APPLIED CATALYSIS B-ENVIRONMENTAL
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2018
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IF 11.698
Xiangju Ye,Yinghao Chen,Yahui Wu,Xuemei Zhang,Xuchun Wang,Shifu Chen
In a reaction system, the simultaneously efficient utilization of photogenerated electrons and holes to realize the photocatalytic selective redox reactions of organics has been a hot topic. In this paper, the Zn 3 In 2 S 6 samples were synthesized via a simple solvothermal method with different solvents, which could make full use of photogenerated electrons and holes to achieve the photocatalytic selective transformation of aromatic alcohols to aromatic aldehydes and hydrogen evolution under mild conditions. The results show that the Zn 3 In 2 S 6 synthesized with water (Zn 3 In 2 S 6 -W) exhibits the highest photocatalytic performance among the selected samples, with which the yields of benzaldehyde and hydrogen reach up to 732 and 708.8 μmol under light irradiation (λ ≥ 380 nm) for 4 h, respectively. The molar ratios between aldehydes and hydrogen are close to 1: 1. The apparent quantum efficiency is about 6.48% for wavelength λ = 380 ± 10 nm over Zn 3 In 2 S 6 -W sample. A possible reaction mechanism for the photocatalytic selective transformation of benzyl alcohol to benzaldehyde and hydrogen evolution under light irradiation is proposed. This work highlights that a reaction system is developed to effectively make use of the photogenerated electrons and holes for selective transformation of aromatic alcohols to aromatic aldehydes and hydrogen evolution over Zn 3 In 2 S 6 photocatalysts under mild conditions.
研究领域:
化学
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材料科学
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2018
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IF 6.759
Renshan Wang,Benxia Li,Yi Xiao,Xueqin Tao,Xintai Su,Xiaoping Dong
Ultrathin semiconductor nanosheets decorated with metallic nanoparticles (NPs) are promising in photocatalysis due to the multi-component interactions. The materials with a series of monometallic Pd and bimetallic Au-Pd NPs anchored on Bi 2 WO 6 ultrathin nanosheets were synthesized and developed as photocatalysts for selective oxidation of aromatic alcohols to aromatic aldehyde. By optimizing the metallic contents, a typical sample of Au(0.25)Pd(0.25)-Bi 2 WO 6 exhibited the highest photocatalytic activity among all the prepared photocatalysts including Au(0.5)-Bi 2 WO 6 , Pd( x )-Bi 2 WO 6 , Au( x )Pd( x )-Bi 2 WO 6 ( x represents the weight percentage of metal in the photocatalyst), along with the improved selectivity for producing benzaldehyde. The extended absorption in visible range, higher efficiency for the transfer and separation of photogenerated charge carriers, and the superior ability for generating active radicals of Au(0.25)Pd(0.25)-Bi 2 WO 6 were demonstrated by DRS spectra, photoelectrochemical measurements, and ESR detection. The effect of the active species for selective oxidation of aromatic alcohols was proved to follow the order of h + + O 2 − > h + >> O 2 − . Accordingly, a possible mechanism based on the interfacial cooperation between bimetallic Au-Pd NPs and Bi 2 WO 6 ultrathin nanosheets was proposed to illustrate the photocatalytic process, where the holes accumulated in Bi 2 WO 6 ultrathin nanosheets and O 2 − produced on metallic NPs synergistically promote the selective oxidation of aromatic alcohols.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
Materials
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2023
·Vol. 16
·期 8
·3139
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IF 3.4
Hangwei Jiang,Xiya Chen,Danlan Cui,Kun Lu,Xiao Kong,Xingguang Zhang
Conventional methods to prepare supported metal catalysts are chemical reduction and wet impregnation. This study developed and systematically investigated a novel reduction method based on simultaneous Ti3AlC2fluorine-free etching and metal deposition to prepare gold catalysts. The new series of Aupre/Ti3AlxC2Ty catalysts were characterized by XRD, XPS, TEM, and SEM and were tested in the selective oxidation of representative aromatic alcohols to aldehydes. The catalytic results demonstrate the effectiveness of the preparation method and better catalytic performances of Aupre/Ti3AlxC2Ty, compared with those of catalysts prepared by traditional methods. Moreover, this work presents a comprehensive study on the influence of calcination in air, H2, and Ar, and we found that the catalyst of Aupre/Ti3AlxC2Ty-Air600 obtained by calcination in air at 600 °C performed the best, owing to the synergistic effect between tiny surface TiO2species and Au NPs. The tests of reusability and hot filtration confirmed the catalyst stability.Keywords:Ti3AlC2MAX;gold catalysts;novel reduction method;oxidation of aromatic alcohols
研究领域:
催化化学
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材料科学
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DOI
PubMed
高影响因子
ChemCatChem
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2020
·Vol. 12
·期 8
·2341-2347
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IF 4.853
Bai-Chuan Zhou,Qing-Nan Wang,Xue-Fei Weng,Lei He,Wen-Cui Li,An-Hui Lu
Graphical Direct production of benzyl alcohol : The distribution of aromatic alcohols on cobalt-hydroxyapatite is greatly switched from methylbenzyl alcohol (feeding ethanol) to benzaldehyde (C 7 , BA=O) and benzyl alcohol (C 7 , BA−OH) by cofeeding of methanol and ethanol. Aromatic alcohols, often used for the synthesis of plasticizers, coatings and pharmaceuticals, are currently produced from the oxidation of petroleum-derived aromatic hydrocarbons. Herein, we report a non-petroleum and environmentally friendly route for the production of aromatic alcohols: cofeeding methanol with ethanol over cobalt-hydroxyapatite catalyst, in which the distribution of aromatic alcohols products can be regulated by varying methanol pressure. Co species on hydroxyapatite can activate both methanol and ethanol to yield their corresponding aldehydes (formaldehyde and acetaldehyde). The followed cross- and self-condensations of aldehydes are catalyzed by hydroxyapatite to produce acrolein and 2-butenal, which are the key intermediates for the formation of aromatic oxygenates. The sequential cross-condensation and dehydrocyclization of acrolein and 2-butenal yield benzaldehyde, which is then hydrogenated to benzyl alcohol. The direct production of benzyl alcohol from methanol and ethanol could be regarded as a cutting-edge example, which ensures a promising route for sustainable aromatic alcohols production.
研究领域:
化学工程
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催化科学
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环境科学
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DOI
高影响因子
BIORESOURCE TECHNOLOGY
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2016
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IF 4.917
Jing Yang,Liang Zhao,Chunze Liu,Yuanyuan Wang,Liyi Dai
Efficient catalytic ethanolysis and gasification of kraft lignin were conducted over a versatile supported catalyst Rh/La 2 O 3 /CeO 2 –ZrO 2 to give high-value aromatic alcohols and H 2 -rich gas. The removal of phenolic hydroxyl group was the most prevalent reaction, and importantly, almost no phenols, undesired char and saturating the aromatic ring were detected. Meanwhile, the feedstock and solvent both played key roles in H 2 generation that contributed to the hydrodeoxygenation of liquid components and made the whole catalytic process out of H 2 supply. Reusability tests of catalyst indicated that the crystalline phase transition and agglomeration of support, the loss of noble metal Rh and carbon deposition were the possible reasons for its deactivation in supercritical ethanol. Comparing with water, methanol and isopropanol system, ethanol was the only effective solvent for the depolymerization process.
研究领域:
化学工程
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能源科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2017
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IF 9.446
Jing Ding,Wei Xu,Hui Wan,Dashui Yuan,Chong Chen,Lei Wang,Guofeng Guan,Wei-Lin Dai
Vacancy defect in the semiconductors plays an important role in the improvement of the electronic structure and the increase of specific reaction sites for reactant molecules, and consequently enhancing the photocatalytic activity of semiconductor photocatalysts. Through high-temperature thermal condensation of a nitric acid-pretreated melamine precursor, nitrogen vacancies were successfully introduced in the framework of g-C 3 N 4 . The nitrogen vacancies located at the uncondensed terminal NH x lattice sites were conducive to the enhancement of optical absorption, the improvement of the separation efficiency of the photogenerated charge carrier and the increase of surface area, which was beneficial to the photocatalytic oxidation process. More significantly, the novel CNNA(X) were used as efficient photocatalysts in the green process of aromatic aldehydes from the photocatalytic selective oxidation of aromatic alcohols and the photocatalytic degradation of organic pollutants. CNNA(X) samples exhibited enhanced photocatalytic activity and excellent recyclability and stability. The 68.3% benzyl alcohol conversion and almost 100% selectivity was observed for the CNNA (0.9) photocatalyst, higher than that of pure g-C 3 N 4 . Meanwhile, CNNA (0.9) showed superior photocatalytic degradation performance of organic dyes (RhB and MO). Furthermore, the underlying photocatalytic oxidation mechanism was proposed by the controlled experiments using radical scavengers.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
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2023
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IF 6.1
Bin Wu,Shiyu Wang,Yunjian Ma,Shuguang Yuan,Frank Hollmann,Yonghua Wang
Alcohol oxidases (AOxs) catalyze the aerobic oxidation of alcohols to the corresponding carbonyl products (aldehydes or ketones), producing only H2O2 as the byproduct. The majority of known AOxs, however, have a strong preference for small, primary alcohols, limiting their broad applicability, e.g., in the food industry. To broaden the product scope of AOxs, we performed structure-guided enzyme engineering of a methanol oxidase from Phanerochaete chrysosporium (PcAOx). The substrate preference was extended from methanol to a broad range of benzylic alcohols by modifying the substrate binding pocket. A mutant (PcAOx-EFMH) with four substitutions exhibited improved catalytic activity toward benzyl alcohols with increased conversion and kcat toward the benzyl alcohol from 11.3 to 88.9% and from 0.5 to 2.6 s–1, respectively. The molecular basis for the change of substrate selectivity was analyzed by molecular simulation.
研究领域:
生物化学
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酶学
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食品科学
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DOI
PubMed
高影响因子
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
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2025
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IF 4.7
Lican Wang,Weikun Zhu,Jie Li,Junyi Yue,Jiangyao Chen
H 2 O shows a significant contribution to form oxygen- and hydrogen-containing products during photocatalytic oxidation of aromatic hydrocarbons. However, it was unclear what the roles of atoms in H 2 O in subsequent oxidation of these products. In this study, the photocatalytic oxidation of two aromatic alcohols, benzyl alcohol and phenethyl alcohol, on TiO 2 (79 % anatase and 21 % rutile) were investigated in mixed H 2 O (or H 2 18 O, D 2 O) and O 2 system. Aromatic aldehydes, acids and esters were main aromatic products, while modified TiO 2 and isotope-containing H 2 O did not change the product species. Aromatic aldehydes showed ≤ 0.19 % and ≤ 1.58 % of 18 O- and D-labeling rates, suggesting hardly involvement of H 2 O in their formation. Aromatic acids exhibited a 18 O-labeling rate range of 28.12 %-40.33 % and the highest D-labeling rate of 0.76 %, while a maximum enhancement of 18 O-labeling rate was 0.11 % in the –C=O group of the acids, indicating that H 2 O selectively provided O atom in the formation of –OH group of aromatic acids. The 18 O- and D-labeling rates of aromatic esters were in the range of 9.01 % to 15.95 % and 1.73 % to 8.08 %, suggesting that both oxygen and hydrogen atoms from H 2 O contributed to aromatic ester formation. Further analyzing mass fragmentation confirmed that H 2 O separately contributed its hydrogen and oxygen atoms to the –C=O and R–O groups of the esters. Based on the isotope tracing results, the contribution roles of H 2 O’s hydrogen and oxygen atoms in oxidation of aromatic alcohols to corresponding aromatic products were proposed. The findings in this study help to clarify the role of H 2 O in the oxidation process of aromatic alcohols at the atomic level and comprehensively reveal the oxidation mechanism of the aromatics.
研究领域:
环境科学
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化学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2017
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IF 9.446
Jinghu Zhang,Sugang Meng,Xiangju Ye,Cancan Ling,Sujuan Zhang,Xianliang Fu,Shifu Chen
Selective oxidation of aromatic alcohols to corresponding carbonyl compounds under mild conditions has a promising prospect in industry. In the paper, we successfully prepared a new mode of photothermocatalyst, Zn 3 In 2 S 6 @ZnO composite, which shows dramatically enhanced activity for selective oxidation of benzyl alcohol to benzaldehyde compared with single Zn 3 In 2 S 6 and ZnO under visible light illumination. The enhancement is due to a synergistic effect of low-temperature thermocatalysis on ZnO and photocatalysis on Zn 3 In 2 S 6 . ZnO could weaken bonds of the C H α and the O H. Then the reactive species ( O 2 − and h + ) generated on Zn 3 In 2 S 6 could be easy for selective oxidation of benzyl alcohol to produce benzaldehyde. The photoelectrochemical and photoluminescence (PL) results and a series of control experiments (e.g. reaction temperature and radical scavenger) prove this synergistic effect and proposed mechanism. Moreover, the stable performance and high activity of Zn 3 In 2 S 6 @ZnO for other aromatic alcohols indicate its applicable potential. This study provides a promising way to combine photocatalysis and thermocatalysis for the design of novel and efficient visible-light-driven catalyst for selective oxidation of aromatic alcohols or other organics under mild reaction conditions.
研究领域:
化学
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材料科学
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催化反应
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DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2024
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IF 4.9
Haijiao Jia,Xiao Zhang,Guirong Borjihan,Shengbo Yang,Youxin Li
Using ruthenium chloride as catalyst precursor, magnetic silicon spheres as support, 4-formylphenylboronic acid and ethylenediaminepentaacetic acid as functional ligands, a magnetic heterogeneous nano-ruthenium catalyst (Fe 3 O 4 @SiO 2 -FPBA-DTPA-Ru) was prepared for the first time. It was nano level with 20.17 emu/g saturation magnetic strength and thermal stability under 249.63 °C. Fe 3 O 4 @SiO 2 -FPBA-DTPA-Ru contained 0.38 mmol/g Ru and was successfully used to catalyze the oxidation reactions of 15 aromatic secondary alcohols. Results proved that Fe 3 O 4 @SiO 2 -FPBA-DTPA-Ru as catalyst had good catalytic activity for the oxidation of secondary aromatic alcohols with yields exceeding 90 % for 12 products and 95 % for 10 products. High TON and TOF values (6386 and 9158 h −1 ) in 1-phenylethanol oxidation were obtained. All the reactions of aromatic alcohols were carried out in a solvent-free system, so the prepared catalyst had the characteristics of green and pollution-free. It was’nt suitable for oxidation of aromatic primary alcohols. If there was steric hindrance around the hydroxyl group in substrate, the catalysis also may be limited. The Fe 3 O 4 @SiO 2 -FPBA-DTPA-Ru catalyst also exhibited the advantages of energy saving, satisfactory reusability and stability in 9 consecutive runs. It showed great potential for future large-scale industrial production.
研究领域:
化学
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材料科学
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环境科学
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DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2022
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IF 12.92
Yu-Lan Wu,Ming-Yu Qi,Chang-Long Tan,Zi-Rong Tang,Yi-Jun Xu
ABSTRACT Simultaneously utilizing photogenerated electrons and holes to convert renewable biomass and its derivatives into corresponding value-added products and hydrogen (H 2 ) is a promising strategy to deal with the energy and environmental crisis. Herein, we report a facile hydrothermal method to construct a direct Z-scheme CdS/WO 3 binary composite for photocatalytic coupling redox reaction, simultaneously producing H 2 and selectively converting aromatic alcohols into aromatic aldehydes in one pot. Compared with bare CdS and WO 3 , the CdS/WO 3 binary composite exhibits significantly enhanced performance for this photocatalytic coupled redox reaction, which is ascribed to the extended light harvesting range, efficient charge carrier separation rate and optimized redox capability of CdS/WO 3 composite. Furthermore, the feasibility of converting various aromatic alcohols to corresponding aldehydes coupled with H 2 evolution on the CdS/WO 3 photocatalyst is proved and a reasonable reaction mechanism is proposed. It is hoped that this work can provide a new insight into the construction of direct Z-scheme photocatalysts to effectively utilize the photogenerated electrons and holes for photocatalytic coupled redox reaction.
研究领域:
材料科学
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环境科学
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能源化学
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2025
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IF 6.5
Fengting Hao,Zhaochun Liu,Pengcheng Huang,Wenqian Fu,Jie Ren,Lu Fan,Wei Chen,Tiandi Tang
Zeolite-catalyzed dehydration of fatty alcohols to alkenes is an effective method for biomass conversion. This study extends the reaction to a tandem reaction process that catalyzes the dehydration isomerization of aromatic alcohols to generate internal alkene under mild conditions. By using three acidic zeolites (HZSM-5, USY, and HBeta) as catalysts, it was found that when using HZSM-5, the conversion rate of 3-phenylpropanol was 100% and the selectivity of 1-propenylbenzene was 99.4% at 150 ℃, the conversion rate and selectivity were significantly lower when using USY and HBeta as catalyst. Grand Canonical Monte Carlo (GCMC) was conducted to understand the product selectivity difference, and the results demonstrate that 3-phenylpropanol adsorbs within the HZSM-5 zeolite channels in a distinctive isolated molecular configuration. This adsorption mode exhibits favorable spatial isolation from neighboring catalytic sites, thereby significantly enhancing the monomolecular dehydration pathway and facilitating selective isomerization to yield 1-propenylbenzene. However, the excessive adsorption of 3-phenylpropanol in the large pores of USY and HBeta will facilitate the formation of ether through bimolecular dehydration. Density functional theory (DFT) calculations showed that the dehydration process of 3-phenylpropanol can be achieved through both concerted and stepwise pathways, respectively. While the selectivity between 1-propenylbenzene and 2-propenylbenzene was affected by the stabilization of HZSM-5 to reaction intermediates, proving shape-selective catalysis. In addition, our calculations found that 3-phenylpropanol can directly generate 1-propenylbenzene through a concerted dehydration isomerization (DHI) pathway in HZSM-5. The reaction kinetics using HZSM-5 catalysts show that the activation energy of the dehydration process was higher than that of the isomerization process, while the initial reaction rate showed the opposite result, which was consistent with the trend of the free energy barriers of the dehydration and isomerization processes in DFT calculations. In addition, the reaction orders of the dehydration and isomerization processes were studied separately, and the elementary reaction steps and rate-determining steps were proposed. The experimental results were consistent with the DFT calculations, and the use of HZSM-5 did not favor multi-molecular dehydration pathways.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
危险品化学品经营许可证（带存储）