scholarly journals Catalytic and Sulfur-Tolerant Performance of Bimetallic Ni–Ru Catalysts on HI Decomposition in the Sulfur-Iodine Cycle for Hydrogen Production

Energies ◽  
2021 ◽  
Vol 14 (24) ◽  
pp. 8539
Author(s):  
Lijian Wang ◽  
Kang Zhang ◽  
Yi Qiu ◽  
Huiyun Chen ◽  
Jie Wang ◽  
...  
Keyword(s):  
Active Sites ◽  
Large Scale ◽  
Decomposition Reaction ◽  
Catalytic Performance ◽  
Sulfur Poisoning ◽  
Great Promise ◽  
Sulfur Tolerance ◽  
Sulfur Resistance ◽  
Sulfur Deactivation ◽  
The Stability

The sulfur-iodine (SI) cycle holds great promise as an alternative large-scale process for converting water into hydrogen without CO2 emissions. A major issue regarding the long-term stability and activity of the catalysts is their poor sulfur deactivation resistance in the HI feeding process. In this work, the effect of Ru addition for enhancing the activity and sulfur resistance of SiO2-supported Ni catalysts in the HI decomposition reaction has been investigated. The presence of H2SO4 molecules in the HI results in severe sulfur deactivation of the Ru-free Ni/SiO2 catalysts by blocking the active sites. However, Ni–Ru/SiO2 catalysts show higher catalytic activity without sulfur-poisoning by 25% and exhibit more superior catalytic performance than the Ru-free catalyst. The addition of Ru to the Ni/SiO2 catalyst promotes the stability and activity of the catalysts. The experimental trends in activity and sulfur tolerance are consistent with the theoretical modeling, with the catalytic activities existing in the order Ni/SiO2 < Ni–Ru/SiO2. The effect of Ru on the improvement in sulfur resistance over Ni-based catalysts is attributed to electronic factors, as evidenced by theory modeling analysis and detailed characterizations.

Fe-Modified ZSM-5 and β Zeolites for Direct N2O Decomposition

2012 ◽  
Vol 610-613 ◽  
pp. 94-99 ◽  
Author(s):  
Quan Hui Guo ◽  
Juan Li ◽  
Ying Xia Li
Keyword(s):  
Catalytic Activity ◽  
Active Sites ◽  
Channel Wall ◽  
Decomposition Reaction ◽  
Catalytic Performance ◽  
Iron Ions ◽  
Exchange Method ◽  
Different Types ◽  
Charge Balancing ◽  
Better Than

Fe-modified ZSM-5 and β zeolites were prepared by adopting liquid ion-exchange method and their catalytic performance was studied in the N2O decomposition reaction. The state of Fe loaded on Fe-zeolites was investigated by means of UV-vis diffuse spectra, infrared spectroscopy, EPR and H2-TPR. The results of IR of hydroxyl stretching and UV-vis investigationSubscript texts indicated that part of the iron-ions was introduced into zeolites at the charge-balancing sites. The results of EPR and H2-TPR investigations showed that the same iron species were loaded on ZSM-5 and β zeolites. However, the results of IR of the perturbed anti-symmetric T-O-T vibrations of iron-ions indicated that different types of ZSM-5 and β zeolites resulted in different distributions of charge-balancing iron cations. The iron-ions could replace Brönsted acid protons at the straight channel wall (α sites), intersection of straight and sinusoidal channels (β sites), and sinusoidal channel wall (γ sites) within the ZSM-5 zeolite. In the case of Fe-β zeolites, iron-ions mainly located in the straight channels. We observed that the catalytic activity of the iron ions located on the α sites of ZSM-5 zeolites was better than those of iron ions located on β and γ sites in N2O direct decomposition, since the former was the most easily reduced from Fe3+to Fe2+in H2. Furthermore, it was found that Fe-β zeolite showed higher catalytic activity than Fe-ZSM-5 zeolite. This difference was attributed to the active sites located almost exclusively in the straight zeolite channels.

scholarly journals Simple physical mixing of zeolite prevents sulfur deactivation of vanadia catalysts for NOx removal

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Inhak Song ◽  
Hwangho Lee ◽  
Se Won Jeon ◽  
Ismail A. M. Ibrahim ◽  
Joonwoo Kim ◽  
...  
Keyword(s):  
Active Sites ◽  
Catalytic Reduction ◽  
Dew Point ◽  
Environmental Catalysis ◽  
Y Zeolite ◽  
Sulfur Resistance ◽  
Industrial Facilities ◽  
Physical Mixing ◽  
Sulfur Deactivation ◽  
Huge Challenge

AbstractNOx abatement has been an indispensable part of environmental catalysis for decades. Selective catalytic reduction with ammonia using V2O5/TiO2 is an important technology for removing NOx emitted from industrial facilities. However, it has been a huge challenge for the catalyst to operate at low temperatures, because ammonium bisulfate (ABS) forms and causes deactivation by blocking the pores of the catalyst. Here, we report that physically mixed H-Y zeolite effectively protects vanadium active sites by trapping ABS in micropores. The mixed catalysts operate stably at a low temperature of 220 °C, which is below the dew point of ABS. The sulfur resistance of this system is fully maintained during repeated aging/regeneration cycles because the trapped ABS easily decomposes at 350 °C. Further investigations reveal that the pore structure and the amount of framework Al determined the trapping ability of various zeolites.

scholarly journals Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst

2018 ◽  
Vol 115 (50) ◽  
pp. 12692-12697 ◽  
Author(s):  
Tingting Sun ◽  
Shu Zhao ◽  
Wenxing Chen ◽  
Dong Zhai ◽  
Juncai Dong ◽  
...  
Keyword(s):  
Active Sites ◽  
Density Functional ◽  
Catalytic Performance ◽  
Great Promise ◽  
High Catalytic Activity ◽  
High Porosity ◽  
Porous Architecture ◽  
Hierarchical Porous ◽  
Electrocatalytic Oxygen Reduction ◽  
Ordered Porous

Exploring efficient and cost-effective catalysts to replace precious metal catalysts, such as Pt, for electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) holds great promise for renewable energy technologies. Herein, we prepare a type of Co catalyst with single-atomic Co sites embedded in hierarchically ordered porous N-doped carbon (Co-SAS/HOPNC) through a facile dual-template cooperative pyrolysis approach. The desirable combination of highly dispersed isolated atomic Co-N4 active sites, large surface area, high porosity, and good conductivity gives rise to an excellent catalytic performance. The catalyst exhibits outstanding performance for ORR in alkaline medium with a half-wave potential (E1/2) of 0.892 V, which is 53 mV more positive than that of Pt/C, as well as a high tolerance of methanol and great stability. The catalyst also shows a remarkable catalytic performance for HER with distinctly high turnover frequencies of 0.41 and 3.8 s−1 at an overpotential of 100 and 200 mV, respectively, together with a long-term durability in acidic condition. Experiments and density functional theory (DFT) calculations reveal that the atomically isolated single Co sites and the structural advantages of the unique 3D hierarchical porous architecture synergistically contribute to the high catalytic activity.

scholarly journals Improved SO2 Tolerance of Cu-SAPO-18 by Ce-Doping in the Selective Catalytic Reduction of NO with NH3

Catalysts ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 783
Author(s):  
Shuai Han ◽  
Qing Ye ◽  
Qi Gao ◽  
Hongxing Dai
Keyword(s):  
Selective Catalytic Reduction ◽  
Active Sites ◽  
Catalytic Reduction ◽  
Catalytic Performance ◽  
Sulfur Poisoning ◽  
Remarkable Change ◽  
Exchange Method ◽  
Scr Of No ◽  
Catalytic Active Sites ◽  
The Impact

The Ce-Cu-SAPO-18 catalysts were prepared using the ion exchange method. The impact of sulfur dioxide on catalytic performance of Ce-Cu-SAPO-18 for the selective catalytic reduction (SCR) of NO with NH3 was examined. Detailed characterization of the fresh and sulfur-poisoning Cu-SAPO-18 and Ce-Cu-SAPO-18 samples was conducted. XRD and BET results show that SO2 treatment of the Ce-doped Cu-SAPO-18 (Ce-Cu-SAPO-18-S) sample did not induce a remarkable change in structure, as compared with that of the fresh counterpart. According to in situ DRIFT, H2-TPR, SEM, and EDS results, it is found that the sulfation species attached preferentially to the cerium species, rather than the isolated Cu2+ species. In particular, the TG/DSC results confirm that the sulfate species on the Ce-Cu-SAPO-18-S sample was easier to decompose than that on the Cu-SAPO-18-S sample. The catalytic active sites of Ce-Cu-SAPO-18 were less influenced after SO2 treatment, as demonstrated by the TPR and XPS results. All of the above results show that the Ce-Cu-SAPO-18 sample exhibited better sulfur-resistant performance than the Cu-SAPO-18 sample.

scholarly journals Rh Particles Supported on Sulfated g-C3N4: A Highly Efficient and Recyclable Heterogeneous Catalyst for Alkene Hydroformylation

Catalysts ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1359
Author(s):  
Yukun Shi ◽  
Yang Lu ◽  
Tongxin Ren ◽  
Jie Li ◽  
Qiqige Hu ◽  
...  
Keyword(s):  
Heterogeneous Catalyst ◽  
Large Scale ◽  
Oxygen Vacancies ◽  
Reduction Method ◽  
Nitrogen Adsorption ◽  
Catalytic Performance ◽  
Reaction Conditions ◽  
Optimum Reaction ◽  
The Stability ◽  
Recyclable Heterogeneous Catalyst

The hydroformylation of alkenes with CO and H2 to manufacture aldehydes is one of the most large-scale chemical reactions. However, an efficient and recyclable heterogeneous catalyst for alkene hydroformylation is extremely in demand in academia and industry. In this study, a sulfated carbon nitride supported rhodium particle catalyst (Rh/S-g-C3N4) was successfully synthesized via an impregnation-borohydride reduction method and applied in the hydroformylation of alkenes. The catalysts were characterized by XRD, FTIR, SEM, TEM, XPS, and nitrogen adsorption. The influence of the sulfate content, pressure of syngas, temperature, and reaction time, as well as the stability of Rh/S-g-C3N4, on the hydroformylation was examined in detail. The delocalized conjugated structure in g-C3N4 can lead to the formation of electron-deficient aromatic intermediates with alkenes. The sulphate g-C3N4 has a defected surface owing to the formation of oxygen vacancies, which increased the adsorption and dispersion of RhNPs on the surface of g-C3N4. Therefore, Rh/S-g-C3N4 exhibited an outstanding catalytic performance for styrene hydroformylation (TOF = 9000 h−1), the conversion of styrene could reach 99.9%, and the regioselectivity for the branched aldehyde was 52% under the optimized reaction conditions. The catalytic properties of Rh/S-g-C3N4 were also studied in the hydroformylation of various alkenes and displayed an excellent catalytic performance. Furthermore, the reuse of Rh/S-g-C3N4 was tested for five recycling processes, without an obvious decrease in the activity and selectivity under the optimum reaction conditions. These findings demonstrated that Rh/S-g-C3N4 is a potential catalyst for heterogeneous hydroformylation.

The design and catalytic performance of molybdenum active sites on an MCM-41 framework for the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

2019 ◽  
Vol 9 (3) ◽  
pp. 811-821 ◽  
Author(s):  
Zhao-Meng Wang ◽  
Li-Juan Liu ◽  
Bo Xiang ◽  
Yue Wang ◽  
Ya-Jing Lyu ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Active Sites ◽  
Aerobic Oxidation ◽  
Catalytic Performance ◽  
Mcm 41

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

Catalytic Resonance Theory: Parallel Reaction Pathway Control

2019 ◽  
Author(s):  
M. Alexander Ardagh ◽  
Manish Shetty ◽  
Anatoliy Kuznetsov ◽  
Qi Zhang ◽  
Phillip Christopher ◽  
...  
Keyword(s):  
Chemical Reactions ◽  
Active Site ◽  
Active Sites ◽  
Reaction Pathway ◽  
Control Strategies ◽  
Oscillation Amplitude ◽  
Catalytic Performance ◽  
Parallel Reaction ◽  
Resonance Theory ◽  
Static Conditions

Catalytic enhancement of chemical reactions via heterogeneous materials occurs through stabilization of transition states at designed active sites, but dramatically greater rate acceleration on that same active site is achieved when the surface intermediates oscillate in binding energy. The applied oscillation amplitude and frequency can accelerate reactions orders of magnitude above the catalytic rates of static systems, provided the active site dynamics are tuned to the natural frequencies of the surface chemistry. In this work, differences in the characteristics of parallel reactions are exploited via selective application of active site dynamics (0 < ΔU < 1.0 eV amplitude, 10<sup>-6</sup> < f < 10<sup>4</sup> Hz frequency) to control the extent of competing reactions occurring on the shared catalytic surface. Simulation of multiple parallel reaction systems with broad range of variation in chemical parameters revealed that parallel chemistries are highly tunable in selectivity between either pure product, even when specific products are not selectively produced under static conditions. Two mechanisms leading to dynamic selectivity control were identified: (i) surface thermodynamic control of one product species under strong binding conditions, or (ii) catalytic resonance of the kinetics of one reaction over the other. These dynamic parallel pathway control strategies applied to a host of chemical conditions indicate significant potential for improving the catalytic performance of many important industrial chemical reactions beyond their existing static performance.

Structural/Texture Evolution During Facile Substitution of Ni into ZSM-5 Nanostructure vs. its Impregnation Dispersion Used in Selective Transformation of Methanol to Ethylene and Propylene

2020 ◽  
Vol 23 ◽  
Author(s):  
Parisa Sadeghpour ◽  
Mohammad Haghighi ◽  
Mehrdad Esmaeili
Keyword(s):  
High Temperature ◽  
Physicochemical Properties ◽  
Active Sites ◽  
Catalytic Performance ◽  
Fixed Bed Reactor ◽  
Light Olefins ◽  
Isomorphous Substitution ◽  
Impregnation Method ◽  
Hydrothermal Temperature ◽  
X Ray

Aim and Objective: Effect of two different modification methods for introducing Ni into ZSM-5 framework was investigated under high temperature synthesis conditions. The nickel successfully introduced into the MFI structures at different crystallization conditions to enhance the physicochemical properties and catalytic performance. Materials and Methods: A series of impregnated Ni/ZSM-5 and isomorphous substituted NiZSM-5 nanostructure catalysts were prepared hydrothermally at different high temperatures and within short times. X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray (EDX), Brunner, Emmett and Teller-Barrett, Joyner and Halenda (BET-BJH), Fourier transform infrared (FTIR) and Temperature-programmed desorption of ammonia (TPDNH3) were applied to investigate the physicochemical properties. Results: Although all the catalysts showed pure silica MFI–type nanosheets and coffin-like morphology, using the isomorphous substitution for Ni incorporation into the ZSM-5 framework led to the formation of materials with lower crystallinity, higher pore volume and stronger acidity compared to using impregnation method. Moreover, it was found that raising the hydrothermal temperature increased the crystallinity and enhanced more uniform incorporation of Ni atoms in the crystalline structure of catalysts. TPD-NH3 analysis demonstrated that high crystallization temperature and short crystallization time of NiZSM-5(350-0.5) resulted in fewer weak acid sites and medium acid strength. The MTO catalytic performance was tested in a fixed bed reactor at 460ºC and GHSV=10500 cm3 /gcat.h. A slightly different reaction pathway was proposed for the production of light olefins over impregnated Ni/ZSM-5 catalysts based on the role of NiO species. The enhanced methanol conversion for isomorphous substituted NiZSM-5 catalysts could be related to the most accessible active sites located inside the pores. Conclusion: The impregnated Ni/ZSM-5 catalyst prepared at low hydrothermal temperature showed the best catalytic performance, while the isomorphous substituted NiZSM-5 prepared at high temperature was found to be the active molecular sieve regarding the stability performance.

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