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Chinese Journal of Catalysis
2020, Vol. 41, No. 7
Online: 18 July 2020

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Cover: This special issue is dedicated to Professor Mingyuan He on the occasion of his 80th birthday, in recognition of his distinguished contributions to the innovation in the catalysts and technologies of petroleum refining and petrochemical production, as well as to the development of green chemistry and chemical processes in China.

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Table of Contents for VOL.41 No.7 2020, 41 (7):  0-0.  Abstract ( 11 )   PDF (3009KB) ( 16 )

Editorial

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Preface to Special Issue in Honor of the 80th Birthday of Professor Mingyuan He 2020, 41 (7):  1029-1031.  DOI: 10.1016/S1872-2067(20)63585-9 Abstract ( 73 )   [Full Text(HTML)] () PDF (620KB) ( 187 )

Reviews

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Industrial catalysis: Strategies to enhance selectivity Renyang Zheng, Zhicheng Liu, Yangdong Wang, Zaiku Xie 2020, 41 (7):  1032-1038.  DOI: 10.1016/S1872-2067(20)63578-1 Abstract ( 317 )   [Full Text(HTML)] () PDF (1520KB) ( 522 )   Precise control of catalytic selectivity is a key concept of green chemistry, and also an important driving force for the sustainable development of catalytic industry. Selectivity not only determines the atomic economy of the catalytic process, but also affects the energy consumption of subsequent separation process. The objective of this review is to illustrate successful catalyst design strategies to enhance selectivity, by using several important catalytic cases of petroleum refining and petrochemicals. These industrial applications and cutting-edge research cases mainly use the strategies of coupling, decoupling or confinement of adsorption sites and active sites to tune the diffusion barrier and activation energy barrier in different routes, so as to improve the selectivity of catalyst. Based on the preliminary understanding of selectivity improvement, it is necessary to systematically investigate the selective catalytic processes using combination of multiple strategies, thereby realizing the design of highly selective catalyst over reasonable time scales and space scales.

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Advances in the production technology of hydrogen peroxide Guohua Gao, Yanan Tian, Xiaoxiao Gong, Zhiyong Pan, Keyong Yang, Baoning Zong 2020, 41 (7):  1039-1047.  DOI: 10.1016/S1872-2067(20)63562-8 Abstract ( 2200 )   [Full Text(HTML)] () PDF (631KB) ( 1085 )   This article mainly summarizes various aspects of hydrogen peroxide (H2O2) production through the anthraquinone route, including hydrogenation catalysts, working solution, regeneration technique, hydrogenation reactors, and environmental protection. The advances and breakthrough of SINOPEC in the production of H2O2 through the anthraquinone route is presented in this review, highlighting recent innovative technology on these aspects developed independently. The technical prospect and scientific challenges associated with the direct synthesis method from hydrogen and oxygen are also briefly discussed.

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Regeneration of catalysts deactivated by coke deposition: A review Jibin Zhou, Jianping Zhao, Jinling Zhang, Tao Zhang, Mao Ye, Zhongmin Liu 2020, 41 (7):  1048-1061.  DOI: 10.1016/S1872-2067(20)63552-5 Abstract ( 1145 )   [Full Text(HTML)] () PDF (1398KB) ( 941 )   In industrial catalytic processes, coke deposition can cause catalyst deactivation by covering acid sites and/or blocking pores. The regeneration of deactivated catalysts, thereby removing the coke and simultaneously restoring the catalytic activity, is highly desired. Despite various chemical reactions and methods are available to remove coke, developing reliable, efficient, and economic regeneration methods for catalytic processes still remains a challenge in industrial practice. In this paper, the current progress of regeneration methods such as oxidation (air, ozone and oxynitride), gasification (carbon dioxide and water steam), and hydrogenation (hydrogen) is reviewed, which hopefully can shed some light on the design and optimization of catalysts and the related processes.

Communications

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Controllable direct-syntheses of delaminated MWW-type zeolites Zhendong Wang, Magdalena O. Cichocka, Yi Luo, Bin Zhang, Hongmin Sun, Yi Tang, Weimin Yang 2020, 41 (7):  1062-1066.  DOI: 10.1016/S1872-2067(20)63545-8 Abstract ( 174 )   [Full Text(HTML)] () PDF (1409KB) ( 197 )   Supporting Information A method for the direct syntheses of partially and fully delaminated MWW zeolites is reported herein. Two organic amines were introduced into the hydrothermal synthetic system: hexamethyleneimine (HMI), which acted as the structure-directing agent for the MWW layered structure; and dicyclohexylamine (DCHA), in the role of an in-situ delaminating agent. By varying the amount of DCHA, partially and fully delaminated MWW zeolites having two MWW structure layers and one single layer, respectively, were obtained. These were denoted as SCM-1 (Sinopec Composite Material) and SCM-6, respectively. The delaminated materials possess ultra-large external surface areas, and the transmission electron microscopy images illustrated their layered nature. In the reaction of liquid phase benzene alkylation with ethylene, SCM-1, the double-layered MWW zeolite, exhibited far superior catalytic performance compared to zeolite MCM-22.

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Efficient methane electrocatalytic conversion over a Ni-based hollow fiber electrode Zhikai Guo, Wei Chen, Yanfang Song, Xiao Dong, Guihua Li, Wei Wei, Yuhan Sun 2020, 41 (7):  1067-1072.  DOI: 10.1016/S1872-2067(20)63548-3 Abstract ( 196 )   [Full Text(HTML)] () PDF (931KB) ( 293 )   Supporting Information Natural gas and shale gas, with methane as the main component, are important and clean fossil energy resources. Direct catalytic conversion of methane to valuable chemicals is considered a crown jewel topic in catalysis. Substantial studies on processes including methane reforming, oxidative coupling of methane, non-oxidative coupling of methane, etc. have been conducted for many years. However, owing to the intrinsic chemical inertness of CH4, harsh reaction conditions involving either extremely high temperatures or highly oxidative reactants are required to activate the C–H bonds of CH4 in such thermocatalytic processes, which may cause the target products, such as ethylene or methanol, to be further converted into coke or CO and CO2. It is desirable to adopt a new strategy for direct CH4 conversion under mild conditions. Herein, we report that efficient electrocatalytic oxidation of methane to alcohols at ambient temperature and pressure can be achieved using a NiO/Ni hollow fiber electrode. This work opens a new avenue for direct catalytic conversion of CH4.

Articles

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Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose Fangwei Gu, Haichao Liu 2020, 41 (7):  1073-1080.  DOI: 10.1016/S1872-2067(20)63569-0 Abstract ( 201 )   [Full Text(HTML)] () PDF (847KB) ( 176 )   Supporting Information As the most abundant source of biomass in nature for sustainable production of fuels and chemicals, efficient depolymerization of cellulose under mild conditions, due to the difficulty in selective cleavage of its β-1,4-glycosidic bonds, still remains challenging. Here, we report a novel method for oxidative cleavage of the glycosidic bonds by free radicals. Probed by the cellobiose reaction, it was found that ·OH radicals, generated from the decomposition of H2O2 catalyzed by CuSO4 or CuO/SiO2, were efficient for selective conversion of cellobiose to glucose and gluconic acid at a low temperature of 333 K, and their selectivities reached 30.0% and 34.6%, respectively, at 23.4% cellobiose conversion. Other radicals, such as ·SO4-, also exhibited high efficacy in the cellobiose reaction. Mechanistic studies suggest that the oxidative cleavage of the β-1,4-glycosidic bond by the free radicals involve formation of the carbon radical intermediate via abstraction of the H atom dominantly at the C1 position. Following this oxidative mechanism, treatment of microcrystalline cellulose with ·OH by impregnation with H2O2 and CuSO4 catalyst at 343 K led to significant enhancement in its hydrolysis efficiency. These results demonstrate the effectiveness of this new method in the oxidative cleavage of glycosidic bonds, and its viability for the efficient depolymerization of cellulose at low temperatures, which can be further improved, for example, by exploring new free radicals and optimizing their reactivity and selectivity.

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Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation Nian Hu, Xiao-Yun Li, Si-Ming Liu, Zhao Wang, Xiao-Ke He, Yue-Xin Hou, Yu-Xiang Wang, Zhao Deng, Li-Hua Chen, Bao-Lian Su 2020, 41 (7):  1081-1090.  DOI: 10.1016/S1872-2067(20)63570-7 Abstract ( 65 )   [Full Text(HTML)] () PDF (1179KB) ( 244 )   Supporting Information Copper based catalysts have high potential for the substituent of noble-metal based catalysts as their high selectivity and moderate activity for selective hydrogenation reaction; however, achieving further high catalytic stability is very difficult. In this work, the carbonization process of Cu-based organic frameworks was explored for the synthesis of highly-dispersed Cu supported by hierarchically porous carbon with high catalytic performance for selective hydrogenation of 1,3-butadiene. The porous hierarchy of carbon support and the dispersion of copper nanoparticles can be precisely tuned by controlling the carbonization process. The resultant catalyst carbonized at 600 ℃ exhibits a rather low reaction temperature at 75 ℃ for 100% butadiene conversion with 100% selectivity to butenes, due to its reasonable porous hierarchy and highly-dispersed copper sites. More importantly, unprecedentedly stability of the corresponding Cu catalyst was firstly observed for selective 1,3-butadiene hydrogenation, with both 100% butadiene conversion and 100% butenes selectivity over 120 h of reaction at 75 ℃. This study verifies that a simply control the carbonization process of metal organic frameworks can be an effective way to obtain Cu-based catalysts with superior catalytic performance for selective hydrogenation reaction.

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Efficient electrocatalytic reduction of carbon dioxide to ethylene on copper–antimony bimetallic alloy catalyst Shuaiqiang Jia, Qinggong Zhu, Haihong Wu, Meng'en Chu, Shitao Han, Ruting Feng, Jinghui Tu, Jianxin Zhai, Buxing Han 2020, 41 (7):  1091-1098.  DOI: 10.1016/S1872-2067(20)63542-2 Abstract ( 304 )   [Full Text(HTML)] () PDF (1181KB) ( 424 )   Supporting Information The exploration of efficient electrocatalysts for the reduction of CO2 to C2H4 is of significant importance but is also a challenging subject. Cu-based bimetallic catalysts are extremely promising for efficient CO2 reduction. In this work, we synthesize a series of porous bimetallic Cu-Sb alloys with different compositions for the catalytic reduction of CO2 to C2H4. It is demonstrated that the alloy catalysts are much more efficient than the pure Cu catalyst. The performance of the alloy catalysts depended strongly on the composition. Further, the alloy with a Cu:Sb ratio of 10:1 yielded the best results; it exhibited a high C2H4 Faradaic efficiency of 49.7% and a high current density of 28.5 mA cm-2 at -1.19 V vs. a reversible hydrogen electrode (RHE) in 0.1 M KCl solution. To the best of our knowledge, the electrocatalytic reduction of CO2 to C2H4 using Cu-Sb alloys as catalysts has not been reported. The excellent performance of the porous alloy catalyst is attributed to its favorable electronic configuration, large surface area, high CO2 adsorption rate, and fast charge transfer rate.

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Effect of IB-metal on Ni/SiO2 catalyst for selective hydrogenation of acetylene Hua Liu, Mengqian Chai, Guangxian Pei, Xiaoyan Liu, Lin Li, Leilei Kang, Aiqin Wang, Tao Zhang 2020, 41 (7):  1099-1108.  DOI: 10.1016/S1872-2067(20)63568-9 Abstract ( 63 )   [Full Text(HTML)] () PDF (1048KB) ( 261 )   The IB metal (Au, Ag and Cu) alloyed Pd single atom catalysts had been proved to be efficient in promoting the selectivity for hydrogenation of acetylene to ethylene. As a base metal in the same group as Pd, the Ni-based catalysts are also active for hydrogenation reactions. Herein, the effects of the IB metals on the Ni/SiO2 catalyst for the selective hydrogenation of acetylene were systematically studied. Different from the Pd/SiO2 catalyst, the monometallic Ni/SiO2 catalyst is not active at low temperatures. The addition of the IB metals to the Ni/SiO2 catalysts can greatly enhance the activity. Besides, the catalytic activity of the AgNix/SiO2 and CuNix/SiO2 catalysts increase with the reduction temperature, while the AgNix/SiO2 catalysts are not sensitive to the pretreatment temperature. The origin of the effect of the different IB metals on the Ni-based catalysts for selective hydrogenation of acetylene is discussed based on the characterizations by XRD, TPR and microcalorimetric measurements.

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Crossed intergrowth triggered TS-2 microsphere: Formation mechanism, modification and catalytic performance Hao Xu, Wenwen Tian, Liping Xu, Xin Jin, Teng Xue, Li Chen, Mingyuan He, Peng Wu 2020, 41 (7):  1109-1117.  DOI: 10.1016/S1872-2067(20)63546-X Abstract ( 143 )   [Full Text(HTML)] () PDF (1633KB) ( 168 )   Supporting Information TS-2 microspheres, consisting of intergrown primary nanocrystals, was prepared by controlling the synthetic parameters. The effects of the amount of quaternary ammonium cations as structure-directing agent, H2O/Si ratio, the presence of alcohol and the temperature were carefully investigated on the crystallization process. The high alkalinity was proved to be highly important for the preservation of the microsphere morphology initially formed, due to the unique intergrown stacking style. An alkali treatment with the aqueous solution of structure-directing agent, organic amine and ammonium salt and subsequent Na+ ion-exchange were performed to enhance the catalytic activity of TS-2 microsphere in the cyclohexanone ammoximation reactions, with both the conversion and selectivity higher than 99%. In the continuous reaction, the TS-2 microspheres exhibited to be durable catalyst with potential application in industrial ammoximation processes.

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Solvent-free crystallization of ZSM-5 zeolite on SiC foam as a monolith catalyst for biofuel upgrading Qiuyan Zhu, Yeqing Wang, Lingxiang Wang, Zhiyuan Yang, Liang Wang, Xiangju Meng, Feng-Shou Xiao 2020, 41 (7):  1118-1124.  DOI: 10.1016/S1872-2067(20)63550-1 Abstract ( 107 )   [Full Text(HTML)] () PDF (883KB) ( 244 )   Supporting Information Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy. Here, we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a honeycomb structure (ZSM-5/SiC). Characterizations of the ZSM-5/SiC by scanning electron microscopy, N2 sorption, and X-ray diffraction indicate that the zeolite sheath has been ideally coated on the surface of the SiC foam with high purity and crystallinity. Fixing Pd nanoparticles within the ZSM-5 zeolite crystals delivers a bifunctional Pd@ZSM-5/SiC catalyst, which exhibits high activity and selectivity toward diesel range paraffins in the hydrodeoxygenation of methyl oleate, a model molecule for biofuel. In comparison to the powder Pd@ZSM-5, the Pd@ZSM-5/SiC monolith catalyst shows more efficiency, which is attributed to the fast mass transfer and high heat conductivity on the honeycomb SiC structure. The durability test indicates that the Pd@ZSM-5/SiC catalyst is stable under the reaction and high-temperature regeneration conditions.

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Tunable localized surface plasmon resonances in MoO3-x-TiO2 nanocomposites with enhanced catalytic activity for CO2 photoreduction under visible light Shunji Xie, Haikun Zhang, Guodong Liu, Xuejiao Wu, Jinchi Lin, Qinghong Zhang, Ye Wang 2020, 41 (7):  1125-1131.  DOI: 10.1016/S1872-2067(20)63566-5 Abstract ( 119 )   [Full Text(HTML)] () PDF (620KB) ( 291 )   The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes. Thus far, only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO2 under visible light. The utilization of the localized surface plasmon resonance (LSPR) phenomenon is an attractive strategy for developing visible-light photocatalysts. Herein, we have succeeded in synthesizing plasmonic MoO3-x-TiO2 nanocomposites with tunable LSPR by a simple solvothermal method. The well-structured nanocomposite containing two-dimensional (2D) molybdenum oxide (MoO3-x) nanosheets and one-dimensional (1D) titanium oxide nanotubes (TiO2-NT) showed LSPR absorption band in the visible-light region, and the incorporation of TiO2-NT significantly enhanced the LSPR absorption band. The MoO3-x-TiO2-NT nanocomposite is promising for application in the photocatalytic reduction of CO2 with H2O under visible light irradiation.

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Perpendicular intergrowth ZSM-5 plates with shortened 10-MR pores Ensheng Zhan, Zhiping Xiong, Yan Zhou, Mingrun Li, Pengfei Wang, Weibin Fan, Wenjie Shen 2020, 41 (7):  1132-1139.  DOI: 10.1016/S1872-2067(20)63573-2 Abstract ( 159 )   [Full Text(HTML)] () PDF (1804KB) ( 185 )   ZSM-5 plates with a perpendicular intergrowth structure was synthesized by using a simple amine as the structure directing agent under hydrothermal conditions, in which the mother plate and the perpendicularly standing plates oriented along the (010) and (100) planes of MFI crystals, respectively. During the crystallization process, the mother plate was initially formed on the surface of the amorphous solid gel, while a set of parallel plates perpendicularly grew on its surface, via a homogeneous nucleation mechanism. The mother plate and the perpendicular plates had a similar thickness of 100-200 nm and were characterized by considerably shortened straight and zigzag 10 member ring pores, respectively. This unique intergrowth structure greatly facilitated the diffusion of the reactive molecules in HZSM-5 crystals during methanol conversion to hydrocarbons.

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Chemical looping partial oxidation over FeWOx/SiO2 catalysts Rui Liu, Chunlei Pei, Xianhua Zhang, Sai Chen, Hongfang Li, Liang Zeng, Rentao Mu, Jinlong Gong 2020, 41 (7):  1140-1151.  DOI: 10.1016/S1872-2067(20)63544-6 Abstract ( 103 )   [Full Text(HTML)] () PDF (905KB) ( 208 )   Supporting Information This paper describes the design of a FeWOx-based oxygen carrier for the chemical partial oxidation of methane (CLPOM). Thermodynamic screening and kinetic analyses both forecast the FeWOx-based oxygen carrier as a promising candidate for the production of syngas. The total methane conversion and syngas yield can be dramatically increased with this catalyst compared to the case with the unmodified WO3/SiO2, thereby enabling CLPOM with 62% methane conversion, 93% CO gas-phase selectivity, 94% H2 selectivity, and a 2.4 H2/CO ratio. The catalyst has the advantages of high availability of lattice oxygen to oxidize carbonaceous intermediates in time, together with the formation of an Fe-W alloy to promote the surface reaction. Consequently, it demonstrates excellent catalytic performance with no catalyst deactivation at 900 ℃ and 1 atm. The excellent structural stability plays an essential role in CLPOM. As revealed via XPS and ICP, the phase segregation has not been observed due to the strong interaction between Fe and W, which resulted in the formation of the Fe-W alloy during the reduction processes and the match between the ion oxidation rates of the Fe and W ions in the oxidation stage. The results provide fundamental information on the reaction mechanism of FeWOx/SiO2, and present it as a promising candidate for CLPOM.

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Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene Li Yang, Lijun Shi, Chungu Xia, Fuwei Li 2020, 41 (7):  1152-1160.  DOI: 10.1016/S1872-2067(20)63561-6 Abstract ( 107 )   [Full Text(HTML)] () PDF (913KB) ( 171 )   Supporting Information An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide (CO) as both reductant and carbonyl source, which enables facile access to amides with excellent regioselectivity and broad substrate scope. It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity. Branched amides were mainly obtained with K2PdCl4 as the metal catalyst, and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity. However, phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH3CN)4(OTf)2 was used; monodentate phosphines tended to form branched amides, and bidentate phosphines mainly formed linear amides. Trapping experiments, primary kinetic studies, and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene (further converted to enamide) and aniline, respectively, different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines. Furthermore, the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.