Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

2018 Impact Factor: 2.809

Cover Story   2023, Volume 17 Issue 9
COVER
Windmills and solar photovoltaic panels staggered on top of the mountains and greenery, with vanadium redox flow batteries to provide energy for the human world and life storage. At the bottom, the cell sketch shows the conversions of various valence electrolytes and energy. The enlarged view demonstrates the organic additives with diff [Detail] ...
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, Volume 17 Issue 9

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REVIEW ARTICLE
A review on co-pyrolysis of agriculture biomass and disposable medical face mask waste for green fuel production: recent advances and thermo-kinetic models
Melvin X. J. Wee, Bridgid L. F. Chin, Agus Saptoro, Chung L. Yiin, Jiuan J. Chew, Jaka Sunarso, Suzana Yusup, Abhishek Sharma
Front. Chem. Sci. Eng.. 2023, 17 (9): 1141-1161.  
https://doi.org/10.1007/s11705-022-2230-7

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The Association of Southeast Asian Nations is blessed with agricultural resources, and with the growing population, it will continue to prosper, which follows the abundance of agricultural biomass. Lignocellulosic biomass attracted researchers’ interest in extracting bio-oil from these wastes. However, the resulting bio-oil has low heating values and undesirable physical properties. Hence, co-pyrolysis with plastic or polymer wastes is adopted to improve the yield and quality of the bio-oil. Furthermore, with the spread of the novel coronavirus, the surge of single-use plastic waste such as disposable medical face mask, can potentially set back the previous plastic waste reduction measures. Therefore, studies of existing technologies and techniques are referred in exploring the potential of disposable medical face mask waste as a candidate for co-pyrolysis with biomass. Process parameters, utilisation of catalysts and technologies are key factors in improving and optimising the process to achieve commercial standard of liquid fuel. Catalytic co-pyrolysis involves a series of complex mechanisms, which cannot be explained using simple iso-conversional models. Hence, advanced conversional models are introduced, followed by the evolutionary models and predictive models, which can solve the non-linear catalytic co-pyrolysis reaction kinetics. The outlook and challenges for the topic are discussed in detail.

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RESEARCH ARTICLE
Incorporation of 3-dimensional lycopodium with hydrophobic nature and interconnected nano-channels into polyvinylidene fluoride membranes for desalination applications by vacuum membrane distillation
Saeed Seraj, Toraj Mohammadi, Maryam Ahmadzadeh Tofighy
Front. Chem. Sci. Eng.. 2023, 17 (9): 1162-1182.  
https://doi.org/10.1007/s11705-022-2276-6

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In the present research, for the first time, lycopodium as a novel nanofiller was incorporated into a polyvinylidene fluoride matrix to fabricate lycopodium/polyvinylidene fluoride flat-sheet membrane for desalination applications by vacuum membrane distillation process. The prepared lycopodium/polyvinylidene fluoride membranes and lycopodium were characterized by field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared, energy dispersive X-ray, and mapping analyses. Water contact angle and liquid entry pressure measurements were also performed. Response surface methodology was applied to optimize membrane structure and performance. The optimized lycopodium/polyvinylidene fluoride membrane exhibits superior performance compared to the neat polyvinylidene fluoride membrane in terms of flux, salt rejection, water contact angle, and hydrophobicity. In vacuum membrane distillation experiments, using a 15000 ppm NaCl solution as a feed at 70 °C, the neat polyvinylidene fluoride membrane, optimum membrane, and agglomerated membrane (with high lycopodium loading) demonstrated 3.80, 25.20, and 14.83 LMH flux and 63.30%, 99.99%, 99.96% salt rejection, respectively. This improvement in flux and salt rejection of the optimized membrane was related to the presence of lycopodium with hydrophobic nature and interconnected nano-channels in membrane structure. It was found that lycopodium, as the most hydrophobic material, effectively influences the membrane performance and structure for membrane distillation applications.

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Self-healing polyamide reverse osmosis membranes with temperature-responsive intelligent nanocontainers for chlorine resistance
Qian Yang, Lin Zhang, Xiao Xie, Qiong Sun, Jianguang Feng, Hongzhou Dong, Na Song, Liyan Yu, Lifeng Dong
Front. Chem. Sci. Eng.. 2023, 17 (9): 1183-1195.  
https://doi.org/10.1007/s11705-022-2287-3

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Improving the performance of reverse osmosis membranes remains great challenge to ensure excellent NaCl rejection while maintaining high water permeability and chlorine resistance. Herein, temperature-responsive intelligent nanocontainers are designed and constructed to improve water permeability and chlorine resistance of polyamide membranes. The nanocontainer is synthesized by layer-by-layer self-assembly with silver nanoparticles as the core, sodium alginate and chitosan as the repair materials, and polyvinyl alcohol as the shell. When the polyamide layer is damaged by chlorine attack, the polyvinyl alcohol shell layer dissolves under temperature stimulation of 37 °C, releasing inner sodium alginate and chitosan to repair broken amide bonds. The polyvinyl alcohol shell responds to temperature in line with actual operating environment, which can effectively synchronize the chlorination of membranes with temperature response and release inner materials to achieve self-healing properties. With adding temperature-responsive intelligent nanocontainers, the NaCl rejection of thin film composite membrane decreased by 15.64%, while that of thin film nanocomposite membrane decreased by only 8.35% after 9 chlorination cycles. Effective repair treatment and outstanding chlorine resistance as well as satisfactory stability suggest that temperature-responsive intelligent nanocontainer has great potential as membrane-doping material for the targeted repair of polyamide reverse osmosis membranes.

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Boosting the direct conversion of NH4HCO3 electrolyte to syngas on Ag/Zn zeolitic imidazolate framework derived nitrogen-carbon skeleton
Huiyi Li, Jianmin Gao, Jingjing Shan, Qian Du, Yu Zhang, Xin Guo, Shaohua Wu, Zhijiang Wang
Front. Chem. Sci. Eng.. 2023, 17 (9): 1196-1207.  
https://doi.org/10.1007/s11705-022-2289-1

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The electrochemical reduction of NH4HCO3 to syngas can bypass the high energy consumption of high-purity CO2 release and compression after the ammonia-based CO2 capture process. This technology has broad prospects in industrial applications and carbon neutrality. A zeolitic imidazolate framework-8 precursor was introduced with different Ag contents via colloid chemical synthesis. This material was carbonized at 1000 °C to obtain AgZn zeolitic imidazolate framework derived nitrogen carbon catalysts, which were used for the first time for boosting the direct conversion of NH4HCO3 electrolyte to syngas. The AgZn zeolitic imidazolate framework derived nitrogen carbon catalyst with a Ag/Zn ratio of 0.5:1 achieved the highest CO Faradaic efficiency of 52.0% with a current density of 1.15 mA·cm–2 at –0.5 V, a H2/CO ratio of 1–2 (–0.5 to –0.7 V), and a stable catalytic activity of more than 6 h. Its activity is comparable to that of the CO2-saturated NH4HCO3 electrolyte. The highly discrete Ag-Nx and Zn-Nx nodes may have combined catalytic effects in the catalysts synthesized by appropriate Ag doping and sufficient carbonization. These nodes could increase active sites of catalysts, which is conducive to the transport and adsorption of reactant CO2 and the stability of *COOH intermediate, thus can improve the selectivity and catalytic activity of CO.

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A pseudocapacitive molecule-induced strategy to construct flexible high-performance asymmetric supercapacitors
Yingqi Heng, Xiang Qin, Heng Fang, Genhui Teng, Dawei Zhao, Dongying Hu
Front. Chem. Sci. Eng.. 2023, 17 (9): 1208-1220.  
https://doi.org/10.1007/s11705-023-2304-1

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The combination of high-voltage windows and bending stability remains a challenge for supercapacitors. Here, we present an “advantage-complementary strategy” using sodium lignosulfonate as a pseudocapacitive molecule to regulate the spatial stacking pattern of graphene oxide and the interfacial architectures of graphene oxide and polyaniline. Flexible and sustainable sodium lignosulfonate-based electrodes are successfully developed, showing perfect bending stability and high electronic conductivity and specific capacitance (521 F·g−1 at 0.5 A·g–1). Due to the resulting rational interfacial structure and stable ion-electron transport, the asymmetric supercapacitors provide a wide voltage window reaching 1.7 V, outstanding bending stability and high energy-power density of 83.87 Wh·kg–1 at 3.4 kW·kg–1. These properties are superior to other reported cases of asymmetric energy enrichment. The synergistic strategy of sodium lignosulfonate on graphene oxide and polyaniline is undoubtedly beneficial to advance the process for the construction of green flexible supercapacitors with remarkably wide voltage windows and excellent bending stability.

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Characterization and comparison of organic functional groups effects on electrolyte performance for vanadium redox flow battery
Ling Ge, Tao Liu, Yimin Zhang, Hong Liu
Front. Chem. Sci. Eng.. 2023, 17 (9): 1221-1230.  
https://doi.org/10.1007/s11705-023-2298-8

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The vanadium redox flow battery with a safe and capacity-controllable large-scale energy storage system offers a new method for the sustainability. In this case, acetic acid, methane sulfonic acid, sulfonic acid, amino methane sulfonic acid, and taurine are used to overcome the low electrolyte energy density and stability limitations, as well as to investigate the effects of various organic functional groups on the vanadium redox flow battery. When compared to the pristine electrolyte (0.22 Ah, 5.0 Wh·L–1, 85.0%), the results show that taurine has the advantage of maintaining vanadium ion concentrations, discharge capacity (1.43 Ah), energy density (33.9 Wh·L–1), and energy efficiency (90.5%) even after several cycles. The acetic acid electrolyte is more conducive to the low-temperature stability of the V(II) electrolyte (177 h at −25 °C) than pristine (82 h at −2 °C). The –SO3H group, specifically the coaction of the –NH2 and –SO3H groups, improves electrolyte stability. The –NH2 and –COOH additive groups improved conductivity and electrochemical activity.

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Multi-effect anthraquinone-based polyimide enclosed SnO2/reduced graphene oxide composite as high-performance anode for lithium-ion battery
Lin Wang, Yinjie Kuang, Qian Cui, Junyu Shi, Liubin Song, Qionghua Li, Tianjian Peng
Front. Chem. Sci. Eng.. 2023, 17 (9): 1231-1243.  
https://doi.org/10.1007/s11705-023-2306-z

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The cycling stability of SnO2 anode as lithium-ion battery is poor due to volume expansion. Polyimide coatings can effectively confine the expansion of SnO2. However, linear polyimides are easily dissolved in ester electrolytes and their carbonyls is not fully utilized during charging/discharging process. Herein, the SnO2 enclosed with anthraquinone-based polyimide/reduced graphene oxide composite was prepared by self-assembly. Carbonyls from the anthraquinone unit provide fully available active sites to react with Li+, improving the utilization of carbonyl in the polyimide. More exposed carbonyl active sites promote the conversion of Sn to SnO2 with electrode gradual activation, leading to an increase in reversible capacity during the charge/discharge cycle. In addition, the introduction of reduced graphene oxide cannot only improve the stability of polyimide in the electrolyte, but also build fast ion and electron transport channels for composite electrodes. Due to the multiple effects of anthraquinone-based polyimide and the synergistic effect of reducing graphene oxide, the composite anode exhibits a maximum reversible capacity of 1266 mAh·g−1 at 0.25 A·g−1, and maintains an excellent specific capacity of 983 mAh·g−1 after 200 cycles. This work provides a new strategy for the synergistic modification of SnO2.

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Vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating for high performance zinc-ion batteries
Lin Zhang, Xinghua Qin, Lang Wang, Zifang Zhao, Liwei Mi, Qiongqiong Lu
Front. Chem. Sci. Eng.. 2023, 17 (9): 1244-1253.  
https://doi.org/10.1007/s11705-022-2293-5

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Vanadium oxides as cathode for zinc-ion batteries have attracted much attention because of their high theoretical capacity, flexible layered structure and abundant resources. However, cathodes are susceptible to the collapse of their layered structure and the dissolution of vanadium after repeated long cycles, which worsen their capacities and cycling stabilities. Herein, a synergistic engineering of calcium-ion intercalation and polyaniline coating was developed to achieve the superior electrochemical performance of vanadium pentoxide for zinc-ion batteries. The pre-intercalation of calcium-ion between vanadium pentoxide layers as pillars increase the crystal structure’s stability, while the polyaniline coating on the cathodes improves the conductivity and inhibits the dissolution of vanadium. This synergistic engineering enables that the battery system based-on the polyaniline coated calcium vanadate cathode to deliver a high capacity of 406.4 mAh·g−1 at 1 A·g−1, an ultralong cycle life over 6000 cycles at 10 A·g−1 with 93% capacity retention and high-rate capability. The vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating was verified to effectively improve the electrochemical performance of zinc-ion batteries.

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Facile synthesis of polyaniline nanorods to simultaneously enhance the mechanical properties and wear resistance of epoxy composites
Liu Jiang, Jinian Yang, Jie Dong, Shibin Nie, Yuxuan Xu, Xuesong Feng
Front. Chem. Sci. Eng.. 2023, 17 (9): 1254-1266.  
https://doi.org/10.1007/s11705-023-2297-3

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To enhance the mechanical properties and wear resistance of epoxy resin, polyaniline nanorods were first synthesized using a facile route, and then introduced into the epoxy matrix to yield composites via solution mixing. Several measurements were conducted to investigate the phase structures and compositions of polyaniline nanorods, and their positive influences on the mechanical and tribological properties of epoxy resin were also characterized. The results confirmed that the as-synthesized polyaniline exhibited representative rod-like morphologies and dispersed well in the epoxy matrix, leading to significant enhancements in the tensile strength and elastic modulus of epoxy composites. The highest values of 110.33 MPa and 2.04 GPa were obtained by adding 5%–7% polyaniline nanorods, which were 43% and 62% higher than the pure sample, respectively. The wear rate was increased first and then decreased along with polyaniline nanorods, presenting the lowest value of 2.12 × 10−5 mm3·Nm–1 by adding 5% filler, which was markedly reduced by ca. 70% compared to the control sample. Finally, the possible wear mechanism was proposed and discussed in detail. This study tried to broaden the applications of polyaniline nanorods in the field of tribology.

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Rosin side chain type catalyst-free vitrimers with high cross-link density, mechanical strength, and thermal stability
Yunpeng Shen, Weishan Tang, Jinyang Li, Zhijun Ke, Lirong Liao, Peng Yang, Yuntao Lu, Xiaoping Rao
Front. Chem. Sci. Eng.. 2023, 17 (9): 1267-1279.  
https://doi.org/10.1007/s11705-022-2291-7

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The emergence of vitrimer, a new class of polymer materials can address the problem of recyclability, reprocess ability and recyclability of thermosetting plastics. Rosin, a natural product, is an ideal raw material for the preparation of polymers in a more sustainable way. Nevertheless, due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure, the cross-link density of materials is frequently lowered. In this study, hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids, which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers. It was completely characterized by differential scanning calorimetry test, thermogravimetric analysis, shape memory test and self-healing test. The prepared vitrimers exhibited good self-healing properties, excellent heat resistance (Td = 352 °C) as well as high mechanical properties (tensile strength of 46.75 MPa). The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton. Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy. Moreover, our work expanded the application field of rosin, increased the added value of rosin, and provided a novel method for preparing rosin-based vitrimers with ideal properties.

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Optimization and simultaneous heat integration design of a coal-based ethylene glycol refining process by a parallel differential evolution algorithm
Jiahao Wang, Hao Lyu, Daoyan Liu, Chengtian Cui, Jinsheng Sun
Front. Chem. Sci. Eng.. 2023, 17 (9): 1280-1288.  
https://doi.org/10.1007/s11705-023-2301-4

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Coal to ethylene glycol still lacks algorithm optimization achievements for distillation sequencing due to high-dimension and strong nonconvexity characteristics, although there are numerous reports on horizontal comparisons and process revamping. This scenario triggers the navigation in this paper into the simultaneous optimization of parameters and heat integration of the coal to ethylene glycol distillation scheme and double-effect superstructure by the self-adapting dynamic differential evolution algorithm. To mitigate the influence of the strong nonconvexity, a redistribution strategy is adopted that forcibly expands the population search domain by exerting external influence and then shrinks it again to judge the global optimal solution. After two redistributive operations under the parallel framework, the total annual cost and CO2 emissions are 0.61%/1.85% better for the optimized process and 3.74%/14.84% better for the superstructure than the sequential optimization. However, the thermodynamic efficiency of sequential optimization is 11.63% and 10.34% higher than that of simultaneous optimization. This study discloses the unexpected great energy-saving potential for the coal to ethylene glycol process that has long been unknown, as well as the strong ability of the self-adapting dynamic differential evolution algorithm to optimize processes described by the high-dimensional mathematical model.

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Pd nano-catalyst supported on biowaste-derived porous nanofibrous carbon microspheres for efficient catalysis
Xianglin Pei, Siyu Long, Lingyu Zhang, Zhuoyue Liu, Wei Gong, Aiwen Lei, Dongdong Ye
Front. Chem. Sci. Eng.. 2023, 17 (9): 1289-1300.  
https://doi.org/10.1007/s11705-023-2299-7

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Environmental pollution caused by the presence of aromatic aldehydes and dyes in wastewater is a serious global concern. An effective strategy for the removal of these pollutants is their catalytic conversion, possibly to valuable compounds. Therefore, the design of efficient, stable and long-lifetime catalysts is a worthwhile research goal. Herein, we used nanofibrous carbon microspheres (NCM) derived from the carbohydrate chitin present in seafood waste, and characterized by interconnected nanofibrous networks and N/O-containing groups, as carriers for the manufacture of a highly dispersed, efficient and stable Pd nano-catalyst (mean diameter ca. 2.52 nm). Importantly, the carbonised chitin’s graphitized structure, defect presence and large surface area could promote the transport of electrons between NCM and Pd, thereby endowing NCM supported Pd catalyst with high catalytic activity. The NCM supported Pd catalyst was employed in the degradation of some representative dyes and the chemoselective hydrogenation of aromatic aldehydes; this species exhibited excellent catalytic activity and stability, as well as applicability to a broad range of aromatic aldehydes, suggesting its potential use in green industrial catalysis.

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Efficient flower-like ZnSe/Cu0.08Zn0.92S photocatalyst for hydrogen production application
Ying Wang, Yue Han, Ruiyang Zhao, Jishu Han, Lei Wang
Front. Chem. Sci. Eng.. 2023, 17 (9): 1301-1310.  
https://doi.org/10.1007/s11705-022-2295-3

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Photocatalytic hydrogen production utilizing abundant solar energy to produce high-calorie, clean, and pollution-free hydrogen is an important approach to solving environmental and resource problems. In this work, a high-efficiency flower-like ZnSe/Cu0.08Zn0.92S photocatalyst was constructed through element doping and the formation of a Z-scheme heterojunction. The synergistic effect of Cu doping and the built-in electric field in the heterojunction enhanced light absorption and utilization by the ZnSe/Cu0.08Zn0.92S microflowers, accelerated the separation and transfer of photogenerated electrons and effectively inhibited electron–hole recombination. Thus the photocatalytic hydrogen production ability of the ZnSe/Cu0.08Zn0.92S microflowers was increased significantly. The highly stable ZnSe/Cu0.08Zn0.92S microflowers could provide excellent catalysis of photocatalytic hydrogen production.

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COMMUNICATION
Reconstruction of Cu–ZnO catalyst by organic acid and deactivation mechanism in liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol
Fan Sun, Huijiang Huang, Wei Liu, Lu Wang, Yan Xu, Yujun Zhao
Front. Chem. Sci. Eng.. 2023, 17 (9): 1311-1319.  
https://doi.org/10.1007/s11705-022-2281-9

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A reconstructed Cu–ZnO catalyst with improved stability was fabricated by organic acid treatment method for the liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol. According to the characterization results of the fresh Cu–ZnO and reconstructed Cu–ZnO, three different forms of ZnO were suggested to be presented on the catalysts: ZnO having strong interaction with Cu species, ZnO that weakly interacted with Cu species and isolated ZnO. The first form of ZnO was believed to be beneficial to the formation of efficient active site Cu+, while the latter two forms of ZnO took the main responsibility for the deactivation of Cu–ZnO catalysts in the liquid-phase hydrogenation of diesters. The reconstruction of the Cu–ZnO catalyst by the organic acid treatment method resulted in a new Cu–ZnO catalyst with more Cu+ and less ZnO species that leads to deactivation. Furthermore, the deactivation mechanism of Cu–ZnO catalysts in liquid-phase diester hydrogenation in continuous flow system was proposed: the deposition of the polyesters on the catalysts via transesterification catalyzed by weakly interacted ZnO and isolated ZnO leads to the deactivation. These results provided meaningful instructions for designing highly efficient Cu–Zn catalysts for similar ester hydrogenation systems.

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14 articles