GREEN CHEMISTRY
·
2019
·Vol. 21
·期 19
·5414-5426
·
IF 9.405
Yu Ding,Jingxia Tian,Wei Chen,Yejun Guan,Hao Xu,Xiaohong Li,Haihong Wu,Peng Wu
Copper-based catalysts, with highly dispersed and stabilized Cu nanoparticles, intensified mass transfer and a well-balanced Cu0/Cu+ ratio at low Cu loadings, are highly desirable for the selective hydrogenation of ethylene carbonate to ethylene glycol and methanol, an efficient indirect route of CO2 utilization. A hierarchically core/shell-structured Silicalite-1@Cu composite was developed via a base-assisted chemoselective host–guest interaction between the silicon species of MFI-type Silicalite-1 and external Cu salt source. In situ generated mesoporosity and strong Cu–silicate interaction made the uniform Cu NPs firmly immobilized and highly dispersed outside the core S-1 crystals. The S-1@Cu hybrid possessed the co-existing Cu0/Cu+ active species with a suitable ratio, and served as a highly active, selective and robust catalyst for selective ethylene carbonate hydrogenation, providing a lifetime >350 h together with >99% ethylene carbonate conversion, >99% ethylene glycol yield, and more importantly 93% methanol yield at a relatively low Cu loading of 21.4 wt%.
研究领域:
化学工程
·
催化材料
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 2
·450
·
IF 3.9
Muhammad Naeem Younis,Zhiheng Ren,Chunshan Li,Erqiang Wang,Jie Li
The advancing effects of various alkali and alkaline earth metals (inclusive of K, Ca, and Sr) modified Cu/SiO2catalysts, prepared with a modified precipitation-gel method, were investigated for the production of ethanol via hydrogenation of methyl acetate. Our results showed that Sr-doped catalysts exhibited the best and most consistent results during catalytic tests. A series of techniques, including X-ray diffraction technique, Raman spectroscopy, N2adsorption/desorption, N2O titration method, FTIR spectroscopy, and H2temperature, programmed desorption and reduction (TPD and TPR), and X-ray Photoelectron Spectroscopy, which was used to check the detailed characterization of Sr modification in the catalyst and its structural impacts on the properties of the catalyst. These results demonstrated that the addition of 5%Sr could strengthen the intrinsic stability of the catalyst by formulating the appropriate ratio of Cu+/(Cu0+ Cu+) to facilitate catalytic outcome improvement. The addition of 5%Sr-30%Cu/SiO2under the most favorable conditions, resulting in the peak conversion of MA (95%) and ethanol selectivity (96%), indicates its magnificent catalytic stabilizing effects. Furthermore, the best performing catalyst was compared and tested under various conditions (LHSV and temperatures) and a 300 h long life run.Keywords:hydrogenation;methyl acetate;ethanol;strontium
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 7
·1038
·
IF 3.9
Jincheng Wu,Guoguo Liu,Qin Liu,Yajing Zhang,Fu Ding,Kangjun Wang
The hydrogenation of methyl formate to methanol is considered one of the most effective methods for recycling methyl formate products. We recently developed a highly efficient and cost-effective Cu-SiO2catalyst using the ammonia-evaporation (AE) method. The Cu-SiO2-AE catalyst demonstrated superior performance, achieving a methyl formate conversion of 94.2% and a methanol selectivity of 99.9% in the liquid product. The catalyst also displayed excellent stability over a durability test of 250 h. Compared to the commonly used Cu-Cr catalyst in the industry, the Cu-SiO2-AE catalyst exhibited higher conversion of methyl formate and methanol yield under the same reaction conditions. Characterization results revealed a significant presence of Si-OH groups in the Cu-SiO2-AE catalyst. These groups enhanced the hydrogen spillover effect and improved hydrogenation efficiency by preventing sintering during the reaction to stabilize the Cu species. The strategy employed in this study is applicable to the rational design of highly efficient catalysts for industrial applications.Keywords:Cu-SiO2catalyst;hydrogenation of methyl formate;methanol;catalyst stability
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
AUSTRALIAN JOURNAL OF CHEMISTRY
·
2019
·Vol. 72
·期 6
·417-424
·
IF 1.226
Changna Gan,Yunhao Wang,Chenliang Ye,Cuili Guo,Changna Gan,Yunhao Wang,Chenliang Ye,Cuili Guo
A series of CuZnAl catalysts derived from layered double hydroxide precursors with different Cu/Zn molar ratios were synthesised by a co-precipitation method for methyl acetate hydrogenation. The best catalytic performance was obtained when the Cu/Zn molar ratio reached 0.25 : 1. After fixing the Cu/Zn molar ratio at 0.25 : 1, the effect of aging methods, including ultrasound, high shear mixer stirring, and magnetic stirring, were investigated, which showed that 0.25CuZnAl-u and 0.25CuZnAl-h exhibited a higher conversion and selectivity than that of 0.25CuZnAl-m, especially under low reaction temperatures. The physicochemical properties of the CuZnAl catalysts were characterised by X-ray diffraction, inductively coupled plasma–atomic emission spectroscopy, N2 physisorption, N2O chemisorption, transmission electron microscopy, H2-temperature-programmed reduction, X-ray photoelectron spectroscopy, and H2-temperature-programmed desorption. It was found that compared with 0.25CuZnAl-m, 0.25CuZnAl-u and 0.25CuZnAl-h possessed a stronger interaction between Cu and the support, smaller copper particle size, and higher copper dispersion, which improved the catalytic performance.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2018
·
IF 3.525
Yu Zhang,Chenliang Ye,Cuili Guo,Changna Gan,Xinmeng Tong
A series of indium oxide-modified Cu/SiO 2 catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation. In-Cu/SiO 2 catalyst containing 1.0 wt% In 2 O 3 exhibited the best catalytic activity and stability. The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO 2 increased the copper dispersion, diminished the copper crystallite size, and enriched the surface Cu + concentration. Furthermore, the Cu/SiO 2 catalyst gradually deactivated during the stability test, which was mainly attributed to copper sintering and the valence change in surface copper species. In contrast, indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 9
·4048-4053
·
IF 3.5
Lin Gao,Guoqiang Ding,Lei Zhu,Zhanqiu Yu,Hongju Li,Guoqiang Li,Yulei Zhu,Hongwei Xiang,Xiaodong Wen,Yong Yang,Yongwang Li
The dimethyl maleate hydrogenation activity of Cu, ZnO-X and physically mixed Cu+ZnO-X samples was systematically investigated to probe the essential role of ZnO in ester hydrogenation processes. Cu samples exhibited high CC bond hydrogenation ability with dimethyl succinate as the main product. Comparatively, ZnO was inactive in hydrogenation due to its weak ability to dissociate hydrogen while the CO group could be activated and adsorbed on the ZnO surface. Interestingly, physical mixing with ZnO significantly improved the CO hydrogenation activity of Cu samples. The H2-TPD results reveal the origin of “Cu–ZnO synergy”: hydrogen atoms formed on the copper surface can spill over to the ZnO surface and react with the adsorbed CO group.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2021
·
IF 13.084
Yannan Sun,Qingxiang Ma,Qingjie Ge,Jian Sun
Oxygenated chemicals are essential to modern industries. However, selective syntheses with controllable products are still challenging over a single heterogeneous catalyst. Herein, a confined iron catalyst is designed for balanced syntheses of ethanol and methyl acetate via dimethyl oxalate (DMO) hydrogenation. With the characteristic structure of a microsphere, the Fe@C catalyst promotes the enrichment of hydrogen to reach a tunable selectivity of ethanol (84.3%) and methyl acetate (77.9%). The highest selectivity of methyl acetate is reached at a H2/DMO molar ratio as low as 20, which is the lowest among catalysts reported for DMO hydrogenation by now. The molecule-level mechanism of DMO hydrogenation is further investigated. It proves that Fe5C2 in Fe@C is the main active center of DMO hydrogenation and Fe3O4 promotes the conversion of the intermediate especially in a low H2/DMO molar ratio. This work provides a strategy for tuning targeted oxygenated chemicals.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Zhuo Ma,Yihui Li,Zheng Li,Ziyin Liu,Xuepeng Wang,Yuan Tan,Xingkun Chen,Wei Lu,Yunjie Ding
Increasing dimethyl oxalate (DMO) hydrogenation activity remains a challenge. A Cu catalyst was designed by creating Cu nanoparticles (NPs) over SiO 2 layer formed on the CeO 2 particles (SiO 2 @CeO 2 ) using the ammonia evaporation method followed by the calcination and reduction step. The optimized 30Cu/SiO 2 @5CeO 2 catalyst shows good performance in the micro-packed bed reactor (100 % DMO conversion, 95.9 % ethylene glycol (EG) selectivity, 200 h stability) under the condition of the ratio of H 2 to DMO (H 2 /DMO) = 30, 190 °C and 2 MPa in the run, and CeO 2 was proved to be effective in the DMO hydrogenation process. The exposed CeO 2 on the surface of catalyst was found to facilitate the formation of Cu + by its interaction between adjacent Cu nanoparticles, resulting in the faster adsorption and dissociation of C=O bond on the catalyst surface, according to the characterization results obtained by the XRD, XPS and in situ FT-IR, etc.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2020
·Vol. 12
·期 14
·3670-3678
·
IF 4.853
Mengjiao Zhang,Youwei Yang,Antai Li,Dawei Yao,Yueqi Gao,Busha Assaba Fayisa,Mei-Yan Wang,Shouying Huang,Jing Lv,Yue Wang,Xinbin Ma
Graphical Cu-based catalyst : In the hydrogenation of ethylene carbonate (EC), nanoflower-like catalysts with high fiber density exhibited nearly 98 % EC conversion when the H 2 /EC ratio was decreased to 60, while the catalyst with solid sphere structure required at least a H 2 /EC ratio of 140. This is attributed to the H 2 -enrichment effect of nanoflower-like morphology with dense fibers, which accelerated the reaction rate and achieved excellent activity at a low H 2 /EC ratio. The hydrogenation of ethylene carbonate (EC) to produce methanol and ethylene glycol (EG) is one of the key steps in the promising route for CO 2 utilization on a large scale. However, the high H 2 /EC ratio in feed (usually as 200∼300) is generally required to achieve favorable catalytic activity, inducing the high cost for H 2 circulation in the industrial application. Here, we report a series of nanoflower-like catalysts with curved fibers and open ends, among which the catalyst with the highest fiber density exhibited nearly 98 % EC conversion, 75 % methanol selectivity and over 99 % EG selectivity when the H 2 /EC ratio was decreased to 60. Combining the characterizations of active species distribution and high-pressure H 2 adsorption, it is demonstrated that the nanoflower-like morphology with dense fibers could remarkably enrich the hydrogen adsorption, consequently, accelerate the reaction rate and present an excellent performance at a low H 2 /EC ratio. These insights may provide instructive suggestions for further design of catalysts for the hydrogenation reactions.
研究领域:
催化化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2025
·
IF 6.5
Ziheng Zhen,Antai Li,Tiantian Xiao,Maoshuai Li,Jing Lv,Shouying Huang,Yue Wang,Xinbin Ma
Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO 2 supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO 2 exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO 2 catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H 2 molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.
研究领域:
催化化学
·
材料科学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS COMMUNICATIONS
·
2019
·
IF 3.674
Yan Xu,Yan Wang,Chenguang Wu,Huijiang Huang,Ying Zhang,Jun Nan,Haibin Yu,Yujun Zhao
Activated carbon with different microporous surface area were used to prepare a series of Ru/AC catalysts for the hydrogenation of dioctyl phthalate (DOP) to dioctyl 1,2-cyclohexanedicarboxylate (DOCH). The presence of micropores benefit the dispersion of Ru, but Ru particles encapsulated into the micropores can be hardly accessed by DOP molecule. An appropriate microporous surface area of the support should be crucial important for the preparation of highly efficient catalyst for phthalates hydrogenation. The as-prepared 0.45%Ru/AC-2 catalyst (Micropore surface area = 604 m 2 /g) exhibited the best activity in DOP hydrogenation with a TOF of 1406 h −1 due to its suitable micropore surface area.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
·
IF 17.7
Yannan Sun,Jiafeng Yu,Xingtao Sun,Yu Han,Qingjie Ge,Jian Sun
Molybdenum carbide has shown great potential in various hydrogenation reactions, and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources. In this study, a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed. The MoO 3 precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis, and a structural modifier, Cu, was introduced by sputtering. The Cu deposited by sputtering affected the carburization and phase evolution processes. A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed, with the β -Mo 2 C exhibiting lattice distortions and defects. This defective β -Mo 2 C exhibits high reactivity, and facilitates the C=O hydrogenation process, showing a high reactivity of 83.1% yield in the hydrogenation of dimethyl oxalate. This work provides a new approach to the design and application of molybdenum carbide catalysts.
研究领域:
能源化学
·
催化化学
·
材料科学
✓ 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）