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Table of Content
25 April 2024, Volume 75 Issue 4
    Reviews and monographs
    Research progress of extraction technology in processing different distillate by grade and composition
    Jun LI, Liang ZHAO, Jinsen GAO, Chunming XU
    2024, 75(4):  1065-1080.  doi:10.11949/0438-1157.20240173
    Abstract ( 484 )   HTML ( 36)   PDF (1561KB) ( 252 )  
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    It is an inevitable trend to solve the excess of traditional fuel and develop green, efficient and energy-saving oil processing technology under the background of dual carbon. Developing transformative processing technology under the concept of molecular refining and realizing the transition from “fraction processing” to “component processing” is an important idea for saving energy, reduling consumption and making the best use of materials. Among them, the efficient separation of components is the most important thing to practice the concept of molecular refining and achieve fine processing. The distribution regular of chemical composition of various distillates in China and the current research status of solvent extraction technology in separating arenes, alkanes and heteroatomic compounds are introduced in detail. The separation difficulties caused by composition differences of various oil are discussed, aiming to put forward the pointcut and valuable research direction in the future.

    Recent progress in adsorption and separation of xylene isomers
    Ying LIU, Fang ZHENG, Qiwei YANG, Zhiguo ZHANG, Qilong REN, Zongbi BAO
    2024, 75(4):  1081-1095.  doi:10.11949/0438-1157.20231189
    Abstract ( 318 )   HTML ( 33)   PDF (4973KB) ( 291 )  
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    The separation and purification of xylene isomers is one of the important processes in the petrochemical industry. However, the structures and properties of xylene isomers are extremely close. Conventional distillation and cryogenic crystallization separation methods have high energy consumption and low production efficiency. Simulated moving bed chromatography is the primary technology for separating xylene isomers, but zeolites as the adsorbents are insufficient in terms of adsorption capacity and separation selectivity. Metal-organic frameworks and supramolecular materials possess advantages such as flexible assembly, structural diversity, and adjustable properties. They can achieve highly efficient discrimination and separation of xylene isomers through the construction of polar pore environment and fine-turning of the size and shape of pore channels. This review summarizes the research progress of metal-organic frameworks and supramolecular materials in the adsorption and separation of xylene isomers, discusses the intrinsic mechanisms of xylene isomers' separation from aspects including electrostatic interactions, size sieving, and shape sieving. It also summarizes the problems and limitations of metal-organic frameworks in the field of xylenes separation and provides a prospective on future development directions.

    Fundamental research on microdispersion based on artificial intelligence
    Mengqi LIU, Kai WANG, Guangsheng LUO
    2024, 75(4):  1096-1104.  doi:10.11949/0438-1157.20231406
    Abstract ( 131 )   HTML ( 20)   PDF (1377KB) ( 336 )  
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    Microdispersion is an important part of micro chemical engineering technology. The complexity of equipment and processes imposes many limitations on its related research. Under the guidance of traditional thinking, the basic research on microdispersion follows the approach of “design-experiment-modeling”, resulting in slow progress. In recent years, artificial intelligence (AI) methods have received increasing attention in chemical engineering due to their powerful recognition and regression capabilities. AI-assisted basic research on microdispersion is conducive to forming a new paradigm for understanding micro chemical engineering processes, promoting the development of micro chemical engineering technology. This article introduces the general idea of AI methods and their applicability to microdispersion investigation, reviews the developments of AI technology in microscopic image recognition, droplet and bubble dispersion size prediction, and microdispersion process control and optimization, and offers insights into the prospective directions of micro chemical engineering based on AI technology.

    Advances in nickel catalyzed controlled/living radical polymerization reactions
    Xiaokai CHENG, Wei LI, Jingdai WANG, Yongrong YANG
    2024, 75(4):  1105-1117.  doi:10.11949/0438-1157.20231407
    Abstract ( 178 )   HTML ( 22)   PDF (2390KB) ( 266 )  
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    Controlled/living radical polymerization reactions are developed to take the advantages of mild reaction conditions, well controlled reaction processes and accessible modification of polymer structures to build a variety of organic polymer materials with polar monomers as the starting materials in recent years, of which the fundamental mechanism is the reversible activation/deactivation between radical intermediates and transition-metal catalysts/chain transfer reagents. Because of the different oxidation states and the variable polymerization mechanisms, nickel catalysts have unique advantages in controlled/living radical polymerization. This article reviews the structure of catalysts, polymerization mechanisms and the structure of products of nickel catalyzed atom-transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP). The future development direction and application prospects of controlled/living radical polymerization are prospected.

    Progress in dynamically crosslinked polyolefins derived from ring-opening metathesis polymerization
    Lisheng WU, Jie LIU, Tiantian WANG, Zhenghong LUO, Yinning ZHOU
    2024, 75(4):  1118-1136.  doi:10.11949/0438-1157.20231396
    Abstract ( 195 )   HTML ( 12)   PDF (7077KB) ( 88 )  
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    Ring-opening metathesis polymerization (ROMP) provides a precise and efficient way to prepare polyolefins, which enables the preparation of functional polymer materials with different topological structures. Although thermoplastic olefin polymers can be melted and reprocessed at high temperatures, their low mechanical properties and heat resistance limit their service life under extreme conditions. In general, the thermomechanical properties of polyolefin materials can be greatly improved by crosslinking modification, but it also brings difficulties to the recycling of waste materials. To address above limitations, fabricating dynamically crosslinked polyolefins with dynamic bonds has attracted extensive attentions. These polymers enhance mechanical properties while retaining the ability to be reprocessed. This review article focuses on the recent progress of polyolefins that are synthesized via ring-opening metathesis polymerization and followed by dynamically crosslinking modification. Finally, the development status and future research of this field are summarized.

    Progress in molecular structure design for polyimide membrane materials to enhance CO2 permeation ability
    Zijia ZHANG, Xinyue QIU, Xiang SUN, Zhibin LUO, Haizhong LUO, Gaohong HE, Xuehua RUAN
    2024, 75(4):  1137-1152.  doi:10.11949/0438-1157.20231401
    Abstract ( 193 )   HTML ( 19)   PDF (4390KB) ( 470 )  
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    Membrane technology relying on the difference in gas permeation ability has been widely attempted for carbon dioxide removal from natural gases. Owing to the feature without phase change, membrane technology has remarkable advantage in energy saving. In addition, membrane plants can be manufactured under modularization layout and highly flexible to face the wide change in extraction scale for unconventional resources. Polyimide (PI) is a widely studied glassy polymer membrane material with high decarbonization selectivity and good chemical stability. In recent years, it has been industrially applied in the field of natural gas decarbonization. Even though, molecular structure design is remaining an important research direction for polyimide membrane materials to enhance carbon dioxide permeation ability and then make great savings in both investment and footprint space for membrane plants. In this review, based on the mechanism for gas permeation and separation in glassy polymeric membranes, we have summarized the research progress around aromatic polyimide membrane materials, e.g., tailoring and customizing the isomerized backbone configuration, the steric and bulky side groups, and the locally expanded segments; meanwhile, the internal relevance about these molecular structure design issues on fractional free volume and gas permeation ability are concluded. Furthermore, a concise outlook on future research direction has also been suggested for polyimide membrane materials. Taking into account both the free volume fraction and the free volume hole size distribution range is an important way to simultaneously improve permeability and selectivity.

    Advances in drug nanodelivery systems for the treatment of intracellular bacterial infections
    Xiaojie JU, Wanlu SONG, Chenyu ZHOU, Qiutong SHEN, Yutian LIAO, Jueying GONG, Liangyin CHU
    2024, 75(4):  1153-1166.  doi:10.11949/0438-1157.20231326
    Abstract ( 168 )   HTML ( 12)   PDF (1710KB) ( 69 )  
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    Intracellular bacteria can escape the body's immunity and grow and reproduce normally in the host cell, which are more difficult to remove than extracellular bacteria and can easily cause more serious infections. With traditional antibiotic treatment, the drugs cannot break through the host cell membrane barrier and can easily cause strong toxic side effects and multidrug resistance. Excellent nanocarriers have good biocompatibility and are easy to modify, which is expected to enhance membrane penetration and bacterial targeting of antibacterial drugs through the construction of nanodelivery systems, offering great potential and broad prospects in the treatment of intracellular bacterial infections. This paper introduces various nanoparticles that can be used to treat intracellular bacterial infections, summarizes the mechanisms and methods for enhancing the therapeutic effects of drug nanodelivery systems, and elaborates on the problems that still exist when using nano-drug delivery systems to treat intracellular bacterial infections, in order to provide inspiration for the construction of better drug delivery systems to treat intracellular bacterial infections.

    Research progress on endothermic nanofluid fuels
    Zhouyang SHEN, Kang XUE, Qing LIU, Chengxiang SHI, Jijun ZOU, Xiangwen ZHANG, Lun PAN
    2024, 75(4):  1167-1182.  doi:10.11949/0438-1157.20231127
    Abstract ( 112 )   HTML ( 8)   PDF (3053KB) ( 88 )  
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    Endothermic nanofluid fuel is a new type of fuel that has the potential to solve the problem of overheating hypersonic aircraft engines. In order to explore the cracking performance of endothermic nanofluid fuel and provide reference for subsequent research, this article first introduces the dispersion stability mechanism of nanofluid fuel and outlines its preparation and methods to improve stability. Secondly, the research progress on the cracking of endothermic nanofluid fuels is reviewed. The key factors affecting cracking are analyzed from various aspects such as nano additives, organic protective ligands, reaction mechanisms and pathways. Finally, the future development trend of endothermic nanofluid fuels is proposed.

    Recent progress of metal-organic framework membranes for mono/divalent ions separation
    Binyu MO, Yaxin ZHANG, Guozhen LIU, Gongping LIU, Wanqin JIN
    2024, 75(4):  1183-1197.  doi:10.11949/0438-1157.20231219
    Abstract ( 182 )   HTML ( 15)   PDF (7993KB) ( 419 )  
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    Membrane separation technology with the merits of operational simplicity, high efficiency, and environmental friendliness is considered as one of the most promising separation technologies. Metal-organic framework (MOF) is an emerging separation membrane material. Its tunable channel microstructure, high porosity, and topological diversity make it have good potential in the separation of mono/divalent ions. This article aims to review the research progress of MOF membranes for mono/divalent ions separation over the past two decades and discuss the transport mechanism in depth. It summarizes the membranes fabrication methods systematically and explores the challenges and future research directions of MOF membranes in the field of mono/divalent ions separation.

    Research progress on catalytic dehydrogenation of dodecahydro-N-ethylcarbazole as liquid organic hydrogen carrier
    Yiwei FAN, Wei LIU, Yingying LI, Peixia WANG, Jisong ZHANG
    2024, 75(4):  1198-1208.  doi:10.11949/0438-1157.20231253
    Abstract ( 198 )   HTML ( 13)   PDF (1554KB) ( 336 )  
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    In the context of carbon peak and carbon neutrality, the transformation of energy structure is imperative. The new energy system is mainly based on non-fossil energy and hydrogen energy is an essential energy carrier. At present, hydrogen storage and transportation are the main challenges for its application. Liquid organic hydrogen carrier is a promising alternative for safe and efficient hydrogen storage method. N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NEC/12H-NEC) is a good choice for hydrogen carrier. The high dehydrogenation temperature of 12H-NEC and poor stability of catalysts are the main challenges limiting the large-scale application. Therefore, this paper introduced the dehydrogenation reaction mechanism of 12H-NEC and described its reaction pathway, kinetics and catalytic reaction process. And then, the activity, stability and deactivation mechanism of dehydrogenation catalysts were concluded. The challenges of reactor design were discussed based on the characteristics of the dehydrogenation reaction and typical dehydrogenation reactors were described. Finally, in view of the potential challenges of 12H-NEC dehydrogenation reaction, a prospect for the future application of this technology in the field of hydrogen storage is put forward.

    Application and prospect of organoids-on-chip in the study of nano-drug delivery systems
    Yuwei YANG, Min LI, Zhiying YAO, Qinlin SUN, Yang LIU, Dan GE, Bingbing SUN
    2024, 75(4):  1209-1221.  doi:10.11949/0438-1157.20231262
    Abstract ( 215 )   HTML ( 15)   PDF (2668KB) ( 141 )  
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    Organoids are self-assembling three-dimensional multicellular structures derived from human stem cells, organ-specific progenitor cells or isolated tumor tissues, which could reproduce the key structural features and physiological functions of organs in vitro. As an in vitro culture platform for organoids, microfluidic chips provide opportunities to study the behavior of cells in heterogeneous populations and microenvironments. Therefore, they have become a powerful tool to assist human organ development research, disease modeling, and drug screening. Nanomaterials, as an advanced carrier for drug delivery, can significantly improve the therapeutic effects of drugs and have become the focus of new drug development. Organoids-on-chip not only provide a reliable platform for evaluating the safety and efficacy of nano-drug delivery systems, but also help the design of nanocarriers and personalized treatment. In this review, we give an update on the limitations of traditional two-dimensional cell models and animal models in nano-drug delivery systems evaluation, with an emphasis on the advantages of in vitro platforms by organoids-on-chip. It also summarized the recent application and development of organoids technology and future directions in nano-drug delivery systems.

    Energy storage technologies based on solid-liquid redox-targeting reactions: materials, devices, and kinetics
    Yunxuan LI, Xinyue LIU, Xi CHEN, Wen LIU, Mingyue ZHOU, Xingying LAN
    2024, 75(4):  1222-1240.  doi:10.11949/0438-1157.20231268
    Abstract ( 135 )   HTML ( 13)   PDF (3697KB) ( 334 )  
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    With the advancement of the carbon neutrality and the rapid development of renewable energy, energy storage technology has become a crucial pillar for addressing energy transition and sustainable development. Redox flow battery (RFB) is an electrochemical device used for large-scale energy storage. It has the characteristics of flexible design, large storage capacity, long cycle life, and high safety. However, limited by the solubility of redox mediator molecules, its energy density is relatively low, and there are few practical systems. To meet this challenge, energy storage technologies based on solid-liquid redox-targeting reactions, i.e. redox-targeting flow batteries (RTFBs) have emerged to enhance energy density, maintain excellent flowability and elevate the constraint of traditional RFBs. This review provides a comprehensive perspective of recent research progress in materials, devices, and kinetics related to RTFBs including characteristics of various materials, the design and performance of devices, as well as the characterization and modeling of kinetic processes. The bottleneck of current research is summarized and the insights into future development trends are also provided.

    A review of machine learning potentials and their applications to molecular simulation
    Dongfei LIU, Fan ZHANG, Zheng LIU, Diannan LU
    2024, 75(4):  1241-1255.  doi:10.11949/0438-1157.20231030
    Abstract ( 684 )   HTML ( 50)   PDF (1927KB) ( 862 )  
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    Molecular dynamics simulation has become an important tool for the research and development of chemical engineering processes and technologies. However, the insufficient accuracy of classical molecular dynamics simulations and the high computational cost of ab initio molecular dynamics simulations have restricted the widespread applications of molecular simulation technology. The emergence and development of machine learning technology has led to the rapid development of molecular simulation based on machine learning potentials, which offers an efficient way to achieve a greatly improved accuracy at a lower computing loading, thereby bolstering the potential of molecular simulations in practical applications. This review started by an overview of the development of machine learning potentials with emphasis on the construction methods and principles of machine learning potential models. The techniques associated with machine learning potentials including dataset construction, model training, model transfer and application were detailed. The strengths and weaknesses of different types of machine learning models were also discussed, followed by the prospects for the development and applications machine learning potentials.

    Pt-based oxygen reduction reaction catalysts: from single crystal electrode to nanostructured extended surface
    Mingze SUN, Helai HUANG, Zhiqiang NIU
    2024, 75(4):  1256-1269.  doi:10.11949/0438-1157.20231215
    Abstract ( 183 )   HTML ( 18)   PDF (2651KB) ( 148 )  
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    The development of low-cost, high-performance oxygen reduction platinum-based catalysts is still an important direction in promoting the commercialization of proton exchange membrane fuel cells (PEMFC). The investigations of the single crystal electrode surface showed the factors such as the atomic arrangement, strain between lattices, and coordination environment of the Pt metal are responsible for the activity of oxygen reduction reaction. However, the knowledge gained from extended surfaces of single crystal electrodes cannot entirely guide the design of nanocatalysts due to the see-saw relationship between activity and utilization arising from size effects in nanoparticles. By simulating the properties of single crystal electrodes at the nanoscale, it is possible to expand surface properties and achieve the two-win results to some extent. This paper reviews the theoretical and experimental results regarding the use of extended surface catalysts for the oxygen reduction reaction, and the insights into the remaining challenges and research directions of nanocatalysts are also proposed.

    Research progress in preparation technology of pitch-based carbon anode materials for sodium-ion batteries
    Xi WU, Bo SUN, Yindong LIU, Chuanlei QI, Kaiyi CHEN, Luhai WANG, Chong XU, Yongfeng LI
    2024, 75(4):  1270-1283.  doi:10.11949/0438-1157.20231274
    Abstract ( 381 )   HTML ( 34)   PDF (7044KB) ( 328 )  
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    Recently, sodium-ion batteries (SIBs) have been considered as a promising candidate as a new energy storage technology in the field of energy storage owing to their high safety and low cost of sodium. Carbon anodes act as a vital role in the components of SIBs. However, the related material preparation, sodium storage mechanism research and comprehensive performance improvement are still quite challenging now. Pitch-based precursors own the advantages of low cost, high carbon content and high carbon yield, and they have been considered as potential carbon sources for the synthesis of carbon anodes in SIBs. However, direct high-temperature pyrolysis and carbonization of pitch-based carbon sources will produce highly graphitized carbon with small carbon layer spacing, resulting in relatively low sodium storage capacity. This results an unsatisfied sodium storage capacity. In recent years, many attempts have been made to solve the difficult problems of graphitization and rearrangement for pitch-based carbon sources during the carbonization process. Various strategies have been proposed, such as asphalt modification, structural design, surface modification and carbon recombination. Owing to these efforts, the sodium storage performances of the obtained carbon anodes have been significantly improved. This review summarizes the current technological progress for the preparation of carbon anodes by using pitch as carbon source in detail. We further discuss the crucial problems and possible research priorities of pitch derived carbon anodes for SIBs in future. This review may provide a deep insight into the development of low-cost and high-performance pitch-based carbon anode for SIBs and realize the high-value utilization of pitch-based precursors.

    Advances in light isotopes separation and catalytic labeling
    Tianyi LI, Yutai WU, Yongsheng WANG, Jiarui GU, Yiheng SONG, Fengcheng YANG, Guangping HAO
    2024, 75(4):  1284-1301.  doi:10.11949/0438-1157.20231277
    Abstract ( 148 )   HTML ( 10)   PDF (5134KB) ( 99 )  
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    Stable light isotopes such as hydrogen, carbon, nitrogen and oxygen are widely used in medical drugs, clinical diagnosis, environmental geology and other fields. The enrichment of high-purity isotopes as raw materials to obtain targeted isotope-labeled compounds are core technology for isotope application. Adsorption separation based on quantum effect displays low energy footprint and high efficiency and thus is considered as a promising method for the purification of isotope gases. Catalytic isotope exchange and functional group conversion reactions are important technologies for isotope labeling. The key for both processes is the development of efficient adsorbents and catalysts. This paper summarizes the recent research progress for isotopes separation and catalytic labeling. Then, the development status of key materials is analyzed along with the strategy for performance optimization. Finally, the research challenges and developing trends in this field are prospected.

    Research progress of cationic polymerization in microreactor
    Yuhang HE, Dan XIE, Yangcheng LYU
    2024, 75(4):  1302-1316.  doi:10.11949/0438-1157.20231117
    Abstract ( 141 )   HTML ( 7)   PDF (3002KB) ( 64 )  
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    Cationic polymerization is one of the important methods for preparing polymer materials. However, due to its high reactivity and poor controllability, traditional research on cationic polymerization often faces significant challenges. Microreactor technology has unique advantages in cationic polymerization research due to its excellent process control capabilities. This article presents the research progress on traditional cationic polymerization and living cationic polymerization within microreactors. It discusses the important role of microreactors in improving the controllability, reaction efficiency, and mechanism research of cationic polymerization of isobutene and vinyl ether monomers. Furthermore, it explores the rational design of cationic polymerization systems and equipment.

    Green and biorecyclable materials based on peptide noncovalent chemistry
    Rui CHANG, Ruirui XING, Xuehai YAN
    2024, 75(4):  1317-1332.  doi:10.11949/0438-1157.20231293
    Abstract ( 90 )   HTML ( 11)   PDF (4188KB) ( 50 )  
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    Peptides, as a class of biomolecular building units, have biocompatibility, biodegradability, versatility, and sequence diversity, and can form novel materials with multi-scale structures through noncovalent chemistry. The emergence of these peptide based noncovalent chemical materials provides a method for developing eco-friendly, biodegradable and biorecyclable green biorecyclable materials. However, achieving controllable construction and functionalization of materials from single molecule design through noncovalent chemistry of peptides remains a challenge. Therefore, the article first introduced what noncovalent chemistry of peptides is, mainly describing weak intermolecular interactions. Then, it summarized how to achieve controllable construction of peptide materials from single molecule design, mainly introducing three design strategies. Finally, the applications of peptide-based materials, including biomimetic photosynthesis and photocatalysis, drug delivery and disease diagnosis and therapy, as well as processable materials, were reviewed.

    Fluorescent dyes for super-resolution imaging of organelles
    Wenchao JIANG, Zhaochao XU
    2024, 75(4):  1333-1354.  doi:10.11949/0438-1157.20231376
    Abstract ( 159 )   HTML ( 11)   PDF (8024KB) ( 98 )  
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    Super-resolution microscopy has revolutionized the field of cell biology by providing enhanced imaging capabilities that surpass the diffraction limit of conventional light microscopy. In this context, organic small molecule dyes with unique properties such as photostability, ease modification, and tunable fluorescence switching have gained new development opportunities. This review focuses on fluorescent dyes for super-resolution imaging of different cellular organelles and summarizes the design and targeting strategies of currently available super-resolution fluorescent probes. The paper begins by briefly introducing three major super-resolution imaging techniques, including structured illumination microscopy, stimulated emission depletion microscopy, and single-molecule localization microscopy, and their diverse requirements for the performance of fluorescent dyes. It also highlights fluorescent dyes used in super-resolution imaging of mitochondria, lysosomes, cell membranes, lipid droplets, and nucleus over the past five years. Finally, the article discusses the future challenges in this field.

    Controlled synthesis of high-density ultralong carbon nanotubes: progress and prospects
    Kaixuan LIU, Qinyuan JIANG, Fei WANG, Run LI, Ping ZHU, Kangkang WANG, Yonglu ZANG, Yanlong ZHAO, Rufan ZHANG
    2024, 75(4):  1355-1369.  doi:10.11949/0438-1157.20231204
    Abstract ( 294 )   HTML ( 12)   PDF (10784KB) ( 134 )  
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    Carbon nanotubes (CNTs) have broad application prospects in many cutting-edge industrial applications, such as carbon-based integrated circuits, highly strong and tough fibers, mechanical energy storage, and flexible wearable devices due to their excellent mechanical, electrical, thermal and optical properties. The structures and morphologies (e.g., length, degree of alignment, defect concentration, and degree of cleanliness) of CNTs have a significant impact on their fundamental physical properties. Among various kinds of CNTs, only ultralong CNTs with macroscale lengths, low defect concentrations, and high degrees of alignment can fully demonstrate their intrinsic performance, and meet the strict requirements of cutting-edge fields. The key to realizing the practical applications of ultralong CNTs is to realize their mass production. However, their yields can hardly satisfy the needs, indicating that the synthesis of ultralong CNTs with high densities and yields is still facing numerous challenges. This review discusses the growth mechanisms of ultralong CNTs, analyses the reasons for the low yield of ultralong CNTs, summarizes the methods for synthesizing high-density ultralong CNTs, and introduces the latest advances in the practical applications of ultralong CNTs. Besides, this review also summarizes the scientific and technological challenges and gives an in-depth discussion of the development directions in the synthesis of ultralong CNTs.

    Advances in machine learning-based materials research for MOFs: energy gas adsorption separation
    Yiru WEN, Jia FU, Dahuan LIU
    2024, 75(4):  1370-1381.  doi:10.11949/0438-1157.20231381
    Abstract ( 251 )   HTML ( 14)   PDF (1461KB) ( 157 )  
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    Metal-organic frameworks (MOFs) have attracted much attention in the field of gas adsorption and separation due to their high porosity and ultra-high specific surface area, and the database of MOFs has been enriched as a result. The use of high-throughput computational screening methods can provide rich structural properties and performance data, which is beneficial to screening materials with high performance from a large number of metal-organic framework materials. In order to fully explore the information within the data, machine learning is used as an auxiliary tool that can reveal the implicit metal-organic framework structure and property relationships. To gain a greater understanding of the performance trends of metal-organic framework materials in different applications, especially in gas storage and separation, machine learning methods are also widely used. The latest research progress in machine learning prediction and design of metal-organic framework materials applied to the adsorption and separation of combustible gases is reviewed in terms of the descriptors of metal-organic frameworks suitable for machine learning work, and the screening and prediction of material properties by using machine learning methods, which accelerates the pace of the design and development of metal-organic frameworks, and guides the direction and rules of material synthesis, reducing the cost of manpower and material resources.

    Synthetic biology of yeasts drives green biomanufacturing of succinic acid
    Tao SUN, Meili SUN, Ran LU, Yizi YU, Kaifeng WANG, Xiaojun JI
    2024, 75(4):  1382-1393.  doi:10.11949/0438-1157.20231395
    Abstract ( 244 )   HTML ( 19)   PDF (1631KB) ( 118 )  
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    Succinic acid is an important C4 platform chemical, and its industrial biomanufacturing route has significant advantages, which is a research hotspot. The microorganisms for succinic acid biosynthesis mainly include bacteria and yeasts. Compared with bacteria, although the product yield of yeasts is lower, the yeasts generally have high acid tolerance, therefore, they can synthesize succinic acid under low pH conditions, thus avoiding adding additional neutralization agent to maintain the neutral pH conditions, therefore, the downstream process for yeast-based succinic acid purification is simpler and costs lower. This article reviews the research progress in the use of yeast microorganisms to synthesize succinic acid in recent years, focusing on the synthetic biology transformation strategies of yeast production strains represented by Saccharomyces cerevisiae, Yarrowia lipolytica, and Issatchenkia orientalis. Finally, the future directions for green biomanufacturing of succinic acid by constructing yeast cell factories are proposed.

    Review on polyolefin elastomers with dynamic-chemical cross-linking
    Yangke XIAO, Yinlong CHANG, Ping LI, Wenjun WANG, Bogeng LI, Pingwei LIU
    2024, 75(4):  1394-1413.  doi:10.11949/0438-1157.20231408
    Abstract ( 182 )   HTML ( 10)   PDF (6892KB) ( 203 )  
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    Polyolefin elastomer (POE) is a high-end polyolefin material that is copolymerized from ethylene and α-olefin. It has excellent properties such as chemical stability, weather resistance and electrical insulation, and is widely used in various fields such as photovoltaic, automobile and cable. Dynamic-chemical cross-linking (DCC) can further improve its mechanical properties and thermal stability, and expand its application range while ensuring its processability. This paper reviews the preparation methods of DCC POEs, including one-step direct cross-linking and multistep cross-linking after functionalization. The functionalization methods, such as post-functionalization and copolymerization of ethylene and functional monomer, are elaborated. The characterization methods of DCC POEs and the relationship between their chain structure, aggregation structure and properties are discussed. The future prospects of DCC POEs are also presented. This paper aims to provide theoretical guidance and technical support for the controlled synthesis, structure-activity relationship study and high value application of DCC POEs, and to promote the innovation and development of high-end polyolefin materials.

    Application and research progress of functional packings in high-gravity rotating packed bed
    Ting CHENG, Weizhou JIAO, Youzhi LIU
    2024, 75(4):  1414-1428.  doi:10.11949/0438-1157.20231272
    Abstract ( 117 )   HTML ( 20)   PDF (4157KB) ( 374 )  
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    As the core component of the rotating packed bed, the packing is an important place where the microscopic mixing and mass transfer reaction processes of materials occur. The structure, material composition and filling mode of the packings determine the function of the packings, which directly affect the mass transfer performance, service life and application range of the rotating packed bed, so it is particularly important to enhance the function of the packings. By changing the surface properties, adjusting the shape and designing the structure of the commonly used packings, the functional packings are imbued with functional properties such as adsorption, catalysis and hydrophobic, which shows excellent results in improving the performance and operation effect of the rotating packed bed. In this paper, the main classification and characteristics of functional packings in rotating packed beds were reviewed, the application of functional random and structured packings in rotating packed beds in recent years was summarized, the aspects of enhancing mass transfer characteristics and improving liquid flow behavior were analyzed for explaining the functional characteristics of packings, and the development direction and industrialization prospect of functional packings were prospected.

    Research progress in theoretical calculation of pharmaceutical formulation design
    Zheng ZHANG, Wuqiong WANG, Yajing ZHANG, Kangjun WANG, Yuanhui JI
    2024, 75(4):  1429-1438.  doi:10.11949/0438-1157.20231278
    Abstract ( 109 )   HTML ( 12)   PDF (2031KB) ( 330 )  
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    Pharmaceutical formulations are not only related to the national economy and people's livelihood but also the strategic focus of national security and technological competition. Theoretical calculations play an important role in the design of pharmaceutical formulation, and modern theoretical calculation methods of pharmaceutical formulation design have been paid much attention. Theoretical calculation has important applications in the design of pharmaceutical formulations. In recent years, the development models of pharmaceutical formulations have gradually changed to the big data-driven intelligent design model with the rapid development of emerging technologies such as artificial intelligence. This article first explains the importance of theoretical calculations in the design of pharmaceutical formulations. Then, the review focuses on the current research status of theoretical calculations in pharmaceutical formulation design. Among them, various calculation methods and advantages/disadvantages were analyzed and summarized in depth such as molecular simulation, thermodynamic calculation, and artificial intelligence. On these bases, the challenges and prospects that theoretical calculations faced in designing pharmaceutical formulations were discussed. This review can provide reference and guidance for the intelligent design of pharmaceutical formulations.

    Advances on continuous-flow synthesis of drugs in microreactors
    Xiao XUE, Minjing SHANG, Yuanhai SU
    2024, 75(4):  1439-1454.  doi:10.11949/0438-1157.20231416
    Abstract ( 180 )   HTML ( 19)   PDF (2483KB) ( 116 )  
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    Due to small characteristic size of microreactors, it has a large specific surface area, high mixing efficiency, fast heat and mass transfer efficiency, and can accurately control the reaction process. Compared with the traditional synthesis in batch, the single/multi-step synthesis of drugs in microreactors can achieve the advantages of high selectivity, high efficiency and intrinsic process safety. This article reviews the recent research progress in continuous-flow synthesis of drugs and their intermediates in three commonly used microreactors, including capillary microreactors, plate microreactors and micropacked bed reactors, as well as other new microreactors. The advantages of different types of microreactors are summarized from the perspective of homogeneous and heterogeneous reactions. Finally, the development directions of continuous-flow synthesis of drugs in the future are prospected.

    Controlled preparation of droplets, particles and capsules by microfluidics and their applications
    Xiaoying JI, Yuan ZHENG, Xiaopeng LI, Zhen YANG, Wei ZHANG, Shirui QIU, Qianying ZHANG, Canghai LUO, Dongpeng SUN, Dong CHEN, Dongliang LI
    2024, 75(4):  1455-1468.  doi:10.11949/0438-1157.20231328
    Abstract ( 275 )   HTML ( 15)   PDF (6780KB) ( 249 )  
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    Microfluidics has unique advantages in the controlled preparation of droplets, particles and capsules. Microfluidics could precisely control the size, distribution, structure and composition of droplets, particles and capsules, which are widely used in the field of biomedicine, food and cosmetics. This review comprehensively summarizes the device design, preparation strategy and industrial application for the controlled preparation of droplets, particles and capsules by microfluidics. In addition, the application of multiphase flow numerical simulation of the preparation process of droplets, particles and capsules and the optimization of experimental parameters are also highlighted, as well as the parallel scale-up strategy of microfluidic devices to achieve mass production of droplets, particles and capsules. This review will provide an important guide for the preparation and application of droplets, particles and capsules.

    Application and optimization of carbon supports in proton exchange membrane fuel cells
    Binbin FENG, Mingjia LU, Zhihong HUANG, Yiwen CHANG, Zhiming CUI
    2024, 75(4):  1469-1484.  doi:10.11949/0438-1157.20231409
    Abstract ( 263 )   HTML ( 23)   PDF (3087KB) ( 346 )  
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    As the energy crisis and environmental pollution continue to intensify, there is an increasingly urgent need for devices with high energy conversion efficiency and low pollution. Proton exchange membrane fuel cell (PEMFC), as a green energy conversion device with high efficiency and zero pollution, is considered as a promising alternative to traditional energy. At present, making automotive fuel cell systems competitive in the market still faces challenges in terms of cost and durability. The current mainstream way to reduce costs is to reduce the platinum load on the catalyst. However, lower platinum loading usually means a smaller catalyst surface area and greater mass transfer resistance, resulting in loss of performance. In addition, the durability problem is also a major obstacle restricting the development of fuel cell vehicles, especially the problem of carbon corrosion. From the perspective of optimizing carbon supports, this review first combined the current research status in the field of carbon supports, and proposed the characteristics of ideal carbon supports by comparing commercial carbon supports and novel carbon supports. Secondly, based on the theory of oxygen transport resistance, different optimization strategies were discussed from the aspect of optimizing the mass transfer ability of carbon supports, including the construction of ordered column array structure, the regulation of pore structure and the regulation of surface properties of carbon supports. Among them, optimizing the pore structure of carbon supports to enhance the local mass transfer capacity is a commonly employed strategy, and mesoporous carbon supports are a prominent example of this strategy. Ordered column arrays, represented by vertically aligned carbon nanotubes (VACNT), have attracted wide attention due to their high ordered structure, efficient transport path and high catalyst utilization potential. However, they still face difficulties in water management and large-scale manufacturing. In addition to the above two strategies, the uniform distribution of the ionomer film through the surface modification of the carbon supports is also conducive to mass transfer. Then, in terms of carbon corrosion, considering the impact of carbon corrosion on the durability of PEMFC, strategies to improve the corrosion resistance of carbon supports were reviewed according to the reaction and theoretical analysis of carbon corrosion, including improving the degree of graphitization, physical coating, adding OER catalyst, surface treatment and increasing the hydrophobicity of supports. The obvious and direct way to improve the corrosion resistance of carbon supports is to increase the graphitization degree of carbon supports by high temperature calcination to obtain stable carbon structure. Finally, the development direction of carbon supports in the future is prospected, which can provide reference for the construction and design of novel carbon supports.

    Fluid dynamics and transport phenomena
    Stable flow characteristics of Geldart C particles of desulfurization ash in a loop-coupled riser
    Chengxiu WANG, Dashan SONG, Zhihui LI, Xiao YANG, Xingying LAN, Jinsen GAO, Chunming XU
    2024, 75(4):  1485-1496.  doi:10.11949/0438-1157.20231197
    Abstract ( 106 )   HTML ( 5)   PDF (2557KB) ( 57 )  
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    The proportion of CO2 emissions for industrial production is about 70% of the total CO2 release. It is important to capture this part of the CO2 emission for carbon peaking and carbon neutrality goals. Flue gas emissions contain a large amount of oxides of sulphur which are harm to the facilities and catalysts. Therefore, deep desulfurization technology of flue gas is key to CO2 capture process. Circulating fluidized bed semi-dry flue gas desulfurization has attracted wide attention because of its high desulfurization efficiency, no pollution, and controllable residence time. The desulfurization agent in the circulating fluidized bed is mostly desulfurized ash particles which are obviously Geldart C particles. Due to the desulfurized characteristics like strong adhesion, problems are prone to occur during the operation of the fluidized bed. To improve the fluidization situation, this research designed and built a loop-coupled riser reactor with an inner diameter of 100 mm, 300 mm in height, an inner diameter of an outer cylinder of 160 mm, 760 mm in the height, and a conveying section of 75 mm in inner diameter and 12.6 m in height. Under two operating conditions, namely Ug = 4 m/s, Gs = 45 kg/(m2·s) and Ug = 7 m/s, Gs = 25 kg/(m2·s), the pressure distribution, standard deviation and power of the pressure were investigated. It can be considered that when the gas velocity in the annulus zone is 0.4 m/s, the circulation flow in the loop part can reach stable with a continuous dense-phase flow. Then, the distribution of particle flow characteristics including solids holdup and particle velocity in the loop-coupled riser reactor was studied. Experiments have found that the design of circulating flow can strengthen the flow characteristics of Geldart C particles, greatly increase the solid content of Geldart C particle desulfurization ash in the coupling reactor, and achieve stable operation of the Geldart C particle circulation fluidization device. Meanwhile, these results may provide some guide for design new types of reactors for Geldart C particle of emission control.

    Model development and validation of structural two-fluid model for heat transfer in a gas-solid bubbling fluidized bed
    Jinpeng ZHAO, Yongmin ZHANG, Bin LAN, Jiewen LUO, Bidan ZHAO, Junwu WANG
    2024, 75(4):  1497-1507.  doi:10.11949/0438-1157.20231332
    Abstract ( 153 )   HTML ( 17)   PDF (1634KB) ( 155 )  
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    The mesoscale structures such as clusters and bubbles have a significant impact on the flow, transfer, and reaction process of heterogeneous gas-solid systems. This article proposes a structural two-fluid model for simulating the hydrodynamics and heat transfer in a complex gas-solid system. Based on the different flow control mechanisms, the bubbling fluidized bed system is treated as two interpenetrating fluids that are the fluids of gas-dominated bubble phase and the particle-dominated emulsion phase. With this fundamental idea, we establish the governing equations and constitutive relationships considering the influence of mesoscale structure. Reasonable empirical correlations are utilized to close the interphase drag force, the emulsion phase viscosity, the interphase heat transfer coefficient, and the thermal conductivity of each fluid. Present structural two-fluid model in conjunction with an explicit resolution of hydrodynamic and thermal boundary layer is employed to simulate a bubbling fluidized bed system with a vertical heating tube. The simulation results demonstrate that the structural two-fluid model accurately predicts the axial distribution of solid holdup as well as the bed-to-wall heat transfer coefficient, specifically, the relative error between the simulated and experimental values of the wall heat transfer coefficient in the dense phase regime is less than 10%, and the simulated wall heat transfer coefficient in the dilute phase regime is in the same order of magnitude as the experimental value. It shows that the structural two-fluid heat transfer model can accurately describe the flow heat transfer characteristics of the gas-solid two-phase in the bubbling bed system.

    Catalysis, kinetics and reactors
    Low energy consumption preparation of anhydrous calcium chloride from hydrated calcium chloride based on reaction coupling
    Yaqing ZANG, Yijun ZHANG, Jinzhao WANG, Qian WANG, Dianqing LI, Junting FENG, Xue DUAN
    2024, 75(4):  1508-1518.  doi:10.11949/0438-1157.20231410
    Abstract ( 122 )   HTML ( 8)   PDF (2508KB) ( 59 )  
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    Under the urgent need to reduce the energy consumption of industrial thermal dehydration processes, this work reports a new strategy for low-energy dehydration of hydrated calcium chloride coupled with low-temperature water-gas shift (WGS) reaction based on the basic principle of reaction coupling. Using industrial-garde hydrated calcium chloride as raw material, water with certain chemical reactivity in hydrated calcium chloride was directly used as a reactant in the water-gas shift reaction. The experimental results showed that the residual crystallized water number was reduced to 0.38 via this coupling process at 413 K for 2 h, while there is 0.37 via the tradition way at 413 K for 3 h. In this way, a type Ⅰ industrial anhydrous calcium chloride product (CaCl2·0.38H2O) was prepared by coupling catalytic dehydration with the treatment time shortened by 1/3, indicating that the coupled catalytic dehydration strategy is conducive to saving energy consumption. In situ FTIR and CO-TPD-MS experiments showed that CO can be chemically or quasi-chemically adsorbed on the surface of hydrated calcium chloride samples, and MS analysis detected CO2 and H2 in the dehydration products, indicating that coupled catalytic dehydration indeed occurred. Furthermore, SEM, BET and MIP showed that the anhydrous CaCl2 prepared by coupling WGS reaction dehydration has abundant pore structures, which are formed during coupling WGS reaction dehydration from the surface. The results of the water vapor adsorption test showed that the pore structure is beneficial to increasing the contact area with water, so that it showed a faster water absorption rate than commercial anhydrous calcium chloride. The low-energy consuming coupled catalytic dehydration strategy reported in this work is expected to show universality for the dehydration of more materials.

    Preparation of five-fold twinned copper nanowires@polypyrrole and their electrocatalytic conversion of nitrate to ammonia
    Xiaoqing YAN, Ying ZHAO, Yuzhe ZHANG, Honghui OU, Qizhong HUANG, Huagui HU, Guidong YANG
    2024, 75(4):  1519-1532.  doi:10.11949/0438-1157.20240007
    Abstract ( 106 )   HTML ( 14)   PDF (6872KB) ( 55 )  
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    Reasonable design of nanostructured catalysts with high activity, selectivity, stability, and low cost is a significant challenge for achieving efficient electrocatalytic reduction of nitrate to ammonia. In this study, we successfully prepared a five-fold twinned copper nanowires@polypyrrole (T-CuNW@ppy) by hydrothermal coupled in-situ reduction method, which achieved ammonia production activity under low bias voltage, improved Faradaic efficiency, and significantly improved corrosion resistance. At a bias of -0.4 V (vs RHE), the T-CuNW-10 exhibited an impressive ammonia synthesis activity of 13.83 mg·mg-1·h-1; while at a bias of -0.7 V (vs RHE) it reached 23.24 mg·mg-1·h-1. Furthermore, the Faradaic efficiency of NO2- and NH3 is a close to 100%. Additionally, the corrosion current is reduced to 3.14 μA·cm-2. Overall, our findings demonstrate that this catalyst not only exhibits high efficiency and stability in nitrate reduction performance but also provides valuable insights for the development and design of industrial application-oriented catalysts.

    Preparation of high adhesion Pd/SiO2/NF monolithic catalyst and its hydrogenation performance
    Yu HAN, Le ZHOU, Xin ZHANG, Yong LUO, Baochang SUN, Haikui ZOU, Jianfeng CHEN
    2024, 75(4):  1533-1542.  doi:10.11949/0438-1157.20231296
    Abstract ( 105 )   HTML ( 15)   PDF (2459KB) ( 45 )  
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    The high-speed scouring and strong centrifugal force of the liquid in the rotating packed bed reactor (RPB) can easily cause the coating and active components of the monolithic catalyst to fall off the surface of the matrix and cause losses, which limits the application of monolithic catalysts in RPB reactors. Therefore, it is important to investigate the adhesion of coatings and active components to improve the catalytic activity and lifetime of monolithic catalysts in the RPB reactor. In this work, the SiO2 coating was deposited on nickel foam by the high gravity spraying method to prepare Pd/SiO2(x)/NF monolithic catalysts. The monolithic catalysts were characterized by ultrasonic oscillation test, BET, XRD, SEM and XPS. When the rotational speed was 1200 r/min, the monolithic catalyst had the excellent adhesion performance, and the mass loss rate of the coating was 4%. The Pd/SiO2(1200)/NF monolithic catalyst exhibited good catalytic activity in the hydrogenation of p-nitroanisole (PNA) to p-aminoanisole (PA) reaction in the RPB reactor, and the conversion of PNA was 98.9% within 180 min. This work provides a new strategy for the development of stable monolithic catalysts.

    Efficient synthesis of fluoroethylene carbonate via phase transfer catalysis using [bmim][BF4]
    Fangtao JIANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN, Jing ZHANG
    2024, 75(4):  1543-1551.  doi:10.11949/0438-1157.20231271
    Abstract ( 124 )   HTML ( 10)   PDF (2166KB) ( 382 )  
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    As one of the key components in lithium battery electrolyte additives, fluoroethylene carbonate (FEC) is primarily produced industrially using the halogen exchange process. During the FEC synthesis, a substitution reaction between potassium fluoride (KF) and chloroethylene carbonate (CEC) occurs, the rate of which has been limited by the interphase mass transfer of KF. Meanwhile, the CEC is susceptible to an elimination reaction to form by-product of vinylene carbonate. To address these issues, the effect of phase transfer catalyst (PTC) structure on the interphase mass transfer of KF and reaction energy barriers were investigated. It was revealed that the optimized conditions consist of [bmim][BF4] (1-butyl-3-methylimidazolium tetrafluoroborate) as the PTC, acetonitrile as the solvent, a reaction temperature of 81.6℃, and a KF∶CEC molar ratio of 2.5∶1. Under the optimized reaction conditions, an unprecedently high yield of FEC (91.94%, molar fraction) was achieved. Density functional theory calculations suggested that the [bmim][BF4] can form complexes with the KF in acetonitrile to increase the nuclear distance between K+ and F- and decrease the free energy of solvation of KF. As a result, the interphase mass transfer of KF was facilitated and the energy barrier of the substitution reaction between KF and CEC was reduced, which contributed to the efficient production of FEC from CEC.

    Study on design of polymeric ionic liquids and the performance for selective oxidation of cyclohexane
    Ruirui WANG, Ying JIN, Yumei LIU, Mengyue LI, Shengwen ZHU, Ruiyi YAN, Ruixia LIU
    2024, 75(4):  1552-1564.  doi:10.11949/0438-1157.20231301
    Abstract ( 68 )   HTML ( 11)   PDF (2762KB) ( 124 )  
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    Different molecular weights of poly(vinylimidazole) were synthesized by using vinyl imidazole as a monomer and different amounts of initiators. Thermogravimetric (TG) analysis showed that the polymer had good thermal stability. A series of polymeric ionic liquids (PIL) were synthesized by quaternization of the optimal polymer with three different alkyl chain lengths: 1-chlorooctadecane, 1-chlorododecane, and 1-chlorohexane. The chemical structure and morphology of the polymeric ionic liquids were analyzed by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and contact angle testing. The catalytic performance of PIL-C18, PIL-C12, and PIL-C6 for selective cyclohexane oxidation was investigated. Furthermore, PIL-C12 was selected to conduct in-depth research on the influence of ion rates (PIL-C12-X, X=10, 25, 50, 75, 100) on catalytic performance. The results showed that the length of alkyl chain segment and the ionic ratio could effectively influence the hydrophobicity and active site of the catalysts to improve the performance with the conversion of 21.8% and selectivity of 41.5% for cyclohexane oxidation to adipic acid.

    Strong wave-absorbing catalyst cooperates with microwave energy to enhance fructose dehydration to produce 5-hydroxymethylfurfural
    Anran XU, Kai LIU, Na WANG, Zhenyu ZHAO, Hong LI, Xin GAO
    2024, 75(4):  1565-1577.  doi:10.11949/0438-1157.20240105
    Abstract ( 87 )   HTML ( 9)   PDF (3868KB) ( 206 )  
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    Multihole hollow carbon spheres (MHCS) were prepared by using a hard template method. The effects of heat treatment temperature, metal loading, and etching on the electromagnetic parameters of MHCS were systematically studied. Among the prepared carbon spheres, MHCS-800 with high dielectric loss (ε″ = 213) was selected as the support for catalysts, while SCS-800 (ε″ = 50) and SCS (ε″ = 0.08) served as control groups. These carbons after sulfonation were used to catalyze the hydrolysis of fructose. Based on the reaction kinetics under microwave (MW) and conventional heating conditions, the influence of dielectric loss on the MW-assisted catalytic effect was investigated. The results showed that the conversion rate can reach 97.7% within 5 min using MHCS-800-SO3H as catalysts under 80 W MW power irradiation. Besides, the reaction rate constant (k) under MW is 0.76 min-1, which is 8.97 times of that under conventional heating (k=0.0847 min-1). The MW enhancement effect occurred in MHCS-800-SO3H is much more significant compared with SCS-800-SO3H and SCS-SO3H (where k values were increased by 164.9% and 11.9%, respectively). The above results can be attributed to the combination of the hollow porous structure and the high graphitization degree of MHCS-800, which is conducive to the formation of “hotspots” on the surface of catalyst particles, thereby accelerating catalytic reactions.

    Preparation of high-efficiency iron-cobalt bimetallic site oxygen reduction electrocatalysts by step-by-step metal loading method
    Xudong JIA, Bolong YANG, Qian CHENG, Xueli LI, Zhonghua XIANG
    2024, 75(4):  1578-1593.  doi:10.11949/0438-1157.20240073
    Abstract ( 88 )   HTML ( 9)   PDF (8109KB) ( 56 )  
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    Transition metals and nitrogen-doped carbon (M-N-C) have risen to prominence as alternatives to platinum-based catalysts, acclaimed for their superior electrocatalytic activity and comparatively lower production costs. However, current M-N-C catalysts usually involve a combination of metal salts, nitrogen-containing substances and carbon supports. The resulting catalysts after heat treatment and acid washing processes lack sufficient performance in terms of active site density and mass transfer capacity. In this paper, Fe, Co bimetallic doped M-N-C catalysts were prepared by step-by-step metal loading method. Taking advantage of the competitive effect of Zn2+ and Co2+, a small-sized and uniform Zn-Co-ZIFs bimetallic zeolite imidazole framework was successfully synthesized. Subsequently, the maximum number of Fe atoms is embedded into the C-Zn-Co-ZIFs-H+ precursor structure without forming metal clusters, so that it can generate a large number of FeCo—N x active sites after pyrolysis. This refinement engenders a substantial augmentation in the Fe active site content of the FeCo-N-C-2 catalyst (1.9%, mass fraction), and a profound optimization of its microporous and mesoporous architecture (860 m2·g-1), culminating in enhanced electrochemical activity and stability. The catalyst exhibited half-wave potentials (E1/2) for oxygen reduction reaction (ORR) of 0.806 V in 0.1 mol·L-1 HClO4 and 0.921 V in 0.1 mol·L-1 KOH, maintaining 91.21% and 95.32% of its activity respectively after 50000, 45000 s of a constant voltage test. Moreover, this catalyst has achieved peak power densities of 746 mW·cm-2 in proton exchange membrane fuel cells (PEMFCs) and 164 mW·cm-2 in alkaline zinc-air flow batteries (ZAFBs), demonstrating its superior performance.

    Microwave induced construction of highly dispersed Pd/FeP catalysts and their electrocatalytic performance
    Ang LI, Zhenyu ZHAO, Hong LI, Xin GAO
    2024, 75(4):  1594-1606.  doi:10.11949/0438-1157.20231388
    Abstract ( 91 )   HTML ( 12)   PDF (6785KB) ( 429 )  
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    As a novel method of process intensification, microwave technology has been widely used in material preparation. The selective heating characteristic of microwave-absorbing support can lead to the formation of local overheating domains, inducing the deposition of catalyst over the support surface, which is promising to construct highly dispersed Pd-based catalysts that are crucial to improve their electrocatalytic activity and therefore promote the performance of formic acid fuel cells. With the aim to explore the feasibility of facile fabrication of highly dispersed Pd-based catalysts induced by microwave, this study first prepared microwave-absorbing ferrous phosphide (FeP) particles in the shape of hollow sea urchin using a hydrothermal method to serve as catalyst support, where Pd was deposited through ethylene glycol reduction under conventional heating and microwave heating methods, respectively. XRD, TEM, and SEM technologies were used to characterize the morphology and microstructure of Pd/FeP products, and to explore the effect of microwave heating on the dispersion of metal palladium particles on the catalyst surface. The catalytic activity of the prepared catalyst was evaluated using cyclic voltammetry and linear voltammetry. By exploring the structure-activity relationship between the structure of catalysts and their electrocatalytic activity, the strengthening mechanism of microwave synthesis on the performance of Pd/FeP catalyst was revealed. The experimental results indicate that the microwave-absorbing hollow sea urchin shaped FeP can induce the in situ deposition of Pd due to the formation of local “hot spots”, inducing the generation of highly dispersed Pd-based catalysts. Compared to traditionally prepared catalysts, the electrochemical active area of these catalysts obtained from microwave synthesis has a 3.5-fold increase, while the electrocatalytic oxidation performance of formic acid increases by about 54 times.

    Separation engineering
    Controllable construction of Cu(Ⅰ) in Y zeolite for adsorptive separation of ethylene/ethane
    Kaibo ZHANG, Jiaxin SHEN, Yuxia LI, Peng TAN, Xiaoqin LIU, Linbing SUN
    2024, 75(4):  1607-1615.  doi:10.11949/0438-1157.20231199
    Abstract ( 80 )   HTML ( 6)   PDF (1388KB) ( 51 )  
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    The similarity in the physical properties of ethylene (C2H4) and ethane (C2H6) makes their selective separation one of the most challenging chemical separation processes. Utilizing the π-complexation between Cu(Ⅰ) active species and C2H4, Cu(Ⅰ)-based adsorbents can achieve their selective separation, significantly reducing the cost and environmental impact resulting from the high energy consumption of traditional distillation processes. Cu(Ⅰ)-based adsorbents are prepared by reducing Cu(Ⅱ)-containing samples, but the uncontrollable Cu(Ⅱ) reduction, low Cu(Ⅰ) yields, and high energy consumption have been the obstacles to the application of Cu(Ⅰ)-based materials. Here, a selective reduction strategy has been successfully employed to selectively construct Cu(Ⅰ) active sites in Y zeolite, enabling the selective separation of C2H4/C2H6 under mild conditions. Using formaldehyde (HCHO) vapor diffusion transfer to react with Cu(Ⅱ) in zeolite, the selective construction of Cu(Ⅰ) at low temperature (140℃) was achieved. Compared to the original Cu(Ⅱ)Y, Cu(Ⅰ)Y exhibits excellent C2H4/C2H6 selective separation performance. Cu(Ⅰ)Y achieves a selectivity of 16.3, far higher than the selectivity of Cu(Ⅱ) of 3.2. Finally, the formation mechanism of Cu(Ⅱ) is revealed, in which Cu(Ⅱ) in the zeolite is selectively converted to Cu(Ⅰ) along with the production of CO2 and H2O.

    Adsorption properties of functionalized porous carbon nitride materials for uranium
    Yuan MENG, Shan NI, Yafeng LIU, Wenjie WANG, Yue ZHAO, Yudan ZHU, Liangrong YANG
    2024, 75(4):  1616-1629.  doi:10.11949/0438-1157.20231276
    Abstract ( 108 )   HTML ( 11)   PDF (7136KB) ( 49 )  
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    The separation and enrichment of uranium from seawater and wastewater is of great significance to the sustainable development of energy and environmental protection. A porous carbon nitride adsorbent (d-g-CN) rich in cyano groups and hydroxyl groups was prepared through one-step alkalization and heat-condensation polymerization of melamine, and its adsorption performance for uranium was studied. The results of adsorption experiments showed that under the conditions of pH=6.0 and 298 K, the adsorption of uranium by d-g-CN reached equilibrium in about 3 h, and the saturated adsorption capacity was 2476.23 mg∙g-1. The adsorption process conformed to the pseudo second order kinetic model and Freundlich isotherm model. In addition, d-g-CN had excellent selectivity and cyclicity. When there were many competitive ions in the solution, the adsorption distribution coefficient of d-g-CN for uranium reached 1.48×104 ml∙g-1. The adsorption efficiency remained about 89.5% after six cycles. Because the large specific surface area of d-g-CN provided more adsorption sites, and functional groups of cyano and hydroxyl had coordination effect with uranium, d-g-CN showed excellent adsorption performance, and had certain application potential in the extraction of low concentration uranium.

    Research and industrial application of coupled impurity removal technology in CHPPO process oxidation liquids
    Xiao DONG, Zhishan BAI, Xiaoyong YANG, Wei YIN, Ningpu LIU, Qifan YU
    2024, 75(4):  1630-1641.  doi:10.11949/0438-1157.20231413
    Abstract ( 102 )   HTML ( 8)   PDF (2527KB) ( 55 )  
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    Cumene hydroperoxide (CHPPO) is a new green process for producing propylene oxide. However, how to remove impurities such as organic acids and Na+ from the cumene oxidation solution has always been a key issue in the CHPPO process. Addressing problems like high investment, large footprint, and poor mass transfer effects of existing alkali water washing tower units, a coupled impurity removal technology based on static mixing and coalescence separation was developed through pilot and semi-industrial trials. This research also studied the effect of various operational conditions on the separation performance of the coupled technology, achieving efficient impurity removal from cumene oxidation liquid. The results show that under conditions with a 1.5% NaOH solution concentration, alkali solution usage at 4%—5% of the oxidation liquid feed volume, pure water usage at 3%—5%, and self-circulation volume at 10%—15%, the processed oxidation liquid had a total acid content below 10 mg/L and Na+ content below 0.5 mg/L. Furthermore, the coupled impurity removal technology was industrially applied for the first time in a petrochemical setting, resulting in processed oxidation liquid with an organic acid content of 33 mg/L and Na+ content of 0.4 mg/L, meeting the technical requirements for pretreatment in the epoxidation section. This also led to a 5% reduction in alkali and water usage, significantly enhancing the green attributes of the facility. This technology offers a highly promising option for solving deep purification issues in oxidation liquids and advancing the development of the epichlorohydrin synthesis process.

    Preparation of ZTIF based hydrophobic micro-mesoporous carbon and their adsorption and separation performance of 5-hydroxymethylfurfural
    Tiantian LYU, Min YUAN, Jiang WANG, Meizhen GAO, Jiahui YANG, Hong XU, Jinxiang DONG, Qi SHI
    2024, 75(4):  1642-1654.  doi:10.11949/0438-1157.20231418
    Abstract ( 96 )   HTML ( 6)   PDF (4715KB) ( 180 )  
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    The stock solution of 5-hydroxymethylfurfural (5-HMF) that has undergone acidic catalytic conversion of biomass is composed of a low-concentration aqueous solution and multi-component acidic by-products levulinic acid (LA) and formic acid (FA). Therefore, the design of 5-HMF separation adsorbents requires hydrophobicity, acid resistance, and high selectivity. In this work, porous carbon with acid resistance, hydrophobicity and suitable micro-mesoporous distribution were obtained by controlling carbonization temperature and activation conditions using high N-content zeolitic tetrazolate-imidazolate frameworks (ZTIFs) as precursors, and the π-π interaction between porous carbon and 5-HMF can be used to achieve efficient enrichment and separation of 5-HMF in acid-containing aqueous solution. Three types of ZTIF-8 based porous carbon with different N-content and micro-mesoporous distribution were obtained by controlling carbonization temperature and activating alkali carbon ratio using ZTIF-8 as precursor. The relationship between the N-content and micro-mesoporous distribution of ZTIF-8 based porous carbon and the adsorption and separation performance of 5-HMF has been established. NCZTIF-8700C-800A2, with low N-content and abundant large micropores and small mesopores (12—30 Å), is an adsorbent for efficient enrichment and separation of 5-HMF from aqueous solutions containing acidic by-products.

    Process system engineering
    Targeted intelligent molecular generation framework based on fragments chemical space
    Huaqiang WEN, Quanhu SUN, Weifeng SHEN
    2024, 75(4):  1655-1667.  doi:10.11949/0438-1157.20230992
    Abstract ( 127 )   HTML ( 11)   PDF (2696KB) ( 233 )  
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    Molecular generation has emerged as a cost-effective and rapid approach for advancing the design and optimization of solvents for separation, reaction, catalysts, functional materials, pharmaceuticals, and other molecules. Existing molecular generation models, mainly based on deep learning frameworks, suffer from limited transparency and struggle to explore local chemical spaces effectively. In this work, we propose a function-driven molecular intelligent generation framework based on molecular fragment chemical space. Using molecular functional indicators as the direction for generation, and the “scaffolds-decorations” set of generated molecules as the basis, this framework explored the molecular fragment chemical space to facilitate targeted molecule generation. In addition, by using the chemical space deconstruction model proposed in this work, new structures from neighboring chemical spaces of excellent molecular structures are derived, thus enriching the variety of new molecules. By demonstrating the generation of drug-like molecules as an example, this framework starts from a smaller set of excellent molecules (644) and ultimately generates five times more excellent molecules (3158) of the same level, which illustrates the framework's ability to efficiently evolve a multitude of novel and high-quality molecules on the basis of diverse samples. This framework can combine functional objectives and constraints in actual chemical processes to promote new optimal designs such as green solvents at the process scale.

    Surface and interface engineering
    Foam rupture properties of mineral base oils based on molecular dynamics simulation
    Kang ZHOU, Jianxin WANG, Hai YU, Chaoliang WEI, Fengqi FAN, Xinhao CHE, Lei ZHANG
    2024, 75(4):  1668-1678.  doi:10.11949/0438-1157.20231251
    Abstract ( 101 )   HTML ( 11)   PDF (4407KB) ( 50 )  
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    Foam in lubricating oil increases wear between equipment, and reducing foam in oil can effectively reduce energy consumption. Representative hydrocarbon components of four mineral base oils were selected to construct a molecular simulation system of foam liquid film. The microscopic mechanism of the liquid film rupture process is analyzed through molecular dynamics simulations, and the rupture time of the one-component and mixed-component liquid film is calculated as the stability metric of the liquid film. On this basis, the effects of base oil structures, the additive and antifoam agent on the rupture time of oil-based foam film are analyzed. The results show that the appearance of initial holes in the process of liquid film rupture will significantly accelerate the rupture process. After adding additives and anti-foam agents to each base oil system, the change in the time of liquid film rupture was consistent with the change in diffusion coefficient, which was in line with the drainage mechanism of foam rupture. This work aims to analyze the stability and rupture mechanism of oil-based foams at the molecular level, and to explore ways to reduce the foam in lubricating oil.

    Biochemical engineering and technology
    Mitochondria-targeted rhodamine photosensitizers for tumor fluorescence imaging
    Shupeng WANG, Jianjun DU, Yao YAO, Jiangli FAN, Xiaojun PENG
    2024, 75(4):  1679-1686.  doi:10.11949/0438-1157.20231417
    Abstract ( 126 )   HTML ( 20)   PDF (2560KB) ( 102 )  
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    Two examples of fluorescent dyes RDMID-C and RDMID-N using rhodamine as the parent were designed and synthesized. The results showed that the dyes exhibited low cytotoxicity, good biocompatibility, and the ability to target mitochondria. The fluorescence dyes showed higher co-localization coefficient with commercial mitochondrial dyes in co-localization experiments, and had longer retention time in tumors, which could be used for tumor fluorescence imaging.

    Energy and environmental engineering
    Design and performance of 5 kW reforming methanol high temperature proton exchange membrane fuel cell system
    Jin ZHANG, Zhibin GUO, Laiming LUO, Shanfu LU, Yan XIANG
    2024, 75(4):  1697-1704.  doi:10.11949/0438-1157.20231383
    Abstract ( 230 )   HTML ( 18)   PDF (1081KB) ( 114 )  
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    Compared with pure hydrogen, liquid methanol has the advantages of convenient storage and transportation, wide range of sources, and high volume energy density. It can also be used to produce hydrogen through on-site reforming and combine it with high-temperature proton exchange membrane fuel cells (HT-PEMFC) to generate electricity. It is expected to solve the challenge of using hydrogen in low-temperature PEMFC. In this work, an HT-PEMFC stack and a methanol reformer (MSR) were employed. The HT-PEMFC stack shows an output of 5.46 kW@80 A at 160℃ and H2/air atmosphere. Meanwhile, the MSR has a gas flow rate of 5 m3/h, where the content of the syngas is 74.8% for H2, 1% for CO and 24.2% for CO2. When the MSR and HT-PEMFC were integrated into the system with parallel configuration for the two thermal subsystems, the power output of the system is consistent with the value of the stack at H2/air atmosphere. More importantly, the methanol aqueous solution (volume ratio 6∶4) consumption rate of the system is only 0.81 kg/(kW·h). In conclusion, the MSR/HT-PEMFC system shows promising applications in stationary energy supply and emergency power supply.

    Material science and engineering, nanotechnology
    Performance and mechanism of novel antimony oxo cluster photoresist
    Youming SI, Lingfeng ZHENG, Pengzhong CHEN, Jiangli FAN, Xiaojun PENG
    2024, 75(4):  1705-1717.  doi:10.11949/0438-1157.20231414
    Abstract ( 153 )   HTML ( 27)   PDF (3081KB) ( 131 )  
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    With the increasing integration of semiconductor industry, higher requirements are put forward for lithographic materials. In recent years, metal- oxygen oxo clusters (MOCs) photoresists have been widely studied due to the small size and flexible structure design. At present, antimony-based photoresistsare limited to antimony-containing complexes. In this paper, a novel antimony-oxygen oxo cluster photoresist was developed, and the advantages of the self-assembly strategy was demonstrated by comparing the solubility difference between metal-organic assembled Sb4O-1 and self-assembled Sb4O-2. Atomic force microscopy (AFM) confirmed that Sb4O-2 photoresists can form smooth films with a low roughness value (root mean square roughness<0.3 nm). Electron beam lithography (EBL) demonstrated the excellent patterning ability of Sb4O-2 photoresist(line width<50 nm), and theoretical calculations supported a novel self-assembled Sb4O-2 “ligand dissociation” mechanism analyzed by X-ray photoelectron spectroscopy (XPS). This work inspired the exploration of additional metal oxygen oxo cluster materials.

    Fluorine spectrum analysis and structural characterization of Y-type perfluoropolyether carboxylic acid
    Wenhui ZHANG, Ruyi TANG, Xili CUI, Huabin XING
    2024, 75(4):  1718-1723.  doi:10.11949/0438-1157.20231411
    Abstract ( 165 )   HTML ( 9)   PDF (873KB) ( 61 )  
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    Perfluoropolyether and their derivatives (PFPEs) are a class of fluoropolymers with high added value. Their specific physicochemical properties make them have a good commercial prospect. At present, domestic related products are heavily dependent on imports, and there is a lack of research on PFPEs, especially on Y-type PFPEs, so it is urgent to strengthen the development and research in related fields. Nuclear magnetic resonance fluorine spectroscopy (19F NMR) is an important technique for the structure analysis of perfluorinated polyether compounds. However, due to technical blockade and difficulties in preparation, the analysis of 19F NMR spectroscopy of Y-type PFPE carboxylic acid (PFPE-CA) is still not perfect. In this study, appropriate sample preparation conditions were used to obtain a clear 19F NMR spectrum of Y-type PFPE-CA, and chemical shifts of F atoms in different chemical environments in the main chain and end group were assigned. The composition of the active mixture and the number average molecular weight of the sample can be calculated by integrating the spectral peaks. This analysis method is accurate and fast, and provides a research basis for the breakthrough of production and separation technology of Y-type PFPEs.

    Spray-anti-solvent crystallization method for preparing doped aluminum powder composite microspheres
    Jing LIU, Wenbo YANG, Yingdi LYU, Shengyang TAO
    2024, 75(4):  1724-1734.  doi:10.11949/0438-1157.20231397
    Abstract ( 123 )   HTML ( 7)   PDF (6862KB) ( 243 )  
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    Nano-aluminum powder is widely used in the field of energetic composite materials as a high-energy additive. However, the preparation of high sphericity aluminum powder doped composite microspheres is faced with a series of challenges. In this paper, a spray-crystallization method for the preparation of composite functional microspheres formed by nano-aluminum powder and organic molecules was explored by using the method of spray and anti-solvent crystallization. Through the self-designed internal mixing three-flow air atomization nozzle, the precursor liquid is atomized into liquid droplets. After receiving in the anti-solvent receiving bath, the solvent and anti-solvent rapidly mutual diffusion and mass transfer process occur. The energetic molecular simulation sucrose octaacetate (SOA) is precipitated in the droplet, the aluminum powder is wrapped in it, and the aluminum powder doped composite microspheres are obtained after washing and drying. In this paper, by adjusting suitable conditions such as atomization, solvent and anti-solvent, additives, etc., the phenomenon of low sphericity and agglomeration of the composite microspheres after drying was successfully solved. Finally, the doped aluminum powder microsphere composite material with narrow particle size distribution, uniform morphology, good dispersion, sphericity and high compactness was prepared.