In-situ FTIR to unravel the bifunctional nature of aromatics hydrogenation synergy on zeolite / metal catalysts

Author(s):  
Nuno Batalha ◽  
Jean-Dominique Comparot ◽  
Anthony Le Valant ◽  
Ludovic Pinard

Acid sites, in particular Brønsted sites, are often reported to enhance the catalytic performance of metal catalysts, like platinum, in hydrogenation. The significant boost in catalytic performance suggests a bifunctional...

2019 ◽  
Vol 107 (3) ◽  
pp. 304
Author(s):  
Habib Hammoudi ◽  
Souhila Bendenia ◽  
Isabelle Batonneau-Gener ◽  
Jean-dominique Comparot ◽  
Kheira Marouf-Khelifa ◽  
...  

X zeolites were prepared by ion-exchange with Cu2+ and/or Zn2+ cations, at different concentrations of the exchange solution, and characterized by thermal analysis and nitrogen adsorption. The acidity of the samples was investigated by pyridine adsorption–desorption followed by in situ Fourier transform infrared (FTIR) spectroscopy. Desorption was carried out at 150, 250 and 350 °C. The objective is to estimate the nature and concentration of acid sites. A comparison between the binary (Cu(x)X, Zn(x)X) and ternary (CuZn(x)X) exchanges was also established (x = level of exchange) through the Cu(43)X, Zn(48)X and CuZn(50)X samples. Lewis acidity decreases overall with desorption temperature and the level of exchange. As the latter increases, there is a conversion of some Lewis sites into those of Brønsted during thermal treatment. In return, the concentration of Brønsted sites increases with the degree of exchange. The Brønsted acidity of CuZn(50)X at 350 °C is more important than the sum of those of Cu(43)X and Zn(48)X with respectively values of 73, 32 and 15 μmol g−1. Besides, the concentration of Brønsted sites for CuZn(50)X increases with desorption temperature. These features indicate the presence of a synergetic effect amplifying the strength of these sites when Cu2+ and Zn2+ cations compete for the occupancy of sites distributed in zeolite cavities.


2020 ◽  
Vol 4 (4) ◽  
pp. 1-3
Author(s):  
Liu L

The mesoporous ZSM-5 zeolite containing MoCoP/Al2O3 catalyst (C12-ZSM5) with the mixture of Al2O3 and mesoporous ZSM- 5 zeolite as carrier was synthesized. The catalytic performance of C12-ZSM5 catalyst was evaluated by the hydrodesulfurization (HDS) of different diesel feedstock. The carriers and catalysts were characterized by N2 adsorption-desorption, pyridine-FTIR, X-ray diffraction (XRD) and CO in-situ FTIR (CO-FTIR) techniques. Results showed that mesoporous ZSM-5 can improve the acidity of the catalyst and increase the number of MoCoS active phases. The C12-ZSM5 catalyst had low HDS and HDN activity, because the acidic sites of mesoporous ZSM-5 were easily occupied by nitrogen compounds. The HDS activity of C12-ZSM5 catalyst was fully exploited by using graded packing technology, the sulfur content of product oil was 5.9 ng/μL. The relative HDS activity of C12-ZSM5 catalyst is 1.47 times that of FHUDS-8 catalyst.


2020 ◽  
Vol 218 ◽  
pp. 03032
Author(s):  
Chenxi Li ◽  
Fanwei Meng ◽  
Qing Ye

A series of xCe-Fe/ZSM-5 (x = 0, 0.25, 0.5 wt%) samples were prepared by the impregnation method, and the catalytic activity was evaluated by the selective catalytic reduction of NOx with ammonia (NH3-SCR). The physicochemical properties of prepared samples were characterized by various techniques such as X-ray diffraction (XRD), Brunner-Emmet-Teller (BET) measurement, hydrogen temperatureprogrammed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), ammonia temperatureprogrammed desorption (NH3-TPD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). XRD and BET results demonstrated that Ce and Fe species were uniform dispersed on the surface of the ZSM-5 zeolite and the micropore structure of ZSM-5 was still maintained. H2-TPR analysis indicated that the doping of Ce created more isolated Ce4+ and Fe3+ on the surface of catalysts, and the abundant Ce4+ and Fe3+ could enhance the reduction ability of catalysts. XPS analysis suggested that the doping of Ce could generate more oxygen vacancies, thereby increasing the number of chemisorption oxygen. According to the in-situ DRIFTS and NH3-TPD results, Ce species provided more acidic sites, which is beneficial to the NH3 adsorption ability of ZSM-5 zeolite. Additionally, the abundant chemisorption oxygen, medium and strong Brønsted acid sites, excellent NH3 adsorption ability and outstanding reduction property are beneficial to the NH3-SCR reaction. Among all prepared samples, the 0.25Ce-Fe/ZSM-5 sample possessed the widest reaction temperature window and the best catalytic performance (NO conversion over 98% at 350-450 °C), which was associated with the abundant acid sites and remarkable adsorption ability of NH3, outstanding redox ability and abundant chemisorption oxygen after the doping of Ce.


2014 ◽  
Vol 900 ◽  
pp. 390-393
Author(s):  
Ming Jian Luo ◽  
Bing Hu ◽  
Xin Yue Liu

An easy-operation in-situ FTIR cell is designed and used for the investigation of dehydroxylation and pyridine adsorption FTIR study. The dehydroxylation FTIR spectra of MCM-41 indicate that the isolated, geminal, and oxygen perturbed silanol vibrated at about 3745, 3735 and 3520 cm-1, respectively. Py-FTIR spectra indicate that MCM-41 has none Lewis and Brönsted acid sites while the acid amount and acid strength of AlMCM-41 increase with the decrease of Si/Al.


2020 ◽  
Vol 8 ◽  
Author(s):  
Qiang Wei ◽  
Pengfei Zhang ◽  
Xiaodong Liu ◽  
Wenbin Huang ◽  
Xiayun Fan ◽  
...  

Ni-modified ZSM-5 zeolites with different nickel contents were successfully prepared by the in situ synthesis method and the impregnation method. The synthesized samples were characterized by XRD, SEM, N2 adsorption–desorption isothermals, and Py-FTIR. The characterization results show that both the textural properties and crystallization of Ni-modified ZSM-5 zeolites were preserved well, and their acidic properties can be modulated after nickel modification. The corresponding NiMo catalysts supported on Ni-modified ZSM-5 zeolites were prepared by the incipient wetness co-impregnation method, and their catalytic performances were evaluated in n-octane hydroconversion. Compared to the those modified by the in situ synthesis method, ZSM-5 zeolite-supported catalysts modified by the impregnation method exhibit higher stability and higher isomerization selectivity. This is due to the synergistic effect between Brønsted acid sites and Lewis acid sites on the Ni-modified ZSM-5 zeolites, especially for the NiMo/1Ni-Z5 catalyst.


Molecules ◽  
2019 ◽  
Vol 24 (19) ◽  
pp. 3462 ◽  
Author(s):  
Yiren Wang ◽  
Yang Chang ◽  
Min Liu ◽  
Anfeng Zhang ◽  
Xinwen Guo

A general strategy for preparing shaped toluene methylation catalysts with enhanced para-selectivity and stability is developed by extruding ZSM-5 zeolite with attapulgite as a binder. The novel attapulgite/ZSM-5 extrudate exhibited significantly higher para-selectivity and stability in comparison to the conventional alumina-bound ZSM-5 extrudate. The catalyst samples have been characterized by in situ X-ray diffraction, scanning electron microscope (SEM), NH3 temperature programmed desorption (TPD), thermogravimetric analysis (TGA) as well as n-hexane/cyclohexane physical adsorption. The enhanced catalytic performance of attapulgite/ZSM-5 extrudate is correlated with the in-situ modification of acid sites in the catalyst by mobile alkaline species, which is introduced via extrusion with attapulgite. Moreover, a higher para-selectivity was obtained over attapulgite-bound modified ZSM-5 extrudate. Such facile and universal strategy of extruding ZSM-5 catalysts with attapulgite as binder could pave a way for preparation of shaped zeolite-base catalyst with enhanced catalytic performance.


2017 ◽  
Vol 5 (5) ◽  
pp. 2083-2094 ◽  
Author(s):  
M. Manzoli ◽  
F. Vindigni ◽  
T. Tabakova ◽  
C. Lamberti ◽  
D. Dimitrov ◽  
...  

A strong influence of the amount of the Co3O4 promoter on the catalytic performance in methanol oxidation of different gold catalysts supported on ceria was observed.


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