APPLIED CATALYSIS A-GENERAL
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2024
·
IF 4.7
Yingdan Ye,Han Wang,Yibin Zhang,Huaiyuan Zhao,Weichen Du,Ping Chen,Zhaoyin Hou
Chemical upcycling of end-of-life plastics is an economically and environmentally feasible way to tackle plastics crisis. Among them, methanol alcoholysis of polylactic acid (PLA) is a promising approach, which can produce methyl lactate (MLA) that can be further converted to lactide to achieve a sustainable development. In this work, a series of WO x /ZrP catalysts with WO x active sites in low coverage and high surface area were synthesized via anchoring WO x species on the surface of zirconium phosphate (ZrP). Characterizations indicated that the strong interaction between WO x and ZrP promoted the formation of WO x active sites in low coverage. In particular, 10 %WO x /ZrP catalyst was highly active and stable for the alcoholysis of PLA plastics under mild conditions due to the abundant WO x active sites and strong acidity. The yield of MLA over 10 %WO x /ZrP catalyst reached 94.5 % within 4 h at 160 °C, which was superior to the performance of traditional solid acids ( α -ZrP, HZSM-5, H β and Amberlyst-45). In addition, 10 %WO x /ZrP was versatile for the alcoholysis of discarded PLA-based products and could be recycled at least five times. The prominent performance of 10 %WO x /ZrP catalyst and the possible reaction mechanism were discussed.
研究领域:
化学工程
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环境科学
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材料科学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Xincheng Cao,Shuya Jia,Yao Zhang,Feng Long,Yuwei Chen,Peng Liu,Xiaolei Zhang,Junming Xu,Jianchun Jiang
Fundamental knowledge of the active site requirements for the activation of C−O bonds on heterogeneous catalysts is essential for the design of efficient hydrodeoxygenation catalysts. Pt−WOx (x < 3) catalysts have shown activity and selectivity for the C−O bond breaking of various biomass-derived oxygenates. Yet, the nature of the active sites and the structure−performance relationship have not been well understood because of the intimate coupling of multiple sites. Here, we construct a hybrid catalyst with integrated defective tungsten oxide (e.g., WO2.72) and Pt/C to investigate the role of multiple sites (e.g., metal sites, Bro̷nsted acid, and oxygen vacancy) that are active toward the hydrogenolysis of esters to alkanes in Pt−WOx catalysts. Experimental and theoretical results suggest that oxygen vacancies derived from the defective tungsten oxide (WOx) supply coordinatively unsaturated sites to adsorb and activate the oxygen atom of the carbonyl group of esters, while Pt metal provides an active hydrogen atom for this process. More importantly, it is found that the hydroxyl derived from W−OH in WOx, as a typical Bro̷nsted acid site, can contribute to the adsorption and activation of the C−O bond of esters. The synergistic effect of oxygen vacancies and Bro̷nsted acid sites results in a remarkably efficient acyl C−O bond cleavage of esters, which boosts the hydrodeoxygenation of esters under mild conditions (T ≤ 200 °C). These insights into the structure−performance relationships offer rational methods for designing efficient catalysts for low-temperature hydrodeoxygenation of biomass-derived esters.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2023
·
IF 7.2
Zhou Yang,Hongwei Niu,Laiyu Xia,Le Li,Meng Xiang,Chengbin Yu,Zhiqian Zhang,Shuang Dong
Electrocatalytic water splitting is regarded as the most efficient way of producing novel hydrogen energy , but is suffering from high overpotential and sluggish kinetics of oxygen evolution reaction (OER). Some organics including glycerol have been added to ameliorate the shortcomings of OER, but the selectivity of electrocatalysts is of great importance. Herein, a rare-earth metal Eu 3 O 4 /WO x heterojunction with nonstoichiometric O is designed and prepared, the Eu 3 O 4 /WO 2.72 stands out from the crowd for which shows the best electrocatalytic performances that the glycerol oxidation reaction (GOR) potential is only 1.33 V at 10 mA cm −2 . In addition, Eu 3 O 4 /WO 2.92 and Eu 3 O 4 /WO 2.72 show low overpotentials of 141 mV and 129 mV at 10 mA cm −2 for hydrogen evolution reaction (HER) compared with the benchmark Pt/C electrocatalyst. Eu 3 O 4 /WO 2.72 heterojunction shows an ultralow cell voltage of 1.17 V in 1 M KOH with 0.1 M glycerol. Our study opens up a fashion-forward way for the designation of rare-earth metal heterojunction electrocatalysts in the biodiesel glycerol oxidation linking to hydrogen evolution.
研究领域:
能源材料
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电化学
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催化化学
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产品关联
DOI
高影响因子
LANGMUIR
·
2025
·
IF 3.9
Xinpeng Li,Lingling Zou,Mei-hua Zhu,Wenjun Yuan,Hongjie Peng,Qingshen Wu,Ziming Li,Rui Liu,Xiang-Shu Chen,Hidetoshi Kita
1-Hexene epoxidation is difficult to achieve for the low electron cloud density of long-chain terminal olefin double bonds structure; the development of efficient and stable catalysts is the key to achieving the highly efficient epoxidation of 1-hexene. The titanosilicate/H2O2 system has been the most promising and environmentally friendly epoxidation route in recent research, and the WOx@HTS-1 nanoparticles were successfully prepared by an etching–impregnation–recrystallization strategy in this work. Unique structures of the WOx@HTS-1 nanoparticles could achieve the effects of “killing three birds with one stone” for 1-hexene epoxidation. I. Hierarchical structure and “hollow nests” could significantly enhance the accessibility of the active sites, shorten the transmission path, and improve the diffusion efficiency of the reactants and products. II. Titanium active centers and metal oxide active sites had significant and efficient synergistic catalytic effects on 1-hexene epoxidation. III. Fine WOx particles were highly dispersed on the hollow nests of WOx@HTS-1 nanoparticles, which prevented the sintering and poisoning of WOx clusters during the reaction process and ensured excellent stability of the catalysts by the restricted-domain effect. Attractively, 1-hexene conversion and 1,2-epoxyhexane selectivity were more than 90 and 96% with WOx@HTS-1 nanoparticles and H2O2, respectively, which provided many opportunities for the directional design of nanoparticles and their application in emerging catalytic fields.
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产品关联
DOI
PubMed
高影响因子
FUEL
·
2021
·
IF 6.609
Dawang Chu,Zhicheng Luo,Yingying Xin,Chengzhen Jiang,Shaofeng Gao,Zhihao Wang,Chen Zhao
The chemo-catalytic production of ethanol from nonedible lignocellulosic biomass is essential for mitigating energy shortage. In this work, we developed a multifunctional Pd-Cu-WO x /SiO 2 catalyst for the one-pot aqueous-phase conversion of cornstalk-derived cellulose to ethanol with a yield of 42.5C% at 300 °C and 4 MPa H 2 . Kinetic studies demonstrated that the transformation of cellulose to ethanol followed a number of consecutive steps namely, cellulose hydrolysis to glucose with H + in hot water (k 1 ), glucose conversion to glycolaldehyde over W species (k 2 ), glycolaldehyde hydrogenation to ethylene glycerol (EG) over Pd (k 3 ), and EG hydrogenolysis to ethanol over Cu (k 4 , rate-determining step). The individual rates were well balanced on Pd, Cu, and WO x species to achieve an ethanol formation rate of 0.163 g·g Cat . −1 h −1 . The addition of Au to Cu-WO x species led to a relatively low k 3 and thus the formation of a substantial amount of humins, while the Ru introduction catalyzed the over-hydrogenolysis of ethanol to methane and ethane with a high rate, thereby lowering the selectivity to ethanol. The characterization results showed that both the electronic properties of Cu + species and the Cu + /Cu 0 ratio on the Pd-Cu-WO x /SiO 2 catalyst contributed to a specific C O bond cleavage, especially for EG hydrogenolysis to ethanol during the cellulose conversion.
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DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Yue Zhang,Lin Li,Fei Liu,Haifeng Qi,Leilei Zhang,Weixiang Guan,Yuefeng Liu,Aiqin Wang,Tao Zhang
The selective reduction of primary amides to the corresponding amines is a key reaction in both pharmaceutical chemistry and the polymer industry; yet, it requires a stoichiometric amount of expensive and environmentally unfriendly hydride reagents. Hydrodeoxygenation (HDO), on the other hand, is a highly desired environmentally benign alternative; yet, it presents significant challenges in activity and selectivity control. In this work, we have developed a bifunctional 2Ru1W/SiO2 catalyst, which afforded 93.6% conversion and 83.7% selectivity of the primary amine after reaction for 12 h for the HDO of cyclohexanecarboxamide at 433 K, and the initial reaction rate reached 48.2 h–1, 1 order of magnitude higher than other catalysts reported earlier. The catalyst also presented excellent reusability and substrate diversity. The performances of various Ru–W/SiO2 catalysts critically depend on the synergy between W and Ru, with the best performance accessible at the W/Ru atomic ratio of 0.27. Characterizations and reaction kinetics have revealed that Ru promoted the reduction of W6+ to W5+ via hydrogen spillover, and the resultant low-coordinated W5+ is responsible for the selective activation of the C═O bond of the amide, leading to almost zero reaction order with respect to the amide and much lower apparent activation energy over the 2Ru1W/SiO2 bimetallic catalysts in contrast to the first order and higher activation energy over Ru/SiO2. Nevertheless, W/Ru ratios higher than 0.27 resulted in larger WOx domains and lower valence states of W, which adsorbed the amide substrate so strongly that the catalyst surface was poisoned, leading to a dramatic decrease in both activity and selectivity. The catalyst strategy as well as the mechanism understanding presented in this work will provide insights into the bifunctional catalyst design used for other demanding chemical transformations.
研究领域:
催化化学
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材料科学
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环境化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2026
·Vol. 16
·期 7
·613
·
IF 4.5
Xin Wang,Yunkai Zhou,Qingsong Wang,Dongxue Liang,Wenjia Li,Zhou Zhang,Mingqiang Zhu,Jia Wang
Hydrolysis of cellulose to produce ethanol has become an effective way to utilize biological resources, but its large-scale industrial application has been limited. In this study, a one-pot catalytic conversion process for transforming cellulose into ethanol was developed. Meanwhile, multifunctional Mo/Pt/WOx/Al2O3catalysts were prepared by loading nano-alumina (Nano-Al2O3) via a stepwise impregnation method. The influence of catalysts with varying metal ratios on the types of products generated during the cellulose hydrolysis process to ethanol was examined. The catalyst with 0.1% Mo, 2% Pt, and 7.5% W loadings showed the best selectivity. With an ethanol yield of 45.3% after heating at 5 MPa H2and 518 K for 2 h. Nano-Al2O3can provide suitable active sites. The addition of W5+and Mo0increased the surface oxygen vacancy density and enhanced the hydrodeoxidation and metal anchoring capacity of the catalyst. The solid solution structure facilitates electron transfer from W and Mo atoms to Pt atoms, forming electron-rich Ptδ-species, promoting the hydrolysis of cellulose and the formation of ethanol.
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产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Shuai Yang,Yifeng Chen,Haiwei Guo,Xunzhu Jiang,Jiawen Ma,Xinyang Li,Zhao Chen,Xiaodong Ma
The current catalysts for polychlorinated aromatics (PCAs) oxidation showed either poor low-temperature catalytic activity, low mineralization ability or bad stability, and developing oxygen vacancies enriched catalysts with abundant acid sites is a potential solution for the above drawbacks. Herein, oxygen vacancies enriched Nb-WO X were developed for o -DCB ( o -dichlorobenzene, a PCAs model compound) oxidation, and they showed notably better low-temperature catalytic activity with T 50% <350 °C than did commercial WO 3 (T 50% >400 °C) under the WHSV of 36000 mL g −1 h −1 . Nb-WO X supported Ru exhibited even lower T 50% (173 °C) and T 90% (238 °C), as well as high CO X yield with >99% ratio of CO 2 to CO and good stability (>99% conversion for 500 mins) when with 1.5 wt% Ru loading at 300 °C. The above phenomenon was attributed to the abundant oxygen vacancies and acid sites in Nb-WO X that contributed to the better redox property, stronger interaction with Ru species and the removal of accumulated chloride. The o -DCB oxidation mechanism revealed that the higher CO 2 ratio to CO on Ru/Nb-WO X arose from the deep oxidation of CO byproducts. The work described here will instruct us to degrade PCAs effectively through catalysts design.
研究领域:
催化化学
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环境科学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2019
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IF 12.221
Mengrui Zhang,Vikram Singh,Xuefu Hu,Xinyi Ma,Jingkun Lu,Chao Zhang,Jingping Wang,Jingyang Niu
Design and synthesis of high-performance heterogeneous catalysts are of immense interest in chemical industries. Herein, ultrafine H2O coordinated WOx nanoparticles (H2O–WOx, average diameter 2.24 nm) embedded into porous carbon matrix have been obtained via space-confinement pyrolysis with postmodification oxidation approach. The synthesized H2O–WOx nanoparticles exhibit high activities toward olefin epoxidation reaction using H2O2 as oxidant. In epoxidation of cis-cyclooctene, the turnover frequency of the catalyst can achieve as high as 949 h–1, an activity comparable to the highest of all reported early transition-metal based catalysts. UV–vis spectra and controlled catalytic experiments have been performed to ascertain the possible active site in the catalyst: compared with traditional WO3 and peroxide coordinated W-(η2-O2) species, the water coordinated H2O–WOx can transform to hydroperoxide HOO–WOx in the presence of H2O2, and the HOO–WOx species can be further activated by proton acid to enhance its catalytic activities.
研究领域:
化学工程
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催化科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMISTRY
·
2020
·Vol. 38
·期 5
·453-457
·
IF 3.826
Chuang Li,Guangyue Xu,Xiang Zhang,Yao Fu
Summary of main observation and conclusion The conversion of fructose to 1,2-propylene glycol (PG) is an important process from cellulosic biomass to high-value added chemicals. Herein, Ru-WO x /hydroxyapatite (HAP) catalyst was employed for this reaction and reached up to 91.3% yield of PG at 180 °C, 1 MPa initial hydrogen for 8 h in water. On this catalyst, Ru and WO x were highly dispersed on HAP support and they interacted with each other to form a special catalytic center. The lack of isolated Ru or RuW alloy site led to a moderate activity for hydrogenolysis and hindered the further conversion of PG to propanol. The weak basic HAP support efficiently prevented the humin formation. This precisely controlled catalyst has potential in green PG production.
研究领域:
化学工程
·
可再生资源转化
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Wei Jia,Hang Song,Dandan Wang,Chengfeng Zhou,Yuling Zhao,Yuandong Cui,Haoxi Ben,Xiaoli Yang
The sustainable conversion of cellulose to C2 alcohols (ethylene glycol and ethanol) represents a promising sustainable pathway to reduce reliance on fossil resources. However, achieving an effective balance between hydrolysis, C–C bond cleavage, and hydrogenation has remained a challenge. In this study, Pd/WOx catalysts with tunable Pd nanoparticle sizes (1.81–4.46 nm) were developed to investigate the structure–performance relationship. Catalytic evaluations revealed a volcano-type correlation between Pd particle size and C2 alcohol selectivity, with the 3Pd/WOx catalyst, featuring Pd nanoparticles averaging ∼3.0 nm, achieving a maximum selectivity of 78.5% under mild conditions (water solvent, 230 °C, 5 MPa H2, 4 h). Structural and chemical analyses revealed that smaller Pd clusters retained excess oxygen vacancies but lacked hydrogenation capacity, while larger Pd nanoparticles reduced accessible hydrogenation sites and acidity. Mechanistic studies showed that WOx oxygen vacancies promoted cellulose hydrolysis, Pd–O(H)–W sites facilitated glucose adsorption and C–C cleavage to glycolaldehyde, and adjacent Pd0 sites enabled efficient hydrogenation. This work highlights the critical role of Pd particle size in optimizing acid–hydrogenation synergy, providing a green and efficient strategy for biomass valorization without additives or toxic solvents.
研究领域:
催化
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纳米技术
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绿色化学
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生物质转化
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2020
·
IF 3.99
Binglong Yu,Jie Wang,Xiaoyun Mo,Xiaoxin Yang,Wenlong Wang,Xiulan Cai
Tungsten oxide (WO x ) is an important n-type semiconductor, which has attracted wide attention in the fields of gas sensing materials, photocatalysis , photoluminescence and electrochemistry due to its excellent electro-optical properties. However, the application potential of WO x -based nanomaterials in biomedicine has been neglected. In this paper, we firstly synthesized tungsten oxide nanowires (WO x NWs) by one-step method using tungsten chloride and triethylene glycol as raw materials, and reported an effective surface engineering strategy for polyglycerol-functionalized tungsten oxide nanowires (WO x -PG) to enhance their colloidal stability, biocompatibility , and selective toxicity to specific cancer cells in dispersion media . The WO x -PG was further derivatized and covalently combined with FA (WO x -PG-FA) as a drug targeting vector to deliver doxorubicin (DOX) to cancer cells. Compared with WO x NWs, WO x -PG exhibits smaller size (30−90 nm), more uniform distribution, better solubility and biocompatibility. The hemolysis rate of PG-modified WO x NWs was significantly reduced, being only 1.35 % at 200 μg/ml. The in vitro drug release percentage of WO x -PG-FA/DOX reached 80.78 % within 48 h at pH 5.2. In vitro toxicity assays and confocal laser scanning microscope (CLSM) results indicated that PG-functionalized WO x NWs were not cytotoxic, and WO x -PG-FA/DOX had highly selective cytotoxicity on HeLa cells. These results indicate that WO x -PG-FA is a potential drug carrier for effective targeting of cancer therapy.
研究领域:
材料科学
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生物医学工程
·
药学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）