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Chinese Journal of Catalysis
2015, Vol. 36, No. 2
Online: 21 January 2015

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Table of Contents for VOL.36 No.2 2015, 36 (2):  0-0.  Abstract ( 189 )   PDF (1677KB) ( 471 )

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Oxide-supported Aun(SR)m nanoclusters for CO oxidation Weili Li, Qingjie Ge 2015, 36 (2):  135-138.  DOI: 10.1016/S1872-2067(14)60233-3 Abstract ( 387 )   [Full Text(HTML)] () PDF (722KB) ( 593 )

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Layered double hydroxide and related catalysts for hydrogen production and a biorefinery Wei Wang, Zhenxin Xu, Zhanglong Guo, Chengfa Jiang, Wei Chu 2015, 36 (2):  139-147.  DOI: 10.1016/S1872-2067(14)60229-1 Abstract ( 446 )   [Full Text(HTML)] () PDF (1359KB) ( 699 )   Layered double hydroxides (LDHs) have received much attention for their unique properties. As solid catalysts, LDHs and their derivates have been widely studied and applied for their excellent catalytic performance. Several synthesis methods of LDHs were briefly introduced, and the applications of LDHs and related catalysts for hydrogen production and a biorefinery were emphasized in this article. The prospects for LDH related compounds in the synthesis of new materials and their catalytic application in green catalysis systems were also presented.

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Pd confined in grass-like graphene layers on monolithic cordierite as the catalyst for hydrogenation of 4-carboxybenzaldehyde Gonggang Liu, Linyu Yu, Yuchao Zhu, Xiaoguang Guo, Yonghua Zhou, Hongqi Ye 2015, 36 (2):  148-152.  DOI: 10.1016/S1872-2067(14)60256-4 Abstract ( 243 )   [Full Text(HTML)] () PDF (1200KB) ( 554 )   Pd nanoparticles were confined in grass-like graphene layers on monolithic cordierite by using NH2-ion liquid C7H14ClN3 functionalized graphene sheets. These were used as the catalyst for the hydrogenation of 4-carboxybenzaldehyde. The catalyst exhibited high stability compared to Pd/activated carbon catalyst due to the inhibition of Pd leaching and aggregation.

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Controllable oxidation for oil recovery: Low temperature oxidative decomposition of heavy oil on a MnO2 catalyst Cheng Fan, Qiang Zhang, Fei Wei 2015, 36 (2):  153-159.  DOI: 10.1016/S1872-2067(14)60236-9 Abstract ( 265 )   [Full Text(HTML)] () PDF (553KB) ( 587 )   Heavy oil is a readily available alternative energy resource with a reserve that is more than twice that of conventional light oil. In situ combustion is one of the most promising strategies for heavy oil exploitation, and the modulating of the oxidation behavior of heavy oil is an efficient way to expand the applicability of the in situ combustion method. MnO2 nanoparticles were employed to facilitate the cracking of heavy compounds, promote heat production, and improve recovery efficiency. The oxidative decomposition rate of heavy oil was doubled in the low temperature interval, and the heat release rate was accelerated in the high temperature interval. The increased weight loss at low temperature was attributed to the decomposition of heavy components. The detection of incomplete oxidation products by mass spectroscopy under excessive oxygen flow at high temperature indicated a diffusion controlled process of oil combustion. The same amount of CO2 from the combustion of less fuel demonstrated an increased oxidation degree of the products. The apparent activation energies of the oxidation reactions were decreased by 10-30 kJ/mol at low temperature and 20-40 kJ/mol at high temperature by the addition of MnO2. MnO2 can render in situ combustion more feasible for various oil reservoirs, and is also promising for other thermal recovery processes for improved oil recovery.

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Supported Au-Ni nano-alloy catalysts for the chemoselective hydrogenation of nitroarenes Haisheng Wei, Xing Wei, Xiaofeng Yang, Guangzhao Yin, Aiqin Wang, Xiaoyan Liu, Yanqiang Huang, Tao Zhang 2015, 36 (2):  160-167.  DOI: 10.1016/S1872-2067(14)60254-0 Abstract ( 263 )   [Full Text(HTML)] () PDF (1065KB) ( 747 )   A modified two-step approach was developed for the synthesis of uniform and highly dispersed Au-Ni alloy nanoparticles on a silica support. The supported Au-Ni alloy nanoparticles were investigated for the chemoselective hydrogenation of substituted nitroarenes, which showed a strong synergistic effect between Au and Ni. The best catalyst was AuNi3/SiO2 that afforded a selectivity to 3-vinylaniline of 93.0% at a 3-nitrostyrene conversion of 90.8% after 70 min under mild conditions.

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Rh-PPh3-polymer@mesosilica composite catalyst for the hydroformylation of 1-octene Xiaoming Zhang, Shengmei Lu, Mingmei Zhong, Yaopeng Zhao, Qihua Yang 2015, 36 (2):  168-174.  DOI: 10.1016/S1872-2067(14)60228-X Abstract ( 356 )   [Full Text(HTML)] () PDF (834KB) ( 580 )   Rh-PPh3-polymer@mesosilica composites were prepared by the polymerization of mixtures of divinylbenzene (DVB) and 4-vinyl-triphenylphosphine monomer in the nanopores of mesoporous silicas followed by coordination with Rh(acac)(CO)2 (acac =acetylacetonate). These catalysts were characterized by XRD, N2 sorption, TEM, FT-IR, and TG, and could efficiently catalyze the hydroformylation of 1-octene with higher activity than a pure polymer catalyst because of their high surface area and large pore volume, which were beneficial for the exposure of active sites and mass transport. Through the control of pore size and pore connectivity by using different mesoporous silica (MCM-41, SBA-15, and FDU-12), the activity and selectivity can be controlled. Rh-PPh3-polymer@FDU-12 with a cage-like mesostrucuture showed lower activity but slightly higher selectivity than the catalyst with a 2-D hexagonal mesostructure (Rh-PPh3-polymer@SBA-15 or Rh-PPh3-polymer@MCM-41). By varying the polymer content in the nanopores of the mesosilica, the activity and selectivity (92%-96%) can also be tuned. The solid composite catalyst can be recycled without loss of activity, but a decrease in selectivity was observed.

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Elucidation of oxygen reduction reaction pathway on carbon-supported manganese oxides Luhua Jiang, Qiwen Tang, Jing Liu, Gongquan Sun 2015, 36 (2):  175-180.  DOI: 10.1016/S1872-2067(14)60249-7 Abstract ( 337 )   [Full Text(HTML)] () PDF (589KB) ( 595 )   The oxygen reduction reaction (ORR) is a complex process. This is particularly the case for carbon-supported electrocatalysts in alkaline electrolytes, because carbon can catalyze the ORR via a two-electron transfer to generate hydroperoxide (HO2-), which subsequently undergoes either chemical decomposition to generate O2 and OH- (HODR) or electrochemical reduction to OH- (HORR). In this study, we elucidated the ORR pathway on a series of carbon-supported manganese oxides, which have been extensively studied as electrocatalysts in alkaline electrolytes. A comparison of the turnover frequencies of the HODR and HORR showed that although an apparent four-electron transfer process was identified when the HO2- yield was measured using the rotating ring disk electrode technique, the real ORR pathway involved a two-electron transfer process to generate HO2-, with subsequent chemical decomposition of HO2-. These results will help us to understand the intrinsic catalytic behavior of carbon-supported transition-metal oxides for the ORR in alkaline electrolytes.

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A first principles study of the energetics and core level shifts of anion-doped TiO2 photocatalysts Wuchen Ding, Weixue Li 2015, 36 (2):  181-187.  DOI: 10.1016/S1872-2067(14)60165-0 Abstract ( 389 )   [Full Text(HTML)] () PDF (536KB) ( 601 )   We present a comprehensive and improved density functional theory (DFT) calculation of anion-doped (anion = B, C, N, F, P, S) anatase and rutile TiO2. The first part is a first principles calculation of the core level shifts (CLS) for various anion dopants in both anatase and rutile TiO2. The CLS results revealed that interstitial N had a higher N 1s binding energy than substitutional N, which agreed well with experimental results. The calculation also showed that for B-, C-, S-, and P-doped TiO2, the interstitial dopant had an energy that is higher than that of a substitutional dopant, which is similar to N-doped TiO2. However, for F-doped TiO2, the energy of the substitutional dopant is higher, and this is irrespective of the TiO2 crystallography. We also calculated the enthalpy of doping and found that the substitutional dopant had a higher enthalpy than the interstitial dopant. The results revealed that substitutional doping required severe experimental conditions, whereas interstitial doping only requires modest wet chemistry conditions.

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Titania-supported Pt catalyst reduced with HCHO for HCHO oxidation under mild conditions Huayao Chen, Zebao Rui, Hongbing Ji 2015, 36 (2):  188-196.  DOI: 10.1016/S1872-2067(14)60192-3 Abstract ( 443 )   [Full Text(HTML)] () PDF (780KB) ( 895 )   A series of Pt/TiO2(P25) catalysts were prepared by both impregnation (IM) and deposition-precipitation (DP) methods followed by reduction using either a HCHO solution or a H2 stream. The effects of the preparation and reduction conditions and the Pt loading level on structural properties and performance during HCHO oxidation were then studied based on the assessment of adsorbed species on the catalyst surfaces using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results indicated that Pt/P25 prepared by DP and reduced with HCHO exhibited homogeneously dispersed Pt nanoparticles with appropriate particle size in addition to a high concentration of chemisorbed oxygen, and also showed high activity for HCHO oxidation. A HCHO conversion of 98% with stable performance over more than 100 h was achieved over Pt/P25 produced using DP and HCHO reduction at 30 ℃, even with a 0.4% Pt loading. Pt/P25 synthesized using DP with H2 reduction was less effective at promoting formate decomposition and thus showed less HCHO oxidation activity, likely because of lower levels of chemisorbed oxygen. The Pt/P25 made using IM and H2 reduction had the highest amount of chemisorbed oxygen but also the largest Pt particles, resulting in the lowest activity for both the formation of formate species and formate decomposition into CO species, and thus showed low HCHO oxidation activity.

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Influence of support properties on H2 selective catalytic reduction activities and N2 selectivities of Pt catalysts Xinyan Li, Xiaoxiao Zhang, Yongzhen Xu, Ye Liu, Xinping Wang 2015, 36 (2):  197-203.  DOI: 10.1016/S1872-2067(14)60197-2 Abstract ( 375 )   [Full Text(HTML)] () PDF (648KB) ( 690 )   The selective catalytic reduction of NOx by H2 (H2-SCR) was studied over Pt/MgO, Pt/γ-Al2O3, Pt/ZrO2, and Pt/HZSM-5 catalysts. The H2-SCR activities and N2 selectivities of the catalysts were strongly influenced by the amounts of Pt metal in the catalysts and the NOx adsorption capacities of the supports. The acidic surface of HZSM-5 increased the amount of metallic Pt on the support, decreasing the NOx adsorption capacity, resulting in much higher H2-SCR activity and N2 selectivity. The inferior activities of Pt/MgO and Pt/γ-Al2O3 are ascribed to the low amounts of metallic Pt and large NOx adsorption capacities of the supports as a result of their basic surfaces. Based on these results and in situ Fourier transform infrared spectroscopic studies of the reaction, it is proposed that the reduction products of nitrite/nitrate species at the Pt/support interface are N2 or N2O, depending on the relative amounts of active hydrogen and nitrous species involved in the reduction.

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Simple primary amine catalyzed aerobic reductive ring-cleavage of isoxazole motif Zhongkui Zhao, Renzhi Li, Yu Li, Guiru Wang 2015, 36 (2):  204-208.  DOI: 10.1016/S1872-2067(14)60200-X Abstract ( 414 )   [Full Text(HTML)] () PDF (523KB) ( 473 )   A clean and highly efficient catalytic aerobic reductive ring-cleavage of 3-methylanthra[1,2-c]isoxazole-6,11-dione to 1-amino-2-acetylanthraquinone was performed using simple organic amines as organocatalysts and water as a green reaction medium. This method provides a new clean transformation of isoxazole-containing compounds to the corresponding ortho-amino ketones. The catalytic performance of various organic amines was carefully screened, and simple organic primary amines were found to be promising practical catalysts with outstanding catalytic performance. Isopropylamine as the organocatalyst gave 97.2% conversion of 3-methylanthra[1,2-c]isoxazole-6,11-dione, with 97.2% selectivity to 1-amino-2-acetylanthraquinone, in the presence of oxygen only, using 1 equiv. of hydrazine hydrate at room temperature for 3 h. A possible mechanism is also proposed.

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Amorphous metal-aluminophosphate catalysts for aldol condensation of n-heptanal and benzaldehyde to jasminaldehyde A. Hamza, N. Nagaraju 2015, 36 (2):  209-215.  DOI: 10.1016/S1872-2067(14)60206-0 Abstract ( 341 )   [Full Text(HTML)] () PDF (498KB) ( 678 )   Amorphous aluminophosphate (AlP) and metal-aluminophosphates (MAlPs, where M = 2.5 mol% Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of n-heptanal and benzaldehyde were investigated. The nitrogen adsorption-desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature-programmed desorption of NH3 and CO2 revealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X-ray amorphous and powder X-ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M-O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75% with a yield of 65%. The best conversion of n-heptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.

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Improved hydrogen evolution on glassy carbon electrode modified with novel Pt/cetyltrimethylammonium bromide nanoscale aggregates Jahan-Bakhsh Raoof, Sayed Reza Hosseini, Seyedeh Zeinab Mousavi-Sani 2015, 36 (2):  216-220.  DOI: 10.1016/S1872-2067(14)60207-2 Abstract ( 215 )   [Full Text(HTML)] () PDF (718KB) ( 769 )   A novel, cost-effective, and simple electrocatalyst based on a Pt-modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Amphiphilic CTAB molecules were adsorbed on GCE by immersion in a CTAB solution. The positively charged hydrophilic layer, which consisted of small aggregates of average size less than 100 nm, was used for accumulation and complexation of [PtCl6]2- anions by immersing the electrode in K2PtCl6 solution. The modified electrode was characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, impedance spectroscopy, and electrochemical methods. The electrocatalytic activity of the Pt particles in the hydrogen evolution reaction (HER) was investigated. The results show that the CTAB surfactant enhances the electrocatalytic activity of the Pt particles in the HER in acidic solution.

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Highly photostable palladium-loaded TiO2 nanotubes and the active species in the photodegradation of methyl orange Xiaojing Hu, Yukun Shi, Baolin Zhu, Shoumin Zhang, Weiping Huang 2015, 36 (2):  221-228.  DOI: 10.1016/S1872-2067(14)60213-8 Abstract ( 379 )   [Full Text(HTML)] () PDF (1171KB) ( 742 )   Highly photostable palladium-loaded TiO2 nanotubes (Pd/TNTs) were prepared by a simple photo-decomposition method and characterized by inductively coupled plasma, X-ray diffraction, UV-visible light diffuse reflectance spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy, N2 adsorption-desorption, and photocurrent measurement. TEM images showed that the samples had a tubular structure. XPS results revealed that most of the palladium was present as Pd0. The photocatalytic performance was evaluated by monitoring the catalytic activity for the degradation of methyl orange solution under both UV and simulated sunlight irradiation. Pd/TNTs with 0.3 wt% Pd displayed higher activity than P25. The active species in the photocatalytic process were investigated by using different types of active species scavengers. hvb+ was the major reactive species in the photodegradation over the Pd/TNTs.

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A highly efficient Rh-modified Pd/Al2O3 close-coupled catalyst Ruimei Fang, Yajuan Cui, Sijie Chen, Hongyan Shang, Zhonghua Shi, Maochu Gong, Yaoqiang Chen 2015, 36 (2):  229-236.  DOI: 10.1016/S1872-2067(14)60214-X Abstract ( 367 )   [Full Text(HTML)] () PDF (561KB) ( 610 )   The close-coupled catalysts Pd/Al2O3 and Rh-Pd/Al2O3 were prepared by the impregnation method and characterized by H2 temperature-programmed reduction, CO chemisorption, and X-ray photoelectron spectroscopy. Both overall catalytic activity and specific reactions associated with C3H8 elimination were assessed. The light-off temperature and complete conversion temperature decreased by 23 and 18 ℃, respectively, upon addition of Rh to the Pd/Al2O3 catalyst. The addition of Rh promotes the catalytic activity during C3H8 reactions, particularly in the presence of NO. The introduction of Rh not only inhibits sintering of PdOx and increases the dispersion of these same species, but also changes the electronic state of the PdOx in the catalyst.

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I2/ionic liquid as a highly efficient catalyst for per-O-acetylation of sugar under microwave irradiation Xingquan Xiong, Chao Yi, Qian Han, Lin Shi, Sizhong Li 2015, 36 (2):  237-243.  DOI: 10.1016/S1872-2067(14)60219-9 Abstract ( 251 )   [Full Text(HTML)] () PDF (606KB) ( 639 )   A practical and highly efficient approach was developed to synthesize peracetylated sugar derivatives using a recyclable iodine/PEG400-based ionic liquid catalyst (I2/IL). The peracetylated sugars were readily obtained in a few minutes in excellent yields (90%-99%, 13 examples) on a multi-gram scale (50.0 mmol) by the reaction of sugar and acetic anhydride under microwave irradiation in the absence of a volatile organic solvent. The desired product was easily obtained by simple extraction with toluene from the reaction mixture, and I2/ILs can be readily recovered and reused at least six times without obvious loss in the yield. When the scale of the per-O-acetylation reaction was increased to 50.0 mmol, the desired product was still obtained in 90% yield after five recycles.

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Preparation of magnetic nanocomposites of solid acid catalysts and their applicability in esterification Huanwang Jing, Xiaomei Wang, Yong Liu, Anqi Wang 2015, 36 (2):  244-251.  DOI: 10.1016/S1872-2067(14)60221-7 Abstract ( 345 )   [Full Text(HTML)] () PDF (1156KB) ( 771 )   Solid acid catalysts are superior to traditional liquid acids because they are noncorrosive, environmentally benign, and recyclable. In addition, nano-magnetic solid acid catalysts are preferable as they exhibit large specific surface areas together with good acidity and are also readily separated from the post-reaction mixture. Three component nano-magnetic solid catalysts TiO2-Al2O3-Fe3O4 and CeO2-Al2O3-Fe3O4 and a four component catalyst ZrO2-Al2O3-CeO2-Fe3O4 were synthesized by a co-precipitation method and were subsequently characterized by inductively coupled plasma-atomic emission spectroscopy, Brunauer-Emmett-Teller surface area analysis, X-ray diffraction, transmission electron microscopy, and thermal gravimetric analysis. Their catalytic activities were also evaluated in the esterification reaction of acetic acid with n-butanol. The results demonstrated that these rare earth-based magnetic nanocomposites exhibited good catalytic activity.

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Fischer-Tropsch synthesis: Characterizing and reaction testing of Co2C/SiO2 and Co2C/Al2O3 catalysts Yanpeng Pei, Yunjie Ding, Juan Zang, Xiangen Song, Wenda Dong, Hejun Zhu, Tao Wang, Weimiao Chen 2015, 36 (2):  252-259.  DOI: 10.1016/S1872-2067(14)60179-0 Abstract ( 331 )   [Full Text(HTML)] () PDF (604KB) ( 874 )   SiO2- and Al2O3-supported Co2C catalysts were prepared by carburizing supported Co precursors with CO. The catalysts were characterized by N2 physisorption, X-ray diffraction and H2 temperature-programmed reduction techniques, and evaluated by the Fischer-Tropsch (F-T) reaction. The results showed that SiO2- and Al2O3-supported Co2C catalysts could be successfully obtained but sufficient carburization time was required. All of the as-prepared supported Co2C catalysts exhibited activity and selectivity towards alcohols. It is considered that surface metallic Co species contributed to the activity, surface Co2C species were responsible for the formation of alcohols, and bulk Co2C species were inert during the F-T reaction.