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RENEWABLE ENERGY · 2023 · IF 8.7

Effect of Lewis and Brønsted acidity in Ni/ZSM-5 on catalytic reductive etherification of furfural and alcohols

Mengxue Song,Chonghao Qiu,Pengfei Ma,Jiawei Zhong,Zhuohan Zhang,Weiping Fang,Wenjing Song,Jianqiang Fan,Weikun Lai

Reductive etherification is an attractive and practical strategy to convert bio-platform compounds into valuable chemicals. In directed synthesis of furfuryl ethers, reductive etherification of bioderived furfurals is still challenging due to the complexity of catalytic reaction . Herein, reductive etherification of furfural with alcohol was investigated over Ni/ZSM-5 catalyst, which found that Si/Al ratios in ZSM-5 played an important role on the catalytic performance. For Ni/ZSM-5 with Si/Al ratio of 50, 80.9% yield of furfuryl ether at 90.8% conversion of furfural was achieved under the condition of 2 MPa H 2 and 180 °C for 3 h in isopropanol. The catalyst exhibited superior stability and recyclability during the consecutive cycle run. Catalysts characterization demonstrated that both acidic properties and furfural adsorption were influenced by the Si/Al ratios in Ni/ZSM-5, which correlated to the reaction route and catalytic performance. Lewis acid sites enhanced furfural hydrogenation into furfuryl alcohol, while Brønsted acid sites on ZSM-5 effectively catalyzed sequential etherification of furfuryl alcohol to furfuryl ether. Under optimization conditions, various furfuryl ethers could be obtained with yields above 80% over Ni/ZSM-5 catalyst in different primary alcohols, demonstrating the general versatility of the approach. Our findings offered opportunities to develop an efficient furfuryl ethers synthesis method .

CAS / MDL: 78-10-4
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 22 ·10593-10603 · IF 3.3

A green process for separation and recovery of 5-hydroxymethylfurfural from carboxylic acid–choline chloride deep eutectic solvents

Hui Han,Man Zhang,Yingming Zhu,Kejing Wu,Yingying Liu,Binshen Wang,Houfang Lu,Bin Liang

Deep eutectic solvents (DESs) have the advantages of low cost, non-toxicity, and biodegradability for the catalytic conversion of fructose to 5-hydroxymethylfurfural (5-HMF). However, the efficient separation of 5-HMF from DESs is essential and challenging for its high-value utilization. In this study, the efficient separation of 5-HMF from eight carboxylic acid-based DESs was achieved by four cycles of extraction using tetrahydrofuran (THF) with an overall extraction efficiency of more than 80.0% (30 °C). Besides, the addition of 1 mol L−1 NaCl solution can significantly improve the extraction efficiency from 30.0% to 42.0%. In addition, the process of recovery and reuse of the extractant was proved to be quite effective, in which the purity of 5-HMF in the recovered product and the amount of THF in the recycled extractant can reach up to 90.0% and 97.0%, respectively. Finally, a thorough procedure for the preparation, separation, and recovery of 5-HMF was carried out to assess the viability of the optimized separation and recovery process. The results reveal outstanding extraction efficiency (77.9%), excellent yield of 5-HMF (63.3%), and high purity of 5-HMF in the final product (86.0%). This work expands the range of possible uses for 5-HMF by demonstrating an efficient and environmentally friendly method for separating and recovering 5-HMF while ensuring the reuse of the extractant.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Preparation, separation and purification of 5-hydroxymethylfurfural from sugarcane molasses by a self-synthesized hyper-cross-linked resin

Xue-fang Chen,Hai-long Li,Xu-ran Ji,Zhi-jie Shen,Hai-jun Guo,Shi-miao Yao,Meng-kun Wang,Lian Xiong,Xin-de Chen

Sugarcane molasses is a by-product in the process of sugar production, which has characteristics of large quantity, low price and easy to pollute the environment. High-valued utilization of sugarcane molasses has important research significance. In this work, 5-hydroxymethylfurfural (HMF) was obtained through hydrolyzing sugarcane molasses, and was separated from the hydrolysate by a designed hyper-cross-linked adsorption resin (HCLR). The optimal conditions for adsorption/desorption of HMF by HCLR were obtained. On this basis, the adsorption kinetics, equilibrium and thermodynamic behavior of HMF onto HCLR were studied, and the adsorption mechanism of HMF onto HCLR was clarified. At last, HMF with a highest purity of 96.0% and an average purity of 93.2% were obtained through fixed bed dynamic adsorption/desorption study. Overall, this work provides a complete process route from sugarcane molasses to high-value product of HMF, and provides theoretical and technical references for the efficient and comprehensive utilization of sugarcane molasses resources.

CAS / MDL: 7705-08-0
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JOURNAL OF SOLID STATE CHEMISTRY · 2022 · IF 3.656

Fabrication of sheet-like HZSM-5 zeolites with various SiO2/Al2O3 and process optimization in hexane catalytic cracking

Jiale Zhu,Siyan Yan,Guohao Xu,Xuedong Zhu,Fan Yang

A variety of HZSM-5 zeolites with different b-axis thicknesses and SiO 2 /Al 2 O 3 were fabricated by simply modifying urea content and Al source feeding in the initial gel, respectively. Multiple characterization technologies including XRD , SEM, N 2 adsorption-desorption, NH 3 -TPD and Py-IR were employed to investigate physicochemical properties of these samples and the possible crystallization mechanism was proposed that adsorption of urea molecules on (010) facet was the key factor for fabricating thin-sheet HZSM-5 zeolites. The results of hexane cracking reaction revealed that the selectivities of light olefins reached 46.5% when controlling b-axis thickness to 340 ​nm, exceeding the control sample by 12.2%. Furthermore, the effect of SiO 2 /Al 2 O 3 under this b-axis thickness was also investigated and concluded that keeping SiO 2 /Al 2 O 3 to 200 could exhibit the optimum catalytic performance with the conversion of 95.5% and light olefins selectivities of 56.7%. The reaction conditions were optimized to be 600 ​°C at the N 2 flow rate of 25 ​mL/min and WHSV of 3 h −1 to arouse the best performance. Under this condition, the distribution of ethene and propene was quite close to that of thermodynamic equilibrium. Based on these results, the primary and secondary products were uncovered, and further the reaction pathway of hexane cracking was disclosed. This new strategy to synthesize sheet-like catalysts for enhancing the catalytic properties in hexane cracking also laid a solid foundation for the study of the catalysts on light oil cracking in industry.

CAS / MDL: 57-13-6
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ChemistrySelect · 2022 ·Vol. 7 ·期 45 ·e202203721 · IF 2.307

Ratiometric Detection of Al Based on the Mixing of D-penicillamine-Functionalized Copper Nanoclusters with Pyridoxal 5’-phosphate

Weihua Yu,Jianhua Kuang,Qingqing Hu,Zhonghua Wang,Yunwen Liao,Zhengjun Cheng

Graphical A new ratio fluorescent probe (RF-probe) based on the mixing of red-emitting D-penicillamine (DPA) stabilized copper nanoclusters (DPA-CuNCs) with pyridoxal 5’-phosphate (PLP) was designed for sensitive and selective determination of Al 3+ . The excess accumulation of nonessential Al 3+ in the human body can cause serious health problems, thus there is significant interest in the detection of Al 3+ . A new ratio fluorescent probe (RF-probe) based on the mixing of red-emitting D-penicillamine (DPA) stabilized copper nanoclusters (DPA-CuNCs) with pyridoxal 5’-phosphate (PLP) was designed for sensitive and selective determination of Al 3+ . The −CHO group of PLP is expected to form an imine linkage with the free −NH 2 group available of the DPA on the surface of DPA-CuNCs. The content of Al 3+ could be mensurated by the as-prepared RF-probe with a linear response in the range of 1.33–46.67 μmol ⋅ L −1 , and corresponding limit of detection (LOD) was calculated to be 0.33 μmol ⋅ L −1 . Moreover, the RF-probe was successfully extended to the assay of Al 3+ in aluminum carbonate chewing tablets, baking powder, pond water and drink water with satisfactory results compared to the standard atomic absorption spectroscopy (AAS).

CAS / MDL: 52-67-5
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RENEWABLE ENERGY · 2023 · IF 8.7

Preparation of composite HZSM-5 catalyst by green template and catalytic the pyrolysis of biomass to produce aromatics

Xiaohua Li,Jiayuan Sun,Shanshan Shao,Jinlong Yan,Yixi Cai

In this study, HZSM-5 was modified by green templates (cellulose, starch and glucose), the mesoporous structure was successfully introduced, and the prepared composite catalyst was used for the catalytic pyrolysis of biomass to prepare aromatics hydrocarbon. It was revealed that the additionally introduced mesopore pore size was closely related to the size of the template molecule. The formation of pore structures with larger pore sizes on the catalyst was facilitated by larger polysaccharide templates (starch and cellulose). The increase in mesopore pore size was promoted by the cellulose and starch templates, while the increase in the number of mesopores was promoted by the glucose template. The pore size of the catalyst has a great influence on selectivity of BTX. Selectivity of BTX with larger carbon numbers (xylene, trimethylbenzene) was improved by the mesoporous structure with larger pore size. Excellent catalytic performance is also shown on template modified catalysts. The maximum yield of BTX was 10.18 wt%, which was about 1.1times higher than HZSM-5. In addition, the decomposition of macromolecular substances in the pyrolysis gas was promoted by the mesoporous structure of the template-modified catalyst, and the formation of coke on the catalyst was prevented.

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CARBOHYDRATE RESEARCH · 2023 · IF 3.1

Direct conversion of chitin derived N-acetyl-D-glucosamine into 3-acetamido-5-acetylfuran in deep eutectic solvents

Kai Wang,Yunfei Xiao,Changchun Wu,Yimo Feng,Zhipeng Liu,Xi Zhu,Hongjun Zang

3-Acetylamino-5-acetylfuran (3A5AF) is an important nitrogen-containing fine chemical with broad application prospects and high research value. Herein, we report a novel method for the conversion of N-acetyl- d -glucosamine (NAG) to 3A5AF in the choline chloride-based deep eutectic solvents (DESs). The catalytic activities of various DESs have been smoothly screened, and DES 2 (choline chloride/PEG-200/boronic acid = 1/1/0.5) displayed the best catalytic performance. In the absence of any additional solvent, catalyst and additive, product 3A5AF was obtained in 18.3% yield after reacting at 180 °C for 15 min under atmospheric condition. In addition, DES 2 showed a good reusability. The possible reaction pathway was elucidated on the basis of the results of LC-MS and 13 C NMR spectra. This study provided a new perspective for the application of DES in the conversion of chitin biomass.

CAS / MDL: 7512-17-6
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TALANTA · 2022 · IF 6.556

Ultrasensitive photoelectrochemical biosensor for DNA 5-methylcytosine analysis based on co-sensitization strategy combined with bridged DNA nanoprobe

Chuiyu Zhu,Xiao Tian,Qiuyan Li,Zichang Dai,Lina Wang,Huamin Liu,Chenghong Li,Kashif Rafiq Zahid,Chunmei Wu,Hui Huang,Lichao Fang,Qiyuan Huang,Feixue Liu,Jun Deng,Yan Li,Tao Zeng,Junsong Zheng

Altered DNA methylation in the form of 5-methylcytosine (5-mC) patterns is correlated with disease diagnosis, prognosis, and treatment response. Therefore, accurate analysis of 5-mC is of great significance for the diagnosis of diseases. Here, an efficient enhanced photoelectrochemical (PEC) biosensor was designed for the quantitative analysis of DNA 5-mC based on a cascaded energy level aligned co-sensitization strategy coupling with the bridged DNA nanoprobe (BDN). Firstly, Au nanoparticle/graphite phase carbon nitride/titanium dioxide (AuNPs/g-C 3 N 4 @TiO 2 ) nanocomposite was synthesized through in situ growth of AuNPs on g-C 3 N 4 @TiO 2 surface as a matrix to provide a stable background signal. Next, BDN with a high mass transfer rate synthesized from a pair of DNA tetrahedral as nanomechanical handles was used as a capture probe to bind to the target sequence. The polydopamine nanosphere was applied to load with CdTe QDs (PDANS-CdTe QDs) as a photocurrent label of 5-mC antibodies. When the 5-mC existed, a large number of PDANS-Ab-CdTe QDs were introduced to the electrode surface, the formed CdTe QDs/AuNPs/g-C 3 N 4 @TiO 2 co-sensitive structure could effectively enhance the electron transfer capability and photocurrent response rate due to the effective cascade energy level arrangement, leading to a significantly enhanced photocurrent signal. The proposed PEC biosensor manifested a wide range from 10 −17  M to 10 −7  M and a detection limit of 2.2 aM. Meanwhile, the excellent performance indicated the practicability of the designed strategy, thus being capable of the clinical diagnosis of 5-mC.

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

Preparation of gold nanoparticles loaded MOF-199 for SERS detection of 5-hydroxyindole-3-acetic acid in serum

Huimin Zhou,Anni Zhu,Caiyin Wang,Xiaoyu Guo,Ye Ying,Yiping Wu,Xinling Liu,Feng Wang,Ying Wen,Haifeng Yang

5-Hydroxyindole-3-acetic acid (5-HIAA) is regarded as a biomarker for diagnosis of carcinoid tumors, and it is of great significance to developing a precision assay for monitoring 5-HIAA levels. In this work, gold nanoparticles loading on the surface of MOF-199 (Au NPs/MOF-199) is prepared to propose a surface enhanced Raman scattering (SERS) assay for 5-HIAA. When 4-mercaptopyridine (4-MPy) is used as a SERS probe, on Au NPs/MOF-199, limit of detection (LOD) at 10 −9 mol/L can be achieved. In addition, Au NPs/MOF-199 substrate with good preparation reproducibility shows long-term storage stability at 4 °C. Under optimal condition, the Au NPs/MOF-199-based SERS method is applied to determine 5-HIAA in serum. The concentration linear range is from 10 −9 to 10 −5 mol/L and LOD is of 6.40 × 10 −11 mol/L. Much importantly, Au NPs/MOF-199 substrate exhibits specific response toward 5-HIAA against other metabolites in the serum due to the capturing selectivity from porous MOF-199. The recoveries obtained on spiked human serum samples locate in the span from 94.30% to 106.00% with RSD of 4.01–7.43%. Au NPs/MOF-199-based SERS sensing strategy is a promising avenue for on-field monitoring biomedical species for clinic diagnosis purpose.

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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Mechanistic Insights into the Selective Oxidation of 5-Hydroxymethylfurfural over Au/TiO2 Catalysts under Photoexcited and Dark States

Wenqing Yu,Ying Wang,Hanwen Zhang,Qiao Zhang,Shengyang Wang,Zhiting Liu,Guangxing Yang,Feng Peng

The 5-hydroxymethylfurfural oxidation reaction (HMFOR) is regarded as a promising approach to produce biomass-derived highly valuable chemical products. 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA) as a typical product via selective oxidation of the aldehyde group in HMF was obtained on Au/anatase and Au/rutile catalysts under photoexcited and dark states. The results show that the HMF oxidation reactivities of Au/rutile and Au/anatase were improved under visible light irradiation compared with those under dark conditions, and the increase of the activity is more obvious as the reaction temperature decreases. The kinetic studies showed that visible light irradiation reduced the energy barrier of the HMF oxidation reaction and promoted the reaction activities. The radical capture and EPR experiments were further used to explore the mechanisms of the HMF oxidation reaction under both conditions over Au/TiO2 catalysts. The evidence indicated that the main active species were 1O2 and trace amounts of •O2– under dark conditions, while the main active species were •O2–, 1O2, and h+ under visible light irradiation conditions for both Au/rutile and Au/anatase catalysts.

CAS / MDL: 13463-67-7 1317-80-2
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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2023 · IF 5.7

Ultra-low temperature sintered (1–x)BaV2O6-xLiF ceramics for ULTCC and 5 G millimeter-wave antenna applications

Juan Liu,Bing Liu,Cheng Chao Hu,Qing Wei Zhou,Kai Xin Song

(1– x )BaV 2 O 6 - x LiF ( x  = 0.025, 0.05, 0.10, 0.15) ceramics with an ultra-low sintering temperature of 475 °C were synthesized using the standard solid-state reaction method. The ceramics demonstrated a remarkable enhancement in the quality factor ( Qf ), reaching a maximum value of 16,800 GHz at x  = 0.10, which is 5.6 times higher than that of pure BaV 2 O 6 ceramics obtained in this work. A near-zero temperature coefficient of resonant frequency ( τ f = 1.44 ppm/°C) was simultaneously achieved, together with a dielectric constant ε r of 11.54. Additionally, the chemical compatibility between the present ceramics and the Al electrode was confirmed. Moreover, a millimeter-wave antenna with an excellent S 11 value of −50.3 dB, and a large bandwidth of 3.44 GHz was fabricated using the 0.9BaV 2 O 6 -0.1LiF ceramic as the dielectric resonator . These results highlight the potential application prospects of (1– x )BaV 2 O 6 - x LiF ceramics in the ultra-low temperature co-fired ceramic technology and 5 G millimeter-wave antennas.

CAS / MDL: 513-77-9 1314-62-1
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JOURNAL OF THE ENERGY INSTITUTE · 2023 · IF 5.7

New insights into the effects of potassium species on the Hg0 removal performance of MnOx/HZSM-5 adsorbent

Yongjin Hu,Zhichang Jiang,Runxian Wang,Shujie Gao,Hui Liu,Haining Wang,Dong Ye

In this article, the effects of K species, including K 2 O, KCl, and K 2 SO 4 , on the Hg 0 removal capability of MnO x /HZSM-5 adsorbent were investigated. Adding K 2 O and K 2 SO 4 interfered with the Hg 0 removal process; as the loading amount of these two K species increased, this adverse impact became more obvious. This was because the added K 2 O or K 2 SO 4 lowered the acidity and oxidizability of the adsorbents via the interactions with MnO x , which exerted an inhibitory effect on the adsorption and oxidation of Hg 0 . By contrast, introducing KCl made almost no adverse impacts on the Hg 0 elimination ability of the adsorbents. With rising the KCl content to 4 wt%, even ∼92.7% Hg 0 removal efficiency was obtained. This could be attributed to the presence of Cl − ; with the guidance of high-valence-state metal cations and O 2 , Cl − could be converted to active chlorine species, which was capable of transforming Hg 0 to HgCl 2 . This finding supplied a theoretical basis for developing new adsorbents that were capable of stably operating in the power plants with high-alkali-content coal utilized.

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