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    Chinese Journal of Catalysis
    2019, Vol. 40, No. 7
    Online: 18 July 2019

    Cover:

    Various active centers, including bare nanoparticles, metal or metal oxides encapsulated partly by carbon layers and single-atoms, co-exists on the nitrogen-doped carbon supported metal catalysts. Many transformations can be catalyzed by these catalysts due to the synergy effect between several active sites. They have a great potential for many valuable reactions in industry. This special issue collects 13 papers with 1 perspective, 4 full reviews, 1 communication and 7 original research papers.

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    Contents
    Table of Contents for VOL.40 No.7
    2019, 40 (7):  0-0. 
    Abstract ( 57 )   PDF (3986KB) ( 134 )  
    Editorial
    Perspective
    Rational design of hydrogenation catalysts using nitrogen-doped porous carbon
    Yuzhuo Chen, Zhe Wang, Shanjun Mao, Yong Wang
    2019, 40 (7):  971-979.  DOI: 10.1016/S1872-2067(19)63353-X
    Abstract ( 233 )   [Full Text(HTML)] () PDF (1345KB) ( 732 )  
    Review
    Recent advances in heterogeneous catalytic hydrogenation and dehydrogenation of N-heterocycles
    Zhongzhe Wei, Fangjun Shao, Jianguo Wang
    2019, 40 (7):  980-1002.  DOI: 10.1016/S1872-2067(19)63336-X
    Abstract ( 494 )   [Full Text(HTML)] () PDF (3205KB) ( 962 )  

    The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines (py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemicals, and fine chemicals. Over the past few decades, great breakthroughs have been achieved in the controlled synthesis of efficient heterogeneous catalysts used for the selective hydrogenation of functionalized quinoline compounds, which allow one to correlate the structure-property relationships. In this review, we will summarize the recent significant progress achieved in this field covering the synthetic strategies, microstructural and chemical features, catalytic performance, and internal relationships. State-of-the-art noble metal-based single (Pd, Pt, Ru, Rh, Ir and Au) and bi/multi-metallic catalysts (RuCu, AuPd, and PdNi) are first introduced, followed by a summary of earth-abundant metal-based catalysts (Co, Fe, Ni, and Cu). Finally, the dehydrogenation of N-heterocycles is introduced to form a reversible hydrogenation/dehydrogenation system for H2 storage, which can be employed in a liquid organic hydrogen system. Furthermore, the reaction mechanism and future research direction in these areas are also discussed. This review will deepen our understanding of the catalytic transformation of N-heterocycles and provide guidance for researchers on the rational design of catalysts.

    Visible light promoted difunctionalization reactions of alkynes
    Xiang Ren, Zhan Lu
    2019, 40 (7):  1003-1019.  DOI: 10.1016/S1872-2067(19)63278-X
    Abstract ( 392 )   [Full Text(HTML)] () PDF (1225KB) ( 652 )  

    Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon (sp3), carbon (sp2), and other heteroatom (P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light; the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products; here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C-C bonds and C-X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.

    Selective oxidation of glycerol in a base-free aqueous solution: A short review
    Lihua Yang, Xuewen Li, Ping Chen, Zhaoyin Hou
    2019, 40 (7):  1020-1034.  DOI: 10.1016/S1872-2067(19)63301-2
    Abstract ( 400 )   [Full Text(HTML)] () PDF (831KB) ( 705 )  

    Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.

    Crystal phase regulation in noble metal nanocrystals
    Qiaoli Chen, Tianchun Cheng, Hongya Fu, Yihan Zhu
    2019, 40 (7):  1035-1056.  DOI: 10.1016/S1872-2067(19)63385-1
    Abstract ( 448 )   [Full Text(HTML)] () PDF (2742KB) ( 758 )  

    Noble metal nanocrystals (NCs) are often densely packed in their most stable forms that are determined by a combination of effects arising from the electronic, magnetic, geometric, and phononic properties of the NCs. These packing modes usually include the densest packed polytypes of Barlow packings and more open or distorted packings with slightly lower atomic packing factors. The structural modulation strategies of NCs towards the better performances for diverse applications are usually limited to the crystal size, shape, and surface control, which have been robustly studied and documented. An exciting emerging field related to structural engineering of noble metal NCs turns out to be the crystal phase control, which allows the chemical synthesis of energetically high-lying phases of NCs and leads to intriguing performances in catalysis and energy conversion. This article provides a comprehensive review of crystal phase regulation that endows both noble metal and noble-metal-based alloy NCs with unique electronic structures and enhanced performances. The basic principles, general design rationale, synthetic approaches, and structural characterizations for a variety of successful case studies related to crystal phase engineering are reviewed and discussed. In the end, the perspectives and challenges associated with the development of a more controllable chemical synthetic strategy towards the high-energy phases of noble metal NCs are put forward.

    Communication
    Tuning catalytic selectivity of propane oxidative dehydrogenation via surface polymeric phosphate modification on nickel oxide nanoparticles
    Kaimin Du, Mengjia Hao, Zhinian Li, Wei Hong, Juanjuan Liu, Liping Xiao, Shihui Zou, Hisayoshi Kobayashi, Jie Fan
    2019, 40 (7):  1057-1062.  DOI: 10.1016/S1872-2067(18)63199-7
    Abstract ( 174 )   [Full Text(HTML)] () PDF (640KB) ( 468 )  

    Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand to tune the selectivity of propane oxidative dehydrogenation. Beneficial from the weakened affinity of propene, NiO modified with polymeric phosphate shows a selectivity 2-3 times higher than NiO towards the production of propene. The success of this regulation verifies the feasibility of ligand modification in high-temperature gas-phase reactions and shines a light on its applications in other important industrial reactions.

    Articles
    Rational construction of cross-linked porous nickel arrays for efficient oxygen evolution reaction
    Kaili Zhang, Shengjue Deng, Yu Zhong, Yadong Wang, Jianbo Wu, Xiuli Wang, Xinhui Xia, Jiangping Tu
    2019, 40 (7):  1063-1069.  DOI: 10.1016/S1872-2067(18)63194-8
    Abstract ( 130 )   [Full Text(HTML)] () PDF (1401KB) ( 428 )  

    It is important but challenging to design and fabricate an efficient and cost-effective electrocatalyst for the oxygen evolution reaction (OER). Herein, we report free-standing 3D nickel arrays with a cross-linked porous structure as interesting and high-performance electrocatalysts for OER via a facile one-step electrodeposition method. The 3D nickel arrays are strongly anchored on the substrate, forming self-supported electrocatalysts with reinforced structural stability and high electrical conductivity. Because of their increased active surface area, abundant channels for electron/ion transportation and enhanced electronic conductivity, the designed 3D nickel arrays exhibit superior electrocatalytic OER performance with a low overpotential (496 mV at 50 mA cm-2) and a small Tafel slope (43 mV dec-1) as well as long-term stability (no decay after 24 h) in alkaline solution. Our proposed rational design strategy may open up a new way to construct other advanced 3D porous materials for widespread application in electrocatalysis.

    Mechanistic insight into N2O formation during NO reduction by NH3 over Pd/CeO2 catalyst in the absence of O2
    Liping Sheng, Zhaoxia Ma, Shiyuan Chen, Jinze Lou, Chengye Li, Songda Li, Ze Zhang, Yong Wang, Hangsheng Yang
    2019, 40 (7):  1070-1077.  DOI: 10.1016/S1872-2067(19)63328-0
    Abstract ( 121 )   [Full Text(HTML)] () PDF (679KB) ( 358 )  

    N2O is a major by-product emitted during low-temperature selective catalytic reduction of NO with NH3 (NH3-SCR), which causes a series of serious environmental problems. A full understanding of the N2O formation mechanism is essential to suppress the N2O emission during the low-temperature NH3-SCR, and requires an intensive study of this heterogeneous catalysis process. In this study, we investigated the reaction between NH3 and NO over a Pd/CeO2 catalyst in the absence of O2, using X-ray photoelectron spectroscopy, NH3-temperature-programmed desorption, NO-temperature-programmed desorption, and in-situ Fourier-transform infrared spectroscopy. Our results indicate that the N2O formation mechanism is reaction-temperature-dependent. At temperatures below 250℃, the dissociation of HON, which is produced from the reaction between surface H·adatoms and adsorbed NO, is the key process for N2O formation. At temperatures above 250℃, the reaction between NO and surface N·, which is produced by NO dissociation, is the only route for N2O formation, and the dissociation of NO is the rate-determining step. Under optimal reaction conditions, a high performance with nearly 100% NO conversion and 100% N2 selectivity could be achieved. These results provide important information to clarify the mechanism of N2O formation and possible suppression of N2O emission during low-temperature NH3-SCR.

    Solid-state CTAB-assisted synthesis of mesoporous Fe3O4 and Au@Fe3O4 by mechanochemistry
    Jiahua Zhao, Yuan Shu, Pengfei Zhang
    2019, 40 (7):  1078-1084.  DOI: 10.1016/S1872-2067(19)63288-2
    Abstract ( 190 )   [Full Text(HTML)] () PDF (627KB) ( 595 )  

    Mesoporous iron oxides have shown excellent performance in many research areas such as catalysts, biosensors, enzyme immobilization, heavy metal adsorption, and drug delivery. The state-of-the-art synthesis methods are mostly wet chemistry processes. This paper reports a solvent-free approach for the rapid synthesis of mesoporous Fe3O4 (specific surface area up to 170 m2/g) and Au@Fe3O4 (highly dispersed Au nanoparticles, average particle size:~4 nm). With different amounts of added template agent, cetyltrimethylammonium bromide (CTAB), the pore structure could easily be adjusted. More importantly, the mesoporous Fe3O4 exhibited good catalytic activity in carbon monoxide (CO) oxidation, outperforming commercially purchased Fe3O4 with 100% CO conversion at around 274℃ vs. 490℃ for the commercial product.

    Cobalt phosphide nanocage@ferric-zinc mixed-metal phosphide nanotube hierarchical nanocomposites for enhanced overall water splitting
    Xiaowei Hu, Yongheng Yin, Wei Liu, Xingwang Zhang, Hongxiu Zhang
    2019, 40 (7):  1085-1092.  DOI: 10.1016/S1872-2067(19)63299-7
    Abstract ( 144 )   [Full Text(HTML)] () PDF (610KB) ( 422 )  

    Hierarchical nanostructures have attracted widespread interest owing to their unique properties compared to their bulk counterparts. Thus, they are considered promising electrocatalytic materials. In this work, a novel hierarchical porous nanocomposite of cobalt phosphide nanocage@ferric-zinc mixed-metal phosphide nanotubes (denoted CoP@ZnFeP) was fabricated using a self-assembly approach. Because of their structural and compositional merits, the as-prepared phosphide hybrids have abundant catalytic active sites and high porosity for facile mass diffusion. In an alkaline electrolyte, the CoP@ZnFeP flower-like hybrids displayed enhanced catalytic activity for the hydrogen evolution reaction and the oxygen evolution reaction compared with a mechanical mixture of CoP and ZnFeP nanoparticles. The CoP@ZnFeP hierarchical nanocomposites also showed excellent activity for the overall water splitting reaction, yielding a water-splitting current of 10 mA/cm2 on the application of just 1.6 V, as well as excellent durability (24-h long-term operation) in a two-electrode system. Our design methodology may create opportunities to search for highly efficient and robust non-precious metal catalysts with applications in high-performance energy conversion and storage devices.

    Design of fast crystallization of nanosized zeolite omega crystals at higher temperatures
    Fen Zhang, Ling Zhang, Zhichao Yang, Shichao Han, Qiuyan Zhu, Liang Wang, Chenguang Liu, Xiangju Meng, Feng-Shou Xiao
    2019, 40 (7):  1093-1099.  DOI: 10.1016/S1872-2067(19)63280-8
    Abstract ( 159 )   [Full Text(HTML)] () PDF (499KB) ( 554 )  

    Fast crystallization of nanosized zeolite crystals is a very popular process used for practical zeolite catalyst applications. Herein, we report a designer crystallization process for nanosized zeolite omega crystals based on the relationship between the crystallization time and temperature in the Arrhenius equation. Compared to the conventional hydrothermal synthesis of zeolite omega (72 h at room temperature and 240 h at 100℃, MAZ-100), the crystallization of zeolite omega presented in this work only requires a very short time interval (5 h at 180℃, MAZ-180). Physicochemical characterizations, including XRD, SEM, N2 sorption isotherms, and 27Al MAS NMR show that the product of zeolite omega (MAZ-180) has good crystallinity and uniform nanocrystals. More importantly, after the loading of Pt nanoparticles (0.5 wt%), the Pt/H-MAZ-180 catalyst exhibits higher isomer selectivity and lower cracking selectivity than those of the Pt/H-MAZ-100 catalyst in the hydroisomerization of n-dodecane. These results suggest the potential applications of these omega nanocrystals as supporting catalyst compounds in industrial processes.

    Elimination of 1,2-dichloroethane over (Ce,Cr)xO2/Nb2O5 catalysts: synergistic performance between oxidizing ability and acidity
    Jie Wan, Peng Yang, Xiaolin Guo, Renxian Zhou
    2019, 40 (7):  1100-1108.  DOI: 10.1016/S1872-2067(18)63203-6
    Abstract ( 67 )   [Full Text(HTML)] () PDF (1564KB) ( 394 )  

    A series of (Ce,Cr)xO2/Nb2O5 catalysts with different (Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane (DCE), which is one of the typical chlorinated volatile organic compound pollutants. The textural properties were characterized by X-ray diffraction, N2 adsorption/desorption isotherms, UV-Raman spectroscopy, and scanning electron microscopy. The surface acidity and the redox properties were characterized by ammonia temperature-programmed desorption and H2 temperature-programmed reduction, respectively. The results show that the addition of a proper amount of (Ce,Cr)xO2 over Nb2O5 significantly improves the intrinsic catalytic activity towards the deep oxidation of DCE, and only a very small amount of C2H3Cl is detected as the byproduct of the oxidation process. Further study reveals the existence of an obvious synergistic effect between Nb2O5, with abundant strong acid sites, and (Ce,Cr)xO2, with strong oxidation sites, as the strong acid sites of Nb2O5 promote the adsorption and dehydrochlorination of DCE, while the strong oxidation sites of (Ce,Cr)xO2 contribute to the deep oxidation of the reactant, intermediates, and byproducts.

    Preparation of highly dispersed iron species over ZSM-5 with enhanced metal-support interaction through freeze-drying impregnation
    Lisong Fan, Dangguo Cheng, Fengqiu Chen, Xiaoli Zhan
    2019, 40 (7):  1109-1115.  DOI: 10.1016/S1872-2067(18)63198-5
    Abstract ( 357 )   [Full Text(HTML)] () PDF (540KB) ( 612 )  

    Supported metal catalysts play a vital role in the chemical industry, and the metal-support interaction is an important property of the catalyst. However, in the traditional impregnation method, it is difficult to obtain sufficient metal-support interactions owing to the mobility of the metal precursor during evaporation drying. Here, freeze drying is applied during impregnation instead of evaporation drying for enhancing the metal-support interactions. 57FeZSM-5 was chosen as a representative catalyst. A quantitative analysis was conducted based on Mössbauer spectroscopy. Compared with traditional evaporation-drying catalyst, freeze-drying catalyst has stronger metal-support interactions. In addition, more iron species are confined in the channel and smaller metal sizes and less diversity are obtained. The compositional change is also proved because of the superior performance of the freeze-drying catalyst during N2O decomposition. This method can be extended to other supported metal catalysts prepared through an impregnation method, which can be used to tune the metal-support interactions and metal sizes.