450 )   [Full Text(HTML)] () PDF (1515KB) ( 994 )   A magnetic CoFe2O4/CdS nanocomposite was prepared via one-step hydrothermal decomposition of cadmium diethanoldithiocarbamate complex on the surface of CoFe2O4 nanoparticles at a low temperature of 200℃. The nanocomposite was characterised by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), scanning electron microscopy, energy-dispersive X-ray spectroscopy(EDX), UV-visible spectroscopy, transmission electron microscopy(TEM), N2 gas sorption analysis, X-ray photoelectron spectroscopy(XPS), and vibrating sample magnetometry. The FT-IR, XRD, EDX and XPS results confirmed the formation of the CoFe2O4/CdS nanocomposite. Based on the TEM analysis, the CoFe2O4/CdS nanocomposite constituted nearly uniform, sphere-like nanoparticles of ~20 nm in size. The optical absorption spectrum of the CoFe2O4/CdS nanocomposite displayed a band gap of 2.21 eV, which made it a suitable candidate for application in sono/photocatalytic degradation of organic pollutants. Accordingly, the sonocatalytic activity of the CoFe2O4/CdS nanocomposite was evaluated towards the H2O2-assisted degradation of methylene blue, rhodamine B, and methyl orange under ultrasonic irradiation. The nanocomposite displayed excellent sonocatalytic activity towards the degradation of all dyes examined-the dyes were completely decomposed within 5-9 min. Furthermore, a comparison study revealed that the CoFe2O4/CdS nanocomposite is a more efficient sonocatalyst than pure CdS; thus, adopting the nanocomposite approach is an excellent means to improve the sonoactivity of CdS. Moreover, the magnetic properties displayed by the CoFe2O4/CdS nanocomposite allow easy retrieval of the catalyst from the reaction mixture for subsequent uses.

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Methanol-to-olefin induction reaction over SAPO-34 You Zhou, Liang Qi, Yingxu Wei, Cuiyu Yuan, Mozhi Zhang, Zhongmin Liu 2016, 37 (9):  1496-1501.  DOI: 10.1016/S1872-2067(15)61110-X Abstract ( 611 )   [Full Text(HTML)] () PDF (417KB) ( 1175 )   The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system. We found that the whole induction period could be divided into three reaction stages. Further investigation of the reaction kinetics revealed that this induction reaction behavior was different from that over H-ZSM-5 catalyst. Compared with the H-ZSM-5, the generation of initial active centers is easier over SAPO-34 because of its limited diffusivity and the spatial confinement effect of the cages. However, the autocatalysis reaction stage is difficult over SAPO-34 because of the continuous formation of inactive methyladamantanes.

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Sustainable synthesis of ammonium nickel molybdate for hydrodesulfurization of dibenzothiophene Huan Liu, Changlong Yin, Hongyu Zhang, Chenguang Liu 2016, 37 (9):  1502-1512.  DOI: 10.1016/S1872-2067(16)62453-1 Abstract ( 358 )   [Full Text(HTML)] () PDF (1581KB) ( 1424 )   This paper reports a sustainable, water-assisted, solid-state method for synthesizing ammonium nickel molybdate((NH4)HNi2(OH)2(MoO4)2, ANM), a precursor for an unsupported hydrodesulfurization(HDS) catalyst. The associated ANM formation mechanism is also discussed. The synthesis route consists of physical mixing of the raw materials, water-assisted grinding and heating. The formation mechanism involves replacement of a Mo atom by a Ni atom, generating the metastable intermediate(NH4)4(NiH6Mo6O24)·5H2O. Heating of this intermediate at 120℃ removes the added water and produces ANM. Catalysts prepared by this method exhibit almost the same physicochemical properties and catalytic performance during the HDS of dibenzothiophene as materials made from ANM synthesized by a chemical precipitation procedure. Compared with traditional hydrothermal or chemical precipitation methods, this water-assisted, solid-state synthesis provides several significant advantages, including simplifying the synthetic procedure, reducing waste and energy costs and increasing product yields. These features will be highly important with regard to allowing the application of ANM in industrial-scale processes involving HDS reactions. This waterassisted, solid-state strategy can also be extended to the synthesis of isomorphous compounds such as ammonium cobalt(zinc and copper) molybdate.

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Effect of promoters on the selective hydrogenolysis of glycerol over Pt/W-containing catalysts Jia Wang, Nian Lei, Chaojun Yang, Yang Su, Xiaochen Zhao, Aiqin Wang 2016, 37 (9):  1513-1520.  DOI: 10.1016/S1872-2067(16)62479-8 Abstract ( 497 )   [Full Text(HTML)] () PDF (579KB) ( 998 )   Diverse promoters, including noble metals(such as Ru, Ir and Rh) and transition metal oxides(such as Re, La, Fe, Zr, Sn and Ce oxides) were introduced into Pt/WOx and Pt/WOx/Al2O3 catalysts to investigate the ability of these promoters to modify activity and selectivity during glycerol hydrogenolysis to 1,3-propanediol. Among these, La exhibited the greatest promotional effect; the introduction of 0.1% La to the Pt/WOx improved activity, selectivity and stability, although the significant increase in selectivity came at the cost of a slight activity loss in the case of the Pt/WOx/Al2O3 catalyst. Transmission electron microscopy, high angle annular dark field scanning tunneling electron microscopy and NH3-temperature programmed desorption all demonstrated that the introduction of La generates a greater quantity of acidic sites on the catalyst surface, and that the majority of the La species are associated with Pt particles. Most of the other additives resulted in only minimal improvements or even detrimental effects with regard to both activity and selectivity, although some appear to improve the stability of the catalyst.

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Promotional effects of Er incorporation in CeO2(ZrO2)/TiO2 for selective catalytic reduction of NO by NH3 Qijie Jin, Yuesong Shen, Shemin Zhu, Xihong Li, Min Hu 2016, 37 (9):  1521-1529.  DOI: 10.1016/S1872-2067(16)62450-6 Abstract ( 524 )   [Full Text(HTML)] () PDF (660KB) ( 870 )   A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method. The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determine the appropriate Er dosage. The catalysts were characterized using X-ray diffraction, N2 adsorption, NH3 temperature-programmed desorption, H2 temperature-programmed reduction, photoluminescence spectroscopy, electron paramagnetic resonance spectroscopy, and X-ray photoelectron spectroscopy. The results showed that the optimum Er/Ce molar ratio was 0.10; this catalyst had excellent resistance to catalyst poisoning caused by vapor and sulfur and gave more than 90% NO conversion at 220-395℃ and a gas hourly space velocity of 71 400 h-1. Er incorporation increased the Ti3+ concentrations, oxygen storage capacities, and oxygen vacancy concentrations of the catalysts, resulting in excellent catalytic performance. Er incorporation also decreased the acid strength and inhibited growth of TiO2 and CeO2 crystal particles, which increased the catalytic activity. The results show that high oxygen vacancy concentrations and oxygen storage capacities, large amounts of Ti3+, and low acid strengths give excellent SCR activity.

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Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether Meixia Wang, Shouying Huang, Jing Lü, Zaizhe Cheng, Ying Li, Shengping Wang, Xinbin Ma 2016, 37 (9):  1530-1538.  DOI: 10.1016/S1872-2067(16)62484-1 Abstract ( 648 )   [Full Text(HTML)] () PDF (1024KB) ( 1541 )   Among the reactions catalyzed by zeolites there are some that exhibit high selectivity due to the spatial confinement effect of the zeolite framework. Tailoring the acidity, particularly the distribution and location of the Brönsted acid sites in the zeolite is effective for making it a better catalyst for these reactions. We prepared a series of H-mordenite(H-MOR) samples by varying the composition of the sol-gel, using different structure directing agents and post-treatment. NH3-TPD and IR characterization of adsorbed pyridine were employed to determine the amount of Brönsted acid sites in the 8-membered ring and 12-membered ring channels. It was shown that controlled synthesis was a promising approach to improve the concentration of Brönsted acid sites in MOR, even with a low Al content. Using an appropriate composition of Si and Al in the sol-gel favored a higher proportion of Brönsted acid sites in the 8-membered ring channels. HMI as a structure-direct agent gave an obvious enrichment of Brönsted acid sites in the 8-membered ring. Carbonylation of dimethyl ether was used as a probe reaction to examine the modification of the acid properties, especially the Brönsted acid sites in the 8-membered ring channels. There was a linear relationship between methyl acetate formation and the number of Brönsted acid sites in the 8-membered ring channels, demonstrating the successful modification of acid properties. Our results provide information for the rational design and modification of zeolites with spatial constraints.

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Enantioselective epoxidation of unfunctionalized olefins by Jacobsen's catalyst immobilized on amino-modified ZnPS-PVPA Jing Huang, Yan luo, Jiali Cai 2016, 37 (9):  1539-1549.  DOI: 10.1016/S1872-2067(16)62489-0 Abstract ( 382 )   [Full Text(HTML)] () PDF (1425KB) ( 815 )   Catalytic asymmetric epoxidation of alkenes is a powerful method for the synthesis of chiral organic compounds. A recyclable chiral Jacobsen's catalyst immobilized on ZnPS-PVPA on diamines gave high catalytic activity(conversion > 99%, ee > 99%) in the asymmetric epoxidations of unfunctionalized olefins. The synergistic effect of the support ZnPS-PVPA and the linkage as well as chiral salen Mn center contributed to the chirality of the product. The stability(recycled nine times) and the ease of use in large scale reactions(200 times scale) indicated a catalyst useful for industrial use.

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Thiol-free route to diaryl sulfides by Cu catalyzed coupling of sodium thiosulfate with aryl halides Najmeh Nowrouzi, Mohammad Abbasi, Hadis Latifi 2016, 37 (9):  1550-1554.  DOI: 10.1016/S1872-2067(16)62486-5 Abstract ( 457 )   [Full Text(HTML)] () PDF (407KB) ( 921 )   A method for the synthesis of diaryl sulfides from aryl halides in polyethylene glycol was reported. Inodorous Na2S2O3·5H2O, which is readily available as a stable salt, is an effective source of sulfur in the presence of CuI as catalyst.

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One-step synthesis of Pt@ZIF-8 catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol Chuang Li, Mingming Zhang, Xin Di, Dongdong Yin, Wenzhen Li, Changhai Liang 2016, 37 (9):  1555-1561.  DOI: 10.1016/S1872-2067(16)62497-X Abstract ( 837 )   [Full Text(HTML)] () PDF (10853KB) ( 1870 )   A catalyst consisting of platinum nanoparticles on a ZIF-8 support(Pt@ZIF-8) was synthesized in a straightforward one-step procedure, by adding a nanostructured platinum sol during the formation of ZIF-8 at room temperature. Pt@ZIF-8 was highly porous and well crystallized. The Pt nanoparticles were well dispersed within the ZIF-8 support. In the hydrogenation of 1,4-butynediol, Pt@ZIF-8 exhibited high activity, excellent selectivity for 1,4-butenediol of greater than 94%, and reusability. The Pt@ZIF-8 catalyst did not require further additives. The favorable catalytic performance was attributed primarily to the modification of the ZIF-8 support by the platinum nanoparticles.

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Nitrogen-doped ordered mesoporous carbon: Effect of carbon precursor on oxygen reduction reactions Xiao-hua Li, Kai Wan, Quan-bing Liu, Jin-hua Piao, Yu-ying Zheng, Zhen-xing Liang 2016, 37 (9):  1562-1568.  DOI: 10.1016/S1872-2067(16)62498-1 Abstract ( 602 )   [Full Text(HTML)] () PDF (572KB) ( 1015 )   Aniline, pyrrole and phenanthroline, which have different nitrogen compositions, are used as carbon precursors to synthesize nitrogen-doped ordered mesoporous carbons(NOMCs) by the nanocasting method. The effect of the precursor on the resultant NOMC is extensively investigated by nitrogen adsorption-desorption measurements, scanning electron microscopy, X-ray photoelectron spectroscopy(XPS), cyclic voltammetry and rotating ring-disk electrode measurements. Salient findings are as follows. First, the precursor has a significant influence on the specific surface area and textural properties. The NOMC materials derived from pyrrole(C-PY-900: 765 m2/g) and phenanthroline(C-Phen-900: 746 m2/g) exhibit higher specific surface areas than the aniline analog(C-PA-900: 569 m2/g). Second, the XPS results indicate that the total nitrogen content(ca. 3.1-3.3 at%) is similar for the three carbon sources, except for a slight difference in the nitrogen configuration. Furthermore, the content of the nitrogen-activated carbon atoms is found to closely depend on the precursor, which is the highest for the phenanthroline-derived carbon. Third, the electrochemical results reveal that the electrocatalytic activity follows in the order C-PA-900 < C-PY-900 < C-Phen-900, confirming that the nitrogen-activated carbon atoms are the active sites for the oxygen reduction reaction(ORR). In summary, the precursor has considerable influence on the composition and textural properties of the NOMC materials, of which the ORR electrocatalytic activity can be enhanced through optimization of the NOMCs.

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Chemoselective transfer hydrogenation to nitroarenes mediated by oxygen-implanted MoS2 Chaofeng Zhang, Xu Wang, Mingrun Li, Zhixin Zhang, Yehong Wang, Rui Si, Feng Wang 2016, 37 (9):  1569-1578.  DOI: 10.1016/S1872-2067(16)62504-4 Abstract ( 434 )   [Full Text(HTML)] () PDF (2151KB) ( 1231 )   We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst(O-MoS2). O-MoS2 was prepared by incomplete sulfiidation and reduction of an ammonium molybdate precursor. A number of Mo-O bonds were implanted in the as-synthesized ultrathin O-MoS2 nanosheets. As a consequence of the different coordination geometries of O(MoO2) and S(MoS2), and lengths of the Mo-O and Mo-S bonds, the implanted Mo-O bonds induced obvious defects and more coordinatively unsaturated(CUS) Mo sites in O-MoS2, as confirmed by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and extended X-ray absorption fine structure characterization of various MoS2-based materials. O-MoS2 with abundant CUS Mo sites was found to efficiently catalyze the chemoselective reduction of nitroarenes to arylamines.