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Chinese Journal of Catalysis
2018, Vol. 39, No. 5
Online: 18 May 2018


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Liang et al. reported the usage of 2D flower-like cobalt to produce formic acid via electroreduction of CO₂. The reaction, which is a key step to constitute the global carbon cycle, is shown in the picture and detailed information can be seen in the pages of 914–919.

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Table of Contents for VOL.39 No.5 2018, 39 (5):  0-0.  Abstract ( 162 )   PDF (1851KB) ( 766 )

Reviews

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Single-atom catalysis:Bridging the homo-and heterogeneous catalysis Fang Chen, Xunzhu Jiang, Leilei Zhang, Rui Lang, Botao Qiao 2018, 39 (5):  893-898.  DOI: 10.1016/S1872-2067(18)63047-5 Abstract ( 1136 )   [Full Text(HTML)] () PDF (1130KB) ( 2534 )   Single-atom catalysis, the catalysis by single-atom catalysts (SACs), has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field. SACs have the advantages of both homogeneous catalysts (isolated active sites) and heterogeneous catalysts (stable and easy to separate), and are thus predicted to be able to bridge the homo-and heterogeneous catalysis. This prediction was first experimentally demonstrated in 2016. In this mini-review, we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a) Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson's catalyst; b) a Pt/Al2O3SAC has shown excellent performance in hydrosilylation reaction; and c) M-N-C SACs (M=Fe, Co etc.) have been applied in the activation of C-H bonds. All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts. These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.

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Recent advances on controllable and selective catalytic oxidation of cyclohexene Hongen Cao, Boran Zhu, Yufan Yang, Lin Xu, Lei Yu, Qing Xu 2018, 39 (5):  899-907.  DOI: 10.1016/S1872-2067(18)63050-5 Abstract ( 764 )   [Full Text(HTML)] () PDF (903KB) ( 980 )   Because of multiple potential reaction sites and variable oxidation depths, oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups, such as 7-oxabicyclo[4.1.0]heptane, trans/cis-cyclohexane-1,2-diol, cyclohex-2-en-1-ol, cyclohex-2-en-1-one, and even adipic acid. These products are broadly and abundantly used intermediates in the chemical industry; therefore, controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry, thus becoming the aim of synthetic and catalytic chemists in the field. Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance. This short review summarizes the recent advances on this subject, and the contents are mainly classified based on the chosen oxidants. We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.

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A viewpoint on catalytic origin of boron nitride in oxidative dehydrogenation of light alkanes Lei Shi, Dongqi Wang, Anhui Lu 2018, 39 (5):  908-913.  DOI: 10.1016/S1872-2067(18)63060-8 Abstract ( 541 )   [Full Text(HTML)] () PDF (3492KB) ( 1821 )   Oxidative dehydrogenation of light alkanes to alkenes is an attractive alternative route for industrial direct dehydrogenation because of favorable thermodynamic and kinetic characteristics, but encounters difficulties in selectivity control for alkenes because of over-oxidation reactions that produce a substantial amount of undesired carbon oxides. Recent progress has revealed that boron nitride is a highly promising catalyst in the oxidative dehydrogenation of light alkanes because of its superior selectivity for and high productivity of light alkenes, negligible formation of CO2, and remarkable catalyst stability. From this viewpoint, recent works on boron nitride in the oxidative dehydrogenations of ethane, propane, butane, and ethylbenzene are reviewed, and the emphasis of this viewpoint is placed on discussing the catalytic origin of boron nitride in oxidative dehydrogenation reactions. After analyzing recent progress in the use of boron nitride for oxidative dehydrogenation reactions and finding much new evidence, we conclude that pure boron nitride is catalytically inert, and an activation period is required under the reaction conditions; this process is accompanied by an oxygen functionalization at the edge of boron nitride; the B-O species themselves have no catalytic activity in C-H cleavage, and the B-OH groups, with the assistance of molecular oxygen, play the key role in triggering the oxidative dehydrogenation of propane; the dissociative adsorption of molecular oxygen is involved in the reaction process; and a straightforward strategy for preparing an active boron nitride catalyst with hydroxyl groups at the edges can efficiently enhance the catalytic efficacy. A new redox reaction cycle based on the B-OH sites is also proposed. Furthermore, as this is a novel catalytic system, there is an urgent need to develop new methods to optimize the catalytic performances, clarify the catalytic function of boron species in the alkane ODH reactions, and disclose the reaction mechanism under realistic reaction conditions.

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A highly efficient flower-like cobalt catalyst for electroreduction of carbon dioxide Gang Yang, Zhipeng Yu, Jie Zhang, Zhenxing Liang 2018, 39 (5):  914-919.  DOI: 10.1016/S1872-2067(18)63021-9 Abstract ( 527 )   [Full Text(HTML)] () PDF (1670KB) ( 1503 )   Electrochemical conversion of CO2 into fuel has been regarded as a promising approach to achieve the global carbon cycle. Herein, we report an efficient cobalt catalyst with a unique flower-like morphology synthesized by a green and facile hydrothermal method, in which n-butylamine is used as the capping agent. The resultant catalyst shows superior electrocatalytic activity toward CO2 electroreduction, which is highly selective for generating formate with a Faraday efficiency of 63.4%. Electrochemical analysis reveals that the oxide on the surface is essential for the electrocatalysis of the CO2 reduction reaction. Cyclic voltammograms further suggest that this catalyst is highly active for the oxidation of reduced product, and can thus be seen as a bifunctional catalyst.

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Fe-TiO2 and Fe2O3 quantum dots co-loaded on MCM-41 for removing aqueous rose bengal by combined adsorption/photocatalysis Guoqiang Shen, Lun Pan, Zhe Lü, Chongqing Wang, Fazal-e-Aleem, Xiangwen Zhang, Ji-Jun Zou 2018, 39 (5):  920-928.  DOI: 10.1016/S1872-2067(17)62976-0 Abstract ( 404 )   [Full Text(HTML)] () PDF (3065KB) ( 1230 )   Adsorption and photodegradation are promising approaches for removing organic pollutions. In this study, we combined these two processes by co-loading Fe-TiO2 and Fe2O3 quantum dots (QDs) on porous MCM-41, using a simple hydrolysis method. X-ray diffraction, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy results indicated that Fe-TiO2 QDs are formed at low Fe precursor concentrations, while additional Fe2O3 QDs are formed at higher Fe precursor concentrations. The Fe2O3 and Fe-TiO2 QDs impart high adsorption capacity and high photoactivity to the porous MCM-41, respectively. Thus, their combination results in a synergic effect of the adsorption and photodegradation. The highest-performing sample exhibits excellent performance in removing rose bengal from aqueous solution.

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Effective removal of the protective ligands from Au nanoclusters by ambient pressure nonthermal plasma treatment for CO oxidation Yuan Tan, Hua Liu, Xiao Yan Liu, Aiqin Wang, Changjun Liu, Tao Zhang 2018, 39 (5):  929-936.  DOI: 10.1016/S1872-2067(18)63018-9 Abstract ( 319 )   [Full Text(HTML)] () PDF (3914KB) ( 1005 )   We used a dielectric barrier discharge (DBD) plasma technique to eliminate the protective ligand of ZnAl-hydrotalcite-supported gold nanoclusters. We used X-ray powder diffraction, ultraviolet-visible spectrophotometry, thermogravimetric analysis, and high angle annular dark-field-scanning transmission electron microscopy characterization to show that the samples pretreated with/without DBD-plasma displayed different performances in CO oxidation. The enhanced activity was obtained on the plasma-treated samples, implying that the protective ligand was effectively removed via the plasma technique. The crystal structure of the plasma-treated samples changed markedly, suggesting that the plasma treatment could not only break the chemical bond between the gold and the protective agent but could also decompose the interlayer ions over the hydrotalcite support. The particle sizes of the gold after DBD-plasma treatment implied that it was a good way to control the size of the gold nanoparticles under mild conditions.

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Cloning, overexpression, and characterization of a novel organic solvent-tolerant lipase from Paenibacillus pasadenensis CS0611 Jiaxin Gao, Xiaoyang Ou, Pei Xu, Minhua Zong, Wenyong Lou 2018, 39 (5):  937-945.  DOI: 10.1016/S1872-2067(18)63033-5 Abstract ( 282 )   [Full Text(HTML)] () PDF (1298KB) ( 950 )   We found a novel lipase gene in the Paenibacillus pasadenensis CS0611 strain. The lipase gene sequence was cloned into the pET-28a expression vector to construct a recombinant lipase protein containing 6×His tags at the C-and N-termini, respectively. High-level expression of the lipase in E.coli BL21 (DE3) was obtained upon induction with IPTG at 20℃. The recombinant lipase activity was approximately 1631-fold higher than the wild type. His-tagged recombinant lipase was purified rapidly and efficiently by using Ni-charged affinity chromatography with 63.5% recovery and a purification factor of 10.78. The purified lipase was stable in a broad range of temperatures and pH values, with the optimal temperature and pH being 50℃ and 7.0, respectively. Its activity was stimulated to different degrees in the presence of metal ions such as Ca2+, Mg2+, and some non-ionic surfactants. In addition, the purified lipase was activated by a series of water-miscible organic solvents such as some short carbon chain alcohols and was highly tolerant to some water-immiscible organic solvents.

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The role of graphene coating on cordierite-supported Pd monolithic catalysts for low-temperature combustion of toluene Wen Li, Hongqi Ye, Gonggang Liu, Hongchao Ji, Yonghua Zhou, Kai Han 2018, 39 (5):  946-954.  DOI: 10.1016/S1872-2067(18)63015-3 Abstract ( 327 )   [Full Text(HTML)] () PDF (1272KB) ( 1327 )   Supporting Information In the present work, a Pd/graphene/cordierite (Pd/Gr/Cor) composite was prepared as a monolithic catalyst for low-temperature combustion of toluene. We mainly focused on understanding the role of graphene coating through investigation of catalytic performance and adsorption behavior of the composite. Compared with the traditional Pd/Cor catalyst without graphene coating, Pd/Gr/Cor catalyst delivered much higher activity and stability for toluene catalytic combustion in both dry and moist conditions. Transmission electron microscopy (TEM) and hydrophobic characterizations indicated that graphene coating can considerably improve the dispersity of Pd nanoparticles and enhance the hydrophobicity of the cordierite support. The adsorption behavior of the above two catalysts, including adsorption isothermal, adsorption kinetics, and adsorption thermodynamics were carefully investigated. The simulation results indicated that a large amount of toluene was adsorbed on graphene surface through relatively weak interaction, whereas only a relatively small amount of toluene was adsorbed on Pd surface with strong affinity. The adsorption thermal calculation indicated that the adsorption of toluene on graphene was a process with reduced entropy, indicating highly-ordered assembly of toluene molecular on graphene. It is the significant concentration and affinity gap between graphene and Pd that ensures a simultaneously and rapid transfer of toluene during the reaction process.

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Enhancement of catalytic activity by homo-dispersing S2O82--Fe2O3 nanoparticles on SBA-15 through ultrasonic adsorption Qingyan Chu, Jing Chen, Wenhua Hou, Haoxuan Yu, Ping Wang, Rui Liu, Guangliang Song, Hongjun Zhu, Pingping Zhao 2018, 39 (5):  955-963.  DOI: 10.1016/S1872-2067(17)63007-9 Abstract ( 460 )   [Full Text(HTML)] () PDF (1777KB) ( 800 )   Mesoporous superacids S2O82--Fe2O3/SBA-15 (SFS) with active nanoparticles are prepared by ultrasonic adsorption method. This method is adopted to ensure a homo-dispersed nanoparticle active phase, large specific surface area and many acidic sites. Compared with bulk S2O82--Fe2O3, Brönsted acid catalysts and other reported catalysts, SFS with an Fe2O3 loading of 30% (SFS-30) exhibits an outstanding activity in the probe reaction of alcoholysis of styrene oxide by methanol with 100% yield. Moreover, SFS-30 also shows a more excellent catalytic performance than bulk S2O82--Fe2O3 towards the alcoholysis of other ROHs (R=C2H5-C4H9). Lewis and Brönsted acid sites on the SFS-30 surfaces are confirmed by pyridine adsorbed infrared spectra. The highly efficient catalytic activity of SFS-30 may be attributed to the synergistic effect from the nano-effect of S2O82--Fe2O3 nanoparticles and the mesostructure of SBA-15. Finally, SFS-30 shows a good catalytic reusability, providing an 84.1% yield after seven catalytic cycles.

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Green and efficient epoxidation of methyl oleate over hierarchical TS-1 Yue Wei, Gang Li, Qiang Lü, Chuanying Cheng, Hongchen Guo 2018, 39 (5):  964-972.  DOI: 10.1016/S1872-2067(18)63014-1 Abstract ( 345 )   [Full Text(HTML)] () PDF (1328KB) ( 1012 )   The epoxidation of methyl oleate (MO) was conducted in the presence of aqueous H2O2 as the oxidant and hierarchical TS-1 (HTS-1) as the catalyst; the catalyst was synthesized using polyquaternium-6 as the mesopore template. The effects of various parameters, i.e., H2O2/C=C molar ratio, oxidant concentration, amount of the catalyst, reaction temperature, and time, were systematically studied. Furthermore, response surface methodology (RSM) was used to optimize the conditions to maximize the yield of epoxy MO and to evaluate the significance and interplay of the factors affecting the epoxy MO production. The H2O2/C=C molar ratio and catalyst amount were the determining factors for MO epoxidation, wherein the maximum yield of epoxy MO reached 94.9% over HTS-1 under the optimal conditions.

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Enhancing the photocatalytic activity and photostability of zinc oxide nanorod arrays via graphitic carbon mediation Xuewei Zhang, Xueliang Zhang, Xin Wang, Lequan Liu, Jinhua Ye, Defa Wang 2018, 39 (5):  973-981.  DOI: 10.1016/S1872-2067(18)63010-4 Abstract ( 648 )   [Full Text(HTML)] () PDF (2526KB) ( 1180 )   Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide (ZnO)-based photocatalysts. In this paper, we report the fabrication of graphitic-carbon-mediated ZnO nanorod arrays (NRAs) with enhanced photocatalytic activity and photostability for CO2 reduction under visible light irradiation. ZnO NRA/C-x (x=005, 01, 02, and 03) nanohybrids are prepared by calcining pre-synthesized ZnO NRAs with different amounts of glucose (0.05, 0.1, 0.2, and 0.3 g) as a carbon source via a hydrothermal method. X-ray photoelectron spectroscopy reveals that the obtained ZnO NRA/C-x nanohybrids are imparted with the effects of both carbon doping and carbon coating, as evidenced by the detected C-O-Zn bond and the C-C, C-O and C=O bonds, respectively. While the basic structure of ZnO remains unchanged, the UV-Vis absorption spectra show increased absorbance owing to the carbon doping effect in the ZnO NRA/C-x nanohybrids. The photoluminescence (PL) intensities of ZnO NRA/C-x nanohybrids are lower than that of bare ZnO NRA, indicating that the graphitic carbon layer coated on the surface of the ZnO NRA significantly enhances the charge carrier separation and transport, which in turn enhances the photoelectrochemical property and photocatalytic activity of the ZnO NRA/C-x nanohybrids for CO2 reduction. More importantly, a long-term reaction of photocatalytic CO2 reduction demonstrates that the photostability of ZnO NRA/C-x nanohybrids is significantly increased in comparison with the bare ZnO NRA.

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CoNiP/NC polyhedrons derived from cobalt-based zeolitic imidazolate frameworks as an active electrocatalyst for oxygen evolution Jintang Li, Guiqing Du, Xian Cheng, Pingjing Feng, Xuetao Luo 2018, 39 (5):  982-987.  DOI: 10.1016/S1872-2067(18)63030-X Abstract ( 438 )   [Full Text(HTML)] () PDF (1722KB) ( 1712 )   Supporting Information The oxygen evolution reaction (OER) plays an important role in the development of energy conversation and storage technologies including water splitting and metal-air batteries, where the development of electrocatalysts is paramount. In this study, cobalt-nickel phosphide/N-doped porous carbon polyhedron electrocatalysts (CoNiP/NC) were prepared by a facile two-step carbonization method and subsequent phosphorization calcination in an Ar atmosphere using cobalt-based zeolitic imidazolate frameworks (ZIFs) as precursors. Among the electrocatalysts obtained by controlling the carbonization and phosphorization temperature, the CoNiP/NC700 catalyst, where 700 refers to the calcination temperature (℃), exhibited superior electrocatalytic activity for the OER with an onset overpotential of approximate 220 mV and an overpotential of approximate 300 mV in alkaline solution at a current density of 10 mA/cm2. The CoNi/NC and Co/NC Samples were also tested for comparison and CoNiP/NC exhibited the better electrocatalytic activity at all the temperatures tested. The superior electrocatalytic activity of the phosphorization hybrid material can be attributed to the superior synergistic effect of Co, Ni, P and C due to their strong electron coupling interactions. The interconnected amorphous carbon anchored the active Co compounds to avoid aggregation and maintained conducting channels for electron transfer. The composite electrocatalyst prepared herein is a promising candidate for use in electrocatalytic OERs.

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Layered double hydroxide-like Mg3Al1-xFex materials as supports for Ir catalysts:Promotional effects of Fe doping in selective hydrogenation of cinnamaldehyde Weiwei Lin, Haiyang Cheng, Xiaoru Li, Chao Zhang, FengyuZhao, Masahiko Arai 2018, 39 (5):  988-996.  DOI: 10.1016/S1872-2067(18)63042-6 Abstract ( 309 )   [Full Text(HTML)] () PDF (1943KB) ( 691 )   Supported Ir catalysts were prepared using layered double hydrotalcite-like materials, such as Mg3Al1-xFex, containing Fe and Al species in varying amounts as supports. These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde (CAL). When x was changed from 0 (Ir/Mg3Al) to 1 (Ir/Mg3Fe), the rate of CAL hydrogenation reached a maximum at approximately x=0.25, while the selectivity to unsaturated alcohol, i.e., cinnamyl alcohol, monotonously increased from 44.9% to 80.3%. Meanwhile, the size of the supported Ir particles did not change significantly with x, remaining at 1.7 ±0.2 nm, as determined by transmission electron microscopy. The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X-ray photoelectron spectroscopy. The surface of the supported Ir particles was also examined through the in-situ diffuse reflectance infrared Fourier-transform of a probe molecule of CO. On the basis of these characterization results, the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed. The significant factors are the electron transfer from Fe2+ in the Mg3Al1-xFex support to the dispersed Ir particles and the surface geometry.

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Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO2 to epoxides Xiying Fu, Xinyao Jing, Lili Jin, Lilong Zhang, Xiaofeng Zhang, Bin Hu, Huanwang Jing 2018, 39 (5):  997-1003.  DOI: 10.1016/S1872-2067(18)63023-2 Abstract ( 323 )   [Full Text(HTML)] () PDF (983KB) ( 684 )   The catalytic synthesis of cyclic carbonates via the cycloaddition of CO2 to epoxides is a standard methodology for CO2 fixation. For this purpose, chiral basket-handle porphyrin-Co complexes were devised, prepared, and fully characterized by nuclear magnetic resonance, mass spectrometry, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and specific rotation. The proposed metalloporphyrin catalysts were synthesized with either 1,1'-bi-2-naphthol or L-phenylalanine, which have different chirality, and then applied to the coupling of propylene oxide and CO2 for generating chiral cyclic carbonates with good enantioselectivity under extremely mild conditions in the presence of tetrabutyl ammonium chloride as a co-catalyst. The good enantioselectivity in the cycloaddition reaction is attributed to a synergistic interplay between the chiral porphyrin catalysts and the substrate. The mechanism and enantioselectivity of the asymmetric cycloaddition reaction is discussed.

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Bimetallic Cr-In/H-SSZ-13 for selective catalytic reduction of nitric oxide by methane Jun Yang, Yupeng Chang, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li 2018, 39 (5):  1004-1011.  DOI: 10.1016/S1872-2067(18)63054-2 Abstract ( 310 )   [Full Text(HTML)] () PDF (1333KB) ( 1317 )   Supporting Information Bimetallic Cr-In/H-SSZ-13 zeolites were prepared by wet impregnation and investigated for selective catalytic reduction of nitric oxide by methane (CH4-SCR). Reduction-oxidation treatments led to close contact and interaction between Cr and In species in these zeolites, as revealed by transmission electron microscopy and X-ray photoelectron spectroscopy. Compared to monometallic Cr/H-SSZ-13 and In/H-SSZ-13, the bimetallic catalyst system exhibited dramatically enhanced CH4-SCR performance, i.e., NO conversion greater than 90% and N2 selectivity greater than 99% at 550℃ in the presence of 6% H2O under a high gas hourly space velocity of 75 000/h. The bimetallic Cr-In/H-SSZ-13 showed very good stability in CH4-SCR with no significant activity loss for over 160 h. Catalytic data revealed that CH4 and NO were activated on the In and Cr sites of Cr-In/H-SSZ-13, respectively, both in the presence of O2 during CH4-SCR.