CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Jie Xiong,Shuo Wu,Bing Sun,Yiding Zhang,Botao Zhu,Lai Feng
W 18 O 49 with separately dispersed Ni sites was prepared as the electrocatalyst for electro-oxidation reaction of 5-hydroxymethylfurfural (HMFOR). • Ni 0.33 &W 18 O 49 promotes efficient HMFOR to 2,5-furandicarboxylic acid (FDCA) with a high yield rate (YR FDCA ) of ⁓3.37 mmol cm -2 h -1 . • Experimental and computational results reveal an indirect pathway for HMFOR, where the in-situ formed NiO(OH) acts as the proton acceptor. • A nickel foam‖Ni 0.33 &W 18 O 49 pair enables continuous production of FDCA with a high YR FDCA of ca. 0.279 g cm -2 h -1 . The electro-oxidation reaction of 5-hydroxymethylfurfural (HMFOR) provides an ideal solution for addressing the sustainable production of 2,5-furandicarboxylic acid (FDCA), a critical precursor for biodegradable polymer synthesis. However, HMFOR over non-precious catalysts may suffer from low current density and hence insufficient FDCA yield rate (YR FDCA ). In this work, a series of W 18 O 49 nanostructures with interstitially doped Ni 2+ sites (Ni x &W 18 O 49 ) are employed as the model catalyst for HMFOR. Among them, the optimal candidate Ni 0.33 &W 18 O 49 exhibits a superior performance in terms of an impressive YR FDCA of 2.88 mmol cm −2 h −1 and good durability, outperforming that of α-Ni(OH) 2 with continuously dispersed Ni-(μ 2 -OH)-Ni species. Experimental and theoretical studies reveal that the Ni&W 18 O 49 with an isolated Ni 2+ site follows an indirect pathway, where the in-situ formed NiO(OH) serves as a proton acceptor during HMFOR. It also surpasses α -Ni(OH) 2 in terms of remarkably reduced reaction barrier. Finally, an electrode pair of NF‖Ni 0.33 &W 18 O 49 is constructed to enable continuous productions of H 2 and FDCA with a high YR FDCA of 1.79 mmol cm −2 h −1 in a flowing single cell. This work thus provides fundamental insights into the design of Ni-based catalysts for highly efficient electro-oxidation of HMF to FDCA.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2026
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IF 6.7
Xincen Wang,Yishao Ma,Pingchuan Ma,Chenyu Yang,Minmin Han,Zhaoying Li,Yan He
HTL of rhamnose and glucuronic acid enables 5-methylfurfural production • Formic acid enhances MF via synergistic acid catalysis and hydrogen donation • Alcohol-water co-solvents and aqueous phase recycling further promote MF formation • Aqueous phase recycling achieves the highest MF relative content of 68.9% Hydrothermal liquefaction (HTL) provides a promising route for converting algal carbohydrates into value-added furan-based chemicals; however, achieving selective production of 5-methylfurfural (MF) remains challenging due to the complex competition among dehydration, hydrogenation, condensation, and polymerization reactions. In this study, rhamnose and glucuronic acid serve as representative model compounds of algal sulfated polysaccharides to investigate the regulation of MF formation through three in-situ hydrogen donation strategies, including formic acid addition, alcohol-water co-solvents, and aqueous phase recycling. The results demonstrate that hydrogen donation significantly alters the HTL reaction network by enhancing hydrogen transfer and stabilizing reactive intermediates, thereby promoting the selective formation of MF. Formic acid addition improves MF selectivity through the synergistic effects of acid catalysis and hydrogen donation, while alcohol-water co-solvents optimize the reaction microenvironment and suppress secondary polymerization. Among the investigated strategies, aqueous phase recycling exhibits the best performance by establishing an autocatalytic reaction environment, achieving a maximum MF relative content of 68.9% after the second recycling cycle.Furthermore, response surface methodology further identifies formic acid concentration and reaction temperature as the dominant factors affecting MF formation, while reaction time mainly exhibits a nonlinear effect. The systematic comparison of in-situ hydrogen-transfer strategies and the identification of aqueous-phase recycling as an effective approach for enhancing MF selectivity highlight the main contribution of this work. These findings provide insights into selective MF production from algal carbohydrate resources. Download: Download high-res image (205KB) Download: Download full-size image
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PETROLEUM CHEMISTRY
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2025
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IF 1.1
Jiang Ning,Mao Min,Wang Qingyin,Wang Gongying
MOF-5 is a classic metal-organic framework (MOF) crystal. However, synthesis of high-quality crystals usually requires an expensive N , N ′-diethylformamide (DEF) solvent, and a high molar ratio of a raw material (Zn 2+ : BDC 2– = 3‒5 : 1). More critically, its extreme instability against water vapor has caused researchers to do not use it. In this study, we achieved some important breakthroughs by using inexpensive N , N ′-dimethylformamide (DMF) solvent and meticulously optimizing synthesis parameters combined with a specialized micro-open solvothermal method. With a reduced molar ratio of a raw material (1.47 : 1), we successfully synthesized crystals exhibiting excellent phase structure and morphology, high surface area, out standing water vapor stability, and strong CO 2 adsorption capacity. The results show that the DEF replacement with DMF and reduction of the raw material molar ratio from 3 : 1 to 1.47 : 1 provides an increase of the BET surface area from ~935 to 2388 m 2 /g, and an improvement of the CO 2 adsorption capacity from ~0.8 to 2.5 mmol/g (298 K, 100 kPa). Breakthrough curves reveal that in simulated separation experiments for the flue gas and natural gas containing low CO 2 concentrations (10‒20%), the dynamic separation selectivity for CO 2 /N 2 reaches 22, while that for CO 2 /CH 4 remains stable at 4. Notably, the selectivity remained nearly unaffected by the pressure variation; this phenomenon is promising for enhancing the capture and purification of a low-concentration CO 2 from the flue gas and natural gas. It is important that the improved MOF-5 crystals prepared under optimal synthetic conditions maintained the stable phase structure and morphology even after 14-day exposure to humid air (relative humidity >70%), successfully overcoming the challenge posed by a water vapor.
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ACS Sustainable Chemistry & Engineering
·
2023
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IF 8.4
Wenyan Zhang,Haoyu Zhang,Yirong Feng,Tingting Ma,Fengyang Liu,Shuangfei Zhao,Jiming Yang,Yuguang Li,Dong Ji,Weiwei Tang,Xiaowei Li,Zheng Fang,Wei He,Kai Guo
In this article, the photocatalytic polymerization of 5-hydroxymethylfurfural (HMF) was applied in the preparation of photo-generated humins (L-H) for the first time. The molecular weight and furan ring content of L-H would be increased by introducing HMF into low-molecular-weight humins (LMW-H) extracted from spoiled HMF under visible light. Compared with humins prepared by the thermal-acid method (A-H), the molecular weight of L-H was less than 800 g/mol; therefore, L-H exhibited great solubility in various solvents and high chemical reactivity for structure modification. Also, the structure units had great differences between L-H and A-H. A-H only consisted of 2,5-dioxo-6-hydroxyhexanal (DHH) and HMF, while L-H also included the 5-hydroxy-4-keto-pentenoic acid (HKPA) generated by reacting HMF with singlet-oxygen. Then, the furan-based polymers were obtained through the classic Diels–Alder (DA) reaction to realize resource utilization of L-H. HKPA units in L-H provided more reaction sites for DA reaction. Characterizations by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectrum, microscopy, differential scanning calorimetry (DSC), and tensile properties proved that the polymer DA-L-H containing D–A bonds had self-healing properties, and the recovery efficiency could reach 92.8%. Through the utilization of biomass waste humins, the recycling of resources and sustainable economic development could be realized.
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CARBOHYDRATE POLYMERS
·
2023
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IF 11.2
Hengye Li,Xingwei Han,Wenjie Yu,Lin Zhang,Wenwen Bie,Meijie Wei,Zhongxia Wang,Fenying Kong,Wei Wang
Herein, through knitting benzylated β-cyclodextrin (BnCD) by dimethoxypillar[5]arene (P[5]), porous copolymers (P[5]-BnCDs) containing two kinds of macrocycles were synthesized with yields not <97 %. The molar ratio of P[5]/BnCD greatly influenced the P[5]-BnCDs' porosity and adsorption performance. When the molar ratio of P[5]/BnCD was 4/1, the P[5]-BnCD (4-1), demonstrated a surface area up to 515.95 m 2 /g and showed fast adsorption kinetic , high adsorption capacity and good reusability towards the model organic micropollutants (OMPs). The adsorption fitted well with the pseudo-second-order and the Langmuir models, while the thermodynamic studies revealed spontaneous physisorption process. The adsorption mechanism was dominant by host-guest and hydrophobic interactions and the adsorption at environmentally relevant concentrations experiments showed the practicality and superiority in extraction of the OMPs at μg/L level. This study paves a way for the development of versatile porous organic polymers with multiple macrocycles for efficient removal of OMPs from water.
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MICROPOROUS AND MESOPOROUS MATERIALS
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2023
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IF 5.2
Tingjun Fu,Lihan Jia,Guoqiang Hou,Zhong Li
Dealuminization over aluminium-containing ZSM-5 could create silanol nests and improve catalytic activity for alkylation of toluene with methanol. However, obviously damaged microporous structure seriously accelerated catalyst deactivation. Here, we demonstrate highly stable alkylation on ZSM-5 by deboronation treatment over boron-containing ZSM-5. 11 B MAS NMR, 1 H MAS NMR and OH-IR suggested that silanol nests with hydrogen bonds were created at the expenses of the removal of skeleton-B atoms. The formed silanol nests promote the adsorption of toluene, inhibit the methanol self-reaction and corresponding the deep alkylation process. Therefore, alkylation efficiency and toluene conversion could reach 70.8% and 33.5%, respectively. Importantly, the microporous structure of deboronized ZSM-5 was well maintained during deboronation, which determined a greatly improved catalytic stability compared with that of traditional dealuminized ZSM-5. Moreover, the deboronized ZSM-5 still presented relatively good catalytic stability under a higher methanol feedstock although the coke deposition was accelerated.
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COLLOIDS AND SURFACES B-BIOINTERFACES
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2023
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IF 5.8
Zaifei Zhuang,Xin Cheng,Liyan Cao,Guiqiang He,Jian Zhou,Yanxia Wei
Textile dye wastewater has the characteristics of high concentration, complex composition and changeable color degree and pH, which is difficult to be effectively and completely treated, and easy to cause environmental pollution. Here, a strategy of secondary bond interface assembly of polyethyleneimine on zein microparticles (PEI) ( [email protected] ) was constructed to achieve rapid and efficient removal of Reactive Black 5 (RB5), which is one of the most widely used reactive dyes in the textile industry. Structural analysis indicated that the as-prepared PEI layer immobilized on zein microparticles was constructed based on the interface assembly dominated by hydrophobic interactions and electrostatic attraction between PEI molecules and zein chains. The novel interface showed excellent absorption performance for RB5 with an absorption capacity of 631.0 mg·g -1 , rapid adsorption in 2 min, wide pH range of 4–10. Mechanism analysis suggested the effective adsorption of RB5 by [email protected] microparticles was mainly attributed to secondary bond interface such as electrostatic interaction and hydrogen bond between RB5 and PEI immobilized on the surface of zein microparticles. Moreover, due to the presence of secondary bond interface, RB5 adsorbed on microparticles can be easily desorbed by using 0.01 M NaOH. Therefore, the strategy of secondary bond interface assembly with polyethyleneimine on zein microparticles has high potential for practical application in the treatment of dye-containing wastewater.
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Journal of Food Measurement and Characterization
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2023
·Vol. 17
·期 3
·3185-3193
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IF 3.4
Man Ziyi,Chen Ruihuan,Feng Yi,Xiao Jibo,Yang Hailong,Wu Xiangting
The complexes of epigallocatechin (EGC) and 5-hydroxymethylfurfural (5-HMF) were respectively constructed in water-soluble and ethanol-soluble systems to study the reducing effect of EGC on harmful substance 5-HMF in food. The results showed that EGC and 5-HMF can be combined by non-covalent way in water-soluble and ethanol-soluble systems, and the main force were hydrogen bond. Scanning electron microscope, X-ray diffractometer and differential scanning calorimeter displayed that EGC combined with 5-HMF in the form of co-amorphous complexes. Fourier transform infrared spectroscopy, 1 H-NMR spectroscopy and molecular dynamics simulation confirmed that EGC can form O–H⋯O hydrogen bonds with adjacent 5-HMF molecules. Thin-layer chromatography and in vitro digestive juice assay further proved that no free 5-HMF were observed after EGC and 5-HMF formed complexes. The results indicated that EGC and 5-HMF can form an EGC-5-HMF co-amorphous complexes through intermolecular hydrogen bonding, thereby changing the stability of free 5-HMF. EGC has favorable potential for the control of 5-HMF in food.
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Nano Research
·
2023
·Vol. 16
·期 5
·6670-6678
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IF 9.9
Jing Tianyun,Yang Shaokang,Feng Yonghai,Li Tingting,Zuo Yunpeng,Rao Dewei
Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural (HMF) to the higher value-added 2,5-furandicarboxylic acid (FDCA). However, these catalysts still suffer from unsatisfactory activity and poor selectivity. A series of N-doped carbon-supported Co-based dual-metal nanoparticles (NPs) have been designed, among which the Co-Cu 1.4 -CN x exhibits enhanced HMF oxidative activity, achieving FDCA formation rates 4 times higher than that of pristine Co-CN x , with 100% FDCA selectivity. Density functional theory (DFT) calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the d-band center of Co-Cu 1.4 -CN x , thus reducing the energy barriers for the conversion of HMF to FDCA. Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.
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DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 27
·9456-9464
·
IF 4
Xiu He,ZhenZhen Mo,Huiling Liu,Cheng Wang
The synthesis of furan-based platform chemicals from abundant and renewable biomass-based hexoses plays an important role in the development and utilization of biomass energy. The electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR) represents a promising route for synthesizing the 2,5-furandicarboxylic acid (FDCA) product which is a high value-added biomass-based monomer. Interface engineering is an effective strategy to adjust the electronic structure, optimize the adsorption of intermediates, and expose more active sites, thus attracting extensive attention for designing efficient HMFOR electrocatalysts. Herein, a NiO/CeO2@NF heterostructure with an abundant interface is designed for boosting the HMFOR performance under alkaline conditions. At 1.475 V vs. RHE, the conversion of HMF is nearly 100%, the selectivity of FDCA is 99.0%, and the faradaic efficiency is as high as 98.96%. The NiO/CeO2@NF electrocatalyst also exhibits robust stability for HMFOR for 10 cycles. When coupled with the cathode hydrogen evolution reaction (HER) in alkaline medium, the yields of FDCA and hydrogen production are 197.92 and 600 μmol cm−2 h−1, respectively. The NiO/CeO2@NF catalyst is also suitable for the electrocatalytic oxidation of other biomass-derived platform compounds. The abundant interface between NiO and CeO2, which can regulate the electronic properties of Ce and Ni atoms, improve the oxidation state of Ni species, regulate intermediate adsorption, and promote electron/charge transfer, makes the most contribution to high HMFOR performance. This work will provide a simple route for the design of heterostructured materials and reveal the application prospect of interface engineering for promoting the upgrading of biomass derivatives.
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APPLIED CATALYSIS A-GENERAL
·
2023
·
IF 5.5
Yunye Wang,Mengdie Guo,Ya Wang,Xinjie Liu,Xiaopeng Li,Cuong Pham-Huu,Xuemei Liao
Catalytic oxidation of biomass derived 5-Hydroxymethylfurfural (HMF) feedstock is a promising route to produce value-added chemicals 2, 5-diformylfuran (DFF). Here, we find that incorporating monatomic Ru into the crystalline lattice of α-MnO 2 can trigger synergetic catalysis for aerobic oxidation of HMF. Ru species can not only act as active sites for HMF conversion, but also activate surface oxygen species by creating rich oxygen vacancies on the α-MnO 2 . As result, such catalyst delivers much higher DFF productivity than that of Ru located in the tunnel of support (110 °C, 1.5 MPa, 1 h) and state-of-the-art Ru-based catalysts. Furthermore, the direct conversion of fructose into DFF was realized by combination of Amberlyst-15 and Ru-MnO 2 HT catalyst in one-pot via two-step. Characterization and kinetic results indicated that atomically dispersed Ru hosted in the crystalline lattice of support created abundant oxygen vacancies and thus weakened the Mn-O bond, resulting in facile lattice oxygen activation.
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Drug Design Development and Therapy
·
2023
·
IF 4.8
Zhen Yu,Shixin Chan,Xu Wang,Rui Sun,Ming Wang,Zhenglin Wang,Xiaomin Zuo,Jiajie Chen,Huabing Zhang,Wei Chen
Purpose To evaluate the effect of 5-fluorouracil (5-FU) combined with rutaecarpine (RUT) on the antiproliferative, anti-migratory, and apoptosis-promoting ability of colorectal cancer (CRC) cells and explore the underlying mechanism.Methods The antiproliferative effects of RUT and 5-FU on CRC cells were evaluated using MTT and colony formation assays. Anti-migration was assessed by cell scratch and transwell tests. The synergistic effect of RUT and 5-FU was assessed by isobologram and combination index analysis using CompuSyn software. The effects of RUT and 5-FU on cell apoptosis were detected by flow cytometry. Differences in protein expression levels with or without RUT and/or 5-FU treatment were assessed by Western blot. Moreover, a mouse xenograft model of CRC was established to investigate the antitumor effect of RUT and 5-FU in vivo, and Ki67 and cleaved caspase-3 expression was detected by immunofluorescence.Results In this study, we found that 5-FU combined with RUT can inhibit the proliferative, migratory, and antiapoptotic abilities of CRC cells to a significantly greater extent than either RUT or 5-FU alone both in vivo and in vitro. Western blot analysis showed that the level of signal transducer and activator of transcription 3 (STAT3) phosphorylation in CRC cells was significantly reduced after combination therapy compared with that seen with the respective monotherapies. In addition, combination therapy influenced the STAT3 signaling pathway, namely, it inhibited the expression of c-Myc, CDK4, and Bcl-2 while enhancing that of the proapoptotic protein cleaved caspase-3. Immunofluorescence staining further showed that the expression of Ki67 and cleaved caspase-3 was significantly downregulated and upregulated, respectively, in tumor tissues of mice treated with combination therapy compared with that observed with 5-FU treatment alone.Conclusion Combined therapy with 5-FU and RUT exerted a superior curative effect in CRC than treatment with either single drug alone and has potential as a novel therapeutic modality for the treatment of CRC.
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