Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

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Formation of CaCO3 hollow microspheres in carbonated distiller waste from Solvay soda ash plants
Wenjiao Xu, Huaigang Cheng, Enze Li, Zihe Pan, Fangqin Cheng
Frontiers of Chemical Science and Engineering    2022, 16 (11): 1659-1671.   https://doi.org/10.1007/s11705-022-2173-z
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For decades, distiller waste and CO2 were not the first choice for production of high valued products. Here, CaCO3 hollow microspheres, a high-value product was synthesized from such a reaction system. The synthetic methods, the formation mechanism and operational cost were discussed. When 2.5 L·min–1·L–1 CO2 was flowed into distiller waste (pH = 11.4), spheres with 4–13 μm diameters and about 2 μm shell thickness were obtained. It is found that there is a transformation of CaCO3 particles from solid-cubic nuclei to hollow spheres. Firstly, the Ca(OH)2 in the distiller waste stimulated the nucleation of calcite with a non-template effect and further maintained the calcite form and prevented the formation of vaterite. Therefore, in absence of auxiliaries, the formation of hollow structures mainly depended on the growth and aging of CaCO3. Studies on the crystal morphology and its changes during the growth process point to the inside–out Ostwald effect in the formation of hollow spheres. Change in chemical properties of the bulk solution caused changes in interfacial tension and interfacial energy, which promoted the morphological transformation of CaCO3 particles from cubic calcite to spherical clusters. Finally, the flow process for absorption of CO2 by distiller waste was designed and found profitable.

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Smart systems engineering contributing to an intelligent carbon-neutral future: opportunities, challenges, and prospects
Xiaonan Wang, Jie Li, Yingzhe Zheng, Jiali Li
Frontiers of Chemical Science and Engineering    2022, 16 (6): 1023-1029.   https://doi.org/10.1007/s11705-022-2142-6
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This communication paper provides an overview of multi-scale smart systems engineering (SSE) approaches and their applications in crucial domains including materials discovery, intelligent manufacturing, and environmental management. A major focus of this interdisciplinary field is on the design, operation and management of multi-scale systems with enhanced economic and environmental performance. The emergence of big data analytics, internet of things, machine learning, and general artificial intelligence could revolutionize next-generation research, industry and society. A detailed discussion is provided herein on opportunities, challenges, and future directions of SSE in response to the pressing carbon-neutrality targets.

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Design and optimization of reactive distillation: a review
Chang Shu, Xingang Li, Hong Li, Xin Gao
Frontiers of Chemical Science and Engineering    2022, 16 (6): 799-818.   https://doi.org/10.1007/s11705-021-2128-9
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Reactive distillation process, a representative process intensification technology, has been widely applied in the chemical industry. However, due to the strong interaction between reaction and separation, the extension of reactive distillation technology is restricted by the difficulties in process analysis and design. To overcome this problem, the design and optimization of reactive distillation have been widely studied and illustrated for plenty of reactive mixtures over the past three decades. These design and optimization methods of the reactive distillation process are classified into three categories: graphical, optimization-based, and evolutionary/heuristic methods. The primary objective of this article is to provide an up-to-date review of the existing design and optimization methods. Desired and output information, advantages and limitations of each method are stated, the modification and development for original methodologies are also reviewed. Perspectives on future research on the design and optimization of reactive distillation method are proposed for further research.

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A review on membrane distillation in process engineering: design and exergy equations, materials and wetting problems
Stefano Capizzano, Mirko Frappa, Francesca Macedonio, Enrico Drioli
Frontiers of Chemical Science and Engineering    2022, 16 (5): 592-613.   https://doi.org/10.1007/s11705-021-2105-3
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One of the problems that most afflicts humanity is the lack of clean water. Water stress, which is the pressure on the quantity and quality of water resources, exists in many places throughout the World. Desalination represents a valid solution to the scarcity of fresh water and several technologies are already well applied and successful (such as reverse osmosis), producing about 100 million m3·d−1 of fresh water. Further advances in the field of desalination can be provided by innovative processes such as membrane distillation. The latter is of particular interest for the treatment of waste currents from conventional desalination processes (for example the retentate of reverse osmosis) as it allows to desalt highly concentrated currents as it is not limited by concentration polarization phenomena. New perspectives have enhanced research activities and allowed a deeper understanding of mass and heat transport phenomena, membrane wetting, polarization phenomena and have encouraged the use of materials particularly suitable for membrane distillation applications. This work summarizes recent developments in the field of membrane distillation, studies for module length optimization, commercial membrane modules developed, recent patents and advancement of membrane material.

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Anticorrosive composite self-healing coating enabled by solar irradiation
Zhentao Hao, Si Chen, Zhifeng Lin, Weihua Li
Frontiers of Chemical Science and Engineering    2022, 16 (9): 1355-1366.   https://doi.org/10.1007/s11705-022-2147-1
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Self-healing coatings for long-term corrosion protection have received much interest in recent years. However, most self-healing coatings rely on healants released from microcapsules, dynamic bonds, shape memory, or thermoplastic materials, which generally suffer from limited healing times or harsh conditions for self-healing, such as high temperature and UV radiation. Herein, we present a composite coating with a self-healing function under easily accessible sunlight by adding Fe3O4 nanoparticles and tetradecanol into epoxy resin. Tetradecanol, with its moderate melting point, and Fe3O4 nanoparticles serve as a phase-change component and photothermal material in an epoxy coating system, respectively. Fe3O4 nanoparticles endow this composite self-healing coating with good photothermal properties and a rapid thermal response time under simulated solar irradiation as well as outdoor real sunlight. Tetradecanol can flow to and fill defects by phase transition at low temperatures. Therefore, artificial defects created in this type of self-healing coating can be healed by the liquified tetradecanol induced by the photothermal effect of Fe3O4 nanoparticles under simulated solar irradiation. The healed coating can still serve as a good barrier for the protection of the underlying carbon steel. These excellent properties make this self-healing coating an excellent candidate for various engineering applications.

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Review on design, preparation and performance characterization of gelled fuels for advanced propulsion
Kang Xue, Jinwen Cao, Lun Pan, Xiangwen Zhang, Ji-Jun Zou
Frontiers of Chemical Science and Engineering    2022, 16 (6): 819-837.   https://doi.org/10.1007/s11705-021-2122-2
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With the increasing demand for high-performance and safe fuels in aerospace propulsion systems, gelled fuels have attracted increasing attention. Because of their unique structure, gelled fuels exhibit the advantages of both solid and liquid fuels, such as high energy density, controllable thrust and storage safety. This review provides an overview on design, preparation and performance characterization of gelled fuels. The composition, preparation process and gelation mechanism of gelled high-energy-density fuels are described. Considering these aspects, the rheology and flow behavior of gelled fuels is summarized in terms of the shear thinning property, dynamic viscoelasticity and thixotropy. Moreover, the progress of atomization of gelled fuels is reviewed with a focus on the effect of atomizing nozzles. In addition, the experiments and theoretical models of single droplet combustion and combustor combustion are described. Finally, research directions for the development and application of gelled fuels are suggested.

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Chemically triggered life control of “smart” hydrogels through click and declick reactions
Xing Feng, Meiqing Du, Hongbei Wei, Xiaoxiao Ruan, Tao Fu, Jie Zhang, Xiaolong Sun
Frontiers of Chemical Science and Engineering    2022, 16 (9): 1399-1406.   https://doi.org/10.1007/s11705-022-2149-z
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The degradation of polymeric materials is recognized as one of the goals to be fulfilled for the sustainable economy. In this study, a novel methodology was presented to synthesize multiple highly cross-linked polymers (i.e., hydrogels) through amine–thiol scrambling under mild conditions. Amine-terminated poly(ethylene glycol) (PEG-NH2) was reacted with the representative conjugate acceptors to synthesize hydrogels in organic and aqueous solutions, respectively. The materials above exhibited high water-swelling properties, distributed porous structures, as well as prominent mechanical strengths. It is noteworthy that the mentioned hydrogels could be degraded efficiently in hours to release the original coupling partner, which were induced by ethylene diamine at ambient temperature through amine-amine metathesis. The recovered PEG-NH2 reagent could be employed again to regenerate hydrogels. Due to the multiple architectures and functions in polymeric synthesis, degradation and regeneration, a new generation of “smart” materials is revealed.

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Optimising the oil phases of aluminium hydrogel-stabilised emulsions for stable, safe and efficient vaccine adjuvant
Lili Yuan, Xiao-Dong Gao, Yufei Xia
Frontiers of Chemical Science and Engineering    2022, 16 (6): 973-984.   https://doi.org/10.1007/s11705-021-2123-1
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To increase antibody secretion and dose sparing, squalene-in-water aluminium hydrogel (alum)-stabilised emulsions (ASEs) have been developed, which offer increased surface areas and cellular interactions for higher antigen loading and enhanced immune responses. Nevertheless, the squalene (oil) in previous attempts suffered from limited oxidation resistance, thus, safety and stability were compromised. From a clinical translational perspective, it is imperative to screen the optimal oils for enhanced emulsion adjuvants. Here, because of the varying oleic to linoleic acid ratio, soybean oil, peanut oil, and olive oil were utilised as oil phases in the preparation of aluminium hydrogel-stabilised squalene-in-water emulsions, which were then screened for their stability and immunogenicity. Additionally, the underlying mechanisms of oil phases and emulsion stability were unravelled, which showed that a higher oleic to linoleic acid ratio increased anti-oxidative capabilities but reduced the long-term storage stability owing to the relatively low zeta potential of the prepared droplets. As a result, compared with squalene-in-water ASEs, soybean-in-water ASEs exhibited comparable immune responses and enhanced stability. By optimising the oil phase of the emulsion adjuvants, this work may offer an alternative strategy for safe, stable, and effective emulsion adjuvants.

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A review on the application of nanofluids in enhanced oil recovery
Jinjian Hou, Jinze Du, Hong Sui, Lingyu Sun
Frontiers of Chemical Science and Engineering    2022, 16 (8): 1165-1197.   https://doi.org/10.1007/s11705-021-2120-4
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Enhanced oil recovery (EOR) has been widely used to recover residual oil after the primary or secondary oil recovery processes. Compared to conventional methods, chemical EOR has demonstrated high oil recovery and low operational costs. Nanofluids have received extensive attention owing to their advantages of low cost, high oil recovery, and wide applicability. In recent years, nanofluids have been widely used in EOR processes. Moreover, several studies have focused on the role of nanofluids in the nanofluid EOR (N-EOR) process. However, the mechanisms related to N-EOR are unclear, and several of the mechanisms established are chaotic and contradictory. This review was conducted by considering heavy oil molecules/particle/surface micromechanics; nanofluid-assisted EOR methods; multiscale, multiphase pore/core displacement experiments; and multiphase flow fluid-solid coupling simulations. Nanofluids can alter the wettability of minerals (particle/surface micromechanics), oil/water interfacial tension (heavy oil molecules/water micromechanics), and structural disjoining pressure (heavy oil molecules/particle/surface micromechanics). They can also cause viscosity reduction (micromechanics of heavy oil molecules). Nanofoam technology, nanoemulsion technology, and injected fluids were used during the EOR process. The mechanism of N-EOR is based on the nanoparticle adsorption effect. Nanoparticles can be adsorbed on mineral surfaces and alter the wettability of minerals from oil-wet to water-wet conditions. Nanoparticles can also be adsorbed on the oil/water surface, which alters the oil/water interfacial tension, resulting in the formation of emulsions. Asphaltenes are also adsorbed on the surface of nanoparticles, which reduces the asphaltene content in heavy oil, resulting in a decrease in the viscosity of oil, which helps in oil recovery. In previous studies, most researchers only focused on the results, and the nanoparticle adsorption properties have been ignored. This review presents the relationship between the adsorption properties of nanoparticles and the N-EOR mechanisms. The nanofluid behaviour during a multiphase core displacement process is also discussed, and the corresponding simulation is analysed. Finally, potential mechanisms and future directions of N-EOR are proposed. The findings of this study can further the understanding of N-EOR mechanisms from the perspective of heavy oil molecules/particle/surface micromechanics, as well as clarify the role of nanofluids in multiphase core displacement experiments and simulations. This review also presents limitations and bottlenecks, guiding researchers to develop methods to synthesise novel nanoparticles and conduct further research.

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Fabrication of high-performance pervaporation composite membrane for alkaline wastewater reclamation
Guiqin Bai, Jianzhong Xia, Bing Cao, Rui Zhang, Junquan Meng, Pei Li
Frontiers of Chemical Science and Engineering    2022, 16 (5): 709-719.   https://doi.org/10.1007/s11705-021-2078-2
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Pervaporation desalination has a unique advantage to recycle concentrated salt solutions. The merit can be applied to treat alkaline wastewater if the membrane has superior alkali-resistance. In this paper, we used polyethylene microfiltration membrane as the substrate and deposited a glutaraldehyde crosslinked sodium carboxymethylcellulose layer by spray-coating. Pervaporation flux of the composite membrane reached 35 ± 2 kg·m–2·h–1 with a sodium chloride rejection of 99.9% ± 0.1% when separating a 3.5 wt-% sodium chloride solution at 70 °C. The desalination performance was stable after soaking the membrane in a 20 wt-% NaOH solution at room temperature for 9 d and in a 10 wt-% NaOH solution at 60 °C for 80 h. Moreover, the membrane was stable in 4 wt-% sulfuric acid and a 500 mg·L−1 sodium hypochlorite solution. In a process of concentrating a NaOH solution from 5 to 10 wt-% at 60 °C, an average water flux of 23 kg·m–2·h–1 with a NaOH rejection over 99.98% was obtained.

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Catalysis of semihydrogenation of acetylene to ethylene: current trends, challenges, and outlook
Toyin D. Shittu, Olumide B. Ayodele
Frontiers of Chemical Science and Engineering    2022, 16 (7): 1031-1059.   https://doi.org/10.1007/s11705-021-2113-3
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Ethylene is an important feedstock for various industrial processes, particularly in the polymer industry. Unfortunately, during naphtha cracking to produce ethylene, there are instances of acetylene presence in the product stream, which poisons the Ziegler–Natta polymerization catalysts. Thus, appropriate process modification, optimization, and in particular, catalyst design are essential to ensure the production of highly pure ethylene that is suitable as a feedstock in polymerization reactions. Accordingly, carefully selected process parameters and the application of various catalyst systems have been optimized for this purpose. This review provides a holistic view of the recent reports on the selective hydrogenation of acetylene. Previously published reviews were limited to Pd catalysts. However, effective new metal and non-metal catalysts have been explored for selective acetylene hydrogenation. Updates on this recent progress and more comprehensive computational studies that are now available for the reaction are described herein. In addition to the favored Pd catalysts, other catalyst systems including mono, bimetallic, trimetallic, and ionic catalysts are presented. The specific role(s) that each process parameter plays to achieve high acetylene conversion and ethylene selectivity is discussed. Attempts have been made to elucidate the possible catalyst deactivation mechanisms involved in the reaction. Extensive reports suggest that acetylene adsorption occurs through an active single-site mechanism rather than via dual active sites. An increase in the reaction temperature affords high acetylene conversion and ethylene selectivity to obtain reactant streams free of ethylene. Conflicting findings to this trend have reported the presence of ethylene in the feed stream. This review will serve as a useful resource of condensed information for researchers in the field of acetylene-selective hydrogenation.

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A review on the forward osmosis applications and fouling control strategies for wastewater treatment
Linwei Zhu, Chun Ding, Tengyang Zhu, Yan Wang
Frontiers of Chemical Science and Engineering    2022, 16 (5): 661-680.   https://doi.org/10.1007/s11705-021-2084-4
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During the last decades, the utilization of osmotic pressure-driven forward osmosis technology for wastewater treatment has drawn great interest, due to its high separation efficiency, low membrane fouling propensity, high water recovery and relatively low energy consumption. This review paper summarizes the implementation of forward osmosis technology for various wastewater treatment including municipal sewage, landfill leachate, oil/gas exploitation wastewater, textile wastewater, mine wastewater, and radioactive wastewater. However, membrane fouling is still a critical issue, which affects water flux stability, membrane life and operating cost. Different membrane fouling types and corresponding fouling mechanisms, including organic fouling, inorganic fouling, biofouling and combined fouling are therefore further discussed. The fouling control strategies including feed pre-treatment, operation condition optimization, membrane selection and modification, membrane cleaning and tailoring the chemistry of draw solution are also reviewed comprehensively. At the end of paper, some recommendations are proposed.

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Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions
Yao Shi, Zhao Li, Changfeng Yang, Zhanlin Yang, Zhenhui Lv, Chong Peng, Bao-Lian Su, Weikang Yuan, Xinggui Zhou, Xuezhi Duan
Frontiers of Chemical Science and Engineering    2022, 16 (6): 897-908.   https://doi.org/10.1007/s11705-021-2127-x
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Catalyst particle shapes and pore structure engineering are crucial for alleviating internal diffusion limitations in the hydrodesulfurization (HDS)/hydrodenitrogenation (HDN) of gas oil. The effects of catalyst particle shapes (sphere, cylinder, trilobe, and tetralobe) and pore structures (pore diameter and porosity) on HDS/HDN performance at the particle scale are investigated via mathematical modeling. The relationship between particle shape and effectiveness factor is first established, and the specific surface areas of different catalyst particles show a positive correlation with the average HDS/HDN reaction rates. The catalyst particle shapes primarily alter the average HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. An optimal average HDS/HDN reaction rate exists as the catalyst pore diameter and porosity increase, and this optimum value indicates a tradeoff between diffusion and reaction. In contrast to catalyst particle shapes, the catalyst pore diameter and the porosity of catalyst particles primarily alter the surface HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. This study provides insights into the engineering of catalyst particle shapes and pore structures for improving HDS/HDN catalyst particle efficiency.

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Mobile CRISPR-Cas9 based anti-phage system in E. coli
Zhou Cao, Yuxin Ma, Bin Jia, Ying-Jin Yuan
Frontiers of Chemical Science and Engineering    2022, 16 (8): 1281-1289.   https://doi.org/10.1007/s11705-022-2141-7
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Escherichia coli is one of the most important microbial cell factories, but infection by bacteriophages in the environment may have a huge impact on its application in industrial production. Here, we developed a mobile CRISPR-Cas9 based anti-phage system for bacteriophages defense in E. coli. Two conjugative plasmids pGM1 (phosphoglucomutase 1) and pGM2 carrying one and two guide RNAs, respectively, were designed to defend against a filamentous phage. The results showed that the pGM1 and pGM2 could decrease the phage infection rate to 1.6% and 0.2% respectively in infected cells. For preventing phage infection in E. coli, the pGM2 decreased the phage infection rate to 0.1%, while pGM1 failed to block phage infection. Sequence verification revealed that point mutations in protospacer or protospacer adjacent motif sequences of the phage genome caused loss of the defense function. These results support the potential application of MCBAS in E. coli cell factories to defend against phage infections.

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Unravelling the bottleneck of phosphonic acid anchoring groups aiming toward enhancing the stability and efficiency of mesoscopic solar cells
Ajendra Kumar Vats, Pritha Roy, Linjun Tang, Shuzi Hayase, Shyam S. Pandey
Frontiers of Chemical Science and Engineering    2022, 16 (7): 1060-1078.   https://doi.org/10.1007/s11705-021-2117-z
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Novel near-infrared sensitizers with different anchoring groups aiming toward improved stability and efficiency of dye-sensitized solar cells were synthesized. Adsorption of these dyes on the mesoporous TiO2 surface revealed the dye adsorption rate of –CH=CH–COOH (SQ-139)>–CH=C(CN)COOH (SQ-140)>–PO3H2 (SQ-143)>–CH=C(CN)PO3H2 (SQ-148)>–CH=C(CN)PO3H–C2H5 (SQ-157)>–PO3H–C2H5 (SQ-151)> –CH=CH–COOH(–PO3H2) (SQ-162). The binding strength of these dyes on mesoporous TiO2 as investigated by dye desorption studies follows SQ-162>SQ-143>SQ-148>SQ-139≫SQ-157~SQ-151≫SQ-140 order. The acrylic acid anchoring group was demonstrated to be an optimum functional group owing to its fast dye adsorption rate and better binding strength on TiO2 along with good photoconversion efficiency. Results of dye binding on TiO2 surface demonstrated that SQ-162 bearing double anchoring groups of phosphonic and acrylic acid exhibited>550 times stronger binding as compared to dye SQ-140 having cyanoacrylic acid anchoring group. SQ-140 exhibited the best photovoltaic performance with photon harvesting mainly in the far-red to near-infrared wavelength region having short circuit current density, open-circuit voltage and fill factor of 14.28 mA·cm–2, 0.64 V and 0.65, respectively, giving the power conversion efficiency of 5.95%. Thus, dye SQ-162 not only solved the problem of very poor efficiency of dye bearing only phosphonic acid while maintaining the extremely high binding strength opening the path for the design and development of novel near-infrared dyes with improved efficiency and stability by further increasing the π-conjugation.

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Chemical reactions of oily sludge catalyzed by iron oxide under supercritical water gasification condition
Houjun Zhang, Fang Chen, Jipeng Xu, Jinli Zhang, You Han
Frontiers of Chemical Science and Engineering    2022, 16 (6): 886-896.   https://doi.org/10.1007/s11705-021-2125-z
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Supercritical water gasification is a promising technology in dealing with the degradation of hazardous waste, such as oily sludge, accompanied by the production of fuel gases. To evaluate the mechanism of Fe2O3 catalyst and the migration pathways of heteroatoms and to investigate the systems during the process, reactive force field molecular dynamics simulations are adopted. In terms of the catalytic mechanisms of Fe2O3, the surface lattice oxygen is consumed by small carbon fragments to produce CO and CO2, improving the catalytic performance of the cluster due to more unsaturated coordination Fe sites exposed. Lattice oxygen combines with •H radicals to form water molecules, improving the catalytic performance. Furthermore, the pathway of asphaltene degradation was revealed at an atomic level, as well as products. Moreover, the adsorption of hydroxyl radical on the S atom caused breakage of the two C–S bonds in turn, forming •HSO intermediate, so that the organic S element was fixed into the inorganic liquid phase. The heteroatom O was removed under the effects of supercritical water. Heavy metal particles presented in the oily sludge, such as iron in association with Fe2O3 catalyst, helped accelerate the degradation of asphaltenes.

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Surface-tailoring chlorine resistant materials and strategies for polyamide thin film composite reverse osmosis membranes
Pei Sean Goh, Kar Chun Wong, Tuck Whye Wong, Ahmad Fauzi Ismail
Frontiers of Chemical Science and Engineering    2022, 16 (5): 564-591.   https://doi.org/10.1007/s11705-021-2109-z
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Polyamide thin film composite membranes have dominated current reverse osmosis market on account of their excellent separation performances compared to the integrally skinned counterparts. Despite their very promising separation performance, chlorine-induced degradation resulted from the susceptibility of polyamide toward chlorine attack has been regarded as the Achilles’s heel of polyamide thin film composite. The free chlorine species present during chlorine treatment can impair membrane performance through chlorination and depolymerization of the polyamide selective layer. From material point of view, a chemically stable membrane is crucial for the sustainable application of membrane separation process as it warrants a longer membrane lifespan and reduces the cost involved in membrane replacement. Various strategies, particularly those involved membrane material optimization and surface modifications, have been established to address this issue. This review discusses membrane degradation by free chlorine attack and its correlation with the surface chemistry of polyamide. The advancement in the development of chlorine resistant polyamide thin film composite membranes is reviewed based on the state-of-the-art surface modifications and tailoring approaches which include the in situ and post-fabrication membrane modifications using a broad range of functional materials. The challenges and future directions in this field are also highlighted.

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Integrating of metal-organic framework UiO-66-NH2 and cellulose nanofibers mat for high-performance adsorption of dye rose bengal
Yuyao Han, Lei Xia, Xupin Zhuang, Yuxia Liang
Frontiers of Chemical Science and Engineering    2022, 16 (9): 1387-1398.   https://doi.org/10.1007/s11705-022-2154-2
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UiO-66-NH2 is an efficient material for removing pollutants from wastewater due to its high specific surface area, high porosity and water stability. However, recycling them from wastewater is difficult. In this study, the cellulose nanofibers mat deacetylated from cellulose acetate nanofibers were used to combine with UiO-66-NH2 by the method of in-situ growth to remove the toxic dye, rose bengal. Compared to previous work, the prepared composite could not only provide ease of separation of UiO-66-NH2 from the water after adsorption but also demonstrate better adsorption capacity (683 mg∙g‒1 (T = 25 °C, pH = 3)) than that of the simple UiO-66-NH2 (309.6 mg∙g‒1 (T = 25 °C, pH = 3)). Through the analysis of adsorption kinetics and isotherms, the adsorption for rose bengal is mainly suitable for the pseudo-second-order kinetic model and Freundlich model. Furthermore, the relevant research revealed that the main adsorption mechanism of the composite was electrostatic interaction, hydrogen bonding and π–π interaction. Overall, the approach depicts an efficient model for integrating metal-organic frameworks on cellulose nanofibers to improve metal-organic framework recovery performance with potentially broad applications.

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Nanofiltration for drinking water treatment: a review
Hao Guo, Xianhui Li, Wulin Yang, Zhikan Yao, Ying Mei, Lu Elfa Peng, Zhe Yang, Senlin Shao, Chuyang Y. Tang
Frontiers of Chemical Science and Engineering    2022, 16 (5): 681-698.   https://doi.org/10.1007/s11705-021-2103-5
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In recent decades, nanofiltration (NF) is considered as a promising separation technique to produce drinking water from different types of water source. In this paper, we comprehensively reviewed the progress of NF-based drinking water treatment, through summarizing the development of materials/fabrication and applications of NF membranes in various scenarios including surface water treatment, groundwater treatment, water reuse, brackish water treatment, and point of use applications. We not only summarized the removal of target major pollutants (e.g., hardness, pathogen, and natural organic matter), but also paid attention to the removal of micropollutants of major concern (e.g., disinfection byproducts, per- and polyfluoroalkyl substances, and arsenic). We highlighted that, for different applications, fit-for-purpose design is needed to improve the separation capability for target compounds of NF membranes in addition to their removal of salts. Outlook and perspectives on membrane fouling control, chlorine resistance, integrity, and selectivity are also discussed to provide potential insights for future development of high-efficiency NF membranes for stable and reliable drinking water treatment.

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Hydrophilic modification of poly(aryl sulfone) membrane materials toward highly-efficient environmental remediation
Fan Yang, Junhui Huang, Lijun Deng, Yanqiu Zhang, Guodong Dang, Lu Shao
Frontiers of Chemical Science and Engineering    2022, 16 (5): 614-633.   https://doi.org/10.1007/s11705-021-2115-1
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Poly(aryl sulfone) as a typical membrane material has been widely used due to excellent mechanical, chemical and thermal stability. However, the inherent hydrophobicity of poly(aryl sulfone) based membranes bears with the fouling issue during applications, which makes the membrane tending to adsorb contaminants on the surface so as to result in decreased separation performance and lifetime. In this critical review, we give a comprehensive overview on characterizations of hydrophilic membrane and diverse hydrophilic modification approaches of poly(aryl sulfone) membranes, predominantly including bulky, blending and surface modification technology. The discussions on the different modification methods have been provided in-depth. Besides, focusing on modification methods and performance of modified membranes, the related mechanisms for the performance enhancement are discussed too. At last, the perspectives are provided to guide the future directions to develop novel technology to manipulate the hydrophilicity of poly(aryl sulfone) membranes toward diverse practical and multi-functional applications.

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Recent progress in hydrodynamic characteristics research and application of annular centrifugal extractors
Hang Yang, Xiaoyong Yang, Xiao Dong, Zhaojin Lu, Zhishan Bai, Yinglei Wang, Fulei Gao
Frontiers of Chemical Science and Engineering    2022, 16 (6): 854-873.   https://doi.org/10.1007/s11705-022-2156-0
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The annular centrifugal extractor (ACE) integrates mixing and separation. It has been widely used in many industrial fields because of its low residence time, compact structure, and high mass transfer efficiency. Most of the literature has focused on flow instabilities, flow visualization, and computational fluid dynamics simulations. More recently, research on hydrodynamic behavior and structural optimization has received widespread attention. With the development of ACE technology, applications have been broadened into several new areas. Hence, this paper reviews research progress regarding ACE in terms of hydrodynamic characteristics and the structural improvements. The latest applications covering hydrometallurgy, nuclear fuel reprocessing, bio-extraction, catalytic reaction, and wastewater treatment are presented. We also evaluate future work in droplet breakup and coalescence mechanisms, structural improvements specific to different process requirements, scaling-up methods, and stability and reliability after scaling-up.

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Multistage-batch bipolar membrane electrodialysis for base production from high-salinity wastewater
Arif Hussain, Haiyang Yan, Noor Ul Afsar, Chenxiao Jiang, Yaoming Wang, Tongwen Xu
Frontiers of Chemical Science and Engineering    2022, 16 (5): 764-773.   https://doi.org/10.1007/s11705-021-2114-2
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Bipolar membrane electrodialysis (BMED) is considered a state-of-the-art technology for the conversion of salts into acids and bases. However, the low concentration of base generated from a traditional BMED process may limit the viability of this technology for a large-scale application. Herein, we report an especially designed multistage-batch (two/three-stage-batch) BMED process to increase the base concentration by adjusting different volume ratios in the acid (Vacid), base (Vbase), and salt compartments (Vsalt). The findings indicated that performance of the two-stage-batch with a volume ratio of Vacid:Vbase:Vsalt = 1:1:5 was superior in comparison to the three-stage-batch with a volume ratio of Vacid:Vbase:Vsalt = 1:1:2. Besides, the base concentration could be further increased by exchanging the acid produced in the acid compartment with fresh water in the second stage-batch process. With the two-stage-batch BMED, the maximum concentration of the base can be obtained up to 3.40 mol∙L–1, which was higher than the most reported base production by BMED. The low energy consumption and high current efficiency further authenticate that the designed process is reliable, cost-effective, and more productive to convert saline water into valuable industrial commodities.

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Solvent-resistant porous membranes using poly(ether−ether ketone): preparation and application
Lixin Xing, Jiaming Wang, Xuehua Ruan, Gaohong He
Frontiers of Chemical Science and Engineering    2022, 16 (11): 1536-1559.   https://doi.org/10.1007/s11705-022-2221-8
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Poly(ether−ether ketone) (PEEK) is a linear aromatic macromolecule, which can form semi-crystalline aggregative status, allowing PEEK materials to have strong environment tolerance and excellent physicochemical properties. PEEK materials have become a promising alternative to fabricate particular membranes used in extreme conditions. In the past few decades, many researches and evolutions have emerged in membrane fabrication with PEEK materials and its applications for treating organic solvents and their mixtures; however, there are little systematic and comprehensive literature to summarize fabrication approaches, compile applications, and elaborate PEEK property-structure relationship. In this review, the main approaches to fabricate PEEK-based membranes are illustrated concretely, including conventional thermal-induced and non-solvent-induced phase separation, and novel chemical-induced crystallization; the representative applications in ultrafiltration, nanofiltration and membrane contactor containing organic solvents are demonstrated systematically. Meanwhile, the mechanism to tune PEEK solubility in solvents, which can be achieved by altering monomers in synthesis processes or changing membrane preparation routes, is deeply analyzed. Moreover, the existing problems and the future prospects are also discussed. This review provides positive guidance for designing and fabricating membranes using PEEK and its derivative materials for task-specific applications in harsh conditions.

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Special issue on “Membranes and Water Treatment”
Congjie Gao, Nanping Xu, Weihong Xing
Frontiers of Chemical Science and Engineering    2022, 16 (5): 561-563.   https://doi.org/10.1007/s11705-021-2136-9
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Nickel-based metal−organic framework-derived whisker-shaped nickel phyllosilicate toward efficiently enhanced mechanical, flammable and tribological properties of epoxy nanocomposites
Yuxuan Xu, Guanglong Dai, Shibin Nie, Jinian Yang, Song Liu, Hong Zhang, Xiang Dong
Frontiers of Chemical Science and Engineering    2022, 16 (10): 1493-1504.   https://doi.org/10.1007/s11705-022-2168-9
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Metal−organic framework-derived materials have attracted significant attention in the applications of functional materials. In this work, the rod-like nickel-based metal−organic frameworks were first synthesized and subsequently employed as the hard templates and nickel sources to prepare the whisker-shaped nickel phyllosilicate using a facile hydrothermal technology. Then, the nickel phyllosilicate whiskers were evaluated to enhance the mechanical, thermal, flammable, and tribological properties of epoxy resin. The results show that adequate nickel phyllosilicate whiskers can disperse well in the matrix, improving the tensile strength and elastic modulus by 13.6% and 56.4%, respectively. Although the addition of nickel phyllosilicate whiskers could not obtain any UL-94 ratings, it enhanced the difficulty in burning the resulted epoxy resin nanocomposites and considerably enhanced thermal stabilities. Additionally, it was demonstrated that such nickel phyllosilicate whiskers preferred to improve the wear resistance instead of the antifriction feature. Moreover, the wear rate of epoxy resin nanocomposites was reduced significantly by 80% for pure epoxy resin by adding 1 phr whiskers. The as-prepared nickel phyllosilicate whiskers proved to be promising reinforcements in preparing of high-performance epoxy resin nanocomposites.

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Thermodynamic analysis of reaction pathways and equilibrium yields for catalytic pyrolysis of naphtha
Dongyang Liu, Yibo Zhi, Yuen Bai, Liang Zhao, Jinsen Gao, Chunming Xu
Frontiers of Chemical Science and Engineering    2022, 16 (12): 1700-1712.   https://doi.org/10.1007/s11705-022-2207-6
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The chain length and hydrocarbon type significantly affect the production of light olefins during the catalytic pyrolysis of naphtha. Herein, for a better catalyst design and operation parameters optimization, the reaction pathways and equilibrium yields for the catalytic pyrolysis of C5–8 n/iso/cyclo-paraffins were analyzed thermodynamically. The results revealed that the thermodynamically favorable reaction pathways for n/iso-paraffins and cyclo-paraffins were the protolytic and hydrogen transfer cracking pathways, respectively. However, the formation of light paraffin severely limits the maximum selectivity toward light olefins. The dehydrogenation cracking pathway of n/iso-paraffins and the protolytic cracking pathway of cyclo-paraffins demonstrated significantly improved selectivity for light olefins. The results are thus useful as a direction for future catalyst improvements, facilitating superior reaction pathways to enhance light olefins. In addition, the equilibrium yield of light olefins increased with increasing the chain length, and the introduction of cyclo-paraffin inhibits the formation of light olefins. High temperatures and low pressures favor the formation of ethylene, and moderate temperatures and low pressures favor the formation of propylene. n-Hexane and cyclohexane mixtures gave maximum ethylene and propylene yield of approximately 49.90% and 55.77%, respectively. This work provides theoretical guidance for the development of superior catalysts and the selection of proper operation parameters for the catalytic pyrolysis of C5–8 n/iso/cyclo-paraffins from a thermodynamic point of view.

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Interlayer-confined two-dimensional manganese oxide-carbon nanotube catalytic ozonation membrane for efficient water purification
Dean Xu, Tong Ding, Yuqing Sun, Shilong Li, Wenheng Jing
Frontiers of Chemical Science and Engineering    2022, 16 (5): 731-744.   https://doi.org/10.1007/s11705-021-2110-6
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Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity. However, its extensive industrial application has been restricted by the low ozone utilization and limited mass transfer of the short-lived radical species. Interlayer space-confined catalysis has been theoretically proven to be a viable strategy for achieving high catalytic efficiency. Here, a two-dimensional MnO2-incorporated ceramic membrane with tunable interspacing, which was obtained via the intercalation of a carbon nanotube, was designed as a catalytic ozonation membrane reactor for degrading methylene blue. Benefiting from the abundant catalytic active sites on the surface of two-dimensional MnO2 as well as the ultralow mass transfer resistance of fluids due to the nanolayer confinement, an excellent mineralization effect, i.e., 1.2 mg O3(aq) mg–1 TOC removal (a total organic carbon removal rate of 71.5%), was achieved within a hydraulic retention time of 0.045 s of pollutant degradation. Further, the effects of hydraulic retention time and interlayer spacing on methylene blue removal were investigated. Moreover, the mechanism of the catalytic ozonation employing catalytic ozonation membrane was proposed based on the contribution of the Mn(III/IV) redox pair to electron transfer to generate the reactive oxygen species. This innovative two-dimensional confinement catalytic ozonation membrane could act as a nanoreactor and separator to efficiently oxidize organic pollutants and enhance the control of membrane fouling during water purification.

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Development of a dual temperature control system for isoprene biosynthesis in Saccharomyces cerevisiae
Jiaxi Lin, Zhen Yao, Xiaomei Lyu, Lidan Ye, Hongwei Yu
Frontiers of Chemical Science and Engineering    2022, 16 (7): 1079-1089.   https://doi.org/10.1007/s11705-021-2088-0
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Conflict between cell growth and product accumulation is frequently encountered in the biosynthesis of secondary metabolites. To address the growth-production conflict in yeast strains harboring the isoprene synthetic pathway in the mitochondria, the dynamic control of isoprene biosynthesis was explored. A dual temperature regulation system was developed through engineering and expression regulation of the transcriptional activator Gal4p. A cold-sensitive mutant, Gal4ep19, was created by directed evolution of Gal4p based on an internally developed growth-based high-throughput screening method and expressed under the heat-shock promoter PSSA4 to control the expression of PGAL-driven pathway genes in the mitochondria. Compared to the control strain with constitutively expressed wild-type Gal4p, the dual temperature regulation strategy led to 34.5% and 72% improvements in cell growth and isoprene production, respectively. This study reports the creation of the first cold-sensitive variants of Gal4p by directed evolution and provides a dual temperature control system for yeast engineering that may also be conducive to the biosynthesis of other high-value natural products.

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Sulfonic acid-functionalized mesoporous silica catalyst with different morphology for biodiesel production
Vinayak Hegde, Parimal Pandit, Pranita Rananaware, Varsha P. Brahmkhatri
Frontiers of Chemical Science and Engineering    2022, 16 (8): 1198-1210.   https://doi.org/10.1007/s11705-021-2133-z
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Sulfonic acid functionalized mesoporous silica based solid acid catalysts with different morphology were designed and fabricated. The synthesized materials were characterized by various physicochemical and spectroscopic techniques like scanning electron microscope-energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface area, thermogravimetric analysis and n-butylamine acidity. The shape of catalysts particles plays an important role in its activity. The sulfonic acid functionalized mesoporous silica catalysts of spherical shape and the cube shape were assessed for catalytic activity in biodiesel production. The catalytic biodiesel production reaction over the catalysts were studied by esterification of free fatty acid, oleic acid with methanol. The effect of various reaction parameters such as catalyst concentration, acid/alcohol molar ratio, catalyst amount, reaction temperature and reaction time on catalytic activity were investigated to optimize the conditions for maximum conversion. It was sulfonated cubic shape mesoporous silica which exhibited better activity as compared to the spherical shape silica catalysts. Additionally, the catalyst was regenerated and reused up to three cycles without any significant loss in activity. The present catalysts exhibit superior performance in biodiesel production and it can be used for the several biodiesel feedstock’s that are rich in free fatty acids.

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Poly(vinylidene fluoride-co-hexafluoro propylene) membranes prepared via thermally induced phase separation and application in direct contact membrane distillation
Jun Pan, Lixun Zhang, Zhaohui Wang, Shi-Peng Sun, Zhaoliang Cui, Naser Tavajohi
Frontiers of Chemical Science and Engineering    2022, 16 (5): 720-730.   https://doi.org/10.1007/s11705-021-2098-y
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A non-toxic and environmentally safe diluent, acetyl tributyl citrate, was employed to prepare poly(vinylidene fluoride)-co-hexafluoropropylene membranes via thermally induced phase separation. Effects of the polymer concentration on the phase diagram, membrane morphology, hydrophobicity, pore size, porosity and mechanical properties (tensile stress and elongation at break) were investigated. The results showed that the pore size and porosity tended to decrease with increasing polymer concentration, whereas the contact angle, liquid entry pressure and mechanical properties showed the opposite trend. In direct contact membrane distillation operation with 3.5 wt-% sodium chloride solution as the feed solution, the prepared membranes performed high salt rejection (>99.9%). Furthermore, the prepared membranes retained excellent performance in long-term stability tests regarding the permeate flux and salt rejection.

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