DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 32
·11076-11084
·
IF 4
Zhuoyou Gao,Mengying Wang,Ningzhao Shang,Wei Gao,Xiang Cheng,Shutao Gao,Yongjun Gao,Chun Wang
Hydrodeoxygenation (HDO) is an indispensable approach to produce renewable biofuels and value-added chemicals using natural biomass and its derivatives. 2,5-Dimethylfuran (DMF) is considered to be a very promising liquid biofuel, and it can be fabricated by HDO of the biomass derivative 5-hydroxymethylfurfural (HMF). Herein, a highly efficient bifunctional catalyst, Co/HAP(Ce), was fabricated by anchoring highly dispersed Co on Ce-doped hydroxyapatite (HAP(Ce)). Co/HAP(Ce) displayed excellent HDO catalytic activity to convert HMF to DMF, and 99% HMF conversion and 96% DMF selectivity can be obtained under 150 °C, 2 MPa H2 conditions for 5 h. Density functional theory calculations revealed that H2 can be more easily activated by Co/HAP(Ce). Systematic studies confirmed that the high activity of Co/HAP(Ce) can be ascribed to the desired acid–alkali properties, highly dispersed cobalt species and strong metal–support interactions. This research provides a cost effective approach for designing efficient catalysts for HDO of biomass and its derivatives.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Xian Shi,Xinyi Xing,Mengya Ruan,Qichun Wei,Ying Guan,Hui Gao,Siquan Xu
Efficient and green catalysis of cellulose to 5-hydroxymethylfurfural (HMF) is currently a challenge that needs a breakthrough. In this study, a series of inexpensive (x)SO 4 2- /HfO 2 heterogeneous catalysts were prepared and exhibited superior catalytic performance for conversion of cellulose into HMF in the green water-tetrahydrofuran monophasic system (H 2 O-THF). An optimal HMF yield of 54% was acquired through detailed evaluation of reaction conditions. Various analyzes including ICP-OES, XRD, SEM, TEM, FTIR, N 2 adsorption–desorption isotherm, XPS, TG, NH 3 -TPD and Py-FTIR were applied to inspected the physicochemical characteristics of the (x)SO 4 2- /HfO 2 catalysts. Meanwhile, the recyclability of the catalyst and the by-products generated during the reaction process were studied and captured, respectively. The results presented herein show that the catalytic system of (30%)SO 4 2- /HfO 2 catalyst combined with H 2 O-THF monophasic solvent is advanced, and it can be both green and efficient without the presence of other additives and promoters, and has great potential in the future.
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2023
·Vol. 13
·期 20
·5892-5901
·
IF 5
Jifang Cui,Zhihao Yu,Linhao Sun,Ming Zhang,Mengyan Guo,Jian Xiong,Yina Qiao,Rui Zhang,Xuebin Lu
Selective photocatalytic oxidation rather than mineralisation is essential for the catalytic valorisation of biomass, which requires precise control of the generation of reactive oxygen species via the rational construction of heterogeneous junctions. In this paper, CdIn2S4/g-C3N4 (CIS/CNNS) heterojunctions were constructed by a microwave-assisted method and used for selective photocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF), a key intermediate for fine chemical synthesis and an important furan-based polymer monomer. According to the electron transfer mechanism of the heterojunctions, the effective separation of charges and holes led to a significant enhancement of the utilization efficiency of photogenerated electrons (PGEs). Specifically, the valence band (VB) potential of the constructed heterojunctions did not reach the oxidation potential of ˙OH/OH−, which avoided the massive generation of strongly oxidizing active species ˙OH and thus increased the reaction selectivity. Under visible light irradiation, 65.2% HMF conversion and 91.5% DFF selectivity could be achieved over CIS/CNNS, with a product yield 3.26 times higher than monomeric CdlIn2S4 and 4.2 times higher than monomeric CNNS. The radical quenching experiments verified that ˙O2− was the predominant active species in the reaction process, and the ˙O2− signal of the composite was significantly enhanced in the ESR characterization, achieving highly selective conversion of HMF to DFF.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Xifeng Zhang,Yuting Li,Juan Wang,Gaofeng Zeng,Qin Zhong
Electrooxidation of 5‑Hydroxymethylfurfural (HMF) is considered a promising strategy for replacing the sluggish oxygen evolution reaction (OER) of electrolytic water, which can reduce the consumption of hydrogen production and the risk of gas mixing and obtain value-added products. Herein, a nanosheet with nanoflower catalyst (H-0.3Co-Ni 3 S 2 ) was synthesized via a one-step hydrothermal process with the assistance of hydrogen peroxide (H 2 O 2 ) for the electrooxidation of HMF. Adding H 2 O 2 and Co can decrease Ni's outer layer electronic cloud density, which benefits the catalyst's oxidation and catalyzes the HMF electrooxidation. H-0.3Co-Ni 3 S 2 shows the superior performance of the HMF electrochemical oxidation with the initial potential of 1.25 V vs. RHE and the voltage of 1.38 V vs. RHE at 200 mA cm −2 under the electrolyte of 1 M KOH with 10 mM HMF. The conversion rate, yield and Faraday efficiency of HMF electrooxidation for H-0.3Co-Ni 3 S 2 in the electrolyte of 1 M KOH with 10 mM HMF are 98.2 %, 97.6 % and 97.6 %, respectively. Besides, we provide a novel stepwise electrolysis strategy that can inhibit OER effectively while electrolyzing large-concentration HMF rapidly. Finally, in an electrolyte of 1 M KOH with 30 mM HMF, the conversion rate, yield and Faraday efficiency achieve 100 %, 91.9 % and 97.4 %, respectively.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2023
·
IF 13.1
Mengxia Li,Tianxi Zheng,Dongfei Lu,Shiwei Dai,Xin Chen,Xinchen Pan,Dibo Dong,Rengui Weng,Gang Xu,Fanan Wang
The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventional thermocatalytic route for the production of high-value-added chemicals from biomass resources. In virtue of the wide potential window with promising Faradic efficiency (FE) towards BHMF, Cu-based electrode has been in the center of investigation. However, its structure–activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory. In this work, we develop a two-step oxidation–reduction strategy to reconstruct the surface atom arrangement of the Cu foam (CF). By combination of multiple quasi-situ/in-situ techniques and density functional theory (DFT) calculation, the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal: Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF, while Cu(100) facet might trigger the accumulation of the by-product 5,5′-bis(hydroxymethy)hydrofurion (BHH). With the optimized composition of the facets on the reconstructed Cu(OH) 2 -ER/CF, the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of −0.15 V versus reversible hydrogen electrode (vs. RHE) in 0.1 M KOH solution. This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF, and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2023
·
IF 8.2
Xinyi Xing,Xian Shi,Mengya Ruan,Qichun Wei,Ying Guan,Hui Gao,Siquan Xu
Introduction of the sulfonic acid group into H-β zeolite to prepare β-SO 3 H bifunctional catalysts for the efficient synthesis of 5-hydroxymethylfurfural (HMF) from cellulose . Catalysts characterization, such as XRD, ICP-OES, SEM (Mapping), FTIR, XPS , N 2 adsorption-desorption isotherm, NH 3 -TPD, Py-FTIR demonstrate the sulfonic acid group was successfully grafted onto the β zeolite. A superior HMF yield (59.4 %) and cellulose conversion (89.4 %) was obtained in the H 2 O(NaCl)/THF biphasic system under 200 °C for 3 h with β-SO 3 H(3) zeolite as catalyst. More valuable, β-SO 3 H(3) zeolite converts other sugars and obtains ideal HMF yield, including fructose (95.5 %), glucose (86.5 %), sucrose (76.8 %), maltose (71.5 %), cellobiose (67.0 %), starch (68.1 %), glucan (64.4 %) and also converts plant material (25.1 % for moso bamboo and 18.7 % for wheat straw) with great HMF yield. β-SO 3 H(3) zeolite catalyst keeps an appreciable recyclability after 5 cycles. Moreover, in the presence of β-SO 3 H(3) zeolite catalyst, the by-products during the production of HMF from cellulose were detected, and the possible conversion pathway of cellulose to HMF was proposed. The β-SO 3 H bifunctional catalyst has excellent potential for the biorefinery of high value platform compound from carbohydrates.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Armin Rezayan,Renfeng Nie,Jianshe Wang,Tianliang Lu,Chunbao Charles Xu,Yongsheng Zhang
Selective cellulose transformation into the 5-hydroxymethylfurfural (HMF), a versatile platform chemical, has been researched using various catalysts, while desirable efficiency remains a challenge. This study revealed an alternative conversion approach to strong acidic/basic catalysis, an efficient one-pot synthesis of HMF without external catalyst from microcrystalline cellulose (MCC), functionalized via milling and subsequent oxidation pretreatment. The outstanding HMF yield (∼55%) was obtained under moderate reaction conditions (3 h, 190 °C), demonstrating the significant impact of functionalized MCC’s characteristics (e.g., reduced crystallinity index (CI), degree of polymerization (DP), and the formed –COOH) and the reaction conditions (e.g., the role of NaCl and H 2 O/THF ratio) for HMF synthesis. The formed –COOH group demonstrated a dual-function i ) in-situ destruction of MCC’s β -1,4-glycosidic linkages during pretreatment ii ) catalyzing hydrolysis/dehydration reactions of carbohydrates to form HMF. Furthermore, chloride ions could selectively promote consecutive reactions. The promising findings in this study provide a greener route to produce HMF from cellulose without using acid/base catalysts through cellulose structure functionalization by green/simple methods.
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2023
·
IF 5.2
Yixuan Zheng,Weiwei Ning,Quanhua Wang,Xueling Wei,Xingyang Li,Meng Pan
Hierarchical ZSM-5 was successfully prepared using l -carnitine and l -lysine as mesoporous templates, and the influence of the dosage of “secondary template” represented by l -carnitine on the formation of hierarchical zeolite was investigated in detail. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption, nuclear magnetic resonance (NMR), thermogravimetric-derivative thermogravimetry (TG-DTG), pyridine infrared and temperature programmed desorption of ammonia (NH 3 -TPD) were used to characterize the structural and textural properties of the as-prepared samples. The results showed that the hydrophilic property of the amino acid template overcame the phase separation and constructed a mesoporous system with an ultra-small size of 2–10 nm in the as-synthesized zeolite crystals. Not only the morphology and grain size, but also the Si/Al ratio and then the acidity of zeolite were affected by the “secondary template”. Catalytic cracking of triisopropylbenzene was chosen as a probe reaction so as to investigate the effect of the fabricated hierarchical porous system on the catalytic performances of the catalysts. The results showed that the introduction of hierarchical pores elevated the external surfaces of the catalyst and therefore significantly improved the catalytic cracking performance of the catalyst for the heavy molecules triisopropylbenzene. At the same time, the introduced mesopore structure also gave the macromolecule reactant a hierarchically cracking process because of the acid active sites located in the different spaces.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2023
·
IF 7.7
Yifan Wu,Guangbing Liang,Xinna Zhao,Hui Wang,Zhenping Qu
It is feasible and profitable to figure out multidiscipline environmental issues synergistically. Coal fly ash based adsorbent materials are widely used in the emission control of volatile organic compounds. A solvent-free method which was more environmental-friendly for ZSM-5 zeolites synthesis from coal fly ash was proposed to eliminate toluene. The results indicated that ZSM-5 zeolites were successfully synthesized from the precursor gel of coal fly ash with 30–60 wt% moisture contents. The SiO 2 /Al 2 O 3 mole ratio of gel was up to 99 after the pretreatment of alkali roasting and acid precipitation. During the synthesis process, the appropriate Na 2 CO 3 -to-SiO 2 ratio was 0.3, and the mesoporous formation would be facilitated along with the moisture content of gel. On the tendency of adsorption testing, the microporous structure was prone to the toluene adsorption, and the desorption was dependent on the mesoporous structure. The maximum adsorption capacity of 75.1 mg·g −1 was observed on S-40 sample, and the minimum desorption activation energy of 39.97 kJ·mol −1 was found on S-60 sample. The humid condition can reduce the toluene adsorption performance, and the maximum adsorption capacity was down to 63.7 mg·g −1 . Additionally, the synthetic ZSM-5 zeolites still have some superiority in economics and ecology when compared with commercial zeolites. The novel synthesis method, preparing controllable ZSM-5 zeolites from coal fly ash with the advantages of low cost and environmental friendliness, exhibited the tremendous application potential in environmental field.
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Xingyilong Zhang,Houfang Lu,Man Zhang,Hui Han,Rubo Tian,Kejing Wu,Yingying Liu,Yingming Zhu,Bin Liang
Low-temperature production of 5-hydroxymethylfurfural (HMF) from fructose in ternary deep eutectic solvents (TerDESs) of choline chloride (ChCl), ethylene glycol (EG), and maleic acid (MalA) is proposed. A fructose conversion of 99.9% and an HMF yield of 87.3% are achieved in TerDES with ChCl/EG/MalA = 3:1:1 at 70 °C in 30 min. The ChCl can effectively activate the hydroxy groups of fructose by lengthening the C–O bonds. The EG can both improve the formation of ChCl–MalA DES with wide ranges of component ratios and reduce the viscosity of the DES. A reaction mechanism considering the synergistic effect of the components in TerDES is suggested to explain the enhanced dehydration of fructose under mild conditions. The recycling results of the TerDES show stable yields of HMF within five recycle runs. This work offers an efficient solution to a green and sustainable process for a high yield of HMF production.
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2023
·
IF 8.7
Yuewen Shao,Mingzhu Guo,Mengjiao Fan,Kai Sun,Guoming Gao,Chao Li,Félix Mérimé Bkangmo Kontchouo,Lijun Zhang,Shu Zhang,Xun Hu
2,5-Dimethylfuran (DMF) is a promising fuel additive. Its selective production from 5-hydroxymethylfurfural (HMF) requires effective hydrodeoxygenation and simultaneous retainment of C C in furan ring, which is challenging over nickel-based catalysts. In this work, an alloying method was explored for selective conversion of HMF to DMF by introducing Fe species into Ni–Al catalysts to form oxyphilic FeNi alloy. The results showed that the formation of alloy in Ni–Fe–Al lowered the capability for adsorption and activation of hydrogen, reducing the activity for hydrogenation of the furan ring in HMF, forming mainly 2,5-dihydroxymethyl furan (DHMF) and 5-methylfurfuryl alcohol (5-MFA). In addition, the oxyphilic FeNi alloy had the high affinity for the adsorption/activation of C–OH in DHMF and 5-MFA, enhancing their hydrogenolysis to DMF. The kinetic study indicated that the hydrogenolysis of 2,5-dihydroxymethyl furan was the rate-determining step, showing a higher Ea (89.2 kJ mol −1 ) than that in hydrogenation of C O in HMF (59.7 kJ mol −1 ). Under optimized condition, DMF with yield of 93.4% from HMF was achieved over 1.5Ni-1.5Fe-1.0Al catalyst. In comparison with Ni–Al, 1.5Ni-1.5Fe-1.0Al also showed much higher resistivity towards sintering of metallic species, rendering the catalyst with superior catalytic stability.
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2019
·Vol. 11
·期 11
·2649-2656
·
IF 4.495
Kuo Zhou,Haiyan Liu,Huimin Shu,Shuwen Xiao,Dechao Guo,Yingxin Liu,Zuojun Wei,Xiaonian Li
Graphical Raney to the rescue ! High value-added 2,5-bisaminomethylfuran was one-pot synthesized from 5-HMF over Raney Ni with a yield of 60.7 %. DFT calculations were conducted to support our speculation that Ni can harmonize NH 3 and H 2 on its surface most suitably for the reductive amination reactions. Reductive amination of furfuryl alcohol, furfural and 5-hydroxymethylfurfural (5-HMF) were carried out on various metal catalysts. Over Raney Ni catalyst, we obtained the highest furfurylamine yields of 81.8 % and 94.0 % from furfuryl alcohol in absence and presence of H 2 , respectively. While furfural was used as the substrate, 100 % yield of furfurylamine could be achieved over Raney Ni under rather moderate conditions. Although 5-HMF was completely converted over all catalysts used, the highest yield of 2,5-bisaminomethylfuran (60.7 %) was obtained over Raney Ni at 160 °C in 12 h. The DFT calculations on the adsorption behavior of NH 3 and H 2 on different metal surfaces showed that the difference of the adsorption energy between NH 3 and H 2 on Ni is lower than those of other metals, indicating that less metal active sites on Ni surface is occupied by NH 3 , which leaves more active sites for dehydrogenation/hydrogenation reactions and in the end promotes the reductive amination reactions.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）