GREEN CHEMISTRY
·
2023
·Vol. 25
·期 12
·4781-4792
·
IF 9.8
Chunxiao Gong,Zhaoyang Ju,Kuichuan Sheng,Ximing Zhang
Improper disposal of large quantities of crustacean shell waste from the food industry has caused serious environmental problems and waste of resources. Shell biorefinery is an emerging concept that upcycles the major components of crustacean shell waste, such as chitin, into value-added chemicals and materials. Producing biomass-derived 5-hydroxymethylfurfural (HMF) has been a hot topic over the past decades, while efficient conversion of shell-derived chitin into HMF is not available due to its water-insoluble and chemically-stable features. Herein, we develop a sustainable and efficient HMF production route from chitin. Chitin was treated with formic acid under mild conditions to synthesize formylated chitin (FC), which was subsequently converted to HMF in dimethyl sulfoxide (DMSO)–H2O media. Results showed that FC achieved a 53.2% HMF yield at 160 °C for 10 min catalyzed by AlCl3 in the co-solvent system (DMSO : H2O = 4 : 1, v/v), which is 11 times higher than the yield obtained from chitin under the same condition. The grafted formyl groups on FC significantly enhanced its noncovalent interactions with DMSO molecules, enhancing the accessibility and reactivity for HMF production. The reaction mechanisms were proposed and simulated with density functional theory calculations, and the intramolecular hydrogen migration is the rate-determining step in the reaction pathways. This study highlights a green and simple approach for chitin valorization.
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高影响因子
BIOMASS & BIOENERGY
·
2023
·
IF 6
Qiuhe Ren,Hong Ma,Wenbo Wang,Chongchong Chen,Jinbin Xiao,Penghua Che,Xin Nie,Yizheng Huang,Kasanneni Tirumala Venkateswara Rao,Chunbao(Charles) Xu
In this study, a mesoporous Nb-W oxide solid acid catalyst was synthesized and characterized in detail by TEM, N 2 physisorption , and Py-FTIR. Effects of the calcination temperature on the pore structure and acid properties were investigated. The results showed that increasing calcination temperature from 400 °C to 600 °C remarkably affected the characteristics of mesoporous Nb-W oxides, with a decrease in specific surface area, pore volume, and acid amount, but an increase in pore size from 5.1 nm to 10.4 nm. Furthermore, a notable decrease was found in both the fructose conversion and HMF yield in the dehydration of fructose to HMF over Nb-W oxides when increasing the calcination temperature, and the catalyst could keep high catalytic activity and selectivity after recycling 4 times. Solvents also played a key role in the fructose dehydration to HMF over the Nb-W oxides, and DMSO was the optimized solvent. 1 H NMR and 13 C NMR experiments revealed that the key intermediate, 4-hydroxy-5-hydroxymethyl-4,5-dihydrofuran-2-carbaldehyde, could generate in DMSO but not in other solvents including NMP, DMF , DMAC, and EG .
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高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2023
·
IF 6
Zhongyuan Sun,Yujiao Xie,Chunjie Wei,Feipeng Wang,Yuan Zhang,Feng Song,Hongyou Cui
Metal chloride aqueous solution is an effective method to promote the conversion of cellulose into 5-hydroxymethylfurfural (HMF). In this work, the influences of sodium chloride (NaCl) and lithium chloride (LiCl) on the conversion of cellulose into HMF in ferric chloride (FeCl 3 ) aqueous solution were investigated. The conversion of glucose and fructose in FeCl 3 –NaCl and FeCl 3 –LiCl aqueous solutions were studied, and the interaction between active species and cellobiose was characterized by UV spectrum and electrospray ion mass spectrometry to explore salt addition on the reaction of cellulose conversion and the active specie. Results showed that the yield of HMF converted from cellulose in FeCl 3 aqueous solution was low, while the yield of HMF was significantly increased when NaCl or LiCl added to the system. In FeCl 3 –NaCl aqueous solutions, the yield of HMF reach a maximum of 40.0% at a concentration of 0.02 M FeCl 3 , and hydrolysis of cellulose was the key step in the conversion of cellulose; In FeCl 3 –LiCl aqueous solutions, the yield of HMF reach a maximum of 36.7% at a concentration of 0.06 M FeCl 3 , and isomerization of glucose was the controlling step. The characterization results illustrated that the addition of NaCl or LiCl changed the active species in FeCl 3 aqueous solutions, and [Fe(OH) 2 ] + and [FeCl 2 (OH) + Li] + were the active species in FeCl 3 –NaCl and FeCl 3 –LiCl aqueous solution for cellulose conversion, respectively.
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高影响因子
RENEWABLE ENERGY
·
2023
·
IF 8.7
Yixuan Yu,Huai Liu,Junhua Zhang,Heng Zhang,Yong Sun,Lincai Peng
Designing highly efficient non-noble metal catalyst for the selective hydrogenolysis of biomass derivatives to fuels and fine chemicals is a key pursuit for sustainable chemical industry but substantially challenging. In this contribution, we report, for the first time, the construction of amorphous bimetal Ni–Fe borides for efficient catalytic hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dimethylfuran (DMF) as a promising biofuel candidate. The as-prepared Ni 1.52 Fe 0.36 BO x catalyst afforded a near-quantitative DMF yield using ethanol as a green solvent under relatively mild operating conditions (1 MPa H 2 , 160 °C and 1 h), leading to an excellent DMF formation rate of 16.5 mmol DMF ·g cat −1 ·h −1 , which is 1.7–16.5 folds higher than the state-of-art nickel-based catalysts. Mechanistic investigations demonstrated that the Fe intervention is conductive to the generation of electron-enriched metal sites and powerful acidic sites in Ni 1.52 Fe 0.36 BO x catalyst, which favored the activation of hydrogen and the cleavage of C–O bond to accelerate the hydrogenolysis process. Moreover, Ni 1.52 Fe 0.36 BO x catalyst exhibited good recyclability as well as universality in the hydrogenolysis of various biomass-derived unsaturated aldehydes. This finding opens a new avenue for highly selective hydrodeoxygenation of renewable biomass feedstock to value-added chemicals with non-noble bimetal hybrids in a green and straightforward manner.
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高影响因子
CARBOHYDRATE RESEARCH
·
2019
·
IF 1.873
Zhe Tang,Jianhui Su
High efficiency conversion of cellulose to 5-hydroxymethylfurfural (HMF) remains a challenge today. A simple solid acid catalyst Boehmite (γ-AlOOH) with high hydrothermal stability was prepared and used as sole catalyst for the direct conversion of cellulose into HMF in mixed reaction solvents of ionic liquid 1-buthyl-3-methylimidazolium chloride (BmimCl) and dimethyl sulfoxide (DMSO). This was aimed at developing an efficient and inexpensive catalyst for the production of HMF. The effects of factors such as water, solvent, catalyst load, temperature and reaction duration were investigated. An impressive HMF yield of 58.4% with 97.2% cellulose conversion was obtained at 160 °C after 2 h. More importantly, the catalyst γ-AlOOH was reused several times without loss of its catalytic properties. After five reaction runs, an HMF yield of 47.8% with 91.0% conversion was also obtained. In addition, the catalyst γ-AlOOH displayed excellent catalytic effects on the degradation of other carbohydrates. High yields of HMF from other carbohydrates such as glucose (61.2%), starch (62.7%) and inulin (70.5%) were achieved using γ-AlOOH as the catalyst. The proposed catalytic method shows a promising potential for HMF preparation, especially for industrial-scale HMF production from renewable bioresources.
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PubMed
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2019
·
IF 2.291
Yu Sang,Hansheng Li
The objective of this work is to investigate the catalytic effect of a series of modified HZSM-5 zeolites on n-decane cracking at 500 °C and atmospheric pressure. The zeolite catalysts were prepared with phosphorus and/or mesopore modification by excessive impregnation and/or hydrothermal treatment , and were characterized with various methods including SEM, TEM , XRD , FTIR, N 2 adsorption-desorption measurement and NH 3 -TPD. Results show that the addition of phosphorus adjusted the distribution and strength of acid sites in the zeolite crystals. The introduced mesoporous structure improved the diffusion of reactants and products in zeolite pores during n-decane cracking. With appropriate acid amounts and distribution, as well as short channels and high specific surface area, the modified HZSM-5 nanoparticles exhibited higher catalytic activity, better light olefins selectivity and longer lifetime, compared with the original HZSM-5 zeolite. The phosphorus modified HZSM-5 zeolites coupling with MCM-41 matrix was proved to be a promising catalyst for the thermal cracking of n-decane.
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2019
·
IF 3.375
Huiyong Chen,Wenjin Shang,Chenbiao Yang,Baoyu Liu,Chengyi Dai,Jianbo Zhang,Qingqing Hao,Ming Sun,Xiaoxun Ma
The hierarchical layered-bulky ZSM-5 (LBZ5) hybrid composites with a core–shell structure were synthesized by epitaxial growth of layered ZSM-5 nanosheets over bulky ZSM-5 crystals. The systematic balance of zeolitic microporosity and interlayered mesoporosity was achieved by elaborate regulation of the ratio between layered phase and bulky phase, resulting in a series of layered-bulky ZSM-5 hybrid composites with the controllable thickness of the layered shell ranging from 98 to 307 nm. The evaluation of catalytic performance in the methanol-to-propylene (MTP) reaction indicated the LBZ5 materials to be candidated catalysts for the MTP process with prolonged catalytic lifetime, superior coke toleration, and enhanced propylene selectivity compared with the parent bulky ZSM-5 (BZ5) and layered ZSM-5 (LZ5) due to their well-retained zeolitic framework, hierarchical meso-/microporosity by the layered-bulky composite structure, and appropriate strong acidity.
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高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2019
·Vol. 33
·期 3
·e4745
·
IF 3.259
Yibing Xie,Langlang Wang,Ping Ning,Xueqian Wang,Qi Wang,Yingjie Zhang,Mengyu Wang
A series of Ce modified catalysts were prepared using equivalent-volumetric ultrasonic impregnation method for AsH 3 removal. The performance of catalytic oxidation of AsH 3 under dynamic conditions was studied under different synthesis and reaction conditions. Through screening tests, the optimum catalyst was impregnated by 10 wt.% Ce (CH 3 COO) 3 precursor and subsequently calcinated at 550 °C. When the reaction temperature reached 170 °C, the Ce-HZSM-5 catalyst could maintain an oxidation efficiency of over 90% in 82 hrs. Furthermore, the chemical structure and properties of the catalyst and its catalytic oxidation mechanism with AsH 3 were analyzed using SEM-EDS, BET, XRD, XPS, H 2 -TPR and FT-IR. The results showed that Ce mainly existed on the catalyst surface in the forms of Ce 4+ and Ce 3+ . In the reaction process, the chemisorbed oxygen played a key role in the transformation between the two valence states. AsH 3 was firstly oxidized to elemental As with the participation of lattice oxygen. Then, the elemental As was partially blown into the rear part of the adsorption column along with the air flow and subsequently, de-sublimed on the column wall. Herein, the elemental As remained on the surface of Ce-HZSM-5 catalyst, which would further oxidize to As 2 O 3 . For the recovery of As, Ce-HZSM-5 proved to be a promising catalyst in AsH 3 removal. Highlights The CeO x modified HZSM-5 catalyst was used to catalytic oxidation of AsH 3 . The Ce-HZSM-5 catalyst could maintain over 90% oxidation efficiency in 82 hrs. AsH 3 was catalytic oxidized to elemental As and H 2 O on the catalyst surface and the As can be collected. The As adsorbed on the catalyst surface can be oxidized to As 2 O 3 but cannot be further oxidized to As 2 O 5 .
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高影响因子
APPLIED CATALYSIS A-GENERAL
·
2018
·
IF 4.521
Liqin Wang,Heqin Guo,Qilong Xie,Jungang Wang,Bo Hou,Litao Jia,Jinglei Cui,Debao Li
Furfural is one of the most valuable biomass platform compounds which is typically prepared from hemicellulose. Conversion of cellulose and its derived hexoses, which are the most abundant resource in nature, to furfural, is a big challenge. The amount of the reactive form (fructofuranose) which was beneficial to the formation of furfural and HMF, was increased when the solvent transformed from water to γ-butyrolactone (GBL)-water. The GBL promoted the adsorption of fructose on HY. The transfer of fructose from the solution to the channels of HY was enhanced with the introducing of GBL in solvent. The HY zeolite with apertures of 7.4 Å was found to promote the formation of acyclic fructose from cyclic fructose (8.6 Å) in the synergy with GBL. The Brønsted acid sites in the channels of HY favored the selective cleavage of the C C bond in acyclic fructose to xylose, and promoted the following dehydration of xylose to furfural, simultaneously. The furfural yield was increased while the 5-hydroxymethylfurfural (HMF) yield was decreased with the decrease of the Brønsted acid sites density. The maximum furfural yield was 37.8% over HY-3, while the maximum HMF yield was 69.2% over HY-1 in the conversion of fructose in GBL-water solvent. In addition, the etherification of HMF was the main factor for the low HMF yield and carbon balance in fructose conversion in GBL-water solvent.
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ORGANIC & BIOMOLECULAR CHEMISTRY
·
2019
·Vol. 17
·期 21
·5381-5391
·
IF 3.49
Chunfeng Jiang,Quan Liu,Jiaming Liu,Kaixuan Liu,Liangliang Tian,Mingfei Duan,Ying Wang,Zhufang Shen,Youjun Xu
A convenient synthesis of novel 3-deoxy-5-hydroxy-1-aminocarbasugars was developed here. The benzyl-protected glucose-derived ketone 12 was selectively converted in high yield to enone 13via retro-Michael elimination of BnOH. The double bond of 13 was regio- and stereo-selectively reduced by the induction of C4-α-OBn to the multi-functionalized 15. 15 contained all the functionalities with similar configurations to carbasugars but with 3-H and 5-OH in the ring, and it would be a very interesting building block for organic synthesis or for bioactive compounds. As one application, 15 was further transformed into 1-amino-carbasugars by the reductive amination and final deprotection of benzyls. The targets were subjected to the in vitro inhibitory activity test against sucrase or maltase. The inhibitory activity of 17b, 17h or 17j against sucrase was nearly similar to that of voglibose. In comparison with voglibose, in vivo results similarly showed that 17b, 17h or 17j could lower the post-prandial blood glucose level after sucrose loading in healthy male ICR mice, while miglitol or acarbose was less effective. The molecular modeling study of some targets or voglibose with human sucrase could explain the inhibiting action.
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PubMed
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 15
·4169-4177
·
IF 9.405
Yang Peng,Xianghua Li,Tian Gao,Teng Li,Weiran Yang
Starch is available in large quantities and at cheap price, especially that from stale rice, root and tuber crops, etc., which makes it desirable for conversion to value-added products. A metal-free approach to convert starch to 5-methylfurfural (5-MF) using hydrochloric acid, sodium iodide and hydrogen in a biphasic solvent system has been developed. 5-MF is an important fine chemical, widely used in food, medicine, pesticides, cosmetics and other industries, and is also considered to be an important bio-gasoline precursor. I− has superior nucleophilic substitution properties and high reactivity towards C–O bond cleavage, which is crucial for this transformation. Under optimal reaction conditions, 38.0% of 5-MF and 45.6% of total organic products can be obtained from starch with 22.5% levulinic acid as the main side product. Besides, 80.8% 5-MF can be directly obtained from 5-hydroxymethylfurfural (HMF) through the same process. To the best of our knowledge, this is the first reported example of a metal-free process to convert starch and HMF directly to 5-MF. The reaction mechanism was well studied. The catalyst system was proved to be stable and was recycled five times without loss of activity.
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高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Zihao Zhang,Siyu Yao,Changxue Wang,Miaomiao Liu,Feng Zhang,Xiaobing Hu,Hao Chen,Xin Gou,Kequan Chen,Yimei Zhu,Xiuyang Lu,Pingkai Ouyang,Jie Fu
Catalytic in situ hydrogenation of 5-hydroxymethylfurfural (5-HMF) to 2,5-dimethylfuran (DMF) has received a great interest in recent years. However, the issue of the consumption of expensive hydrogen donors, such as secondary alcohols, limits its applications. In this work, a ternary CuZnCoO x catalyst, exhibiting a 99% yield of DMF from in situ hydrogenation of 5-HMF with ethanol as economical hydrogen donor, is developed. High resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS-mapping), X-ray diffraction (XRD) and temperature programmed reduction (TPR) reveal the synergy effect of each components. Reaction mechanism studies unravel the CoO x results in promoting in situ H 2 production from ethanol, the zinc oxide accelerates the aldehyde group ( CHO) hydrogenation to hydroxymethyl group ( CH 2 OH) and the formation of Cu-Co alloy significantly facilitate the hydrogenation of 5-HMF. Additionally, this ternary CuZnCoO x catalyst exhibits superior recyclability without losing any activity during 6 cycles experiment.
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高影响因子
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