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    Chinese Journal of Catalysis
    2016, Vol. 37, No. 6
    Online: 30 May 2016

    Cover:

    Environmental pollution is one of the most serious problems that threaten mankind sustainability. The exploitation of new environment-benign materials and the development of green sustainable catalytic processes are ways to tackle the challenges. This special column focuses on “Environmental Catalysis and Materials”, and featured on the cover is the review article “Recent advances in bismuth- containing photocatalysts with heterojunctions” on pages 780–791.

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    Table of Contents
    Table of Contents for VOL.37 No.6
    2016, 37 (6):  0-0. 
    Abstract ( 209 )   PDF (3789KB) ( 436 )  
    Editorial
    Preface to the Special Issue on Environmental Catalysis and Materials
    Shuang-Feng Yin, Chak-Tong Au
    2016, 37 (6):  779-779.  DOI: 10.1016/S1872-2067(15)61120-2
    Abstract ( 320 )   [Full Text(HTML)] () PDF (213KB) ( 795 )  
    Reviews
    Recent advances in bismuth-containing photocatalysts with heterojunctions
    Lang Chen, Jie He, Ying Liu, Peng Chen, Chak-Tong Au, Shuang-Feng Yin
    2016, 37 (6):  780-791.  DOI: 10.1016/S1872-2067(15)61061-0
    Abstract ( 722 )   [Full Text(HTML)] () PDF (1320KB) ( 1761 )  

    Photocatalysis has received much attention owing to current energy and environmental crises. The use of an appropriate photocatalyst is important to a photocatalytic process. The development of photocatalysts that absorb light over a wide range of wavelengths and efficiently separate charge carriers remains a challenge and hot research topic. With strong visible-light-absorption ability, bismuth-containing photocatalysts are of great interest to scientists. However, measures have to be taken to enhance the light absorption efficiency and to lessen the problem of the recombination of charge carriers. Known approaches are the formation of heterojunctions through (1) loading of a noble metal, (2) semiconductor combination, (3) metal and nonmetal doping, (4) carbon-based material modification, and (5) Bi metal loading. The present review summarizes recent advances in this respect. Finally, the future development and potential applications of bismuth-containing photocatalysts with heterojunctions are briefly discussed.

    Recent developments in visible-light photocatalytic degradation of antibiotics
    Di Li, Weidong Shi
    2016, 37 (6):  792-799.  DOI: 10.1016/S1872-2067(15)61054-3
    Abstract ( 1377 )   [Full Text(HTML)] () PDF (2867KB) ( 2402 )  

    With the significant discharge of antibiotic wastewater into the aquatic and terrestrial ecosystems, antibiotic pollution has become a serious problem and presents a hazardous risk to the environment. To address such issues, various investigations on the removal of antibiotics have been undertaken. Photocatalysis has received tremendous attention owing to its great potential in removing antibiotics from aqueous solutions via a green, economic, and effective process. However, such a technology employing traditional photocatalysts suffers from major drawbacks such as light absorption being restricted to the UV spectrum only and fast charge recombination. To overcome these issues, considerable effort has been directed towards the development of advanced visible light-driven photocatalysts. This mini review summarises recent research progress in the state-of-the-art design and fabrication of photocatalysts with visible-light response for photocatalytic degradation of antibiotic wastewater. Such design strategies involve the doping of metal and non-metal into ultraviolet light-driven photocatalysts, development of new semiconductor photocatalysts, construction of heterojunction photocatalysts, and fabrication of surface plasmon resonance-enhanced photocatalytic systems. Additionally, some perspectives on the challenges and future developments in the area of photocatalytic degradation of antibiotics are provided.

    Adsorptive and catalytic properties in the removal of volatile organic compounds over zeolite-based materials
    Ling Zhang, Yuexin Peng, Juan Zhang, Long Chen, Xiangju Meng, Feng-Shou Xiao
    2016, 37 (6):  800-809.  DOI: 10.1016/S1872-2067(15)61073-7
    Abstract ( 986 )   [Full Text(HTML)] () PDF (1020KB) ( 2069 )  

    Volatile organic compounds (VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use of activated carbons as adsorbents and oxide-supported metals as catalysts. Notably, activated carbons easily adsorb water, which strongly hinders the adsorption of VOCs; conventional oxides typically possess relatively low surface areas and random pores, which effectively influence the catalytic conversion of VOCs. Zeolites, in contrast with activated carbons and oxides, can be designed to have very uniform and controllable micropores, in addition to tailored wettability properties, which can favor the selective adsorption of VOCs. In particular, zeolites with selective adsorptive properties when combined with catalytically active metals result in zeolite-supported metals exhibiting significantly improved performance in the catalytic combustion of VOCs compared with conventional oxide-supported catalysts. In this review, recent developments on VOC abatement by adsorptive and catalytic techniques over zeolite-based materials have been briefly summarized.

    Bicarbonate activation of hydrogen peroxide: A new emerging technology for wastewater treatment
    Ali Jawad, Zhuqi Chen, Guochuan Yin
    2016, 37 (6):  810-825.  DOI: 10.1016/S1872-2067(15)61100-7
    Abstract ( 717 )   [Full Text(HTML)] () PDF (1116KB) ( 3125 )  

    The serious limitations of available technologies for decontamination of wastewater have compelled researchers to search for alternative solutions. Catalytic treatment with hydrogen peroxide, which appears to be one of the most efficient treatment systems, is able to degrade various organics with the help of powerful ·OH radicals. This review focuses on recent progress in the use of bicarbonate activated hydrogen peroxide for wastewater treatment. The introduction of bicarbonate to pollutant treatment has led to appreciable improvements, not only in process efficiency, but also in process stability. This review describes in detail the applications of this process in homogeneous and heterogeneous systems. The enhanced degradation, limited or lack of leaching during heterogeneous degradation, and prolonged catalysts stability during degradation are salient features of this system. This review provides readers with new knowledge regarding bicarbonate, including the fact that it does not always harm pollutant degradation, and can significantly benefit degradation under some conditions.

    Recent advances in metal-free catalysts for the synthesis of cyclic carbonates from CO2 and epoxides
    Dong-Hui Lan, Na Fan, Ying Wang, Xian Gao, Ping Zhang, Lang Chen, Chak-Tong Au, Shuang-Feng Yin
    2016, 37 (6):  826-845.  DOI: 10.1016/S1872-2067(15)61085-3
    Abstract ( 807 )   [Full Text(HTML)] () PDF (1061KB) ( 1892 )  

    The aim of “green chemistry” and “atom economy” is to utilize carbon dioxide and replace harmful reactants such as CO and phosgene for the production of cyclic carbonates. In this paper, metal-free catalysts including organic bases, ionic liquids, supported catalysts, organic copolymers and carbon materials for the synthesis of cyclic carbonates by the cycloaddition of carbon dioxide to epoxides are reviewed. Recent advances in the design of the catalysts and the understanding of the reaction mechanism are summarized and discussed. The synergistic effects of organic bases and hydrogen bond donors, organic bases and nucleophilic anions, hydrogen bond donors and nucleophilic anions and active components and supports are highlighted. The challenge is to develop metal-free catalysts suitable for carbon dioxide capture and fixation. The ultimate goal is to synthesize cyclic carbonates in a flow reactor directly using carbon dioxide from industrial flue gas at ambient temperature and atmospheric pressure. By using synergetic effects, a multi-functional approach can meet the design strategy of metal-free catalysts for carbon dioxide adsorption and activation as well as epoxide ring opening.

    Articles
    Preparation of three-dimensional interconnected mesoporous anatase TiO2-SiO2 nanocomposites with high photocatalytic activities
    Weiyang Dong, Youwei Yao, Yaojun Sun, Weiming Hua, Guoshun Zhuang
    2016, 37 (6):  846-854.  DOI: 10.1016/S1872-2067(15)61081-6
    Abstract ( 505 )   [Full Text(HTML)] () PDF (989KB) ( 949 )  

    In this article, we report the preparation of a three-dimensional (3D) interconnected mesoporous anatase TiO2-SiO2 nanocomposite. The nanocomposite was obtained by using an ordered two-dimensional (2D) hexagonal mesoporous anatase 70TiO2-30SiO2-950 nanocomposite (crystallized at 950 ℃ for 2 h) as a precursor, NaOH as an etchant of SiO2 via a “creating mesopores in the pore walls” approach. Our strategy adopts mild conditions of creating pores such as diluted NaOH solution, appropriate temperature and solid/liquid ratio, etc. aiming at ensuring the integrities of mesopores architecture and anatase nanocrystals. XRD, TEM and N2 sorption techniques have been used to systematically investigate the physico-chemical properties of the nanocomposites. The results show that the intrawall mesopores are highly dense and uniform (average pore size 3.6 nm), and highly link the initial mesochannels in a 3D manner while retaining mesostructural integrity. There is no significant change to either crystallinity or size of the anatase nanocrystals before and after creating the intrawall mesopores. The photocatalytic degradation rates of rhodamine B (RhB, 0.303 min-1) and methylene blue (MB, 0.757 min-1) dyes on the resultant nanocomposite are very high, which are 5.1 and 5.3 times that of the precursor; even up to 16.5 and 24.1 times that of Degussa P25 photocatalyst, respectively. These results clearly demonstrate that the 3D interconnected mesopores structure plays an overwhelming role to the increments of activities. The 3D mesoporous anatase TiO2-SiO2 nanocomposite exhibits unexpected-high degradation activities to RhB and MB in the mesoporous metal oxide-based materials reported so far. Additionally, the nanocomposite is considerably stable and reusable. We believe that this method would pave the way for the preparation of other 3D highly interconnected mesoporous metal oxide-based materials with ultra-high performance.

    Novel visible-light-responding InVO4-Cu2O-TiO2 ternary nanoheterostructure: Preparation and photocatalytic characteristics
    Haibo Feng, Yaping Li, Dongming Luo, Gongrong Tan, Jianbo Jiang, Huimin Yuan, Sanjun Peng, Dong Qian
    2016, 37 (6):  855-862.  DOI: 10.1016/S1872-2067(15)61105-6
    Abstract ( 420 )   [Full Text(HTML)] () PDF (1583KB) ( 948 )  

    A novel visible-light-responding InVO4-Cu2O-TiO2 ternary nanoheterostructure was designed on the basis of the strategy of energy gap engineering and prepared through ordinary wet chemistry methods. The as-prepared nanoheterostructure was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and diffuse reflectance ultraviolet-visible spectroscopy (UV-vis/DRS). The TEM and HRTEM images of 10%InVO4-40%Cu2O-50%TiO2 confirm the formation of nanoheterostructures resulting from contact of the nanosized TiO2, Cu2O and InVO4 in the size of 5-20 nm in diameter. The InVO4-Cu2O-TiO2 nanoheterostructure, when compared with TiO2, Cu2O, InVO4, InVO4-TiO2 and Cu2O-TiO2, shows significant enhancement in the photocatalytic performance for the degradation of methyl orange (MO) under visible-light irradiation. With a 9 W energy-saving fluorescent lamp as the visible-light source, the MO degradation rate of 10%InVO4-40%Cu2O-50%TiO2 reaches close to 90% during 5 h, and the photocatalytic efficiency is maintained at over 90% after six cycles. This may be mainly ascribed to the matched bandgap configurations of TiO2, Cu2O and InVO4, and the formations of two p-n junctions by the p-type semiconductor Cu2O with the n-type semiconductors TiO2 and InVO4, all of which favor spatial photogenerated charge carrier separation. The X-ray photoelectron spectroscopy (XPS) characterization for the used 10%InVO4-40%Cu2O-50%TiO2 reveals that only a small shakeup satellite peak appears for Cu(II) species, implying bearable photocorrosion of Cu2O. This work could provide new insight into the design and preparation of novel visible-light-responding semiconductor composites.

    Synthesis of bionic-macro/microporous MgO-modified TiO2 for enhanced CO2 photoreduction into hydrocarbon fuels
    Fang Wang, Yong Zhou, Ping Li, Libang Kuai, Zhigang Zou
    2016, 37 (6):  863-868.  DOI: 10.1016/S1872-2067(15)61111-1
    Abstract ( 403 )   [Full Text(HTML)] () PDF (766KB) ( 1026 )  

    The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2. The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.

    Multichannel charge separation promoted ZnO/P25 heterojunctions for the photocatalytic oxidation of toluene
    Jiejing Kong, Xiaodong Lai, Zebao Rui, Hongbing Ji, Shengfu Ji
    2016, 37 (6):  869-877.  DOI: 10.1016/S1872-2067(15)61093-2
    Abstract ( 495 )   [Full Text(HTML)] () PDF (2708KB) ( 862 )  

    The fabrication of multicomponent heterojunctions is an effective strategy to improve the performance of TiO2 based photocatalysts. We provide a new strategy for improving the charge separation and photocatalytic performance of ZnO/TiO2 composites by the formation of multichannel charge separated heterojunctions. ZnO/P25 composites were prepared by an incipient wetness impregnation method, and applied for the photocatalytic destruction of gaseous toluene. The ZnO/P25 composites consist of anatase TiO2 (ATiO2), rutile TiO2 (RTiO2) and hexagonal zincite structures. The parasitic phase of ZnO in P25 leads to the formation of ZnO(002)/ATiO2(101)/RTiO2(110) heterojunctions that exhibit enhanced light absorption and improved multichannel electron/hole separation. ZnO/P25 heterojunctions can completely oxidize toluene into CO2 and H2O under ultraviolet light irradiation at room temperature, and show enhanced photocatalytic activity in comparison with P25 owing to the efficient electron-hole separation. Such a multichannel charge separated design strategy may provide new insight into the design of highly effective photocatalysts and their potential technological applications.

    NH3 selective catalytic reduction of NO: A large surface TiO2 support and its promotion of V2O5 dispersion on the prepared catalyst
    Xin Liu, Junhua Li, Xiang Li, Yue Peng, Hu Wang, Xiaoming Jiang, Lanwu Wang
    2016, 37 (6):  878-887.  DOI: 10.1016/S1872-2067(15)61041-5
    Abstract ( 449 )   [Full Text(HTML)] () PDF (1010KB) ( 920 )  

    A titania support with a large surface area was developed, which has a BET surface area of 380.5 m2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction (SCR) performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was >80% from 200 to 450 ℃. The temperature window was 100 ℃ wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.

    Resistance to SO2 poisoning of V2O5/TiO2-PILC catalyst for the selective catalytic reduction of NO by NH3
    Simiao Zang, Guizhen Zhang, Wenge Qiu, Liyun Song, Ran Zhang, Hong He
    2016, 37 (6):  888-897.  DOI: 10.1016/S1872-2067(15)61083-X
    Abstract ( 362 )   [Full Text(HTML)] () PDF (619KB) ( 975 )  

    A titania pillared interlayered clay (Ti-PILC) supported vanadia catalyst (V2O5/TiO2-PILC) was prepared by wet impregnation for the selective catalytic reduction (SCR) of NO with ammonia. Compared to the traditional V2O5/TiO2 and V2O5-MoO3/TiO2 catalysts, the V2O5/TiO2-PILC catalyst exhibited a higher activity and better SO2 and H2O resistance in the NH3-SCR reaction. Characterization using TPD, in situ DRIFT and XPS showed that surface sulfate and/or sulfite species and ionic SO42- species were formed on the catalyst in the presence of SO2. The ionic SO42- species on the catalyst surface was one reason for deactivation of the catalyst in SCR. The formation of the ionic SO42- species was correlated with the amount of surface adsorbed oxygen species. Less adsorbed oxygen species gave less ionic SO42- species on the catalyst.

    Effects of acid pretreatment on Fe-ZSM-5 and Fe-beta catalysts for N2O decomposition
    Minfang Wu, Hui Wang, Liangshu Zhong, Xinyan Zhang, Zhengping Hao, Qun Shen, Wei Wei, Guangren Qian, Yuhan Sun
    2016, 37 (6):  898-907.  DOI: 10.1016/S1872-2067(15)61052-X
    Abstract ( 405 )   [Full Text(HTML)] () PDF (1669KB) ( 1066 )  

    Two series of ZSM-5 and beta zeolites were pretreated in 1.0 mol/L HNO3 solution at room temperature for various time periods. The catalytic performances of their Fe-exchanged products in N2O decomposition were evaluated. The Fe-zeolite catalysts were characterized using N2 adsorption-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, ultraviolet-visible spectroscopy, temperature-programmed desorption of NH3, and scanning and transmission electron microscopies. For the ZSM-5 zeolite, acid leaching primarily takes place on the crystal surface and the particle size is reduced, therefore the pore channels are shortened. However, because of the good stability of MFI zeolites, the acid does not greatly penetrate the pore channels and new mesopores are not created. For the beta zeolite, because the amorphous material is inclined to dissolve (deagglomerate), some of the micropores are slightly dilated. The improved catalytic activities can be explained by the increased active Fe loading as a result of structural changes.© 2016, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

    Effects of Co3O4 nanocatalyst morphology on CO oxidation: Synthesis process map and catalytic activity
    Liangpeng Zeng, Kongzhai Li, Fan Huang, Xing Zhu, Hongcheng Li
    2016, 37 (6):  908-922.  DOI: 10.1016/S1872-2067(16)62460-9
    Abstract ( 1034 )   [Full Text(HTML)] () PDF (2086KB) ( 1359 )  

    This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation. A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies (i.e., nanorods, nanosheets, and nanocubes) were successfully synthesized, and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors. The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures (≤ 140 ℃). Nanorods can be synthesized in CoCl2 solution, while Co(NO3)2 solution promotes the formation of nanosheets. Further increasing the synthesis temperature (higher than 140 ℃) results in the formation of nanocubes in either Co(NO3)2 or CoCl2 solution. The reaction time only affects the size of the obtained nanoparticles. The presence of CTAB could improve the uniformity and dispersion of particles. Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co3+ on the surface, much higher reducibility, and better oxygen desorption capacity.

    Effects of Au-Ce strong interactions on catalytic activity of Au/CeO2/3DOM Al2O3 catalyst for soot combustion under loose contact conditions
    Baofang Jin, Yuechang Wei, Zhen Zhao, Jian Liu, Guiyuan Jiang, Aijun Duan
    2016, 37 (6):  923-933.  DOI: 10.1016/S1872-2067(15)61094-4
    Abstract ( 427 )   [Full Text(HTML)] () PDF (4732KB) ( 885 )  

    Au/3DOM (three-dimensionally ordered macroporous) Al2O3 and Au/CeO2/3DOM Al2O3 were prepared using a reduction-deposition method and characterized using scanning electron microscopy, N2 adsorption-desorption, X-ray diffraction, transmission electron microscopy, ultraviolet-visible spectroscopy, temperature-programmed hydrogen reduction, and X-ray photoelectron spectroscopy. Au nanoparticles of similar sizes were well dispersed and supported on the inner walls of uniform macropores. The norminal Au loading is 2%. Al-Ce-O solid solution in CeO2/3DOM Al2O3 catalysts can be formed due to the incorporation of Al3+ ions into the ceria lattice, which causes the creation of extrinsic oxygen vacancies. The extrinsic oxygen vacancies improved the oxygen-transport properties. The strong metal-support interactions between Au and CeO2 increased the amount of active oxygen on the Au nanoparticle surfaces, and this promoted soot oxidation. The activities of the Au-based catalysts were higher than those of the supports (Al2O3 or CeO2/3DOM Al2O3) at low temperature. Au/CeO2/3DOM Al2O3 had the highest catalytic activity for soot combustion, with T10, T50, and T90 values of 273, 364, and 412 ℃, respectively.

    Pt/Co3O4/3DOM Al2O3: Highly effective catalysts for toluene combustion
    Huanggen Yang, Jiguang Deng, Yuxi Liu, Shaohua Xie, Peng Xu, Hongxing Dai
    2016, 37 (6):  934-946.  DOI: 10.1016/S1872-2067(15)61095-6
    Abstract ( 567 )   [Full Text(HTML)] () PDF (1926KB) ( 918 )  

    Three-dimensionally ordered macro-/mesoporous alumina (3DOM Al2O3)-supported cobalt oxide and platinum nanocatalysts (xPt/yCo3O4/3DOM Al2O3, Pt mass fraction (x%) = 0-1.4%, Co3O4 mass fraction (y%) = 0-9.2%) were prepared using poly(methyl methacrylate) templating, incipient wetness impregnation and polyvinyl alcohol-protected reduction. The resulting xPt/yCo3O4/3DOM Al2O3 samples displayed a high-quality 3DOM architecture with macropores (180-200 nm in diameter) and mesopores (4-6 nm in diameter) together with surface areas in the range of 94 to 102 m2/g. Using these techniques, Co3O4 nanoparticles (NPs, 18.3 nm) were loaded on the 3DOM Al2O3 surface, after which Pt NPs (2.3-2.5 nm) were uniformly dispersed on the yCo3O4/3DOM Al2O3. The 1.3Pt/8.9Co3O4/3DOM Al2O3 exhibited the best performance for toluene oxidation, with a T90% value (the temperature required to achieve 90% toluene conversion) of 160 ℃ at a space velocity of 20000 mL g-1 h-1. It is concluded that the excellent catalytic performance of the 1.3Pt/8.9Co3O4/3DOM Al2O3 is owing to well-dispersed Pt NPs, the high concentration of adsorbed oxygen species, good low-temperature reducibility, and strong interaction between the Pt and Co3O4 NPs, as well as the unique bimodal porous structure of the support.

    Low-temperature catalytic oxidation of formaldehyde over Co3O4 catalysts prepared using various precipitants
    Zeyun Fan, Zhixiang Zhang, Wenjian Fang, Xin Yao, Guchu Zou, Wenfeng Shangguan
    2016, 37 (6):  947-954.  DOI: 10.1016/S1872-2067(15)61086-5
    Abstract ( 520 )   [Full Text(HTML)] () PDF (641KB) ( 1038 )  

    Co3O4 catalysts prepared with different precipitants (NH3·H2O, KOH, NH4HCO3, K2CO3 and KHCO3) were investigated for the oxidation of formaldehyde (HCHO). Among these, KHCO3-precipitated Co3O4 (KHCO3-Co) was the most active low-temperature catalyst, and was able to completely oxidize HCHO at the 100-ppm level to CO2 at 90 ℃. In situ diffuse reflectance infrared spectroscopy demonstrated that hydroxyl groups on the catalyst surface were regenerated by K+ and CO32-, thus promoting the oxidation of HCHO. Moreover, H2-temperature programmed reduction and X-ray photoelectron spectroscopy showed that employing KHCO3 as the precipitant increased the Co3+/Co2+ molar ratio on the surface of the Co3O4 catalyst, thus further promoting oxidation. Structural characterization revealed that catalysts precipitated with carbonate or bicarbonate reagents exhibited greater specific surface areas and pore volumes. Overall, these data suggest that the high activity observed during the Co3O4 catalyzed oxidation of HCHO can be primarily attributed to the presence of K+ and CO32- on the Co3O4 surface and the favorable Co3+/Co2+ ratio.

    Ni-based catalysts derived from a metal-organic framework for selective oxidation of alkanes
    Ying Zhou, Jilan Long, Yingwei Li
    2016, 37 (6):  955-962.  DOI: 10.1016/S1872-2067(15)61067-1
    Abstract ( 627 )   [Full Text(HTML)] () PDF (1018KB) ( 1550 )  

    Ni nanoparticles embedded in nitrogen-doped carbon (Ni@C-N) materials were prepared by thermolysis of a Ni-containing metal-organic framework (Ni-MOF) under inert atmosphere. The as-synthesized Ni@C-N materials were characterized by powder X-ray diffraction, N2 adsorption-desorption analysis, scanning electron microscopy, transmission electron microscopy, atomic absorption spectroscopy, and X-ray photoelectron spectroscopy. The MOF-derived Ni-based materials were then examined as heterogeneous catalysts for the oxidation of alkanes under mild reaction conditions. The Ni@C-N composites displayed high activity and selectivity toward the oxidation of a variety of saturated C-H bonds, affording the corresponding oxidation products in good-to-excellent yields. Furthermore, the catalysts could be recycled and reused for at least four times without any significant loss in activity and selectivity under the investigated conditions.

    Synergistic degradation of phenols by bimetallic CuO-Co3O4@γ-Al2O3 catalyst in H2O2/HCO3- system
    Yibing Li, Ali Jawad, Aimal Khan, Xiaoyan Lu, Zhuqi Chen, Weidong Liu, Guochuan Yin
    2016, 37 (6):  963-970.  DOI: 10.1016/S1872-2067(15)61092-0
    Abstract ( 749 )   [Full Text(HTML)] () PDF (634KB) ( 1024 )  

    The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities. However, because of catalyst leaching during degradation, catalysts can be short lived, and therefore expensive, and unsuitable for use in wastewater treatment. In this work, we developed a bimetallic CuO-Co3O4@γ-Al2O3 catalyst for phenol degradation with bicarbonate-activated H2O2. The weakly basic environment provided by the bicarbonate buffer greatly suppresses leaching of active Cu and Co metal ions from the catalyst. X-ray diffraction and X-ray photoelectron spectroscopy results showed interactions between Cu and Co ions in the CuO-Co3O4@γ-Al2O3 catalyst, and these improve the catalytic activity in phenol degradation. Mechanistic studies using different radical scavengers showed that superoxide and hydroxyl radicals both played significant roles in phenol degradation, whereas singlet oxygen was less important.

    Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization
    Ming Zhang, Wenshuai Zhu, Hongping Li, Suhang Xun, Meng Li, Yanan Li, Yanchen Wei, Huaming Li
    2016, 37 (6):  971-978.  DOI: 10.1016/S1872-2067(15)61103-2
    Abstract ( 433 )   [Full Text(HTML)] () PDF (678KB) ( 930 )  

    A series of functional, tungsten-containing mesoporous silica materials (W-SiO2) have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate, which acted as mesoporous template and metal source respectively. These materials were then characterized through X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectra (FTIR), diffuse reflectance spectra (DRS), and N2 adsorption-desorption, which were found to contain tungsten species that were effectively dispersed throughout the structure. The as-prepared materials W-SiO2 were also found to possess a mesoporous structure. The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm, which was close to the average pore size determined from the nitrogen desorption isotherm (2.9 nm). The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene (DBT), which is able to achieve deep desulfurization within 40 min under the optimal conditions (Catalyst (W-SiO2-20) = 0.01 g, temperature = 60 ℃, oxidant (H2O2) = 20 μL). For the removal of different organic sulfur compounds within oil, the ability of the catalyst (W-SiO2-20) under the same conditions to remove sulfur compounds decreased in the order: 4,6-dimethyldibenzothiophene > Dibenzothiophene > Benzothiophene > 1-dodecanethiol. Additionally, they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process. After seven separate catalytic cycles, the desulfurization efficiency was still as high as 90.3%. From the gas chromatography-mass spectrometer analysis, DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction. A mechanism for the heterogeneous desulfurization reaction was proposed.

    Lewis base-assisted Lewis acid-catalyzed selective alkene formation via alcohol dehydration and synthesis of 2-cinnamyl-1,3-dicarbonyl compounds from 2-aryl-3,4-dihydropyrans
    Changhui Liu, Bin Pan, Yanlong Gu
    2016, 37 (6):  979-986.  DOI: 10.1016/S1872-2067(15)61084-1
    Abstract ( 982 )   [Full Text(HTML)] () PDF (663KB) ( 1341 )  

    Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often plagued by the lack of alkene selectivity. In this work, the reaction system can be significantly improved through enhancing the performance of Lewis acid catalysts in the dehydration of activated alcohols by combining with a Lewis base. Observations of the reaction mechanism revealed that the Lewis base component might have changed the reaction rate order. Although both the principal and side reaction rates decreased, the effect was markedly more observed on the latter reaction. Therefore, the selectivity of the dehydration reaction was improved. On the basis of this observation, a new route to synthesize 2-cinnamyl-1,3-dicarbonyl compounds was developed by using 2-aryl-3,4- dihydropyran as a starting substrate in the presence of a Lewis acid/Lewis base combined catalyst system.