Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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A ternary mechanism for the facilitated transfer of metal ions onto metal–organic frameworks: implications for the ‘‘versatility’’ of these materials as solid sorbents
Xiyuan Bu, Ming Tian, Hongqing Wang, Lin Wang, Liyong Yuan, Weiqun Shi
Front. Chem. Sci. Eng.    2022, 16 (11): 1632-1642.   https://doi.org/10.1007/s11705-022-2187-6
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Although metal–organic frameworks offer a new platform for developing versatile sorption materials, yet coordinating the functionality, structure and component of these materials remains a great challenge. It depends on a comprehensive knowledge of a “real sorption mechanism”. Herein, a ternary mechanism for U(VI) uptake in metal–organic frameworks was reported. Analogous MIL-100s (Al, Fe, Cr) were prepared and studied for their ability to sequestrate U(VI) from aqueous solutions. As a result, MIL-100(Al) performed the best among the tested materials, and MIL-100(Cr) performed the worst. The nuclear magnetic resonance technique combined with energy-dispersive X-ray spectroscopy and zeta potential measurement reveal that U(VI) uptake in the three metal–organic frameworks involves different mechanisms. Specifically, hydrated uranyl ions form outer-sphere complexes in the surface of MIL-100s (Al, Fe) by exchanging with hydrogen ions of terminal hydroxyl groups (Al-OH2, Fe-OH2), and/or, hydrated uranyl ions are bound directly to Al(III) center in MIL-100(Al) through a strong inner-sphere coordination. For MIL-100(Cr), however, the U(VI) uptake is attributed to electrostatic attraction. Besides, the sorption mechanism is also pH and ionic strength dependent. The present study suggests that changing metal center of metal–organic frameworks and sorption conditions alters sorption mechanism, which helps to construct effective metal–organic frameworks-based sorbents for water purification.

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Bicontinuous porous membranes with micro-nano composite structure using a facile atomization-assisted nonsolvent induced phase separation method
Jing Wang, Guoyuan Pan, Yu Li, Yang Zhang, Hongwei Shi, Xuanbo Liu, Hao Yu, Muhua Zhao, Yiqun Liu, Changjiang Wu
Front. Chem. Sci. Eng.    2022, 16 (8): 1268-1280.   https://doi.org/10.1007/s11705-022-2143-5
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The micro-nano composite structure can endow separation membranes with special surface properties, but it often has the problems of inefficient preparation process and poor structural stability. In this work, a novel atomization-assisted nonsolvent induced phase separation method, which is also highly efficient and very simple, has been developed. By using this method, a bicontinuous porous microfiltration membrane with robust micro-nano composite structure was obtained via commercially available polymers of polyacrylonitrile and polyvinylpyrrolidone. The formation mechanism of the micro-nano composite structure was proposed. The microphase separation of polyacrylonitrile and polyvinylpyrrolidone components during the atomization pretreatment process and the hydrogen bonding between polyacrylonitrile and polyvinylpyrrolidone molecules should have resulted in the nano-protrusions on the membrane skeleton. The membrane exhibits superhydrophilicity in air and superoleophobicity underwater. The membrane can separate both surfactant-free and surfactant-stabilized oil-in-water emulsions with high separation efficiency and permeation flux. With excellent antifouling property and robust microstructure, the membrane can easily be recycled for long-term separation. Furthermore, the scale-up verification from laboratory preparation to continuous production has been achieved. The simple, efficient, cost-effective preparation method and excellent membrane properties indicate the great potential of the developed membranes in practical applications.

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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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Thermoresponsive block copolymer supported Pt nanocatalysts for base-free aerobic oxidation of 5-hydroxymethyl-2-furfural
Huaxin Qu, Jie Deng, Bei Wang, Lezi Ouyang, Yong Tang, Kai Yu, Lan-Lan Lou, Shuangxi Liu
Front. Chem. Sci. Eng.    2021, 15 (6): 1514-1523.   https://doi.org/10.1007/s11705-021-2092-4
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A base-free catalytic system for the aerobic oxidation of 5-hydroxymethyl-2-furfural was exploited by using Pt nanoparticles immobilized onto a thermoresponsive poly(acrylamide-co-acrylonitrile)-b-poly(N-vinylimidazole) block copolymer, with an upper critical solution temperature of about 45 °C. The Pt nanocatalysts were well-dispersed and highly active for the base-free oxidation of 5-hydroxymethyl-2-furfural by molecular oxygen in water, affording high yields of 2,5-furandicarboxylic acid (up to>99.9%). The imidazole groups in the block copolymer were conducive to the improvement of catalytic performance. Moreover, the catalysts could be easily separated and recovered based on their thermosensitivity by cooling the reaction system below the upper critical solution temperature. Good stability and reusability were observed over these copolymer-immobilized catalysts with no obvious decrease in catalytic activity in the five consecutive cycles.

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Nitrogen distribution in the products from the hydrothermal liquefaction of Chlorella sp. and Spirulina sp.
Tianyi Bao, Yuanyuan Shao, Haiping Zhang, Jesse Zhu
Front. Chem. Sci. Eng.    2022, 16 (6): 985-995.   https://doi.org/10.1007/s11705-021-2126-y
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The high contents of nitrogen-containing organic compounds in biocrude obtained from hydrothermal liquefaction of microalgae are one of the most concerned issues on the applications and environment. In the project, Chlorella sp. and Spirulina sp. were selected as raw materials to investigate the influence of different reaction conditions (i.e., reaction temperature, residence time, solid loading rate) on the distribution of nitrogen in the oil phase and aqueous phase. Three main forms of nitrogen-containing organic compounds including nitrogen-heterocyclic compounds, amide, and amine were detected in biocrudes. The contents of nitrogen-heterocyclic compounds decreased with temperature while amide kept increasing. The effect of residence time on the components of nitrogen-containing organic compounds was similar with that of temperature. However, the influence of solid loading rate was insignificant. Moreover, it was also found that the differences of amino acids in the protein components in the two microalgae might affect the nitrogen distribution in products. For example, nitrogen in basic amino acids of Spirulina sp. preferred to go into the aqueous phase comparing with the nitrogen in neutral amino acids of Chlorella sp. In summary, a brief reaction map was proposed to describe the nitrogen pathway during microalgae hydrothermal liquefaction.

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Solvent-resistant porous membranes using poly(ether−ether ketone): preparation and application
Lixin Xing, Jiaming Wang, Xuehua Ruan, Gaohong He
Front. Chem. Sci. Eng.    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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Utilization of waste vanadium-bearing resources in the preparation of rare-earth vanadate catalysts for semi-hydrogenation of α,β-unsaturated aldehydes
Yang Zhang, Guowu Zhan, Yibo Song, Yiping Liu, Jiale Huang, Shu-Feng Zhou, Kok Bing Tan, Qingbiao Li
Front. Chem. Sci. Eng.    2022, 16 (12): 1793-1806.   https://doi.org/10.1007/s11705-022-2191-x
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Recycling industrial solid waste not only saves resources but also eliminates environmental concerns of toxic threats. Herein, we proposed a new strategy for the utilization of petrochemical-derived carbon black waste, a waste vanadium-bearing resource (V > 30000 ppm (10 −6)). Chemical leaching was employed to extract metallic vanadium from the waste and the leachate containing V was used as an alternative raw material for the fabrication of vanadate nanomaterials. Through the screening of various metal cations, it was found that the contaminated Na+ during the leaching process showed strong competitive coordination with the vanadium ions. However, by adding foreign Ce3+ and Y3+ cations, two rare-earth vanadates, viz., flower-like CeVO4 and spherical YVO4 nanomaterials, were successfully synthesized. Characterization techniques such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, Fourier-transform infrared, and N2 physisorption were applied to analyze the physicochemical properties of the waste-derived nanomaterials. Importantly, we found that rare-earth vanadate catalysts exhibited good activities toward the semi-hydrogenation of α,β-unsaturated aldehydes. The conversion of cinnamaldehyde and cinnamic alcohol selectivity were even higher than those of the common CeVO4 prepared using pure chemicals (67.2% vs. 27.7% and 88.4% vs. 53.5%). Our work provides a valuable new reference for preparing vanadate catalysts by the use of abundant vanadium-bearing waste resources.

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Reduction kinetics of SrFeO3−δ/CaO∙MnO nanocomposite as effective oxygen carrier for chemical looping partial oxidation of methane
Xinhe Wang, Liuqing Yang, Xiaolin Ji, Yunfei Gao, Fanxing Li, Junshe Zhang, Jinjia Wei
Front. Chem. Sci. Eng.    2022, 16 (12): 1726-1734.   https://doi.org/10.1007/s11705-022-2188-5
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Chemical looping reforming of methane is a novel and effective approach to convert methane to syngas, in which oxygen transfer is achieved by a redox material. Although lots of efforts have been made to develop high-performance redox materials, a few studies have focused on the redox kinetics. In this work, the kinetics of SrFeO3−δ–CaO∙MnO nanocomposite reduction by methane was investigated both on a thermo-gravimetric analyzer and in a packed-bed microreactor. During the methane reduction, combustion occurs before the partial oxidation and there exists a transition between them. The weight loss due to combustion increases, but the transition region becomes less inconspicuous as the reduction temperature increased. The weight loss associated with the partial oxidation is much larger than that with combustion. The rate of weight loss related to the partial oxidation is well fitted by the Avrami–Erofeyev equation with n = 3 (A3 model) with an activation energy of 59.8 kJ∙mol‒1. The rate law for the partial oxidation includes a solid conversion term whose expression is given by the A3 model and a methane pressure-dependent term represented by a power law. The partial oxidation is half order with respect to methane pressure. The proposed rate law could well predict the reduction kinetics; thus, it may be used to design and/or analyze a chemical looping reforming reactor.

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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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Fabrication of bimetallic Cu–Zn adsorbents with high dispersion by using confined space for gas adsorptive separation
Yu-Chao Wang, Tian-Tian Li, Li Huang, Xiao-Qin Liu, Lin-Bing Sun
Front. Chem. Sci. Eng.    2022, 16 (11): 1623-1631.   https://doi.org/10.1007/s11705-022-2202-y
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The number of active components and their dispersion degree are two key factors affecting the performance of adsorbents. Here, we report a simple but efficient strategy for dispersing active components by using a confined space, which is formed by mesoporous silica walls and templates in the as-prepared SBA-15 (AS). Such a confined space does not exist in the conventional support, calcined SBA-15, which does not contain a template. The Cu and Zn precursors were introduced to the confined space in the AS and were converted to CuO and ZnO during calcination, during which the template was also removed. The results show that up to 5 mmol·g–1 of CuO and ZnO can be well dispersed; however, severe aggregation of both oxides takes place in the sample derived from the calcined SBA-15 with the same loading. Confined space in the AS and the strong interactions caused by the abundant hydroxyl groups are responsible for the dispersion of CuO and ZnO. The bimetallic materials were employed for the adsorptive separation of propene and propane. The samples prepared from the as-prepared SBA-15 showed superior performance to their counterparts from the calcined SBA-15 in terms of both adsorption capacity of propene and selectivity for propene/propane.

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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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Exceptionally flame-retardant flexible polyurethane foam composites: synergistic effect of the silicone resin/graphene oxide coating
Qian Wu, Jincheng Zhang, Shengpeng Wang, Bajin Chen, Yijun Feng, Yongbing Pei, Yue Yan, Longcheng Tang, Huayu Qiu, Lianbin Wu
Front. Chem. Sci. Eng.    2021, 15 (4): 969-983.   https://doi.org/10.1007/s11705-020-1988-8
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A facile strategy was developed to fabricate flexible polyurethane (PU) foam composites with exceptional flame retardancy. The approach involves the incorporation of graphene oxide (GO) into a silicone resin (SiR) solution, which is then deposited onto a PU foam surface via the dip-coating technique and cured. Fourier-transform infrared spectroscopy, scanning electron microscopy, and Raman spectroscopy measurements demonstrated that the SiR and GO were successfully coated onto the PU skeleton and the intrinsic porous structure of the PU foam remained intact. The effects of SiR and GO on the mechanical and thermal stability and flame retardancy of PU composites were evaluated through compression tests, thermogravimetric analysis, vertical combustion tests, and the limiting oxygen index. The measurement results revealed that the composites (PU@SiR-GO) showed superior flame retardancy and thermal and mechanical stability compared to pristine PU or PU coated with SiR alone. The mechanical and thermal stability and the flame-retardant properties of the PU composites were enhanced significantly with increasing GO content. Based on the composition, microstructure, and surface morphology of PU@SiR-GO composites before and after combustion tests, a possible flame-retardance mechanism is proposed. This work provides a simple and effective strategy for fabricating flame-retardant composites with improved mechanical performance.

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Rare-earth separation based on the differences of ionic magnetic moment via quasi-liquid strategy
Na Wang, Fujian Li, Bangyu Fan, Suojiang Zhang, Lu Bai, Xiangping Zhang
Front. Chem. Sci. Eng.    2022, 16 (11): 1584-1594.   https://doi.org/10.1007/s11705-022-2189-4
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The separation of rare earth elements is particularly difficult due to their similar physicochemical properties. Based on the tiny differences of ionic radius, solvent extraction has been developed as the “mass method” in industry with hundreds of stages, extremely intensive chemical consumption and large capital investments. The differences of the ionic magnetic moment among rare earths are greater than that of ionic radius. Herein, a novel method based on the large ionic magnetic moment differences of rare earth elements was proposed to promote the separation efficiency. Rare earths were firstly dissolved in the ionic liquid, then the ordering degree of them was improved with the Z-bond effect, and finally the magnetic moment differences between paramagnetic and diamagnetic rare earths in quasi-liquid system were enhanced. Taking the separation of Er/Y, Ho/Y and Er/Ho as examples, the results showed that Er(III) and Ho(III) containing ionic liquids had obvious magnetic response, while ionic liquids containing Y(III) had no response. The separation factors of Er/Y and Ho/Y were achieved at 9.0 and 28.82, respectively. Magnetic separation via quasi-liquid system strategy provides a possibility of the novel, green, and efficient method for rare earth separation.

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Lignin-derived dual-function red light carbon dots for hypochlorite detection and anti-counterfeiting
Yixuan Chang, Fanwei Kong, Zihao Zhu, Ziai Wang, Chunxia Chen, Xiaobai Li, Hongwei Ma
Front. Chem. Sci. Eng.    2023, 17 (7): 966-975.   https://doi.org/10.1007/s11705-022-2244-1
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The efficient utilization of natural lignin, which is the main by-product of the cellulose industry, is crucial for enhancing its economic value, alleviating the environmental burden, and improving ecological security. By taking advantage of the large sp2 hybrid domain of lignin and introducing amino functional groups, new lignin-derived carbon dots (SPN-CDs) with red fluorescence were successfully synthesized. Compared with green and blue fluorescent materials, red SPN-CDs have desirable anti-interference properties of short-wave background and exhibit superior luminescence stability. The SPN-CDs obtained exhibited sensitive and distinctive visible color with fluorescence-dual responses toward hypochlorite. Considering this feature, a portable, low-cost, and sensitive fluorescence sensing paper with a low limit of detection of 0.249 μmol∙L–1 was fabricated using the SPN-CDs for hypochlorite detection. Furthermore, a new type of visible-light and fluorescence dual-channel information encryption platform was constructed. Low-concentration hypochlorite can be employed as an accessible and efficient information encryption/decryption stimulus, as well as an information “eraser”, facilitating a safe and diversified transmission and convenient decryption of information. This work opens new avenues for high-value-added applications of lignin-based fluorescent materials.

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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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High-precision standard enthalpy of formation for polycyclic aromatic hydrocarbons predicting from general connectivity based hierarchy with discrete correction of atomization energy
Zihan Xu, Huajie Xu, Lu Liu, Rongpei Jiang, Haisheng Ren, Xiangyuan Li
Front. Chem. Sci. Eng.    2022, 16 (12): 1743-1750.   https://doi.org/10.1007/s11705-022-2184-9
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The standard enthalpy of formation is an important predictor of the reaction heat of a chemical reaction. In this work, a high-precision method was developed to calculate accurate standard enthalpies of formation for polycyclic aromatic hydrocarbons based on the general connectivity based hierarchy (CBH) with the discrete correction of atomization energy. Through a comparison with available experimental findings and other high-precision computational results, it was found that the present method can give a good description of enthalpy of formation for polycyclic aromatic hydrocarbons. Since CBH schemes can broaden the scope of application, this method can be used to investigate the energetic properties of larger polycyclic aromatic hydrocarbons to achieve a high-precision calculation at the CCSD(T)/CBS level. In addition, the energetic properties of CBH fragments can be accurately calculated and integrated into a database for future use, which will increase computational efficiency. We hope this work can give new insights into the energetic properties of larger systems.

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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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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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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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Direct pyrolysis to convert biomass to versatile 3D carbon nanotubes/mesoporous carbon architecture: conversion mechanism and electrochemical performance
Chenxi Xu, Shunli Li, Zhaohui Hou, Liming Yang, Wenbin Fu, Fujia Wang, Yafei Kuang, Haihui Zhou, Liang Chen
Front. Chem. Sci. Eng.    2023, 17 (6): 679-690.   https://doi.org/10.1007/s11705-022-2266-8
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The massive conversion of resourceful biomass to carbon nanomaterials not only opens a new avenue to effective and economical disposal of biomass, but provides a possibility to produce highly valued functionalized carbon-based electrodes for energy storage and conversion systems. In this work, biomass is applied to a facile and scalable one-step pyrolysis method to prepare three-dimensional (3D) carbon nanotubes/mesoporous carbon architecture, which uses transition metal inorganic salts and melamine as initial precursors. The role of each employed component is investigated, and the electrochemical performance of the attained product is explored. Each component and precise regulation of their dosage is proven to be the key to successful conversion of biomass to the desired carbon nanomaterials. Owing to the unique 3D architecture and integration of individual merits of carbon nanotubes and mesoporous carbon, the as-synthesized carbon nanotubes/mesoporous carbon hybrid exhibits versatile application toward lithium-ion batteries and Zn-air batteries. Apparently, a significant guidance on effective conversion of biomass to functionalized carbon nanomaterials can be shown by this work.

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Highly hydrophobic oil−water separation membrane: reutilization of waste reverse osmosis membrane
Zihan Liu, Yang Luo, Lianchao Ning, Yong Liu, Ming Zhang
Front. Chem. Sci. Eng.    2022, 16 (11): 1606-1615.   https://doi.org/10.1007/s11705-022-2200-0
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The increasing applications of seawater desalination technology have led to the wide usage of polyamide reverse osmosis membranes, resulting in a large number of wasted reverse osmosis membranes. In this work, the base nonwoven layer of the wasted reverse osmosis membrane was successfully modified into the hydrophobic membrane via surface deposition strategy including TiO2 and 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS), respectively. Various techniques were applied to characterize the obtained membranes, which were then used to separate the oil–water system. The optimally modified membrane displayed good hydrophobicity with a contact angle of 135.2° ± 0.3°, and its oil–water separation performance was as high as 97.8%. After 20 recycle tests, the oil–water separation performance remained more than 96%, which was attributed to the film adhesion of the anchored TiO2 and PFOTS layer on the surface. This work might provide a new avenue for recycling the wasted reverse osmosis membrane used in oily wastewater purification.

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Floret-like Fe–Nx nanoparticle-embedded porous carbon superstructures from a Fe-covalent triazine polymer boosting oxygen electroreduction
Yong Zheng, Mingjin Li, Yongye Wang, Niu Huang, Wei Liu, Shan Chen, Xuepeng Ni, Kunming Li, Siwei Xiong, Yi Shen, Siliang Liu, Baolong Zhou, Niaz Ali Khan, Liqun Ye, Chao Zhang, Tianxi Liu
Front. Chem. Sci. Eng.    2023, 17 (5): 525-535.   https://doi.org/10.1007/s11705-022-2232-5
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Fe–Nx nanoparticles-embedded porous carbons with a desirable superstructure have attracted immense attention as promising catalysts for electrochemical oxygen reduction reaction. Herein, we employed Fe-coordinated covalent triazine polymer for the fabrication of Fe–Nx nanoparticle-embedded porous carbon nanoflorets (Fe/N@CNFs) employing a hypersaline-confinement-conversion strategy. Presence of tailored N types within the covalent triazine polymer interwork in high proportions contributes to the generation of Fe/N coordination and subsequent Fe–Nx nanoparticles. Owing to the utilization of NaCl crystals, the resultant Fe/N@CNF-800 which was generated by pyrolysis at 800 °C showed nanoflower structure and large specific surface area, which remarkably suppressed the agglomeration of high catalytic active sites. As expect, the Fe/N@CNF-800 exhibited unexpected oxygen reduction reaction catalytic performance with an ultrahigh half-wave potential (0.89 V vs. reversible hydrogen electrode), a dominant 4e transfer approach and great cycle stability (> 92% after 100000 s). As a demonstration, the Fe/N-PCNF-800-assembled zinc–air battery delivered a high open circuit voltage of 1.51 V, a maximum peak power density of 164 mW·cm–2, as well as eminent rate performance, surpassing those of commercial Pt/C. This contribution offers a valuable avenue to exploit efficient metal nanoparticles-based carbon catalysts towards energy-related electrocatalytic reactions and beyond.

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NiCo2O4@quinone-rich N–C core–shell nanowires as composite electrode for electric double layer capacitor
Yanli Fang, Hui Wang, Xuyun Wang, Jianwei Ren, Rongfang Wang
Front. Chem. Sci. Eng.    2023, 17 (4): 373-386.   https://doi.org/10.1007/s11705-022-2223-6
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The bind-free carbon cloth-supported electrodes hold the promises for high-performance electrochemical capacitors with high specific capacitance and good cyclic stability. Considering the close connection between their performance and the amount of carbon material loaded on the electrodes, in this work, NiCo2O4 nanowires were firstly grown on the substrate of active carbon cloth to provide the necessary surface area in the longitudinal direction. Then, the quinone-rich nitrogen-doped carbon shell structure was formed around NiCo2O4 nanowires, and the obtained composite was used as electrode for electric double layer capacitor. The results showed that the composite electrode displayed an area-specific capacitance of 1794 mF∙cm–2 at the current density of 1 mA∙cm–2. The assembled symmetric electric double layer capacitor achieved a high energy density of 6.55 mW∙h∙cm–3 at a power density of 180 mW∙cm–3. The assembled symmetric capacitor exhibited a capacitance retention of 88.96% after 10000 charge/discharge cycles at the current density of 20 mA∙cm–2. These results indicated the potentials in the preparation of the carbon electrode materials with high energy density and good cycling stability.

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Carbon-doped surface unsaturated sulfur enriched CoS2@rGO aerogel pseudocapacitive anode and biomass-derived porous carbon cathode for advanced lithium-ion capacitors
Yunpeng Shang, Xiaohong Sun, Zhe Chen, Kunzhou Xiong, Yunmei Zhou, Shu Cai, Chunming Zheng
Front. Chem. Sci. Eng.    2021, 15 (6): 1500-1513.   https://doi.org/10.1007/s11705-021-2086-2
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As a hybrid energy storage device of lithium-ion batteries and supercapacitors, lithium-ion capacitors have the potential to meet the demanding needs of energy storage equipment with both high power and energy density. In this work, to solve the obstacle to the application of lithium-ion capacitors, that is, the balancing problem of the electrodes kinetic and capacity, two electrodes are designed and adequately matched. For the anode, we introduced in situ carbon-doped and surface-enriched unsaturated sulfur into the graphene conductive network to prepare transition metal sulfides, which enhances the performance with a faster lithium-ion diffusion and dominant pseudocapacitive energy storage. Therefore, the lithium-ion capacitors anode material delivers a remarkable capacity of 810 mAh∙g–1 after 500 cycles at 1 A∙g–1. On the other hand, the biomass-derived porous carbon as the cathode also displays a superior capacity of 114.2 mAh∙g–1 at 0.1 A∙g–1. Benefitting from the appropriate balance of kinetic and capacity between two electrodes, the lithium-ion capacitors exhibits superior electrochemical performance. The assembled lithium-ion capacitors demonstrate a high energy density of 132.9 Wh∙kg–1 at the power density of 265 W∙kg–1, and 50.0 Wh∙kg–1 even at 26.5 kW∙kg–1. After 10000 cycles at 1 A∙g–1, lithium-ion capacitors still demonstrate the high energy density retention of 81.5%.

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Room-temperature hydrogenation of halogenated nitrobenzenes over metal–organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles
Yuemin Lin, Yuanyuan Zhang, Renfeng Nie, Kai Zhou, Yao Ma, Mingjie Liu, Dan Lu, Zongbi Bao, Qiwei Yang, Yiwen Yang, Qilong Ren, Zhiguo Zhang
Front. Chem. Sci. Eng.    2022, 16 (12): 1782-1792.   https://doi.org/10.1007/s11705-022-2220-9
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Ultra-dispersed Ni nanoparticles (7.5 nm) on nitrogen-doped carbon nanoneedles (Ni@NCNs) were prepared by simple pyrolysis of Ni-based metal–organic-framework for selective hydrogenation of halogenated nitrobenzenes to corresponding anilines. Two different crystallization methods (stirring and static) were compared and the optimal pyrolysis temperature was explored. Ni@NCNs were systematically characterized by wide analytical techniques. In the hydrogenation of p-chloronitrobenzene, Ni@NCNs-600 (pyrolyzed at 600 °C) exhibited extraordinarily high performance with 77.9 h–1 catalytic productivity and > 99% p-chloroaniline selectivity at full p-chloronitrobenzene conversion under mild conditions (90 °C, 1.5 MPa H2), showing obvious superiority compared with reported Ni-based catalysts. Notably, the reaction smoothly proceeded at room temperature with full conversion and > 99% selectivity. Moreover, Ni@NCNs-600 afforded good tolerance to various nitroarenes substituted by sensitive groups (halogen, nitrile, keto, carboxylic, etc.), and could be easily recycled by magnetic separation and reused for 5 times without deactivation. The adsorption tests showed that the preferential adsorption of –NO2 on the catalyst can restrain the dehalogenation of p-chloronitrobenzene, thus achieving high p-chloroaniline selectivity. While the high activity can be attributed to high Ni dispersion, special morphology, and rich pore structure of the catalyst.

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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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Electrocatalytic reduction of NO to NH3 in ionic liquids by P-doped TiO2 nanotubes
Shangcong Zhang, Qian Liu, Xinyue Tang, Zhiming Zhou, Tieyan Fan, Yingmin You, Qingcheng Zhang, Shusheng Zhang, Jun Luo, Xijun Liu
Front. Chem. Sci. Eng.    2023, 17 (6): 726-734.   https://doi.org/10.1007/s11705-022-2274-8
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Designing advanced and cost-effective electrocatalytic system for nitric oxide (NO) reduction reaction (NORR) is vital for sustainable NH3 production and NO removal, yet it is a challenging task. Herein, it is shown that phosphorus (P)-doped titania (TiO2) nanotubes can be adopted as highly efficient catalyst for NORR. The catalyst demonstrates impressive performance in ionic liquid (IL)-based electrolyte with a remarkable high Faradaic efficiency of 89% and NH3 yield rate of 425 μg·h−1·mgcat.−1, being close to the best-reported results. Noteworthy, the obtained performance metrics are significantly larger than those for N2 reduction reaction. It also shows good durability with negligible activity decay even after 10 cycles. Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites, thereby enhancing the NO adsorption and facilitating the desorption of *NH3. Moreover, the utilization of IL further suppresses the competitive hydrogen evolution reaction. This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH3 at a high efficiency and rate.

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Co anchored on porphyrinic triazine-based frameworks with excellent biocompatibility for conversion of CO2 in H2-mediated microbial electrosynthesis
Folin Liu, Shaohua Feng, Siyuan Xiu, Bin Yang, Yang Hou, Lecheng Lei, Zhongjian Li
Front. Chem. Sci. Eng.    2022, 16 (12): 1761-1771.   https://doi.org/10.1007/s11705-022-2195-6
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Microbial electrosynthesis is a promising alternative to directly convert CO2 into long-chain compounds by coupling inorganic electrocatalysis with biosynthetic systems. However, problems arose that the conventional electrocatalysts for hydrogen evolution may produce extensive by-products of reactive oxygen species and cause severe metal leaching, both of which induce strong toxicity toward microorganisms. Moreover, poor stability of electrocatalysts cannot be qualified for long-term operation. These problems may result in poor biocompatibility between electrocatalysts and microorganisms. To solve the bottleneck problem, Co anchored on porphyrinic triazine-based frameworks was synthesized as the electrocatalyst for hydrogen evolution and further coupled with Cupriavidus necator H16. It showed high selectivity for a four-electron pathway of oxygen reduction reaction and low production of reactive oxygen species, owing to the synergistic effect of Co–Nx modulating the charge distribution and adsorption energy of intermediates. Additionally, low metal leaching and excellent stability were observed, which may be attributed to low content of Co and the stabilizing effect of metalloporphyrins. Hence, the electrocatalyst exhibited excellent biocompatibility. Finally, the microbial electrosynthesis system equipped with the electrocatalyst successfully converted CO2 to poly-β-hydroxybutyrate. This work drew up a novel strategy for enhancing the biocompatibility of electrocatalysts in microbial electrosynthesis system.

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Multiple input self-organizing-map ResNet model for optimization of petroleum refinery conversion units
Jiannan Zhu, Vladimir Mahalec, Chen Fan, Minglei Yang, Feng Qian
Front. Chem. Sci. Eng.    2023, 17 (6): 759-771.   https://doi.org/10.1007/s11705-022-2269-5
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This work introduces a deep-learning network, i.e., multi-input self-organizing-map ResNet (MISR), for modeling refining units comprised of two reactors and a separation train. The model is comprised of self-organizing-map and the neural network parts. The self-organizing-map part maps the input data into multiple two-dimensional planes and sends them to the neural network part. In the neural network part, residual blocks enhance the convergence and accuracy, ensuring that the structure will not be overfitted easily. Development of the MISR model of hydrocracking unit also benefits from the utilization of prior knowledge of the importance of the input variables for predicting properties of the products. The results show that the proposed MISR structure predicts more accurately the product yields and properties than the previously introduced self-organizing-map convolutional neural network model, thus leading to more accurate optimization of the hydrocracker operation. Moreover, the MISR model has smoother error convergence than the previous model. Optimal operating conditions have been determined via multi-round-particle-swarm and differential evolution algorithms. Numerical experiments show that the MISR model is suitable for modeling nonlinear conversion units which are often encountered in refining and petrochemical plants.

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Molecular dynamics simulation on DNA translocating through MoS2 nanopores with various structures
Daohui Zhao, Huang Chen, Yuqing Wang, Bei Li, Chongxiong Duan, Zhixian Li, Libo Li
Front. Chem. Sci. Eng.    2021, 15 (4): 922-934.   https://doi.org/10.1007/s11705-020-2004-z
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The emergence of MoS2 nanopores has provided a new avenue for high performance DNA sequencing, which is critical for modern chemical/biological research and applications. Herein, molecular dynamics simulations were performed to design a conceptual device to sequence DNA with MoS2 nanopores of different structures (e.g., pore rim contained Mo atoms only, S atoms only, or both Mo and S atoms), where various unfolded single-stranded DNAs (ssDNAs) translocated through the nanopores driven by transmembrane bias; the sequence content was identified by the associating ionic current. All ssDNAs adsorbed onto the MoS2 surface and translocated through the nanopores by transmembrane electric field in a stepwise manner, where the pause between two permeation events was long enough for the DNA fragments in the nanopore to produce well-defined ionic blockage current to deduce the DNA’s base sequence. The transmembrane bias and DNA-MoS2 interaction could regulate the speed of the translocation process. Furthermore, the structure (atom constitution of the nanopore rim) of the nanopore considerably regulated both the translocate process and the ionic current. Thus, MoS2 nanopores could be employed to sequence DNA with the flexibility to regulate the translocation process and ionic current to yield the optimal sequencing performance.

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