Regulating catalytic activity of multi-Ru-bridged polyoxometalate based on active sites differential environment with six-coordinate geometry and five-coordinate geometry transition

Nanoscale ◽  
2021 ◽  
Author(s):  
Jingyang Niu ◽  
Huafeng Li ◽  
Wenjing Chen ◽  
Yujie Zhao ◽  
Yan Zhou ◽  
...  

Five-coordinate geometry around ruthenium with highly exposed active sites have attracted intensive scientific interests due to their superior properties and extensive applications. Herein, we report a series of structurally controllable...

2019 ◽  
Vol 9 (3) ◽  
pp. 811-821 ◽  
Author(s):  
Zhao-Meng Wang ◽  
Li-Juan Liu ◽  
Bo Xiang ◽  
Yue Wang ◽  
Ya-Jing Lyu ◽  
...  

The catalytic activity decreases as –(SiO)3Mo(OH)(O) > –(SiO)2Mo(O)2 > –(O)4–MoO.


1981 ◽  
Vol 46 (7) ◽  
pp. 1577-1587 ◽  
Author(s):  
Karel Jeřábek

Catalytic activity of ion exchangers prepared by partial sulphonation of styrene-divinylbenzene copolymers in reesterifications of ethyl acetate by methanol and propanol, hydrolysis of ethyl acetate and in synthesis of bisphenol A has been compared with data on polymer structure of these catalysts and with distribution of the crosslinking agent, divinylbenzene, calculated from literature data on kinetics of copolymerisation of styrene with divinylbenzene. It was found that the polymer structure of ion exchangers influences catalytic activity predominantly by changing the local concentration of acid active sites. The results obtained indicated that the effect of transport phenomena on the rate of catalytic reactions does not depend on the degree of swelling of the ion exchangers in reaction medium but it is mainly dependent on the relative affinity of reaction components to the acid groups or to the polymer skeleton.


Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2495
Author(s):  
Daniela Pietrogiacomi ◽  
Maria Cristina Campa ◽  
Ida Pettiti ◽  
Simonetta Tuti ◽  
Giulia Luccisano ◽  
...  

Ni/ZrO2 catalysts, active and selective for the catalytic partial oxidation of methane to syngas (CH4-CPO), were prepared by the dry impregnation of zirconium oxyhydroxide (Zhy) or monoclinic ZrO2 (Zm), calcination at 1173 K and activation by different procedures: oxidation-reduction (ox-red) or direct reduction (red). The characterization included XRD, FESEM, in situ FTIR and Raman spectroscopies, TPR, and specific surface area measurements. Catalytic activity experiments were carried out in a flow apparatus with a mixture of CH4:O2 = 2:1 in a short contact time. Compared to Zm, Zhy favoured the formation of smaller NiO particles, implying a higher number of Ni sites strongly interacting with the support. In all the activated Ni/ZrO2 catalysts, the Ni–ZrO2 interaction was strong enough to limit Ni aggregation during the catalytic runs. The catalytic activity depended on the activation procedures; the ox-red treatment yielded very active and stable catalysts, whereas the red treatment yielded catalysts with oscillating activity, ascribed to the formation of Niδ+ carbide-like species. The results suggested that Ni dispersion was not the main factor affecting the activity, and that active sites for CH4-CPO could be Ni species at the boundary of the metal particles in a specific configuration and nuclearity.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Yoottapong Klinthongchai ◽  
Seeroong Prichanont ◽  
Piyasan Praserthdam ◽  
Bunjerd Jongsomjit

AbstractMesocellular foam carbon (MCF-C) is one the captivating materials for using in gas phase dehydrogenation of ethanol. Extraordinary, enlarge pore size, high surface area, high acidity, and spherical shape with interconnected pore for high diffusion. In contrary, the occurrence of the coke is a majority causes for inhibiting the active sites on catalyst surface. Thus, this study aims to investigate the occurrence of the coke to optimize the higher catalytic activity, and also to avoid the coke formation. The MCF-C was synthesized and investigated using various techniques. MCF-C was spent in gas-phase dehydrogenation of ethanol under mild conditions. The deactivation of catalyst was investigated toward different conditions. Effects of reaction condition including different reaction temperatures of 300, 350, and 400 °C on the deactivation behaviors were determined. The results indicated that the operating temperature at 400 °C significantly retained the lowest change of ethanol conversion, which favored in the higher temperature. After running reaction, the physical properties as pore size, surface area, and pore volume of spent catalysts were decreased owing to the coke formation, which possibly blocked the pore that directly affected to the difficult diffusion of reactant and caused to be lower in catalytic activity. Furthermore, a slight decrease in either acidity or basicity was observed owing to consumption of reactant at surface of catalyst or chemical change on surface caused by coke formation. Therefore, it can remarkably choose the suitable operating temperature to avoid deactivation of catalyst, and then optimize the ethanol conversion or yield of acetaldehyde.


Catalysts ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 131 ◽  
Author(s):  
Rola Mohammad Al Soubaihi ◽  
Khaled Mohammad Saoud ◽  
Myo Tay Zar Myint ◽  
Mats A. Göthelid ◽  
Joydeep Dutta

Carbon monoxide (CO) oxidation is considered an important reaction in heterogeneous industrial catalysis and has been extensively studied. Pd supported on SiO2 aerogel catalysts exhibit good catalytic activity toward this reaction owing to their CO bond activation capability and thermal stability. Pd/SiO2 catalysts were investigated using carbon monoxide (CO) oxidation as a model reaction. The catalyst becomes active, and the conversion increases after the temperature reaches the ignition temperature (Tig). A normal hysteresis in carbon monoxide (CO) oxidation has been observed, where the catalysts continue to exhibit high catalytic activity (CO conversion remains at 100%) during the extinction even at temperatures lower than Tig. The catalyst was characterized using BET, TEM, XPS, TGA-DSC, and FTIR. In this work, the influence of pretreatment conditions and stability of the active sites on the catalytic activity and hysteresis is presented. The CO oxidation on the Pd/SiO2 catalyst has been attributed to the dissociative adsorption of molecular oxygen and the activation of the C-O bond, followed by diffusion of adsorbates at Tig to form CO2. Whereas, the hysteresis has been explained by the enhanced stability of the active site caused by thermal effects, pretreatment conditions, Pd-SiO2 support interaction, and PdO formation and decomposition.


Catalysts ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 313
Author(s):  
Heidy Ramirez-Mendoza ◽  
Mafalda Valdez Lancinha Pereira ◽  
Tom Van Gerven ◽  
Cécile Lutz ◽  
Ignacio Julian

The activity and selectivity of Mo/ZSM-5, benchmarking catalyst for the non-oxidative dehydroaromatization of methane, strongly depend on the cluster size, spatial distribution, and chemical environment of the Mo-based active sites. This study discloses the use of an ultrasound-assisted ion-exchange (US-IE) technique as an alternative Mo/ZSM-5 synthesis procedure in order to promote metal dispersion along the zeolite framework. For this purpose, a plate transducer (91.8 kHz) is employed to transmit the ultrasonic irradiation (US) into the ion-exchange reactor. The physico-chemical properties and catalytic activity of samples prepared under the said irradiation procedure and traditional impregnation (IWI) method are critically evaluated. Characterization results suggest that US neither affects the crystalline structure nor the particle size of the parent zeolite. However, US-IE promotes molybdenum species dispersion, avoids clustering at the external fresh zeolite surface and enhances molybdate species anchoring to the zeolite framework with respect to IWI. Despite the improved metal dispersion, the catalytic activity between catalysts synthesized by US-IE and IWI is comparable. This suggests that the sole initial dispersion enhancement does not suffice to boost the catalyst productivity and further actions such ZSM-5 support and catalyst pre-conditioning are required. Nevertheless, the successful implementation of US-IE and the resulting metal dispersion enhancement pave the way toward the application of this technique to the synthesis of other dispersed catalysts and materials of interest.


Author(s):  
Francisco G. Cirujano ◽  
Nuria Martin ◽  
Neyvis Almora-Barrios ◽  
Carlos Martí-Gastaldo

Room temperature one-step synthesis of the peptide-based porous material with a periodic distribution of pockets decorated with lysine side chain active sites behaves as a heterogeneous organocatalyst. The pockets are...


Author(s):  
Hang Lei ◽  
Shangjing Yang ◽  
Runquan Lei ◽  
Qing Zhong ◽  
Qixiang Wan ◽  
...  

Insufficient catalytic activity and self-restacking of 2D MXenes during catalytic processes would lead to limited number of active sites, sluggish ionic kinetics and poor durability, extremely restricting its application in...


Catalysts ◽  
2019 ◽  
Vol 9 (9) ◽  
pp. 724 ◽  
Author(s):  
Yan Cui ◽  
Leilei Xu ◽  
Mindong Chen ◽  
Chufei Lv ◽  
Xinbo Lian ◽  
...  

CuO-based catalysts are usually used for CO oxidation owing to their low cost and excellent catalytic activities. In this study, a series of metal oxide (La2O3, Fe2O3, PrO2, Sm2O3, and MnO2)-doped CuO-based catalysts with mesoporous Ce0.8Zr0.2O2 support were simply prepared by the incipient impregnation method and used directly as catalysts for CO catalytic oxidation. These mesoporous catalysts were systematically characterized by X-ray powder diffraction (XRD), N2 physisorption, transmission electron microscopy (TEM), energy-dispersed spectroscopy (EDS) mapping, X-ray photoelectron spectroscopy (XPS), and H2 temperature programmed reduction (H2-TPR). It was found that the CuO and the dopants were highly dispersed among the mesoporous framework via the incipient impregnation method, and the strong metal framework interaction had been formed. The effects of the types of the dopants and the loading amounts of the dopants on the low-temperature catalytic performances were carefully studied. It was concluded that doped transition metal oxides could regulate the oxygen mobility and reduction ability of catalysts, further improving the catalytic activity. It was also found that the high dispersion of rare earth metal oxides (PrO2, Sm2O3) was able to prevent the thermal sintering and aggregation of CuO-based catalysts during the process of calcination. In addition, their presence also evidently improved the reducibility and significantly reduced the particle size of the CuO active sites for CO oxidation. The results demonstrated that the 15CuO-3Fe2O3/M-Ce80Zr20 catalyst with 3 wt. % of Fe2O3 showed the best low-temperature catalytic activity toward CO oxidation. Overall, the present Fe2O3-doped CuO-based catalysts with mesoporous nanocrystalline Ce0.8Zr0.2O2 solid solution as support were considered a promising series of catalysts for low-temperature CO oxidation.


2019 ◽  
Vol 7 (19) ◽  
pp. 15948-15956 ◽  
Author(s):  
Juan C. Espinosa ◽  
Mercedes Álvaro ◽  
Amarajothi Dhakshinamoorthy ◽  
Sergio Navalón ◽  
Hermenegildo García

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