ChemCatChem
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2021
·Vol. 13
·期 13
·3184-3197
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IF 5.686
Chao Huang,Can Zhu,Mingwei Zhang,Yongwu Lu,Qianhao Wang,Heming Qian,Jiangang Chen,Kegong Fang
Graphical Synergetic effect : The physically mixed CuCoAl|t-ZrO 2 multifunctional catalyst could achieve superior selectivity towards alcohols while simultaneously inhibiting the generation of hydrocarbons from CO hydrogenation. Selective synthesis of higher alcohols from syngas is promising but remains challenging owing to the low stability and selectivity towards higher alcohols. Here we introduce a CuCoAl|t-ZrO 2 (t denotes tetragonal crystal phase) multifunctional catalyst that can achieve an alcohol selectivity of 64.8 % with 79.6 % C 2+ OH, and a total selectivity of alcohols and olefins to 81.7 %. The proper proximity was tuned to increase selectivity towards alcohols and decrease the selectivity towards hydrocarbons. The lower surface [H*]/[C*] ratio due to the stronger basic sites of the CuCoAl|t-ZrO 2 limited alkyl (CH x ) species hydrogenation, and promoted CO insertion and carbon chain growth, resulting in improving the alcohols selectivity. Meanwhile, the weaker adsorption of bridge-type adsorbed CO and the lower decomposition rate of multi-bonded adsorbed CO over CuCoAl|t-ZrO 2 inhibited hydrocarbon generation. The selective promotion of the reaction route via the synergetic effect between CuCoAl and t-ZrO 2 was proposed to boost higher alcohols selectivity. This work may aid the rational design of effective multifunctional catalyst with synergistic effects for tuning selectivity.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2021
·
IF 6.766
Lijie Pei,Jianxin Cao,Fei Liu,Anjie Yang,Mengqin Yao,Tianxiang Zhao,Xiaodan Wang,Sibudjing Kawi
The catalytic properties of bifunctional ZSM-5@t-ZrO 2 catalyst for methanol thiolation were revealed by using methanol and H 2 S as probe molecules. Taking the ZSM-5/t-ZrO 2 physically-blended catalyst, pure ZSM-5 and t-ZrO 2 as control catalysts, we investigated the characteristics of adsorption and transformation of different reaction molecules on or over different catalysts by combination of in-situ diffuse reflectance Fourier transform infrared spectroscopy (Drifts) and a variety of techniques including XRD, XPS, XRF, FT-IR, N 2 adsorption-desorption, CO 2 /NH 3 -TPD, and DSC. The results showed that the synergistic effect of acid sites between ZSM-5 phase and t-ZrO 2 phase in the bifunctional catalyst enhanced the adsorption and dissociation of methanol molecules, while the base sites in t-ZrO 2 phase were mainly responsible for the adsorption and dissociation of H 2 S molecules. Due to the small specific surface area of pure t-ZrO 2 catalyst, precursor species for sulfur deposition and carbon deposition were easily formed. Presulfurization could improve the initial activity of methanol thiolation and shorten the induction period. The dissociation of H 2 S at the base sites was the rate-determining step of the bimolecular reaction, and the appropriate increase of base sites in the bifunctional components could construct the matching formation rate of sulfhydryl and methoxy groups. At the same time, the special composite structure and meso-microporous system of ZSM-5@t-ZrO 2 could effectively reduce the formation rate of carbon and sulfur deposits.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 43
·34451-34455
·
IF 3.84
Yu Liu,Weidong Chi,Hui Liu,Yueyang Su,Liang Zhao
Cubic and tetragonal ZrO2 were synthesized by a sol–gel method using ethanol and glycerol as solvents and ZrOCl2·8H2O as zirconium source. The effect of phase stabilization with amorphous carbon was observed and discussed. The structural evolution, phase transformation and morphological characteristics of powders were investigated by thermogravimetric analysis (TG), differential scanning calorimetric analysis (DSC), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Cubic and tetragonal phase could be generated in this system.
研究领域:
材料科学
·
陶瓷学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2019
·
IF 3.372
Piao Liu,Jianxin Cao,Zheng Xu,Chunliang Yang,Xiaodan Wang,Fei Liu
Core-shell structured ZSM-5@t-ZrO 2 catalysts were prepared by a hydrothermal coating method, and their physicochemical properties, catalytic performance, and deactivation behavior in thiolation reactions were studied using a ZSM-5/t-ZrO 2 physically-blended catalyst as a comparison. Reactions using the core-shell ZSM-5@t-ZrO 2 catalyst were carried out at a pressure of 0.7 MPa, 370 °C, a H 2 S:CH 3 OH molar ratio of 2:1, and a N 2 flow rate of 90 ml·min −1 . The conversion of CH 3 OH, and the selectivity and yield of CH 3 SH under these conditions were 92.07%, 90.89%, and 83.68%, respectively, and the catalytic lifetime was longer than 30 h. Compared with the ZSM-5/t-ZrO 2 physically-blended catalyst, the CH 3 SH yield and the catalytic lifetime of the core-shell structured ZSM-5@t-ZrO 2 catalyst were higher by 5.37% and 150%, respectively. The unique reaction pathway of the shell (t-ZrO 2 , Lewis (L) base active site)-core (ZSM-5, Brǿnsted (B) acid active site) and the Lewis-Brønsted acid active center based on a composite solid-solution interface were mainly responsible for the high activity of the thiolation reaction. Meanwhile, the formation of a micro-mesoporous system increased the diffusion of molecules and reduced the deactivation rate of carbon- and sulfur-containing deposits. Generally, carbon- and sulfur-containing substances deposited on catalysts were mainly composed of polymethylbenzene, polymethyl naphthalene, cyclic elemental sulfur, and other compounds containing C S and S S bonds. Finally, the core-shell structured catalysts showed excellent resistance to deactivation by carbon- and sulfur-containing deposits.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ying Xu,Genkuo Nie,Xiao Jiang,Hongyu Wang,Guihua Yang,Ziyi Yan,Ji-Jun Zou,Hailong Yu,Shitao Yu,Yu Liu
Metal-metal oxide catalysts are robust in selective hydrodeoxygenation of biomass derives. Herein, 1-hexanol in total yield about 76 % is firstly achieved by high selective hydrodeoxygenation of 5-hydroxymethylfurfural over Ni/MCM-41 and Pt-WO X /t-ZrO 2 . By controlling the amount ratio of Ni/Ni 2+ to 0.46, a 99.9 % yield of 2,5-tetrahydrofurandimethanol was achieved from 5-hydroxymethylfurfural by Ni/MCM-41. Subsequently high yield of 76 % of 1-hexanol was obtained by competing pathways of tandem reactions beginning at SN2 reaction at the epoxy atom of 2,5-tetrahydrofurandimethanol to enol/tautomer intermediates and ending with controllable selective hydrogenation. The reaction mechanism is explored and the reaction-oriented regulation is realized by the additional strong BrÖnsted acid sites generated by electron transfer from W to Pt and the appropriate amount of Pt 0 sites of Pt-WO X /t-ZrO 2 , where the ratios of W 5+ /W 6+ and Pt 0 /Pt 2+ are 0.31 and 4.58 respectively. This work provides a new and green method for the synthesis of 1-hexanol and expands the utilization of metal–metal oxide in making value-added products using sustainable feedstocks.
研究领域:
催化
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化学工程
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绿色化学
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生物质转化
✓ 已验证
产品关联
DOI
高影响因子
SOLID STATE SCIENCES
·
2020
·
IF 2.434
Muyan Zhou,Yong Wu,Lingyi Shi,Shiyu Hu,Huanhuan Li,Yinyan Gong,Lengyuan Niu,Xinjuan Liu,Can Li
The large work function difference between two semiconductors will effectively adjust the interfacial electronic distribution and catalytic performances of heterojunction . In this work, a novel t -ZrO 2 /g-C 3 N 4 composite photocatalyst was prepared by integrating t -ZrO 2 nanoparticle with graphitic carbon nitride (g-C 3 N 4 ) film considering the large work function of tetragonal ZrO 2 ( t -ZrO 2 ). With the aid of experimental measurements and density functional theory calculations, the electronic distributions of g-C 3 N 4 film were explicitly adjusted by the supporting t -ZrO 2 nanoparticle on account of the large interfacial internal electric field , which leaded to the improvement of photogenerated carriers mobility and lifetime, the enhancement of reduction ability and the increase of oxidation active sites. Results showed that the photocatalytic activity of the composite sample was increased by 9.4 and 2.9 times compared with g-C 3 N 4 sample for Rhodamine B and tetracycline hydrochloride degradation under visible-light. This modification strategy shall be applied to devise other high-efficient catalysts by selecting semiconductor with suitable work function.
研究领域:
材料科学
·
光催化
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环境化学
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计算材料科学
·
纳米技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）