Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Recent progress of two-dimensional nanosheet membranes and composite membranes for separation applications
Wei Wang, Yanying Wei, Jiang Fan, Jiahao Cai, Zong Lu, Li Ding, Haihui Wang
Front. Chem. Sci. Eng.    2021, 15 (4): 793-819.   https://doi.org/10.1007/s11705-020-2016-8
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Two-dimensional (2D) materials have emerged as a class of promising materials to prepare high-performance 2D membranes for various separation applications. The precise control of the interlayer nanochannel/sub-nanochannel between nanosheets or the pore size of nanosheets within 2D membranes enables 2D membranes to achieve promising molecular sieving performance. To date, many 2D membranes with high permeability and high selectivity have been reported, exhibiting high separation performance. This review presents the development, progress, and recent breakthrough of different types of 2D membranes, including membranes based on porous and non-porous 2D nanosheets for various separations. Separation mechanism of 2D membranes and their fabrication methods are also reviewed. Last but not the least, challenges and future directions of 2D membranes for wide utilization are discussed in brief.

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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
Front. Chem. Sci. Eng.    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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Nickel(II) ion-intercalated MXene membranes for enhanced H2/CO2 separation
Yiyi Fan, Jinyong Li, Saidi Wang, Xiuxia Meng, Yun Jin, Naitao Yang, Bo Meng, Jiaquan Li, Shaomin Liu
Front. Chem. Sci. Eng.    2021, 15 (4): 882-891.   https://doi.org/10.1007/s11705-020-1990-1
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Hydrogen fuel has been embraced as a potential long-term solution to the growing demand for clean energy. A membrane-assisted separation is promising in producing high-purity H2. Molecular sieving membranes (MSMs) are endowed with high gas selectivity and permeability because their well-defined micropores can facilitate molecular exclusion, diffusion, and adsorption. In this work, MXene nanosheets intercalated with Ni2+ were assembled to form an MSM supported on Al2O3 hollow fiber via a vacuum-assisted filtration and drying process. The prepared membranes showed excellent H2/CO2 mixture separation performance at room temperature. Separation factor reached 615 with a hydrogen permeance of 8.35 × 108 mol·m2·s1·Pa1. Compared with the original Ti3C2Tx/Al2O3 hollow fiber membranes, the permeation of hydrogen through the Ni2+-Ti3C2Tx/Al2O3 membrane was considerably increased, stemming from the strong interaction between the negatively charged MXene nanosheets and Ni2+. The interlayer spacing of MSMs was tuned by Ni2+. During 200-hour testing, the resultant membrane maintained an excellent gas separation without any substantial performance decline. Our results indicate that the Ni2+ tailored Ti3C2Tx/Al2O3 hollow fiber membranes can inspire promising industrial applications.

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A review of salting-out effect and sugaring-out effect: driving forces for novel liquid-liquid extraction of biofuels and biochemicals
Chuhan Fu, Zhuoxi Li, Zengran Sun, Shaoqu Xie
Front. Chem. Sci. Eng.    2021, 15 (4): 854-871.   https://doi.org/10.1007/s11705-020-1980-3
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Biofuels and bio-based chemicals are getting more and more attention because of their sustainable and renewable properties and wide industrial applications. However, the low concentrations of the targeted products in their fermentation broths, the complicated components of the broths and the high energy-intensive separation and purification process hinder the competitiveness of biofuels and biochemicals with the petro-based ones. Hence, the production and the separation of biofuels and bio-based chemicals in energy-saving, low-cost and greenness ways become hot topics nowadays. This review introduces the separation technologies (salting-out extraction, salting-out, sugaring-out extraction, and sugaring-out) that extract biobutanol, 1,3-propanediol, 2,3-butanediol, acetoin, organic acids and other bio-based chemicals from fermentation broths/aqueous solutions. Salting-out/sugaring-out extraction and salting-out/sugaring-out technologies display the high separating efficiency and the high targeted product yields. In addition, they are easy to operate and require low cost for separating products. Hence, they are the effective and potential technologies for separating targeted products in the wide industrial applications. The successful research into the salting-out/sugaring-out and salting-out/sugaring-out extraction not only affords biofuels and biochemical but also opens a door for the development of novel separation methods.

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Preface to special issue on “Advanced Materials and Catalysis”
Zhong-Yong Yuan
Front. Chem. Sci. Eng.    2021, 15 (6): 1357-1359.   https://doi.org/10.1007/s11705-021-2119-x
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Novel membrane separation technologies and membrane processes
Yanying Wei, Gongping Liu, Jianquan Luo, Libo Li, Zhi Xu
Front. Chem. Sci. Eng.    2021, 15 (4): 717-719.   https://doi.org/10.1007/s11705-021-2053-y
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Immunological effects of nano-enabled hyperthermia for solid tumors: opportunity and challenge
Xiangsheng Liu, Hui Sun, Xueqing Wang, Huan Meng
Front. Chem. Sci. Eng.    2022, 16 (3): 333-344.   https://doi.org/10.1007/s11705-021-2059-5
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Compared to conventional hyperthermia that is limited by low selectivity and severe side effects, nano-enabled hyperthermia yields great potentials to tackle these limitations for cancer treatment. Another major advance is the observation of immunological responses associated with nano-enabled hyperthermia, which introduces a new avenue, allowing a potential paradigm shift from the acutely effective and cytotoxicity-centric response to the next-phase discovery, i.e., long-lasting and/or systemic anti-tumor immunity. This perspective first discusses the temperature-gradient and the spatially-structured immunological landscape in solid tumors receiving nano-enabled hyperthermia. This includes the discussion about underlying mechanism such as immunogenic cell death, which initiates a profound immunological chain reaction. In order to propagate the immune activation as a viable therapeutic principle, we further discussed the tumor type-specific complexity in the immunological tumor microenvironment, including the creative design of nano-enabled combination therapy to synergize with nano-enabled hyperthermia.

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CO2 capture using membrane contactors: a systematic literature review
Sanaa Hafeez, Tayeba Safdar, Elena Pallari, George Manos, Elsa Aristodemou, Zhien Zhang, S. M. Al-Salem, Achilleas Constantinou
Front. Chem. Sci. Eng.    2021, 15 (4): 720-754.   https://doi.org/10.1007/s11705-020-1992-z
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With fossil fuel being the major source of energy, CO2 emission levels need to be reduced to a minimal amount namely from anthropogenic sources. Energy consumption is expected to rise by 48% in the next 30 years, and global warming is becoming an alarming issue which needs to be addressed on a thorough technical basis. Nonetheless, exploring CO2 capture using membrane contactor technology has shown great potential to be applied and utilised by industry to deal with post- and pre-combustion of CO2. A systematic review of the literature has been conducted to analyse and assess CO2 removal using membrane contactors for capturing techniques in industrial processes. The review began with a total of 2650 papers, which were obtained from three major databases, and then were excluded down to a final number of 525 papers following a defined set of criteria. The results showed that the use of hollow fibre membranes have demonstrated popularity, as well as the use of amine solvents for CO2 removal. This current systematic review in CO2 removal and capture is an important milestone in the synthesis of up to date research with the potential to serve as a benchmark databank for further research in similar areas of work. This study provides the first systematic enquiry in the evidence to research further sustainable methods to capture and separate CO2.

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An overview and recent advances in electrocatalysts for direct seawater splitting
Hao-Yu Wang, Chen-Chen Weng, Jin-Tao Ren, Zhong-Yong Yuan
Front. Chem. Sci. Eng.    2021, 15 (6): 1408-1426.   https://doi.org/10.1007/s11705-021-2102-6
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In comparison to pure water, seawater is widely accepted as an unlimited resource. The direct seawater splitting is economical and eco-friendly, but the key challenges in seawater, especially the chlorine-related competing reactions at the anode, seriously hamper its practical application. The development of earth-abundant electrocatalysts toward direct seawater splitting has emerged as a promising strategy. Highly efficient electrocatalysts with improved selectivity and stability are of significance in preventing the interference of side reactions and resisting various impurities. This review first discusses the macroscopic understanding of direct seawater electrolysis and then focuses on the strategies for rational design of electrocatalysts toward direct seawater splitting. The perspectives of improved electrocatalysts to solve emerging challenges and further development of direct seawater splitting are also provided.

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Imprinted membranes for sustainable separation processes
Laura Donato, Enrico Drioli
Front. Chem. Sci. Eng.    2021, 15 (4): 775-792.   https://doi.org/10.1007/s11705-020-1991-0
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The rapid industrial growth and the necessity of recovering and recycling raw materials increased the interest in the production of highly selective and efficient separation tools. In this perspective, a relevant input was given by the membrane-based technology and the production of imprinted membranes, which possess specific recognition properties at molecular and ionic level, offers the possibility of developing sustainable and green processes. Furthermore, the integration of imprinted membranes with traditional or membrane-based approaches is a promising strategy in the logic of process intensification, which means the combination of different operations in a single apparatus. This work discusses the concept and separation mechanisms of imprinted membranes. Furthermore, it presents an overview of their application in organic solvent nanofiltration, for the removal of toxic agents and recovery solvent, as well as valuable compounds. The recent advances in water treatment, such as pesticide removal and recovery of metal ions, are also discussed. Finally, potential applications of imprinted membranes in hybrid processes are highlighted, and a look into the future of membrane separations for water treatment and recovery of critical raw materials is offered.

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Novel Ag-AgBr decorated composite membrane for dye rejection and photodegradation under visible light
Yixing Wang, Liheng Dai, Kai Qu, Lu Qin, Linzhou Zhuang, Hu Yang, Zhi Xu
Front. Chem. Sci. Eng.    2021, 15 (4): 892-901.   https://doi.org/10.1007/s11705-020-2011-0
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Photocatalytic membranes have received increasing attention due to their excellent separation and photodegradation of organic contaminants in wastewater. Herein, we bound Ag-AgBr nanoparticles onto a synthesized polyacrylonitrile-ethanolamine (PAN-ETA) membrane with the aid of a chitosan (CS)-TiO2 layer via vacuum filtration and in-situ partial reduction. The introduction of the CS-TiO2 layer improved surface hydrophilicity and provided attachment sites for the Ag-AgBr nanoparticles. The PAN-ETA/CS-TiO2/Ag-AgBr photocatalytic membranes showed a relatively high water permeation flux (~ 47 L·m–2·h–1·bar–1) and dyes rejection (methyl orange: 88.22%; congo red: 95%; methyl blue: 97.41%; rose bengal: 99.98%). Additionally, the composite membranes exhibited potential long-term stability for dye/salt separation (dye rejection: ~97%; salt rejection: ~6.5%). Moreover, the methylene blue and rhodamine B solutions (20 mL, 10 mg·L−1) were degraded approximately 90.75% and 96.81% in batch mode via the synthesized photocatalytic membranes under visible light irradiation for 30 min. This study provides a feasible method for the combination of polymeric membranes and inorganic catalytic materials.

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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
Front. Chem. Sci. Eng.    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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An integrated approach for machine-learning-based system identification of dynamical systems under control: application towards the model predictive control of a highly nonlinear reactor system
Ewan Chee, Wee Chin Wong, Xiaonan Wang
Front. Chem. Sci. Eng.    2022, 16 (2): 237-250.   https://doi.org/10.1007/s11705-021-2058-6
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Advanced model-based control strategies, e.g., model predictive control, can offer superior control of key process variables for multiple-input multiple-output systems. The quality of the system model is critical to controller performance and should adequately describe the process dynamics across its operating range while remaining amenable to fast optimization. This work articulates an integrated system identification procedure for deriving black-box nonlinear continuous-time multiple-input multiple-output system models for nonlinear model predictive control. To showcase this approach, five candidate models for polynomial and interaction features of both output and manipulated variables were trained on simulated data and integrated into a nonlinear model predictive controller for a highly nonlinear continuous stirred tank reactor system. This procedure successfully identified system models that enabled effective control in both servo and regulator problems across wider operating ranges. These controllers also had reasonable per-iteration times of ca. 0.1 s. This demonstration of how such system models could be identified for nonlinear model predictive control without prior knowledge of system dynamics opens further possibilities for direct data-driven methodologies for model-based control which, in the face of process uncertainties or modelling limitations, allow rapid and stable control over wider operating ranges.

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Design and optimization of reactive distillation: a review
Chang Shu, Xingang Li, Hong Li, Xin Gao
Front. Chem. Sci. Eng.    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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The use of carbon nanomaterials in membrane distillation membranes: a review
Sebastian Leaper, Ahmed Abdel-Karim, Patricia Gorgojo
Front. Chem. Sci. Eng.    2021, 15 (4): 755-774.   https://doi.org/10.1007/s11705-020-1993-y
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Membrane distillation (MD) is a thermal-based separation technique with the potential to treat a wide range of water types for various applications and industries. Certain challenges remain however, which prevent it from becoming commercially widespread including moderate permeate flux, decline in separation performance over time due to pore wetting and high thermal energy requirements. Nevertheless, its attractive characteristics such as high rejection (ca. 100%) of non-volatile species, its ability to treat highly saline solutions under low operating pressures (typically atmospheric) as well as its ability to operate at low temperatures, enabling waste-heat integration, continue to drive research interests globally. Of particular interest is the class of carbon-based nanomaterials which includes graphene and carbon nanotubes, whose wide range of properties have been exploited in an attempt to overcome the technical challenges that MD faces. These low dimensional materials exhibit properties such as high specific surface area, high strength, tuneable hydrophobicity, enhanced vapour transport, high thermal and electrical conductivity and others. Their use in MD has resulted in improved membrane performance characteristics like increased permeability and reduced fouling propensity. They have also enabled novel membrane capabilities such as in-situ fouling detection and localised heat generation. In this review we provide a brief introduction to MD and describe key membrane characteristics and fabrication methods. We then give an account of the various uses of carbon nanomaterials for MD applications, focussing on polymeric membrane systems. Future research directions based on the findings are also suggested.

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Recovery of free volume in PIM-1 membranes through alcohol vapor treatment
Faiz Almansour, Monica Alberto, Rupesh S. Bhavsar, Xiaolei Fan, Peter M. Budd, Patricia Gorgojo
Front. Chem. Sci. Eng.    2021, 15 (4): 872-881.   https://doi.org/10.1007/s11705-020-2001-2
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Physical aging is currently a major obstacle for the commercialization of PIM-1 membranes for gas separation applications. A well-known approach to reversing physical aging effects of PIM-1 membranes at laboratory scale is soaking them in lower alcohols, such as methanol and ethanol. However, this procedure does not seem applicable at industrial level, and other strategies must be investigated. In this work, a regeneration method with alcohol vapors (ethanol or methanol) was developed to recover permeability of aged PIM-1 membranes, in comparison with the conventional soaking-in-liquid approach. The gas permeability and separation performance, before and post the regeneration methods, were assessed using a binary mixture of CO2 and CH4 (1:1, v:v). Our results show that an 8-hour methanol vapor treatment was sufficient to recover the original gas permeability, reaching a CO2 permeability>7000 barrer.

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Nanofiltration for separation and purification of saccharides from biomass
Xianhui Li, Sheng Tan, Jianquan Luo, Manuel Pinelo
Front. Chem. Sci. Eng.    2021, 15 (4): 837-853.   https://doi.org/10.1007/s11705-020-2020-z
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Saccharide production is critical to the development of biotechnology in the field of food and biofuel. The extraction of saccharide from biomass-based hydrolysate mixtures has become a trend due to low cost and abundant biomass reserves. Compared to conventional methods of fractionation and recovery of saccharides, nanofiltration (NF) has received considerable attention in recent decades because of its high selectivity and low energy consumption and environmental impact. In this review the advantages and challenges of NF based technology in the separation of saccharides are critically evaluated. Hybrid membrane processes, i.e., combining NF with ultrafiltration, can complement each other to provide an efficient approach for removal of unwanted solutes to obtain higher purity saccharides. However, use of NF membrane separation technology is limited due to irreversible membrane fouling that results in high capital and operating costs. Future development of NF membrane technology should therefore focus on improving material stability, antifouling ability and saccharide targeting selectivity, as well as on engineering aspects such as process optimisation and membrane module design.

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Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea
Iulian Patrașcu, Costin S. Bîldea, Anton A. Kiss
Front. Chem. Sci. Eng.    2022, 16 (2): 316-331.   https://doi.org/10.1007/s11705-021-2047-9
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Dimethyl carbonate is an eco-friendly essential chemical that can be sustainably produced from CO2, which is available from carbon capture activities or can even be captured from the air. The rapid increase in dimethyl carbonate demand is driven by the fast growth of polycarbonates, solvent, pharmaceutical, and lithium-ion battery industries. Dimethyl carbonate can be produced from CO2 through various chemical pathways, but the most convenient route reported is the indirect alcoholysis of urea. Previous research used techniques such as heat integration and reactive distillation to reduce the energy use and costs, but the use of an excess of methanol in the trans-esterification step led to an energy intensive extractive distillation required to break the dimethyl carbonate-methanol azeotrope. This work shows that the production of dimethyl carbonate by indirect alcoholysis of urea can be improved by using an excess of propylene carbonate (instead of an excess of methanol), a neat feat that we showed it requires only 2.64 kW·h·kg–1 dimethyl carbonate in a reaction-separation-recycle process, and a reactive distillation column that effectively replaces two conventional distillation columns and the reactor for dimethyl carbonate synthesis. Therefore, less equipment is required, the methanol-dimethyl carbonate azeotrope does not need to be recycled, and the overall savings are higher. Moreover, we propose the use of a reactive distillation column in a heat integrated process to obtain high purity dimethyl carbonate (>99.8 wt-%). The energy requirement is reduced by heat integration to just 1.25 kW·h·kg–1 dimethyl carbonate, which is about 52% lower than the reaction-separation-recycle process. To benefit from the energy savings, the dynamics and control of the process are provided for ±10% changes in the nominal rate of 32 ktpy dimethyl carbonate, and for uncertainties in reaction kinetics.

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Recent progress in the design and fabrication of MXene-based membranes
Kai Qu, Kang Huang, Zhi Xu
Front. Chem. Sci. Eng.    2021, 15 (4): 820-836.   https://doi.org/10.1007/s11705-020-1997-7
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Two-dimensional membranes have attracted significant attention due to their superior characteristics, and their ability to boost both flux and selectivity have led to their reputation as potential next-generation separation membranes. Among them, emerging MXene-based membranes play significant roles in the competitive membrane-separation field. In this mini-review, we systematically discuss the assembly and separation mechanisms of these membranes. Moreover, we highlight strategies based on the crosslinking of MXene nanosheets and the construction of additional nanochannels that further enhance the permeabilities and anti-swelling properties of MXene-based membranes and meet the requirements of practical applications, such as gas-molecule sieving, ion sieving, and other small-molecule sieving. MXene nanosheets can also be used as additives that introduce specific functionalities into hybrid membranes. In addition, extended applications that use MXenes as scaffolds are also discussed.

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Hierarchically porous zeolites synthesized with carbon materials as templates
Huan Wang, Guo Du, Jiaqing Jia, Shaohua Chen, Zhipeng Su, Rui Chen, Tiehong Chen
Front. Chem. Sci. Eng.    2021, 15 (6): 1444-1461.   https://doi.org/10.1007/s11705-021-2090-6
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Hierarchically porous zeolites are promising candidates in catalytic conversion of relatively bulky molecules, and their syntheses have attracted significant attention. From both industrial and scientific perspectives, different carbon materials have been widely employed as hard templates for the preparation of hierarchically porous zeolites during the past two decades. In this review, the progress in synthetic strategies using carbon materials as templates is comprehensively summarized. Depending on the affinity between the carbon templates and zeolite precursors, the substantial strategies for synthesizing hierarchical zeolites are introduced in direct templates and indirect templates. Direct templates methods, by which the carbon materials are directly mixed with precursors gel as hard templates, are first reviewed. Then, we discuss the indirect templates method (crystallization of carbon-silica composites), by which the carbon is produced by in situ pyrolysis of organic-inorganic precursors. In addition, the technique of encapsulating metal species into zeolites crystals with the assistance of carbon templates is also discussed. In the conclusion part, the factors affecting the synthesis of carbon-templated hierarchically porous zeolites are remarked. This review is expected to attract interest in the synthesis strategies of hierarchically porous zeolites, especially cost-effective and large-scale production methodologies, which are essential to the industrial application of hierarchical zeolites.

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A DNA sensor based on upconversion nanoparticles and two-dimensional dichalcogenide materials
Konstantina Alexaki, Davide Giust, Maria-Eleni Kyriazi, Afaf H. El-Sagheer, Tom Brown, Otto L. Muskens, Antonios G. Kanaras
Front. Chem. Sci. Eng.    2021, 15 (4): 935-943.   https://doi.org/10.1007/s11705-020-2023-9
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We demonstrate the fabrication of a new DNA sensor that is based on the optical interactions occurring between oligonucleotide-coated NaYF4: Yb3+; Er3+ upconversion nanoparticles and the two-dimensional dichalcogenide materials, MoS2 and WS2. Monodisperse upconversion nanoparticles were functionalized with single-stranded DNA endowing the nanoparticles with the ability to interact with the surface of the two-dimensional materials via van der Waals interactions leading to subsequent quenching of the upconversion fluorescence. By contrast, in the presence of a complementary oligonucleotide target and the formation of double-stranded DNA, the upconversion nanoparticles could not interact with MoS2 and WS2, thus retaining their inherent fluorescence properties. Utilizing this sensor we were able to detect target oligonucleotides with high sensitivity and specificity whilst reaching a concentration detection limit as low as 5 mol·L–1, within minutes.

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Computational design of structured chemical products
Faheem Mushtaq, Xiang Zhang, Ka Y. Fung, Ka M. Ng
Front. Chem. Sci. Eng.    2021, 15 (5): 1033-1049.   https://doi.org/10.1007/s11705-020-2002-1
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In chemical product design, the aim is to formulate a product with desired performance. Ingredients and internal product structure are two key drivers of product performance with direct impact on the mechanical, electrical, and thermal properties. Thus, there is a keen interest in elucidating the dependence of product performance on ingredients, structure, and the manufacturing process to form the structure. Design of product structure, particularly microstructure, is an intrinsically complex problem that involves different phases of different physicochemical properties, mass fraction, morphology, size distribution, and interconnectivity. Recently, computational methods have emerged that assist systematic microstructure quantification and prediction. The objective of this paper is to review these computational methods and to show how these methods as well as other developments in product design can work seamlessly in a proposed performance, ingredients, structure, and manufacturing process framework for the design of structured chemical products. It begins with the desired target properties and key ingredients. This is followed by computation for microstructure and then selection of processing steps to realize this microstructure. The framework is illustrated with the design of nanodielectric and die attach adhesive products.

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Multifunctional heteroatom zeolites: construction and applications
Qifeng Lei, Chang Wang, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li
Front. Chem. Sci. Eng.    2021, 15 (6): 1462-1486.   https://doi.org/10.1007/s11705-021-2099-x
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Multifunctional heteroatom zeolites have drawn broad attentions due to the possible synergistic effects in the catalytic reactions. Remarkable achievements have been made on the synthesis, characterization and catalytic applications of multifunctional heteroatom zeolite, while a review on this important topic is still missing. Herein, current research status of multifunctional heteroatom zeolites is briefly summarized, aiming to boost further researches. First, the synthesis strategies toward heteroatom zeolites are introduced, including the direct synthesis and postsynthesis routes; then, the spectroscopic techniques to identify the existing states of heteroatom sites and the corresponding physiochemical properties are shown and compared; finally, the catalytic applications of multifunctional heteroatom zeolites in various chemical reactions, especially in one-step tandem reactions, are discussed.

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Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation: entrainer design and process optimization
Ao Yang, Yang Su, Tao Shi, Jingzheng Ren, Weifeng Shen, Teng Zhou
Front. Chem. Sci. Eng.    2022, 16 (2): 303-315.   https://doi.org/10.1007/s11705-021-2044-z
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An energy-efficient triple-column extractive distillation process is developed for recovering tetrahydrofuran and ethyl acetate from industrial effluent. The process development follows a rigorous hierarchical design procedure that involves entrainer design, thermodynamic analysis, process design and optimization, and heat integration. The computer-aided molecular design method is firstly used to find promising entrainer candidates and the best one is determined via rigorous thermodynamic analysis. Subsequently, the direct and indirect triple-column extractive distillation processes are proposed in the conceptual design step. These two extractive distillation processes are then optimized by employing an improved genetic algorithm. Finally, heat integration is performed to further reduce the process energy consumption. The results indicate that the indirect extractive distillation process with heat integration shows the highest performance in terms of the process economics.

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Hybrid method integrating machine learning and particle swarm optimization for smart chemical process operations
Haoqin Fang, Jianzhao Zhou, Zhenyu Wang, Ziqi Qiu, Yihua Sun, Yue Lin, Ke Chen, Xiantai Zhou, Ming Pan
Front. Chem. Sci. Eng.    2022, 16 (2): 274-287.   https://doi.org/10.1007/s11705-021-2043-0
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Modeling and optimization is crucial to smart chemical process operations. However, a large number of nonlinearities must be considered in a typical chemical process according to complex unit operations, chemical reactions and separations. This leads to a great challenge of implementing mechanistic models into industrial-scale problems due to the resulting computational complexity. Thus, this paper presents an efficient hybrid framework of integrating machine learning and particle swarm optimization to overcome the aforementioned difficulties. An industrial propane dehydrogenation process was carried out to demonstrate the validity and efficiency of our method. Firstly, a data set was generated based on process mechanistic simulation validated by industrial data, which provides sufficient and reasonable samples for model training and testing. Secondly, four well-known machine learning methods, namely, K-nearest neighbors, decision tree, support vector machine, and artificial neural network, were compared and used to obtain the prediction models of the processes operation. All of these methods achieved highly accurate model by adjusting model parameters on the basis of high-coverage data and properly features. Finally, optimal process operations were obtained by using the particle swarm optimization approach.

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The prior rules of designing Ti3C2Tx MXene-based gas sensors
Yingying Jian, Danyao Qu, Lihao Guo, Yujin Zhu, Chen Su, Huanran Feng, Guangjian Zhang, Jia Zhang, Weiwei Wu, Ming-Shui Yao
Front. Chem. Sci. Eng.    2021, 15 (3): 505-517.   https://doi.org/10.1007/s11705-020-2013-y
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Working temperature, sensitivity, and selectivity are some of the characteristics of the applied gas sensors. How to design and fabricate an ideal gas sensor working at room temperature is still challenging and attracting lots of interest. Two-dimensional (2D) materials with ultra-thin structure have been demonstrated as a family of ideal candidates to achieve this goal. Among them, Ti3C2Tx MXene, a kind of layered sheet synthesized by selectively etching MAX phases materials, shows remarkable potential to be the sensitive materials solely or in a composite. However, their designing rules are still lacking critical thinking from the viewpoint of the intrinsic property of Ti3C2Tx MXene based materials. In this article, two critical features, i.e., the thickness of the sensitive materials, and the scope of the analytes, are elaborated towards Ti3C2Tx MXene based gas sensors after characterizing the performance of sensing reducing gases (NH3 and CO) and oxidizing gas (NO2). First, the thinner the Ti3C2Tx MXene sensitive layer, the better the sensitivity. Second, the Ti3C2Tx MXene based gas sensor is not suitable for strong and moderate oxidation gas due to its ease of oxidation. These two rules are demonstrated, and could be considered with priority both in the future researches and practical applications.

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Hollow carbon spheres and their noble metal-free hybrids in catalysis
Xiang-Hui Yu, Jin-Long Yi, Ru-Liang Zhang, Feng-Yun Wang, Lei Liu
Front. Chem. Sci. Eng.    2021, 15 (6): 1380-1407.   https://doi.org/10.1007/s11705-021-2097-z
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Hollow carbon spheres have garnered great interest owing to their high surface area, large surface-to-volume ratio and reduced transmission lengths. Herein, we overview hollow carbon sphere-based materials and their noble metal-free hybrids in catalysis. Firstly, we summarize the key fabrication techniques for various kinds of hollow carbon spheres, with a particular emphasis on controlling pore structure and surface morphology, and then heterogeneous doping as well as their metal-free/containing hybrids are presented; next, possible applications for non-noble metal/hollow carbon sphere hybrids in the area of energy-related catalysis, including oxygen reduction reaction, hydrogen evolution reaction, oxygen evolution reaction, water splitting, rechargeable Zn-air batteries and pollutant degradation are discussed; finally, we introduce the various challenges and opportunities offered by hollow carbon spheres from the perspective of synthesis and catalysis.

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Novel lysosome-targeted anticancer fluorescent agents used in zebrafish and nude mouse tumour imaging
Xiuli Chen, Feng Liu, Bin Chen, Haiying Wu, Kun Li, Yongmei Xie, Weihong Kuang, Zhihui Li
Front. Chem. Sci. Eng.    2022, 16 (1): 112-120.   https://doi.org/10.1007/s11705-021-2075-5
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The design of three novel fatty nitrogen mustard-based anticancer agents with fluorophores incorporated into the alkene structure (CXL 118, CXL121, and CXL122) is described in this report. The results indicated that these compounds are selectively located in lysosomes and exhibit effective antitumour activity. Notably, these compounds can directly serve as both reporting and imaging agents in vitro and in vivo without the need to add other fluorescent tagging agents.

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Carbon-coated Ni-Co alloy catalysts: preparation and performance for in-situ aqueous phase hydrodeoxygenation of methyl palmitate to hydrocarbons using methanol as the hydrogen donor
Yinteng Shi, Lin Ai, Haonan Shi, Xiaoyu Gu, Yujun Han, Jixiang Chen
Front. Chem. Sci. Eng.    2022, 16 (4): 443-460.   https://doi.org/10.1007/s11705-021-2079-1
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Carbon-coated Ni, Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method. It was found that the introduction of Co remarkably reduced the carbon microsphere size. The metallic Ni, Co, and Ni-Co alloy particles (mainly 10–12 nm) were uniformly distributed in carbon microspheres. A charge transfer from Ni to Co appeared in the Ni-Co alloy. Compared with those of metallic Ni and Co, the d-band center of the Ni-Co alloy shifted away from and toward the Fermi level, respectively. In the in-situ aqueous phase hydrodeoxygenation of methyl palmitate with methanol as the hydrogen donor at 330 °C, the decarbonylation/decarboxylation pathway dominated on all catalysts. The Ni-Co@C catalysts gave higher activity than the Ni@C and Co@C catalysts, and the yields of n-pentadecane and n-C6n-C16 reached 71.6% and 92.6%, respectively. The excellent performance of Ni-Co@C is attributed to the electronic interactions between Ni and Co and the small carbon microspheres. Due to the confinement effect of carbon, the metal particles showed high resistance to sintering under harsh hydrothermal conditions. Catalyst deactivation is due to the carbonaceous deposition, and the regeneration with CO2 recovered the catalyst reactivity.

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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
Front. Chem. Sci. Eng.    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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