Onset of High Methane Combustion Rates over Supported Palladium Catalysts: From Isolated Pd Cations to PdO Nanoparticles.
ABSTRACT: Industrial low-temperature methane combustion catalyst Pd/Al2O3 suffers from H2O-induced deactivation. It is imperative to design Pd catalysts free from this deactivation and with high atomic efficiency. Using a small-pore zeolite SSZ-13 as support, herein we report well-defined Pd catalysts with dominant active species as finely dispersed Pd cations, uniform PdO particles embedded inside the zeolite framework, or PdO particles decorating the zeolite external surface. Through detailed reaction kinetics and spectroscopic and microscopic studies, we show that finely dispersed sites are much less active than PdO nanoparticles. We further demonstrate that H2O-induced deactivation can be readily circumvented by using zeolite supports with high Si/Al ratios. Finally, we provide a few rational catalyst design suggestions for methane oxidation based on the new knowledge learned in this study.
Project description:Poor low-temperature catalytic activity and durability are the main drawbacks of palladium-based catalysts for methane combustion. Herein, stable and active PdO particles are constructed by incorporating Ti into an alumina support, which makes the catalysts exhibit satisfactory methane combustion activity. The results of comprehensive characterization reveal that an appropriate amount of Ti doping induces the optimization of electron transfer and distribution, thus contributing to the construction and stabilization of active PdO lattices. The reactive oxygen mobility is improved and the optimal PdO/Pd<sup>0</sup> combination is achieved, thanks to the amplified PdO-support interaction. In addition, the acid-base properties are regulated and Brønsted acid sites are generated by virtue of the adjustment of electronic properties, which facilitate stabilization of PdO as well. Hence, the Ti-containing catalyst exhibits superior activity for methane oxidation at low temperatures. Notably, the activity and cyclic performance of the catalyst can be further enhanced when undergoing long-term and isothermal heat treatment under the reactant stream and methane, and it demonstrates a high performance with 90% CH<sub>4</sub> conversion at 340 °C.
Project description:Making use of synergy between urea and citric acid, a core-shell Pd@CeO<sub>2</sub> catalyst with spherical morphology was facilely synthesized by a hydrothermal method. The formation mechanism of the core-shell structure in the presence of citric acid and hydrogen peroxide was studied. Results showed that the Pd@CeO<sub>2</sub> catalyst exhibited high catalytic activity in methane oxidation. Pd nanoparticles were well stabilized by CeO<sub>2</sub> shell encapsulation, resulting in high stability of the catalyst. A high CH<sub>4</sub> conversion of 99% was retained after 50 h on-stream reaction at 500 °C. Additionally, many tiny pores on the CeO<sub>2</sub> shell surface were beneficial for the full contact between reactants and active components. Pd nanoparticles were highly dispersed inside the shell, improving the utilization efficiency of active components. The results also demonstrated that the Pd species in the catalyst existed in the form of oxidation state, mainly in PdO (ca. 66.6%), which played an essential part in methane combustion.
Project description:The transition metal-based catalysts for the elimination of greenhouse gases via methane reforming using carbon dioxide are directly or indirectly associated with their distinguishing characteristics such as well-dispersed metal nanoparticles, a higher number of reducible species, suitable metal-support interaction, and high specific surface area. This work presents the insight into catalytic performance as well as catalyst stability of Ce<sub>x</sub>Sr<sub>1-x</sub>NiO<sub>3</sub> (x = 0.6-1) nanocrystalline perovskites for the production of hydrogen via methane reforming using carbon dioxide. Strontium incorporation enhances specific surface area, the number of reducible species, and nickel dispersion. The catalytic performance results show that CeNiO<sub>3</sub> demonstrated higher initial CH<sub>4</sub> (54.3%) and CO<sub>2</sub> (64.8%) conversions, which dropped down to 13.1 and 19.2% (CH<sub>4</sub> conversions) and 26.3 and 32.5% (CO<sub>2</sub> conversions) for Ce<sub>0.8</sub>Sr<sub>0.2</sub>NiO<sub>3</sub> and Ce<sub>0.6</sub>Sr<sub>0.4</sub>NiO<sub>3</sub>, respectively. This drop in catalytic conversions post strontium addition is concomitant with strontium carbonate covering nickel active sites. Moreover, from the durability results, it is obvious that CeNiO<sub>3</sub> exhibited deactivation, whereas no deactivation was observed for Ce<sub>0.8</sub>Sr<sub>0.2</sub>NiO<sub>3</sub> and Ce<sub>0.6</sub>Sr<sub>0.4</sub>NiO<sub>3</sub>. Carbon deposition during the reaction is mainly responsible for catalyst deactivation, and this is further established by characterizing spent catalysts.
Project description:Increasing the use of natural gas engines is an important step to reduce the carbon footprint of mobility and power generation sectors. To avoid emissions of unburnt methane and the associated severe greenhouse effect of lean-burn engines, the stability of methane oxidation catalysts against steam-induced sintering at low temperatures (<500?°C) needs to be improved. Here we demonstrate how the combination of catalyst development and improved process control yields a highly efficient solution for complete methane oxidation. We design a material based on palladium and hierarchical zeolite with fully sodium-exchanged acid sites, which improves the support stability and prevents steam-induced palladium sintering under reaction conditions by confining the metal within the zeolite. Repeated short reducing pulses enable the use of a highly active transient state of the catalyst, which in combination with its high stability provides excellent performance without deactivation for over 90?h in the presence of steam.
Project description:Non-oxidative dehydroaromatization of methane (MDA) is a promising catalytic process for direct valorization of natural gas to liquid hydrocarbons. The application of this reaction in practical technology is hindered by a lack of understanding about the mechanism and nature of the active sites in benchmark zeolite-based Mo/ZSM-5 catalysts, which precludes the solution of problems such as rapid catalyst deactivation. By applying spectroscopy and microscopy, it is shown that the active centers in Mo/ZSM-5 are partially reduced single-atom Mo sites stabilized by the zeolite framework. By combining a pulse reaction technique with isotope labeling of methane, MDA is shown to be governed by a hydrocarbon pool mechanism in which benzene is derived from secondary reactions of confined polyaromatic carbon species with the initial products of methane activation.
Project description:Sheaf-like CeO2 (CeO2-S) in microscale was prepared by the hydrothermal method, and then etched with KOH aiming to obtain an imperfect fluorite structure (CeO2-SK) with high content of oxygen vacancies and oxygen mobility. With CeO2-S and CeO2-SK as supports respectively, a modified colloidal deposition method was employed to obtain Pd/CeO2 catalysts for being used in lean methane combustion. According to the inductively coupled plasma (ICP), N2 physisorption and scanning electron microscopy (SEM) results, the Pd supported catalysts are very similar in their Pd loading, surface area and morphologies. SEM and transmission electron microscopy (TEM) results revealed various nanorods exposed CeO2 (110) and (100) facets on Pd/CeO2-SK surface after KOH etching. Raman spectra and H2-temperature programmed reduction (H2-TPR) results indicated that Pd/CeO2-SK catalyst has a much higher content of catalytic active PdO species than Pd/CeO2-S catalyst. It was also found that the catalytic performance of Pd/CeO2 in lean methane combustion depends greatly upon the exposing crystal planes and oxygen vacancies content of sheaf-like CeO2, and Pd/CeO2-SK exhibits higher activity than Pd/CeO2-S. The larger amount of CeO2 (110) and (100) planes on Pd/CeO2-SK surface can enhance the formation of oxygen vacancies, active Pd species and migration of lattice oxygen, which all evidently improve the redox ability and catalytic activity of the Pd/CeO2-SK catalysts in lean methane combustion.
Project description:As one of the most important gases that abundantly contribute to air pollution, methane becomes the most leading gas that challenges researchers to utilize it in more functional products such as methanol. In this study, the conversion process involved iron oxide species supported by sodium Y (NaY-Z) zeolite as the catalysts. This work highlighted the preparation of Fe<sub>2</sub>O<sub>3</sub> and Fe<sub>3</sub>O<sub>4</sub> modified NaY zeolite to investigate their catalytic performance on partial oxidation of methane to methanol, with trace amount of oxygen (0.5% in N<sub>2</sub>), in a batch reactor. The as-prepared catalysts were characterized using FTIR, XRD, SEM, and BET. The structure of NaY zeolite and its modified catalysts were confirmed. The pristine NaY-Z shows the highest activity followed by Fe<sub>2</sub>O<sub>3</sub>/NaY-3.52 (3.52 wt% of Fe loading) with high selectivity to formaldehyde (80%). Very high selectivity (∼100%) towards methanol was observed in the reactions on Fe<sub>2</sub>O<sub>3</sub>/NaY-1.70 and Fe<sub>3</sub>O<sub>4</sub>/NaY-2.55 catalysts, although the total amount of product was decreased. It was noticeable that Fe<sub>3</sub>O<sub>4</sub>/NaY-3.22 is an active catalyst and has good selectivity to methanol (70%).
Project description:Mono- and bimetallic Ni-, Ru- and Pt-modified hierarchical ZSM-5 materials were prepared by impregnation technique and characterized by X-ray diffraction (XRD), N<sub>2</sub> physisorption, temperature-programmed reduction (TPR-TGA), ATR-FTIR and solid state NMR spectroscopy. Formation of finely dispersed nickel, ruthenium and platinum species was observed on the bimetallic catalysts. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides and their dispersion and reducibility. The samples' acidity was studied via FTIR spectroscopy of adsorbed pyridine. The changes in the zeolite structure were studied via solid-state NMR spectroscopy. The catalysts were investigated in a gas-phase hydrodeoxygenation, transalkylation and dealkylation reaction of model lignin derivative molecules for phenol production.
Project description:Non-oxidative dehydroaromatization of methane over Mo/ZSM-5 zeolite catalysts is a promising reaction for the direct conversion of abundant natural gas into liquid aromatics. Rapid coking deactivation hinders the practical implementation of this technology. Herein, we show that catalyst productivity can be improved by nearly an order of magnitude by raising the reaction pressure to 15?bar. The beneficial effect of pressure was found for different Mo/ZSM-5 catalysts and a wide range of reaction temperatures and space velocities. High-pressure operando X-ray absorption spectroscopy demonstrated that the structure of the active Mo-phase was not affected by operation at elevated pressure. Isotope labeling experiments, supported by mass-spectrometry and <sup>13</sup> C nuclear magnetic resonance spectroscopy, indicated the reversible nature of coke formation. The improved performance can be attributed to faster coke hydrogenation at increased pressure, overall resulting in a lower coke selectivity and better utilization of the zeolite micropore space.
Project description:Bimetallic Pt-Pd catalysts supported on ceria have been prepared by mechanochemical synthesis and tested for lean methane oxidation in dry and wet atmosphere. Results show that the addition of platinum has a negative effect on transient light-off activity, but for Pd/Pt molar ratios between 1:1 and 8:1 an improvement during time-on-stream experiments in wet conditions is observed. The bimetallic samples undergo a complex restructuring during operation, starting from the alloying of Pt and Pd and resulting in the formation of unprecedented "mushroom-like" structures consisting of PdO bases with Pt heads as revealed by high-resolution transmission electron microscopy (HRTEM) analysis. On milled samples, these structures are well-defined and observed at the interface between palladium and ceria, whereas those on the impregnated catalyst appear less ordered and are located randomly on the surface of ceria and of large PdPt clusters. The milled catalyst prepared by first milling Pd metal and ceria followed by the addition of Pt shows better performances compared to a conventional impregnated sample and also to a sample obtained by inverting the Pd-Pt milling order. This has been ascribed to the intimate contact between Pd and CeO<sub>2</sub> generated at the nanoscale during the milling process.