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Journal of the Taiwan Institute of Chemical Engineers · 2023 · IF 5.7

Fe-Ni bimetallic nanoparticles encapsulated into nanofibrous carbon microspheres as a catalytic nanoreactor for highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran or 2,5-dihydroxymethyltetrahydrofuran

Taimei Cai,Lihua Yao,Jieping Fan,Hailong Peng

Background The highly efficient conversion of renewable biomass-derived platform compounds to high value-added chemicals is one of the most promising solution to the current rapid consumption of fossil resources. Methods Nanofibrous and porous carbon microspheres (NPCMs) were developed from chitin biomass and used to encapsulate Fe-Ni bimetallic nanoparticles for the formation of a novel catalytic nanoreactor (Fe-Ni/NPCMs), which was then used for the selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) or 2,5-dihydroxymethyltetrahydrofuran (DHMTHF). Significant findings The NPCMs consisted of N-doped carbon nanofibers with a high surface area. The Fe-Ni bimetallic nanoparticles were uniformly dispersed on the carbon nanofiber surfaces of the Fe-Ni/NPCMs, resulting in abundant catalytic sites and excellent catalytic performance. Importantly, the Fe-Ni/NPCMs showed highly-selective hydrogenation of HMF to DHMF or DHMTHF with high yields of 93.6% or 94.9% through simply modulating the reaction conditions. Increasing the zero valent iron (Fe 0 ) content in the Fe-Ni/NPCMs significantly promoted the DHMTH selectivity from HMF hydrogenation. Moreover, the Fe-Ni/NPCMs presented high stability and recyclability, and thus they are applicable to other biomass conversions . Therefore, Fe-Ni/NPCMs have promising industrial application in the production of high value-added chemicals from biomass-derived feed-stocks.

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ChemistrySelect · 2023 ·Vol. 8 ·期 16 ·e202300902 · IF 2.1

Dehydration of Xylose and Xylan to Furfural using P-Zr-SBA-15 Catalyst in Aqueous or Biphasic System

Panli Liu,Shengbin Shi,Ruiping Wei,Lijing Gao,Jin Zhang,Guomin Xiao

Graphical P-Zr-SBA-15 catalyst with bifunctional acidity was synthesized by introducing Zr 4+ into the mesoporous material SBA-15 structure for intra skeleton modification, and then impregnated with phosphoric acid solution to modify the outer skeleton. The catalyst exhibits excellent catalytic activity, good thermal stability, and recoverability in the preparation of furfural. A series of bifunctional P-Zr-SBA-15 catalysts with Lewis acid and Brønsted acid sites were prepared by modifying mesoporous material SBA-15 with Zr 4+ and phosphate group, which were used in the conversion of xylose and xylan into furfural. The structure and acidic characteristics of the catalyst were analyzed by X-ray diffraction, Fourier transform infrared spectroscopy, N 2 adsorption desorption, scanning/transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, NH 3 temperature programmed desorption, and pyridine adsorption infrared spectroscopy. The effects of different process parameters on the catalytic performance of the catalyst were studied. when using the xylose and xylan as substrates, the furfural yield were 80.3 % and 68.8 % under the optimal conditions in the H 2 O (NaCl) /toluene (3/3 mL) biphasic solvent system, respectively, and 52.5 % furfural yield was obtained using xylose as substrate in aqueous system. In addition, the catalyst has good thermal stability and easy recovery in the recycling experiment.

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Molecular Catalysis · 2023 · IF 4.6

Insight into the catalytic mechanism of N-doped carbon nanotubes supported CoNi bimetallic catalyst boosts the base-free oxidative esterification of furfural

Xin Yu,Xiaoyi Huang,Wenlong Jia,Jiahong Chen,Shibo Yang,Lincai Peng,Yong Sun,Xing Tang,Xianhai Zeng,Shuliang Yang,Zheng Li,Feng Xu,Lu Lin

Developing active and affordable catalysts for the transformation of biomass platform into value-added chemicals have drawn tremendous attention. Herein, we have successfully prepared a CoNi bimetallic nitrogen-doped carbon nanotubes (CNTs) catalyst, manifesting outstanding catalytic performance for furfural oxidative esterification under base-free conditions (methyl furoate yield >99%), and great recyclability (5th recycle). Importantly, an impressive methyl furoate formation rate of around 1980 μmol methyl furoate ·g cat −1 ·h −1 was achieved, to the best of our knowledge, the result represents one of the highest methyl furoate formation rates. The results revealed that the doping of Ni into the Co x Ni y -CNTs catalyst brings about more active sites. Fourier transforms infrared spectrometer results suggest that the Ni-N x sites are responsible for the adsorption of the substrate with tilted or vertical adsorption. Furthermore, the introduction of Ni facilitates the improvement of basicity, which in turn promotes the β-hydride elimination. All of these active sites boost the overall activity of the catalyst for the oxidative esterification of furfural.

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ENVIRONMENTAL TECHNOLOGY · 2023 · IF 2.8

Selective aqueous-phase hydrogenation of furfural to cyclopentanol over Ni-based CNT catalysts

Haihong Xia,Jing Li,Jun Zhao,Minghao Zhou,Jianchun Jiang

Cyclopentanol (CPL) was an eco-friendly solvent as well as important platform chemical which could be generated from biomass-derived furfural (FFA). In this paper, a series of Ni, Cu, Mo, Co bimetallic catalysts with different metals loadings supported on carbon nanotubes (CNT) were synthesized by an impregnation method for aqueous-phase hydrogenation of FFA to obtain CPL. Various effects of reaction parameters such as reaction solvent, reaction temperature, reaction time and different loading amounts of Ni over bimetallic Ni-based CNT catalysts were fully investigated. Among the catalysts studied, (15 + 5) wt% NiCu/CNT catalysts showed a high conversion of FFA and 88% selectivity towards CPL in water and 96% selectivity towards acetal in methanol at the mild condition of 160℃, 2 MPa hydrogen and 4 h reaction time. NiCu bimetallic synergistic effect was interpreted through H2-TPR and NH3-TPD measurement and a possible pathway was proposed. The features of the CNT-supported catalysts were investigated via XRD, XPS, TEM, H2-TPR and NH3-TPD. The Ni and bimetallic NiCu catalysts synthesized in this work were inexpensive and simple, which made them a promising candidate for the conversion of biomass-derived FFA to CPL.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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CATALYSIS COMMUNICATIONS · 2023 · IF 3.7

Boosting the aqueous-phase production of lactic acid via dual-site activation of carbohydrates

Dan Luo,Qin Wang,Jiansu Ran,Ruixue Yangcheng,Yuntong Cui,Shuang Luo,Jianjian Wang

A series of Zr-based catalysts were prepared using various commercial and cheap organic acids as the coordination agents, and these as-synthesized samples exhibited superior activities to produce lactic acid (LaA) from carbohydrates. Using humic acid (HA) as a typical coordination agent, LaA yield was up to 76% over the resultant Zr-HA, outperforming the most recent reported works. Deeper studies revealed that Zr-HA possessed both acid sites and base sites, and these dual active sites can simultaneously activate xylose, resulting in high yield production of LaA. Besides, Zr-HA also showed excellent reusability and can be reused at least five times.

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Foods · 2023 ·Vol. 12 ·期 11 ·2151 · IF 5.2

Determination and Risk Assessment of Flavor Components in Flavored Milk

Baorong Chen,Xiaodan Wang,Yumeng Zhang,Wenyuan Zhang,Xiaoyang Pang,Shuwen Zhang,Jing Lu,Jiaping Lv

This study aimed to determine chemical composition and assess exposure in flavored milk among Chinese residents, based on risk assessment methodologies of acceptable daily intake (ADI) and toxicological concern threshold (TTC). Esters (32.17%), alcohols (11.19%), olefins (9.09%), aldehydes (8.39%), and ketones (7.34%) comprised the majority of the flavoring samples. Methyl palmitate (90.91%), ethyl butyrate (81.82%), and dipentene (81.82%) had the highest detection rates in flavor samples. This study screened fifteen flavor components of concern and discovered that 2,3,5-trimethylpyrazine, furfural, benzaldehyde, and benzenemethanol were detected in 100% of flavored milk samples. Benzenemethanol was found in the highest concentration (14,995.44 μg kg−1). The risk assessment results revealed that there was no risk for Chinese residents in consuming flavored milk, and the maximum per capita daily consumption of 2,3,5-trimethylpyrazine, furfural, and benzenemethanol were 226.208 g, 140.610 g, and 120.036 g, respectively. This study could provide guidelines for amounts of flavor additive ingredients in milk.Keywords:flavored milk;SPME-GC/MS;flavor components;acceptable daily intake;toxicological concern threshold

✓ 已验证 产品关联 DOI PubMed 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Regulating the Cu0-Cu+ ratio to enhance metal-support interaction for selective hydrogenation of furfural under mild conditions

Jingyun Zhang,Zhen Jia,Shitao Yu,Shiwei Liu,Lu Li,Congxia Xie,Qiong Wu,Youzheng Zhang,Hailong Yu,Yuxiang Liu,Jinhui Pang,Yue Liu

Controllable carbonyl group (C O) hydrogenation is the key to the transformation of furfural molecules into high-value furfuryl alcohol chemicals. Herein, a non-noble copper metal catalyst (Cu/MgO) was prepared for the efficient hydrogenation of furfural to furfuryl alcohol under mild conditions. At 383 K and 2 MPa H 2 , 99.9% conversion of furfural with 99.9% selectivity to furfuryl alcohol was achieved within 80 min while the turnover frequency (TOF) was 56.87 h −1 . The temperature of a reductive pretreatment can be used to tune the nature of the interfaces between reduced copper and the metal oxides present in copper-magnesium oxide catalysts. The valence copper species exhibited unique catalytic properties in the hydrogenation of furfural to furfuryl alcohol. Besides, the Cu/MgO-350 exhibited excellent stability and reusability without significant activity loss. These results were accounted for by the MgO alkaline interface contributing to the effective formation and high dispersion of different valence Cu species. The active site had strong adaptability to the adsorption of reactants and desorption of products, thus avoiding excessive hydrogenation of furfural. According to the analysis of the characterization data, furfural adsorption mainly existed in η 1 (O)-aldehyde binding mode which was consistent with the density functional theory (DFT) calculation. DFT calculations of the reaction process showed that the theoretical results favored the hydrogenation of furfural through a hydroxyalkyl intermediate rather than of an alkoxide intermediate.

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Asia-Pacific Journal of Chemical Engineering · 2023 ·Vol. 18 ·期 5 ·e2937 · IF 1.8

Organodiphosphonate Zr-MOF: A highly efficient catalyst for Meerwein–Ponndorf–Verley reduction of furfural

Xinxin Xia,Hongyang Yu,Pindian Qin,Mingyu Dai,Lixue Jia,Yi Deng,Cuiqin Li,Feng Li

Tetraethyl p -xylenediphosphate is used as the organic ligand to prepare the organodiphosphonate Zr-based metal organic frameworks (ZrP-MOF). The physicochemical characterizations of ZrP-MOF under different hydrothermal and calcination conditions were performed by various analytical techniques. ZrP-MOF was then employed as a catalyst for the catalytic transfer hydrogenation of furfural with alcohol as the hydrogen donor, and the preparation parameters and catalytic properties of ZrP-MOF were investigated. Compared with fresh ZrP-MOF, the furfural conversion of ZrP-MOF calcined at 825 K increased from 43.5% to 95.1%. Calcination can significantly increase the Lewis/Brønsted acid ratio and enlarge the pore structure of ZrP-MOF, which promote the furfural catalytic transfer hydrogenation reaction over Zr-O based on the Meerwein–Ponndorf–Verley reduction.

CAS / MDL: 98-01-1 7699-43-6
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2023 · IF 4.2

Self-Healing and Flame-Retardant Modifications of Epoxy Resins by the Diels–Alder Release-Delivery Strategy for a High-Efficiency and Green Application

Tingting Lian,Shengchang Zhang,Qibin Xu,Kaixiang Wang,Bo Li,Xiangpu Qin,Mengjin Jiang,Pengqing Liu

The sustainability of epoxy thermosets (EPs) and EP-based composites is always limited by the evolution of internal microcracks and flammability. Herein, inspired by the drug release-delivery system for disease treatment, these symptoms of EP are solved efficiently by a multifunctional Diels–Alder (DA) release-delivery system. First, this novel system is fabricated by the cyclization reaction between the furan diene-containing phosphorus derivative and the maleimide dienophile. The resultant DA system is linked to the epoxy resin by the grafting reaction, thus ensuring its uniform dispersion. Being faced with the formation of inner microcracks, the maleimide dienophiles were released from the DA adducts under the mediated action of temperature and then were delivered to the targeted microcracks under the chemical potential difference derived from the variation of free volume. Then, the released maleimide molecules re-connect with the furan groups that existed near the microcracks to complete the repairing of the EP matrix. The skeletal structure of the EP was well preserved throughout the restoration process. Satisfactory flexural strength (105.5 MPa) and excellent crack-healing efficiency (104.5%) can be obtained for the modified EP. After three constant strain cycles, the stress retention rate can be readily maintained (more than 75%). In addition, due to the phosphorus–nitrogen synergistic flame-retardant effect from the DA system, not only the limited oxygen index of the DA-modified EP matrix can be improved to 27.5% but the lower peak release rate and lower total heat release are also observed compared with the unmodified EP.

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Polymers · 2023 ·Vol. 15 ·期 4 ·996 · IF 5

Lignocelluloses-Based Furan-Acetone Adducts as Wood Adhesives for Plywood Production

Lizhen Huang,Wenchang Sun,Li Shuai,Xiaolin Luo,Jing Liu

Plywood is made of wood veneers that are bonded with adhesives such as urea-formaldehyde, phenol-formaldehyde and melamine-formaldehyde resins. The plywood made from formaldehyde-based adhesives not only releases formaldehyde but also relies on fossil resources. In this article, we synthesized furan-acetone adducts from lignocellulosic biomass in one pot. The furan-acetone adducts could be directly used as adhesives with the addition of phosphoric acid as a curing catalyst. Particularly, with the addition of 5 wt% diphenylmethane diisocyanate (MDI) as a crosslinking agent, both the wet and dry bonding strength of the plywood prepared from the adhesives could meet the minimum requirement of 0.7 MPa (Chinese National Standard GB/T 9846-2015). The possible adhesion mechanism is that the penetration of furan-acetone adhesives into vessels and cell lumens followed by crosslinking during hot-pressing forms mechanical interlocking at the interface of wood veneers, which provides the main bonding strength of plywood. The findings presented here could provide a new way for the efficient preparation of aldehyde-free green wood adhesives and the value-added utilization of woody biomass.Keywords:bio-based wood adhesives;aldol condensation;bonding strength;furan-acetone adducts;plywood

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Foods · 2022 ·Vol. 11 ·期 24 ·3997 · IF 5.561

Untargeted Profiling and Differentiation of Volatiles in Varieties of Meat Using GC Orbitrap MS

Youyou Yang,Jing Li,Jiangtao Xing,Weihai Xing,Chaohua Tang,Zhenghua Rao,Junmin Zhang

Volatile compounds play vital roles in food sensory attributes and food quality. An analysis of volatile compounds could illustrate the sensory attributes at the microscale level. Here, untargeted profiling approaches for volatiles in five most-consumed meat species were established using headspace SPME-GC/high resolution Orbitrap MS. An extended high-resolution database of meat volatile compounds was established to enhance the qualification accuracy. Using sulfur-containing compounds, aldehydes, and ketones as the research model, the parameters including fiber coating types, extraction temperature, extraction time, and desorbing time were optimized. Principle component analysis, volcano analysis and partial least squares discriminant analysis were applied to run the classification and the selection of discriminant markers between meat varieties, respectively. Different varieties could be largely distinguished according to the volatiles’ profiles. 1-Octen-3-ol, 1-octen-3-one, 2-pentyl furan and some other furans degraded from n-6 fatty acids would contribute to distinguishing duck meat from other categories, while methyl esters mainly from oleic acid as well as dimethyl sulfoxide and carbon disulfide possibly produced from the sulfur-containing amino acids contributed to the discrimination of beef. Therefore, volatiles’ profiling not only could interpret the aroma style in meat but also could be another promising method for meat differentiation and authentication.Keywords:differentiation;GC-HRMS;SPME;statistical analysis;untargeted profiling;volatiles

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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2022 · IF 5.895

Competitive Formation of 2,3-Butanedione and Pyrazines through Intervention of Added Cysteine during Thermal Processing of Alanine-Xylose Amadori Compounds

Tong Zhou,Xue Xia,Heping Cui,Khizar Hayat,Xiaoming Zhang,Chi-Tang Ho

The intervention of cysteine (Cys) on the formation of 2,3-butanedione and pyrazines was evaluated during the thermal processing of the alanine-xylose Amadori compound (AX-ARP). With the involvement of Cys, the competitive formation of 2,3-butanedione and pyrazines was induced. The formation of 2,3-butanedione in the AX-ARP/Cys model was suppressed due to the inhibitory effect of the precursors of 2,3-butanedione like deoxypentosones, while the added Cys in the AX-ARP/Cys model competed with the recovered alanine (Ala) to capture glyoxal and methylglyoxal to make up for the absence of pyrazines in the AX-ARP model at an initial pH value of 7. The content of pyrazines increased from 0 up to 16.48 μg/L (120 °C, 120 min). Exogenous Cys itself showed lower reactivity with 2,3-butanedione through the Strecker degradation reaction; while the pH was increased to 8, the degradative products of Cys were facilitated to consume the residual 2,3-butanedione giving rise to the formation of 2,4,5-trimethylthiazole at 120 °C. It was the degradative products of Cys that accelerated the reaction for consumption of 2,3-butanedione rather than Cys itself. Additionally, the inhibitory effect of Cys on 2,3-butanedione formation was weakened under a basic condition, while the promotional effect on the formation of pyrazines was further boosted. With more Cys participating in the process of AX-ARP thermal degradation, the formation of 2,3-butanedione was further inhibited, while the yields of pyrazines were increased.

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