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Table of Content
05 September 2020, Volume 71 Issue 9
    Reviews and monographs
    From nanoscale discrete diffusion behavior control to macroscale coal chemical process
    Dali CAI, Hao XIONG, Chenxi ZHANG, Fei WEI
    2020, 71(9):  3849-3865.  doi:10.11949/0438-1157.20200366
    Abstract ( 858 )   HTML ( 42)   PDF (8173KB) ( 1783 )  
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    Based on the manipulation of chemical reactions and chemical bonds, the chemical industry solves transport problems on a spatial and temporal scale that exceeds 12 orders of magnitude, creating and producing new substances for human society. The discovery and use of crude oil have brought the chemical industry into a new era and supported the operation of modern society. However, for China, the resource endowment determines that the development of the coal chemical industry has unique strategic significance. Unlike the hydrocarbon cracking process, the modern new coal chemical industry relies on the self-assembly of small molecular from raw materials and the shape-selective effect of zeolites to produce fuels and chemicals with high selectivity. Therefore, at the sub-nanometer scale, that is, the reaction and transfer behavior of small molecules on shape-selective zeolites can no longer be regarded as continuous, but discrete, which leads to a series of phenomena such as deactivation with pseudo-phase transitions on the macroscale. Based on the discrete transfer phenomena in zeolites at the nanoscale, this paper reviews the research and discovery of a series of new phenomena using graph theory, small-world networks, and advanced characterization methods to analyze the deactivation and transfer phenomena. The atomic-level precise structural modification of the zeolite and the innovation it brings to the macro coal chemical process is introduced. Towards the future, the paradigm for analyzing the discrete behavior in zeolites established in this article will provide a new way of thinking for precisely adjusting the zeolite structure and developing the next generation coal chemical process.

    Recent progress of hydrogel materials in the field of enrichment and separation of metal ions
    Guoyu WEN, Wei WANG, Rui XIE, Xiaojie JU, Zhuang LIU, Liangyin CHU
    2020, 71(9):  3866-3875.  doi:10.11949/0438-1157.20200339
    Abstract ( 1034 )   HTML ( 43)   PDF (3170KB) ( 849 )  
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    As a promising adsorbent material, hydrogel has been widely used in the enrichment and separation of metal ions in industrial wastewaters and environmental sewages due to the high efficiency, easy operation and low energy consumption. In recent years, with the deepening of the research on host-guest recognition and metal ion coordination, the use of hydrogel materials to selectively separate and enrich metal ions has become a research hotspot. This paper reviews recent progress in the field of enrichments and separations of specific metal ions. The research status of the separations and enrichments of rare earth elements, precious metal elements and heavy metal elements by hydrogel materials are mainly introduced.

    Recent advance in transition metal oxide-based materials for oxygen evolution reaction electrocatalysts
    Ling ZHANG, Hongmei CHEN, Zidong WEI
    2020, 71(9):  3876-3904.  doi:10.11949/0438-1157.20200573
    Abstract ( 1189 )   HTML ( 53)   PDF (23182KB) ( 512 )  
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    Using renewable energy to electrolyze water to produce hydrogen is the only way to realize a green hydrogen economy. At present, the large-scale application of this technology is encumbered by the relatively low activity and stability of oxygen evolution reaction (OER) electrocatalysts. The use of cost-effective catalysts can significantly reduce the overpotential of oxygen evolution and improve the economics and power conversion efficiency of the hydrogen production process from electrolysis of water. Among the various candidates, the transition metal oxide-based (TMOs) materials show great prospects and receive ever-increasing research interests because of their diversified surface/bulk structures, natural enrichment, easy accessibility and environmental friendliness. In this review, the latest tactics aiming at enhancing activity via increasing the accessible active sites and promoting intrinsic activity have been summarized. In addition, with special emphasis on the long-term stability, the up-to-data strategies for elevating the stability are introduced. Finally, conclusions and perspectives are also presented.

    Research progress of high-efficiency membrane distillation crystallization process
    Xiaobin JIANG, Guoxin SUN, Gaohong HE
    2020, 71(9):  3905-3918.  doi:10.11949/0438-1157.20200542
    Abstract ( 851 )   HTML ( 42)   PDF (6124KB) ( 389 )  
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    The global shortage of water resources and environmental pollution has made the demands for industrial wastewater treatment, seawater desalination, and comprehensive utilization of high-value solutes increasingly urgent. Membrane distillation crystallization process cannot only make full use of low-quality heat sources, achieve high-purity water-solvent separation, but also achieve salt crystallization preparation, which is of great significance for achieving zero liquid discharge and synergistic efficiency in the separation process. At the same time, membrane distillation crystallization process can also be coupled with multi-stage flash evaporation, multi-effect distillation, nanofiltration, forward infiltration, reverse osmosis and other processes to further improve the overall separation efficiency. In addition, it also has a positive impact on regulating the external morphology of the crystal, preparing crystal products with relatively concentrated crystal size distribution and good flowability. Based on this, this article has discussed several aspects of membrane distillation crystallization principles, process control mechanisms and innovative process applications, and looking forward to the key issues and development trends of membrane distillation crystallization technology in the fields of efficient separation and precise control of the crystallization process.

    Advances in biosynthesis of fatty acids to ω-hydroxyacids and ω-amino acids
    Liangyi DING, Ganggang CHONG, Jiang PAN, Jianhe XU
    2020, 71(9):  3919-3932.  doi:10.11949/0438-1157.20200438
    Abstract ( 655 )   HTML ( 23)   PDF (2462KB) ( 247 )  
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    ω-Hydroxy fatty acids and ω-amino fatty acids can be widely used in the synthesis of polymers such as polyester and polyamide, as well as the production of chemical products such as lubricants, biofuels, and pharmaceutical intermediates. Using of the most abundant natural fatty acids as raw materials to produce fatty acid derivatives has caused extensive researches. In recent years, the biosynthetic reactions for producing medium-chain fatty acid derivatives have become more abundant. This article reviews the research progress in biosynthesis of mid-chain ω-hydroxy fatty acids and ω-amino fatty acids in recent years, indicating the synthetic routes and application potential for the sustainable production of value-added fine chemicals such as 9-hydroxynonanoic acid, 6-aminocaproic acid, and ω-aminododecanoic acid using multi-enzyme cascades.

    Research progress on stability enhancement of CsPbX3 perovskite and photovoltaic devices
    Xiaojia XU, Yongzhen WU, Weihong ZHU
    2020, 71(9):  3933-3949.  doi:10.11949/0438-1157.20200439
    Abstract ( 519 )   HTML ( 13)   PDF (8239KB) ( 140 )  
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    The CsPbX3 (X is halide anions) based all-inorganic perovskites are regarded to be one of the most appealing research hotspots among perovskite photovoltaics in the past few years, mainly due to their superior thermal stability compared to the organic-inorganic hybrid counterparts. At present, the highest photoelectric conversion efficiency of all-inorganic perovskite solar cells has reached 19.03%, which has good development potential. However, the Goldschmidt tolerance factor of this type of perovskite is close to the critical boundary value, which leads to phase instability. Accordingly, numerous works have been published on the stability enhancement of CsPbX3 perovskite in recent years. This review summarizes the progress and strategies in the preparation of stable and efficient all-inorganic perovskite solar cells (PSCs), including the enlargement of tolerance factor, enhancement of activation energy barrier for phase transition (black phase to yellow phase), and decreasing the surface energy as well as modulation of the crystallization procedure. Finally, challenges and perspective of the future development of all-inorganic CsPbX3 based PSCs are presented.

    Advances in engineering electroactive biofilms by synthetic biology approaches
    Jing XU, Zixuan YOU, Junqi ZHANG, Zheng CHEN, Deguang WU, Feng LI, Hao SONG
    2020, 71(9):  3950-3962.  doi:10.11949/0438-1157.20200456
    Abstract ( 625 )   HTML ( 24)   PDF (4554KB) ( 327 )  
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    Electroactive biofilm is a conductive polymer formed by the aggregation of extracellular polysaccharides, proteins, extracellular DNA (etracellular DNA, eDNA), fimbria and other components secreted by electrical energy cells and cross-linking with the cells themselves. Biofilms, which are different from single cells in the form of population aggregation, and play a crucial role in electrocatalytic systems including microbial fuel cells, microbial bioelectrosynthesis for the production of value-added chemicals, metal wastes treatment, and biomedicine. In the natural state, the thickness of electroactive biofilm is relatively thin, the cell quantity is small and the structure is not stable. In this review, we summarize the progress of the research on the modification of electroactive biofilm by synthetic biology in the past five years. We systematically describe the construction control of biofilm, the synthesis of structural components and the transformation of electrical conductivity, so as to realize the electroactive biofilm with high efficiency of electron transfer, and lay a foundation for the further realization of high efficiency of electrocatalysis in the future.

    Synthesis and application of five-membered ring fluoride
    Chengping ZHANG, Feiyao QING, Xiaoqing JIA, Hengdao QUAN
    2020, 71(9):  3963-3978.  doi:10.11949/0438-1157.20200582
    Abstract ( 980 )   HTML ( 36)   PDF (1766KB) ( 1099 )  
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    The synthetic routes for a series of five-membered ring fluorides by using dicyclopentadiene (DCPD), hexachlorocyclopentadiene (HCCPD) or octachlorocyclopentene (OCP) as starting materials are reviewed, including 1,2-dichlorohexafluorocyclopentene (F6-12), 1,3-dichlorohexafluorocyclopentene (F6-13), 1-chlorohepta-fluorocyclopentene (F7-1), 1,1,2,2,3,3,4-heptafluorocyclopentane (F7A), 1,1,2,2,3,3-hexafluorocyclopentane (F6A), cis-1,1,2,2,3,3,4,5-octafluorocyclopentane (cis-F8A), octafluorocyclopentene (F8E), 3,3,4,4,5,5-hexafluorocyclopentene (F6E), 1,3,3,4,4,5,5-heptafluorocyclopentene (F7E) and the application of five-membered ring fluorides in electronic cleaning, electronic etching, and synthesis of electronic fluoride solutions. It is proposed that the synthesis research of five-membered ring fluorides mainly focus on the development of novel synthetic routes, catalysts with high activity and no harm to human health, and green manufacturing. Furthermore, the application research focus on the development of the electronic grade products and the downstream products of five-membered ring fluorides.

    Synthetic biological system construction and green intelligent biological manufacturing
    Lei QIN, Jie YU, Xiaoyu NING, Wentao SUN, Chun LI
    2020, 71(9):  3979-3994.  doi:10.11949/0438-1157.20200516
    Abstract ( 802 )   HTML ( 19)   PDF (2373KB) ( 286 )  
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    The production of chemicals in microbial cell factories is one of the effective ways to solve energy and environmental problems. Many chemical products have been produced by synthetic biology, but production ability and robustness of the strains still needs to been improved. Development of intelligent cell factory and realizing intelligent biological manufacturing is an important approach to improve the production and robustness. This review introduces the research status of intelligent biological manufacturing from five following aspects: protein design, biosensor, metabolism regulation, strain evolution and fermentation process. The development of biological “intelligence” will make an important contribution to improving the production level of industrial biological processes and process energy saving and emission reduction.

    Research progress of low GWP working fluid HFO-1234ze(Z) for high temperature heat pumps
    Di ZHANG, Gang YANG, Dongpeng LIU, Xiaoling ZHANG
    2020, 71(9):  3995-4005.  doi:10.11949/0438-1157.20200538
    Abstract ( 810 )   HTML ( 22)   PDF (1594KB) ( 918 )  
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    High temperature heat pump can effectively recover industrial waste heat to achieve the purpose of energy saving,emission reduction and environmental protection. At present, novel working fluids for the high temperature heat pumps are studied to replace CFC-114 and HFC-245fa. The alternative working fluid should have low global warming potential (GWP) and good working performance. The eco-friendly working fluid HFO-1234ze(Z), whose GWP < 1 and critical temperature above 423 K, is considered as a potential heat pump replacement working fluid. This paper summarizes the research of HFO-1234ze(Z) including the synthesis technology, thermophysical properties, transport properties, and heat transfer performance. The feasibility of application of HFO-1234ze(Z) in high temperature heat pump system is analyzed. It is considered that HFO-1234ze(Z) has good performance and development prospect in high temperature heat pump.

    Research progress of two-dimensional metal organic frameworks and their derivatives for electrocatalytic water splitting
    Jiahuan MA, Weiwei YANG, Yu BAI, Kening SUN
    2020, 71(9):  4006-4030.  doi:10.11949/0438-1157.20200481
    Abstract ( 653 )   HTML ( 23)   PDF (16062KB) ( 214 )  
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    Hydrogen is a kind of renewable clean energy with development prospects. Electrocatalytic water splitting is an effective way to produce hydrogen. So it is crucial to design efficient and economical water splitting electrocatalyst. Two-dimensional metal organic frameworks (MOFs) have a unique two-dimensional layered structure and a flexible and adjustable chemical composition. In recent years, they have been widely used in the field of electrocatalytic water decomposition. Two-dimensional metal organic framework materials can be derivatized to form oxides, phosphides, sulfides, metal-carbon composites and other materials, and they also exhibit good electrocatalytic water splitting performance. Simultaneously, the intrinsic activity and reaction kinetics of two-dimensional MOFs and their derivatives can be effectively optimized through component adjustment and structural modification, thereby improving their electrocatalytic performance. This review introduces the latest research progress of two-dimensional MOFs and their derivatives for electrocatalytic water splitting, and provides perspectives on the future development.

    Research progress of interlayers for lithium-sulfur batteries
    Xin LIU, Pingli FENG, Wenshuo HOU, Zhenhua WANG, Kening SUN
    2020, 71(9):  4031-4045.  doi:10.11949/0438-1157.20200496
    Abstract ( 753 )   HTML ( 29)   PDF (5349KB) ( 463 )  
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    Lithium-sulfur batteries have received widespread attention in recent years because of their high energy density, low cost, and environmental protection. However, a series of problems are caused by polysulfides dissolution and shuttle such as loss of active substances and low utilization. Inserting a functional interlayer between the cathode and the separator is an effective way to solve these problems. We introduced the research progress of interlayer for Li-S battery in recent years. The interlayer of inhibiting polysulfide shuttles, the interlayer with low interfacial resistance and the interlayer of improving the reaction kinetics are classified and summarized. Finally, the future design directions and development prospects of the functional interlayer for Li-S battery system are given.

    Application of metal-porphyrin-based frameworks in photocatalysis
    Meng JIA, Jiabin ZHANG, Yaqing FENG, Bao ZHANG
    2020, 71(9):  4046-4057.  doi:10.11949/0438-1157.20200472
    Abstract ( 850 )   HTML ( 21)   PDF (5504KB) ( 659 )  
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    Metal-organic frameworks (MOFs) are organic-inorganic hybrid porous crystalline materials formed by metal ions or metal clusters and polydentate organic ligands connected by coordination bonds, with a large specific surface area and holes, and the structure is also easy to achieve tailoring. What??s more due to a broad absorption covering nearly all the visible light region, porphyrins can be used as organic linkers to expand the spectral response range of MOFs. Therefore, porphyrin-based MOF materials are widely used in the field of photocatalysis. This paper is to review the applications of metal-porphyrin-based framework materials in photocatalytic hydrogen evolution, oxygen evolution, reduction of CO2, degradation of organic pollutants and photocatalytic selective organic synthesis. In addition, the development of metal-porphyrin-based framework materials in the field of photocatalysis is prospected.

    Metabolic engineering strategies in biosynthesis of amino acids and their derivatives
    Hutao GAO, Xiaolin SHEN, Xinxiao SUN, Jia WANG, Qipeng YUAN
    2020, 71(9):  4058-4070.  doi:10.11949/0438-1157.20200460
    Abstract ( 832 )   HTML ( 18)   PDF (1947KB) ( 399 )  
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    The industrial production of amino acids has a history of more than 100 years, and is mostly used in animal feed and food additives. Many types of amino acids such as L-cysteine, β-alanine, S-adenosylmethionine, 4-hydroxyisocyanine acid and homoserine also have broad applications. Plant extraction and chemical synthesis are the commonly used methods to produce these amino acids and their derivatives. Compared with the way of chemical synthesis or separation and extraction, the use of microbial cells as a platform for the production of amino acids and derivatives has unique advantages such as green safety and sustainability. This review highlights the recent advances in developing metabolic engineering strategies including increase of the carbon sources uptake rate, elimination of the rate-limiting steps, enhancement of the carbon flux through the target pathway, remove of the feed-back inhibition effect and regulation of the intermediates and products transportation for biological production of amino acids and their derivatives. Our goals are to provide a landscape of current works and present guidelines to address future challenges in biosynthesis of amino acids and their derivatives using engineered microorganisms.

    Structure-activity relationships and mechanisms of triterpenoids against virus
    Bingzhi FAN, Yixin WANG, Xiaotian LIAN, Weisong XIE, Yang YU, Jianhua LIANG
    2020, 71(9):  4071-4101.  doi:10.11949/0438-1157.20200495
    Abstract ( 669 )   HTML ( 20)   PDF (6160KB) ( 261 )  
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    Triterpenoids are widely present in nature and have received wide attention because of their anti-tumor, anti-viral, antibacterial, anti-inflammatory and immunomodulatory pharmacological activities. The compounds such as oleanolic acid, ursolic acid, glycyrrhizic acid and betulinic acid in natural triterpenes all showed good anti-viral activity. This review summarizes the advances of triterpenoids and their derivatives exemplified by tetracyclic triterpenes and pentacyclic triterpenes, and focusses on the structure-activity relationships and mechanisms of anti-HIV, anti-influenza, anti-coronavirus and anti-HBV/HCV. Thus, it would provide clues for rational design and development of novel anti-viral agents for the future.

    Progresses of aggregation-induced emission materials in drug delivery and disease treatment
    Yuquan ZHANG, Shuai GUO, Yuhua WENG, Yongfei YANG, Yuanyu HUANG
    2020, 71(9):  4102-4111.  doi:10.11949/0438-1157.20200569
    Abstract ( 646 )   HTML ( 26)   PDF (2671KB) ( 381 )  
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    Drug delivery systems containing fluorescent probes have the advantage of simultaneous diagnosis and treatment in disease research. Traditional organic fluorescein may exhibit a phenomenon of aggregation caused quenching (ACQ) after aggregation at high concentration. In contrast, it is reported that when a class of fluorescein molecules aggregate in solution, a new phenomenon called aggregation-induced emission (AIE) may occur, because the intramolecular motion is restricted, the non-radiative channel of the molecule is suppressed, and the energy is released in the form of light energy under this circumstance. Drug delivery systems and therapeutic modalities based on AIE fluorescein, termed AIEgen, show promising prospects in detecting and treating life-threatening diseases. This article reviews the research progress of AIE fluorescein in drug delivery, photodynamic and photothermal therapy, and looks forward to the challenges and future directions of research in this field.

    Research progress of graphene oxide membrane for water purification
    Long TIAN, Ting LIU, Kening SUN
    2020, 71(9):  4112-4130.  doi:10.11949/0438-1157.20200551
    Abstract ( 714 )   HTML ( 26)   PDF (3794KB) ( 252 )  
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    Graphene oxide membranes have ultra-high water flux, controllable interlayer spacing and excellent separation properties. These outstanding characteristics make graphene oxide membranes promising to be a new generation of membrane materials and used for the precise separation of substances in the water environment. At present, researchers have performed numerous studies on graphene oxide membranes and achieved breakthrough results, including the transfer behavior of water in the membrane, the separation mechanism of the membrane and the preparation methods of the membrane, etc. However, there is still a lack of comprehensive understanding of graphene oxide membranes. This review systematically described the structural properties and structure-effect relationships of graphene oxide membrane, and summarized the typical preparation methods. In terms of the challenges faced by graphene oxide membrane in practical application, we focused on the existing modification methods of graphene oxide membrane. The applications of graphene oxide membrane in various water environments were also discussed. Finally, the future development of graphene oxide membrane was summarized and prospected. The aim of this paper is to provide novel ideas for the design and synthesis of high-performance graphene oxide membranes for water purification.

    Progress in the sulfur resistance of reforming catalysts
    Kening SUN, Qian CHEN, Mingming NIE, Ruijun HOU
    2020, 71(9):  4131-4140.  doi:10.11949/0438-1157.20200547
    Abstract ( 951 )   HTML ( 26)   PDF (1435KB) ( 667 )  
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    Hydrocarbon in-situ reforming hydrogen supply technology based on solid oxide fuel cell (SOFC) is an important distributed and miniaturized hydrogen production solution. Traditional nickel-based reforming catalysts often face sulfur poisoning during the reaction with trace amount of sulfur in the feedstock. In some cases, the existing sulfur may even cause severe safety risks. In this paper, the mechanisms of sulfur poisoning are summarized; the compositions and contents of sulfur species in natural gas, liquefied petroleum gas and liquid hydrocarbon are briefly described; the reported sulfur resistant catalysts for different reforming reactions are reviewed, and the effective and feasible solutions for developing sulfur-tolerant catalysts are summarized. The mechanisms of sulfur poisoning could guide the design of sulfur-resistant reforming catalyst with high performance. Finally, the paper reveals that the improvement of catalytic overall performance, the pretreatment of reforming feedstock and the design of reforming reactor and other comprehensive anti-sulfur strategies are also important research directions.

    Research progress and development tendency of heavy oil in-situ upgrading technologies
    Yingying SUN, Minghui ZHOU, Jia HUANG, Hang JIANG, Jiru YANG, Cheng FAN
    2020, 71(9):  4141-4151.  doi:10.11949/0438-1157.20200498
    Abstract ( 694 )   HTML ( 13)   PDF (1148KB) ( 181 )  
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    As an important unconventional crude oil resource in the world, heavy oil is a significant resource that guarantees country??s energy security, and major engineering needs. At present, heavy oil reservoirs which currently developed by conventional thermal recovery technology are entering the later stage of recovery. The problems of high energy consumption, high pollution and high cost in those reservoirs are becoming more and more serious, so it is in urgent need of recovery technology upgrading. In-situ upgrading of heavy oil is an irreversible reduction of viscosity in the reservoir, which is recognized as one of the most remarkable next-generation heavy oil recovery technologies in recent decade. This paper expounds the technical connotation from the technical mechanism, the modification catalyst and the effect of the production. Based on a large number of representative achievements of major research institutions and enterprises in domestic and overseas, comprehensive classification statistics were conducted on related researches of domestic and overseas according to the type of catalyst, reaction temperature and viscosity reduction effect. Existing field tests are compared by the production method and production effect. Aiming at two key-restricting problems, the next development direction is put forward.

    Fluid dynamics and transport phenomena
    Process intensification of high viscosity extraction system in microreactor via ultrasound-driven microbubbles
    Shuainan ZHAO, Chaoqun YAO, Zhikai LIU, Qiang ZHANG, Guangwen CHEN, Quan YUAN
    2020, 71(9):  4152-4160.  doi:10.11949/0438-1157.20200571
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    Aiming at the problem of weak mass transfer ability in high-viscosity-liquid systems, this paper carried out a study to introduce an inert gas into the ultrasonic microreactor to enhance the mass transfer process of the high-viscosity-liquid extraction system. Extraction of vanillin from aqueous solution to toluene was employed as a model to investigate the oscillation behavior of gas bubbles with varying shape and size as well as elucidate the enhancement mechanism of ultrasound-driven slug and microbubble on mass transfer process, respectively. The results can provide theoretical basis for the utilization of introducing gas on accelerating mass transfer between high viscous liquids. Finally, on the basis of the dimensionless Reynolds number of immiscible liquid and gas phase, and ultrasound input power, an empirical model was put forward to correlate the overall mass transfer coefficients, which shows good agreement with the measured values.

    Experimental study on effect of alcohol surfactants on bubble coalescence in full range of concentrations
    Huahai ZHANG, Yuelin WANG, Tiefeng WANG
    2020, 71(9):  4161-4167.  doi:10.11949/0438-1157.20200477
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    By experimentally measuring the bubble coalescence time of different alcohol surfactants in the full concentration range, the effects of surfactant types and their concentrations on bubble coalescence were studied. The results showed that the addition of alcohol surfactant remarkably inhibited the bubble coalescence, resulting in more stable liquid film and longer bubble coalescence time. With increasing alcohol concentration, the bubble coalescence time increased significantly in the low concentration range, but decreased in the high concentration range. The inhibition of bubble coalescence by alcohol surfactant had a critical concentration. The critical molar fraction corresponding to maximum inhibition on bubble coalescence were 0.0030 and 0.0096 for isopropanol and ethanol, respectively. In addition, by comparing the inhibition effects of different alcohols, the results show that the long-chain alcohols have stronger inhibition on bubble coalescence due to their stronger steric force. Finally, according to the Andrew model analysis, the surface tension gradient is one of the main factors that reflect the ability of the surfactant to inhibit bubble coalescence.

    Catalysis, kinetics and reactors
    Continuous synthesis of 4-bromo-3-methylanisole in modular microreaction system
    Pei XIE, Kai WANG, Jian DENG, Guangsheng LUO
    2020, 71(9):  4168-4176.  doi:10.11949/0438-1157.20200518
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    With the development of microreaction technology and the key issues of liquid-liquid batch bromination process for the synthesis of 4-bromo-3-methylanisole, a modular microreaction system was constructed by taking microreactor and microbead-packed bed as the major functional microdevice units to intensify the bromination of methylanisole. And in this modular microreaction system, the liquid-liquid heterogeneous continuous bromination of 4-bromo-3-methylanisole was studied. The following optimized conditions were obtained, concentration of Br2 (xBr2): 17.5 wt%, molar ratio of Br2 to methylanisole (nBr2/nM): 1.01, initial reaction temperature (T): 0℃, residence time (τ): 0.78 min, with yield of 4-bromo-3-methylanisole more than 98%, and percentage of polybrominated side product less than 1%. Comparing with the conventional batch process, the continuous microreaction technology has obvious advantages. For example, it can change the traditional batch process to a continuous one with a significant increase of productivity (space time yield: 6.5×104 kg/(m3·h)). Besides, since this process is mainly controlled by mass transfer, the modular microreaction system with excellent mass transfer could reduce 50% of polybrominated side product. The study might provide a good foundation for the continuously controllable synthesis of 4-bromo-3-methylanisole in safety.

    Study on sulfur tolerance of NiMox/γ-Al2O3 catalyst for dicyclopentadiene hydrogenation
    Daxin SHI, Airu LI, Zhuqing FANG, Jijuan LI, Qingze JIAO, Qin WU, Caihong FENG, Yun ZHAO, Hansheng LI
    2020, 71(9):  4177-4188.  doi:10.11949/0438-1157.20200529
    Abstract ( 615 )   HTML ( 8)   PDF (1989KB) ( 188 )  
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    The effect of Mo and its addition amount on the sulfur tolerance of Ni catalyst in the hydrogenation of dicyclopentadiene (DCPD) was studied. A series of γ-Al2O3 supported nickel-molybdenum bimetallic catalysts were prepared by the equal volume impregnation method. The performance test of the catalyst was carried out in an autoclave, the feed ratio was the catalyst∶DCPD∶cyclohexane = 1∶10∶100. The reaction was carried out at a temperature of 150℃ and a pressure of 3.5 MPa, with a stirring speed 600 r/min. Before the reaction starts, a certain amount of thiophene was added in cyclohexane in order to know the sulfur resistance of the catalyst. When the concentration of thiophene cyclohexane solution is 500 mg/L, the hydrogenation rate of the double bond of 8, 9 position of dicyclopentadiene is significantly reduced under the catalysis of Ni/γ-Al2O3, and the hydrogenation activity of double bond of 3,4 position is completely suppressed; under NiMo0.2/γ-Al2O3 catalysis, however, the hydrogenation reaction is completed within 4 h, the yield of tetrahydrodicyclopentadiene (endo-THDCPD) reaches 98%, and the sulfur resistance of the catalyst is significantly improved. Among the series of catalysts with different nickel-molybdenum ratios, NiMo0.2/γ-Al2O3 exhibited the best hydrogenation activity and sulfur resistance. Catalyst NiMo0.2/γ-Al2O3 was tested for sulfur resistance with a thiophene concentration range of 0~2000 mg/L. When the concentration of thiophene is low, the NiMo0.2/γ-Al2O3 catalyst has high hydrogenation activity and good selectivity for dicyclopentadiene; as the concentration of thiophene increases, the catalytic performance of the catalyst decreases. When the thiophene concentration is increased to 2000 mg/L, the hydrogenation reaction is extended to 6 hours, and the yield of endo-THDCPD is reduced to 95%.

    Separation engineering
    Recovery of isobutanol from esterified wastewater by PDMS composite membrane
    Chengye ZUO, Rui TU, Xiaobin DING, Weihong XING
    2020, 71(9):  4189-4199.  doi:10.11949/0438-1157.20200850
    Abstract ( 467 )   HTML ( 12)   PDF (1591KB) ( 136 )  
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    The esterification reaction of acetic acid and isobutanol produces isobutyl acetate, which generates a large amount of wastewater containing isobutanol. The conventional biochemical treatment is heavy and wastes resources. The effects of isobutanol concentration on the swelling degree and separation performance of polydimethylsiloxane (PDMS) membrane, the operating parameters of the pervaporation process and the effect of isobutyl acetate on the recovery of isobutanol by PDMS membrane were studied. The results show that with the isobutanol concentration increases from 1%(mass) to 3%(mass), the swelling degree of the PDMS membrane increases first and then stabilizes, the flux of isobutanol increases, and the separation factor is about 15. When the operating temperature increases from 30℃ to 60℃, the flux increases, the separation factor of isobutanol decreases, and the total apparent activation energy is 33.87 kJ/mol. With increase of the flow rate, the isobutanol flux is stability while the separation factor increases slightly. The trace amounts of isobutyl acetate can promote the recovery of isobutanol by the membrane. The recovery rate of isobutanol by PDMS membrane is greater than 94.0%, and the concentration of isobutanol in the retentate can be reduced to 0.1%(mass). The research results can provide a basis for PDMS composite membrane to treat low-concentration organic solvent wastewater.

    Study of PVC hollow fiber membrane grafted with DMAE by low-temperature H2O plasma surface modification
    Mingxing WANG, Xin ZHAO, Tao WANG, Jiaojiao LU, Zhiping ZHAO
    2020, 71(9):  4200-4210.  doi:10.11949/0438-1157.20200510
    Abstract ( 418 )   HTML ( 7)   PDF (2006KB) ( 209 )  
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    Using low temperature water plasma technology, methacryloxybenzyl dimethyl ammonium chloride (DMAE) monomer was grafted on the surface of the three-channel polyvinyl chloride (PVC) hollow fiber membrane (HFMs) to enhance the membrane??s hydrophilic and antibacterial properties. The ATR-FTIR and contact angle analyses revealed that the antibacterial monomers DMAE were grafted onto the HFMs. The hydrophilicity of membranes was greatly improved, resulting in an enhanced permeation of the H2O plasma-treated membrane was twice as high as that of the original membrane. At the same time, PVC-ir-H2O membrane (treated by water plasma technology)exhibited excellent anti-protein absorption ability, of which adsorbing capacity for bovine serum albumin (BSA) decreased by 67% and BSA solution flux increased from 7.7 to 40 kg?m-2?h-1. And the BSA rejection of plasma-treated membrane remained at the same level as that of the original membrane, suggesting the membrane surface damage from plasma irradiation could be neglected. Furthermore, the surface modification on HFMs is relatively uniform along the axial direction of fibers and more environment-friendly. In static antibacterial experiments, the grafted HFMs (PVC-g-DMAE) exhibited bactericidal rate of 100% against gram-negative Escherichia coli (E. coli). In dynamic filtration, the grafted module, PVC-g-DMAE, obtained above 82% bactericidal rate in feed tank. Its E. coli solution flux with 100% rejection was increased by three times as much as that of the original one. This activation-grafting technology exhibited well prospect in application of drinking water treatment membrane module, especially small household water purifiers, arising from the facile operation, low cost, and simple.

    Stable mixed metal-organic framework for efficient C2H6/C2H4 separation
    Puxu LIU, Chaohui HE, Libo LI, Jinping LI
    2020, 71(9):  4211-4218.  doi:10.11949/0438-1157.20200463
    Abstract ( 724 )   HTML ( 19)   PDF (2775KB) ( 290 )  
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    In view of lacking efficient ethane-selective adsorbent for ethane/ethylene separation, a highly stable microporous mixed metal-organic framework, termed as MUV-10(Mn), was synthesized by the solvothermal method and it could efficiently separate C2H6/C2H4 mixture. The structure and morphology of synthesized material was confirmed by XRD, SEM, TGA and BET, etc. Selectivity and corresponding adsorption heat of C2H6 and C2H4 were calculated based on single component adsorption results measured in details. The results show that MUV-10(Mn) features C2H6/C2H4 selectivity about 1.42 and can absorb more C2H6 than C2H4 at room temperature. And it has high acid, alkali and water vapor stability. Addtionally, dynamic breakthrough experiment showed MUV-10(Mn) could extracted low concentration of C2H6 from C2H6/C2H4 mixture (VC2H6?/?VC2H4=1∶9 and 1∶15) to collect C2H4 gas with high purity, which indicates the promising future of MUV-10(Mn) in C2H4 purification.

    Extraction of formic acid with G/O/W microdispersion system
    Zhikang LI, Luwei SHANG, Miaomiao NIE, Wensheng DENG, Jing TAN
    2020, 71(9):  4219-4227.  doi:10.11949/0438-1157.20200502
    Abstract ( 407 )   HTML ( 6)   PDF (1894KB) ( 124 )  
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    The enrichment of formic acid in dilute solution was achieved by complex extraction method. An extraction system with high partition coefficient was determined. The continuum model was then applied for describing mass transfer process and predicting the mass transfer characteristics in O/W system. The rate-limiting step was determined to be mass transfer of formic acid in aqueous phase, by comparison of mass transfer rates between extractant in organic phase and solute in aqueous phase. The effect of dispersion size of organic droplets on mass transfer characteristics in O/W systems was determined, indicating inefficient extraction process with low mass transfer coefficients and surficial area in O/W systems. Inert gas was introduced into extraction system and a G/O/W system was developed. The calculation of mass transfer performance in G/O/W system indicates the addition of microbubbles effectively enhances the mass transfer process. Also, suitable volumetric fraction of inert gas was optimized. According to the calculation, a double-membrane-dispersion-device was designed, with which G/O/W double emulsion was prepared and effective enrichment of formic acid from its dilute solution was realized.

    Surface and interface engineering
    Morphology prediction of lithium plating by finite element modeling and simulations based on non-linear kinetics
    Zhenkang LIN, Yaoxuan QIAO, Wei WANG, Hong YUAN, Cheng FAN, Kening SUN
    2020, 71(9):  4228-4237.  doi:10.11949/0438-1157.20200504
    Abstract ( 568 )   HTML ( 22)   PDF (2997KB) ( 502 )  
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    Lithium metal has a very high theoretical energy density and is one of the most promising anode materials for a new generation of lithium batteries. It is easy to form dendrites during the deposition of lithium metal, which greatly affects the safety and service life of lithium metal batteries. Mechanism of dendrite propagation in lithium metal batteries (LMB) is still to be fundamentally described. Herein, we studied the effects of electrochemical parameters on the behavior of lithium plating at the electrode/electrolyte interface using a tertiary current model by finite-element methods. The results show that dendrite growth is intrinsically influenced by differences in concentration and potential. A higher diffusion coefficient (De) of Li ion in electrolyte is effective to improve uniformity of local concentration and a smaller exchange current density (i0) is essential for reducing sensitivity of interface reaction. Activation polarization is beneficial for uniform plating of lithium. Thus, the polarization curve is extremely important to determine whether lithium deposits uniformly or not. This work results in a new understanding of principles for dendrite growth, and is expected to lead to new insights on strategies for dendrite suppression.

    Biochemical engineering and technology
    Synthesis of (R)-epichlorohydrin catalyzed by cross-linked cell aggregates of epoxide hydrolase
    Shuping ZOU, Zhentao JIANG, Zhicai WANG, Zhiqiang LIU, Yuguo ZHENG
    2020, 71(9):  4238-4245.  doi:10.11949/0438-1157.20200447
    Abstract ( 416 )   HTML ( 5)   PDF (1941KB) ( 195 )  
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    Polyethyleneimine (PEI) flocculation and glutaraldehyde (GA) crosslinking were used to prepare crosslinked cell aggregates (CLCAs) of whole cells of epoxide hydrolase. The effects of PEI concentration, GA concentration and diatomite carrier dosage on the activity recovery of CLCAs were investigated, the results show that the optimal values of PEI concentration, GA concentration and diatomite carrier dosage are 3% (vol), 1% (vol) and 6 g/L, respectively and activity recovery reached 88.4%. Using CLCAs as catalysts, racemic epichlorohydrin ((R,S)-ECH) as substrate, the synthesis of (R)-epichlorohydrin ((R)-ECH) in isooctane / phosphate buffer biphase system was investigated. The results show that under the condition of 3∶7 volume ratio of isooctane to buffer, substrate concentration 800 mmol/L, addition of CLCAs 18 g/L, buffer pH 8.0, temperature 35℃, the molar yield of (R)-ECH reached 45.2%, with 99.1% ee. The operational stability of CLCAs in the two-phase system was investigated, and the viability of 9 batches reused remained basically unchanged, showing good operation stability.

    Immobilization of alcohol dehydrogenase on the surface of polyethylene membrane
    Mengya GUO, Shuxin JI, Fengjuan GU, Zihui MENG, Wenfang LIU, Yanzi WANG
    2020, 71(9):  4246-4254.  doi:10.11949/0438-1157.20200509
    Abstract ( 453 )   HTML ( 5)   PDF (2197KB) ( 153 )  
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    Using polyacrylic acid (PAA) modified polyethylene (PE) membrane as a carrier, two immobilization routes of alcohol dehydrogenase (ADH) were studied, and the catalytic performance of immobilized enzyme was investigated using formaldehyde as a substrate. In the first route, PAA-PE membrane was further modified by polyethyleneimine (PEI) and then ADH was covalently linked by glutaraldehyde (GA) to the surface of PEI/PAA-PE. The results show that the optimal immobilization pH was 6.0, immobilization temperature was 5—15℃, ADH and GA concentrations were 1.0mg/ml and 0.01%(mass). For immobilized enzyme, the optimal reaction pH was 6.5, temperature was 15—30℃, and the highest reaction rate was 9.6 μmol/(L·min), the remaining activity was 47.3% after 10 use cycles. In the second route, ADH was immobilized on PAA-PE membrane with 1-(3-dimethylaminopropyl)-2-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as activators. The results show that the optimal molar ratio of EDC and NHS was 1∶0.5, and the immobilization time was 24 h. For immobilized enzyme, the optimal reaction pH was 6.5, temperature was 20—37℃, and the highest reaction rate was 15.58 μmol/(L·min), 53.8% activity was remained after 10 cycles.

    Interfacial catalytic mechanism of Pseudomonas fluorescens phospholipase B
    Yiwei ZHAO, Fangyan JIANG, Chun LI, Dazhang DAI
    2020, 71(9):  4255-4259.  doi:10.11949/0438-1157.20200527
    Abstract ( 462 )   HTML ( 3)   PDF (1311KB) ( 144 )  
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    The physicochemical property and secondary structure of Pseudomonas fluorescens phospholipase B(Pf-PLB) were analyzed base on its primary structure, and the tertiary structure of Pf-PLB was predicated. A “lid-in, side-out” hypothesis model was put forward to illuminate the possible interfacial catalytic mechanism of Pf-PLB. The structure of Pf-PLB was modified by site-directed mutagenesis, and the proposed mechanism model was verified by combining with the catalytic properties of mutant Pf-PLB.

    Energy and environmental engineering
    Effects of Xinjiang high calcium coal co-firing on melting characteristics of Ca-bearing minerals in ash
    Sheng CHEN, Dunxi YU, Jianqun WU, Yimin XIA, Yueming WANG, Minghou XU
    2020, 71(9):  4260-4269.  doi:10.11949/0438-1157.20200406
    Abstract ( 478 )   HTML ( 6)   PDF (1823KB) ( 469 )  
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    In this study, a high-calcium coal, a high-silicon-aluminum Xinjiang coal and their blends were burnt in a drop tube furnace. The computer-controlled scanning electron microscope (CCSEM) was used to analyze the total ash mineral composition and particle size distribution after combustion. Based on CCSEM analysis, the composition data of single particle ash was obtained. The thermodynamic equilibrium method was used to calculate the liquid phase ratio of minerals in the ash, and the effect of coal blending on the melting characteristics of calcium-containing minerals in the ash was analyzed. The results show that the organically bound Ca easily interacts with other minerals in the coal. The mineral species of Ca-bearing minerals in the bulk ash mainly depend on the included minerals in coal. Co-firing will promote the conversion of calcium-containing aluminosilicate in the ash to calcium-containing complex aluminosilicate, and at the same time promote the melting of calcium-containing minerals. Under low temperature conditions, the particle size distribution of molten calcium-containing minerals in co-fired coal ash is affected by the particle size distribution of the alkali metal; however, under high temperature conditions, co-firing promotes the migration of molten calcium-containing minerals to large particle size ash.

    Investigation on preparation and carbon catalytic ability of in-situ bimetallic nanoparticle YST composite anode
    Haitao CHEN, Jinshuo QIAO, Zhenhuan WANG, Wang SUN, Haijun LI, Kening SUN
    2020, 71(9):  4270-4281.  doi:10.11949/0438-1157.20200497
    Abstract ( 482 )   HTML ( 7)   PDF (5175KB) ( 202 )  
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    In this paper, the structure and performance of in-situ Cu precipitation and CuCo bimetallic precipitation of yttrium-doped strontium titanate (YST) materials as direct carbon fuel cell (DC-SOFCs) anodes were studied. A series of Co doped Y0.08Sr0.92Ti0.9-xCu0.1CoxO3-δ (x = 0, 0.1, 0.2, 0.3) anode materials are prepared by combustion method. XRD, SEM and TEM techniques are used to study the anode materials?? microstructure. When Co doping content reaches to 0.2, the CuCo bimetal nanoparticles are uniformly precipitated on anode after hydrogen reduction. The conductivity test shows that CuCo bimetallic nanoparticles can effectively improve the conductivity of the material. The impedance test in CO atmosphere showed that the smallest polarization impedance is obtained for Co0.2 anode material with precipitated CuCo bimetallic nanoparticles, and its catalytic activity is better than that of other samples. Then, the cell using Y0.08Sr0.92Ti0.7Cu0.1Co0.2 material as the anode exhibits good stability and excellent electrochemical performance at 800℃, with a maximum power density of 591 mW·cm-2. It is shown that the Y0.08Sr0.92Ti0.7Cu0.1Co0.2 is an excellent DC-SOFC anode material.

    Synthesis of bimetallic sulfide CuCo2S4 and its application in lithium-sulfur batteries
    Zhe BAI, Ruijian LI, Wenshuo HOU, Haijun LI, Zhenhua WANG
    2020, 71(9):  4282-4291.  doi:10.11949/0438-1157.20200468
    Abstract ( 693 )   HTML ( 10)   PDF (2653KB) ( 244 )  
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    Lithium-sulfur batteries have received extensive attention in recent years due to the high specific energy. However, their development needs to overcome many problems such as the shuttle effect of intermediate products, the insulation of sulfur, and the volume expansion of the cathode. To effectively suppress the shuttle effect, this paper uses a method derived from Prussian blue analogs to synthesize a spinel bimetallic sulfide CuCo2S4 and use it for the cathode of lithium-sulfur batteries. XRD, SEM, TEM, BET, XPS and other characterizations were used to analyze the crystal structure and morphology of the synthesized materials, and the electrochemical performance of the CuCo2S4-S composite cathode was tested by cyclic voltammetry and galvanostatic charge and discharge process. Studies show that the CuCo2S4-S cathode exhibits excellent electrochemical performance. The first initial capacity is 959 mA·h·g-1 at the rate of 0.2C, and 591 mA·h·g-1 remains after 100 cycles. The high discharge specific capacity and good cycling stability are attributed to the hollow structure inside the CuCo2S4 material that can accommodate the active material sulfur and play a role in physical confinement; at the same time, the polar CuCo2S4 can effectively chemically adsorb polysulfides and suppress capacity loss caused by the shuttle effect of polysulfides.

    Preparation and electrochemical properties of NiMn2O4 spinel oxide cathode
    Yang XIAO, Chunming XU, Xiaoxia YANG, Lihong ZHANG, Wang SUN, Jinshuo QIAO, Zhenhua WANG, Kening SUN
    2020, 71(9):  4292-4302.  doi:10.11949/0438-1157.20200532
    Abstract ( 662 )   HTML ( 12)   PDF (4935KB) ( 474 )  
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    Developing high-performance cathode materials is of great significance to promote the development of intermediate temperature solid oxide fuel cells (IT-SOFCs). In this paper, the spinel-type NiMn2O4 (NMO) electron-ion mixed conductor material was prepared by the sol-gel method, and it was systematically studied as the cathode of IT-SOFCs. It is found that NMO material has stable cubic phase structure by using X-ray diffraction (XRD) and the conductivity of oxygen ions is studied by the technique of electrical conductivity relaxation (ECR). It shows that NMO has excellent oxygen-ion conductivity, which provides guarantee for its electrochemical performance. Impedance spectroscopy measurements of a symmetrical cell shows a low interface impedance, which is only 0.27 Ω·cm-2 at 800℃. At the same time, an anode-supported SOFC with NMO cathode presents a maximum power density of 864.9 mW·cm-2 at 800℃. The above results demonstrate that NiMn2O4 is a potential cathode material for IT-SOFCs.

    Material science and engineering, nanotechnology
    Tribological performance of hexagonal boron nitride supported ionic liquid lubricant additives
    Zhongyi HE, Guangyue JIA, Mengmeng ZHANG, Jincan YAN, Liping XIONG, Hongbing JI
    2020, 71(9):  4303-4313.  doi:10.11949/0438-1157.20200386
    Abstract ( 500 )   HTML ( 7)   PDF (2363KB) ( 396 )  
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    A lubricating additive of ultrasonically exfoliated hexagonal boron nitride supported imidazole oleic acid ionic liquid (OL-IL/h-BN) was prepared, and the structure and morphology were characterized by SEM, TEM, FTIR, TG and XRD. The dispersion performance in polyethylene glycol 400 was tested by using Zeta potential test, and it was found that the dispersion stability was greatly improved. The tribological properties were tested using a four-ball machine, and the results showed that the friction-reducing and anti-wear properties were better than h-BN. The surface morphology and composition of the wear scars were analyzed by SEM and XPS. The XPS analysis results showed that the surface film contained chemical adsorption films and chemical reaction films such as Fe2O3 and B2O3. The formation of these films played an important role in reducing friction and wear resistance.

    Preparation and sodium storage performance of NiCo2S4/N,S-rGO nanocomposites
    Xueting FENG, Qingze JIAO, Qun LI, Caihong FENG, Yun ZHAO, Hansheng LI, Haijun LI, Huiqun CAI
    2020, 71(9):  4314-4324.  doi:10.11949/0438-1157.20200525
    Abstract ( 594 )   HTML ( 16)   PDF (3624KB) ( 307 )  
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    NiCo2S4 is a promising anode material for sodium ion batteries (SIBs). In this paper, a simple one-step method (mixing and heat treatment) was used to synthesize in-situ synthesized NiCo2S4 submicron spheres (NiCo2S4/N,S-rGO) anchored on N, S co-doped reduced graphene oxide. XPS characterization demonstrated electron transfer between NiCo2S4 and N,S-rGO, which confirmed the strong synergistic effect between NiCo2S4 and N,S-rGO. The nanoparticles self-assembled NiCo2S4 spheres effectively promoted ion diffusion, and the excellent electrical and mechanical properties of N,S-rGO not only improved the conductivity of the electrode, but also effectively buffeted the large volume changes of NiCo2S4/N,S-rGO during the charge/discharge process. Benefiting from the unique nano-architecture and strong synergistic effect, NiCo2S4/N,S-rGO applied as anode materials for SIBs presented a high reversible capacity, impressive rate capability and superior long-term stability (396.7 mA·h/g at 0.5 A/g after 130 cycles, 283.3 mA·h/g at 2 A/g after 1000 cycles). Those results open an interesting strategy for rational design and preparation of efficient anode materials for SIBs.