Influence of NiO into the CO2 capture of Li4SiO4 and its catalytic performance on dry reforming of methane
Ontology highlight
ABSTRACT:
SUBMITTER: Gonzalez A
PROVIDER: S-EPMC10830542 | biostudies-literature | 2024 Jan
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Natural gas is a robust and environmentally friendlier alternative to oil resources for energy and chemicals production. However, gas is distributed globally within shales and hydrates, which are generally remote and difficult reserves to produce. The accessibility, transportation, and distribution, therefore, bring major capital costs. With today's low and foreseen low price of natural gas, conversion of natural gas to higher value-added chemicals is highly sought by industry. Dry reforming of methane (DRM) is a technology pathway to convert two critical greenhouse gas components, CH4 and CO2, to syngas, a commodity chemical feedstock. To date, the challenges of carbon deposition on the catalyst and evolution of secondary gas-phase products have prevented the commercial application of the DRM process. The recent exponential growth of renewable electricity resources, wind and solar power, provides a major opportunity to activate reactions by harnessing low-cost carbon-free energy via microwave-heating. This study takes advantage of differences in dielectric properties of materials to enable selective heating by microwave to create a large thermal gradient between a catalyst surface and the gas phase. Consequently, the reaction kinetics at the higher temperature catalyst surface are promoted while the reactions of lower temperature secondary gas-phase are reduced.
| S-EPMC5997706 | biostudies-literature
Project description:Three morphology-controlled CeO₂, namely nanorods (NRs), nanocubes (NCs), and nanopolyhedra (NPs), with different mainly exposed crystal facets of (110), (100), and (111), respectively, have been used as supports to prepare Ru (3 wt.%) nanoparticle-loaded catalysts. The catalysts were characterized by H₂-temperature programmed reduction (H₂-TPR), CO⁻ temperature programmed desorption (CO-TPD), N₂ adsorption⁻desorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (XDS). The characterization results showed that CeO₂-NRs, CeO₂-NCs, and CeO₂-NPs mainly expose (110), (100) and (111) facets, respectively. Moreover, CeO₂-NRs and CeO₂-NCs present higher oxygen vacancy concentration than CeO₂-NPs. In the CO₂ reforming of methane reaction, Ru/CeO₂-NR and Ru/CeO₂-NC catalysts showed better catalytic performance than Ru/CeO₂-NPs, indicating that the catalysts with high oxygen vacancy concentration are beneficial for promoting catalytic activity.
| S-EPMC6385116 | biostudies-literature
Project description:The thermal carburization of MoO3 nanobelts (nb) and SiO2-supported MoO3 nanosheets under a 1 : 4 mixture of CH4 : H2 yields Mo2C-nb and Mo2C/SiO2. Following this process by in situ Mo K-edge X-ray absorption spectroscopy (XAS) reveals different carburization pathways for unsupported and supported MoO3. In particular, the carburization of α-MoO3-nb proceeds via MoO2, and that of MoO3/SiO2 via the formation of highly dispersed MoO x species. Both Mo2C-nb and Mo2C/SiO2 catalyze the dry reforming of methane (DRM, 800 °C, 8 bar) but their catalytic stability differs. Mo2C-nb shows a stable performance when using a CH4-rich feed (CH4 : CO2 = 4 : 2), however deactivation due to the formation of MoO2 occurs for higher CO2 concentrations (CH4 : CO2 = 4 : 3). In contrast, Mo2C/SiO2 is notably more stable than Mo2C-nb under the CH4 : CO2 = 4 : 3 feed. The influence of the morphology of Mo2C and its dispersion on silica on the structural evolution of the catalysts under DRM is further studied by in situ Mo K-edge XAS. It is found that Mo2C/SiO2 features a higher resistance to oxidation under DRM than the highly crystalline unsupported Mo2C-nb and this correlates with an improved catalytic stability. Lastly, the oxidation of Mo in both Mo2C-nb and Mo2C/SiO2 under DRM conditions in the in situ XAS experiments leads to an increased activity of the competing reverse water gas shift reaction.
| S-EPMC9486824 | biostudies-literature
Project description:The two-dimensional morphology of molybdenum oxycarbide (2D-Mo2COx) nanosheets dispersed on silica is found vital for imparting high stability and catalytic activity in the dry reforming of methane. Here we report that owing to the maximized metal utilization, the specific activity of 2D-Mo2COx/SiO2 exceeds that of other Mo2C catalysts by ca. 3 orders of magnitude. 2D-Mo2COx is activated by CO2, yielding a surface oxygen coverage that is optimal for its catalytic performance and a Mo oxidation state of ca. +4. According to ab initio calculations, the DRM proceeds on Mo sites of the oxycarbide nanosheet with an oxygen coverage of 0.67 monolayer. Methane activation is the rate-limiting step, while the activation of CO2 and the C-O coupling to form CO are low energy steps. The deactivation of 2D-Mo2COx/SiO2 under DRM conditions can be avoided by tuning the contact time, thereby preventing unfavourable oxygen surface coverages.
| S-EPMC7532431 | biostudies-literature
Project description:The influence of A- and/or B-site doping of Ruddlesden-Popper perovskite materials on the crystal structure, stability, and dry reforming of methane (DRM) reactivity of specific A2BO4 phases (A = La, Ba; B = Cu, Ni) has been evaluated by a combination of catalytic experiments, in situ X-ray diffraction, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and aberration-corrected electron microscopy. At room temperature, B-site doping of La2NiO4 with Cu stabilizes the orthorhombic structure (Fmmm) of the perovskite, while A-site doping with Ba yields a tetragonal space group (I4/mmm). We observed the orthorhombic-to-tetragonal transformation above 170 °C for La2Ni0.9Cu0.1O4 and La2Ni0.8Cu0.2O4, slightly higher than for undoped La2NiO4. Loss of oxygen in interstitial sites of the tetragonal structure causes further structure transformations for all samples before decomposition in the temperature range of 400 °C-600 °C. Controlled in situ decomposition of the parent or A/B-site doped perovskite structures in a DRM mixture (CH4:CO2 = 1:1) in all cases yields an active phase consisting of exsolved nanocrystalline metallic Ni particles in contact with hexagonal La2O3 and a mixture of (oxy)carbonate phases (hexagonal and monoclinic La2O2CO3, BaCO3). Differences in the catalytic activity evolve because of (i) the in situ formation of Ni-Cu alloy phases (in a composition of >7:1 = Ni:Cu) for La2Ni0.9Cu0.1O4, La2Ni0.8Cu0.2O4, and La1.8Ba0.2Ni0.9Cu0.1O4, (ii) the resulting Ni particle size and amount of exsolved Ni, and (iii) the inherently different reactivity of the present (oxy)carbonate species. Based on the onset temperature of catalytic DRM activity, the latter decreases in the order of La2Ni0.9Cu0.1O4 ∼ La2Ni0.8Cu0.2O4 ≥ La1.8Ba0.2Ni0.9Cu0.1O4 > La2NiO4 > La1.8Ba0.2NiO4. Simple A-site doped La1.8Ba0.2NiO4 is essentially DRM inactive. The Ni particle size can be efficiently influenced by introducing Ba into the A site of the respective Ruddlesden-Popper structures, allowing us to control the Ni particle size between 10 nm and 30 nm both for simple B-site and A-site doped structures. Hence, it is possible to steer both the extent of the metal-oxide-(oxy)carbonate interface and its chemical composition and reactivity. Counteracting the limitation of the larger Ni particle size, the activity can, however, be improved by additional Cu-doping on the B-site, enhancing the carbon reactivity. Exemplified for the La2NiO4 based systems, we show how the delicate antagonistic balance of doping with Cu (rendering the La2NiO4 structure less stable and suppressing coking by efficiently removing surface carbon) and Ba (rendering the La2NiO4 structure more stable and forming unreactive surface or interfacial carbonates) can be used to tailor prospective DRM-active catalysts.
| S-EPMC7783868 | biostudies-literature
Project description:Dry reforming of methane can be used for suppressing the rapid growth of greenhouse gas emissions. However, its practical implementation generally requires high temperatures. In this study, we report an optimal catalyst for low-temperature dry reforming of methane with high carbon coking resistance synthesized from NiYAl alloy. A facile two-step process consisting of preferential oxidation and leaching was utilized to produce structurally robust nanoporous Ni metal and Y oxides from NiYAl4. The catalyst exhibited an optimal carbon balance (0.96) close to the ideal value of 1.0, indicating the optimized dry reforming pathway. This work proposes a facile route of the structural control of active metal/oxide sites for realizing highly active catalysts with long-term durability.
| S-EPMC7254345 | biostudies-literature
Project description:In order to clarify the role of R2O3 in the metal-oxide catalysts derived from complex oxide precursors, a series of R1.5Ca0.5NiO4 (R = Nd, Sm, Eu) complex oxides was obtained. A significant systematic increase in the orthorhombic distortion of the R1.5Ca0.5NiO4 structure (K2NiF4 type, Cmce) from Nd to Eu correlates with a corresponding decrease in their ionic radii. A reduction of R1.5Ca0.5NiO4 in the Ar/H2 gas mixture at 800 °C causes a formation of dense agglomerates of CaO and R2O3 coated with spherical 25-30 nm particles of Ni metal. The size of metal particles and oxide agglomerates is similar in all Ni/(R2O3,CaO) composites in the study. Their morphology is rather similar to the products of redox exsolution obtained by the partial reduction of complex oxides. All obtained composites demonstrated a significant catalytic activity in the dry reforming (DRM) and partial oxidation (POM) of methane at 700-800 °C. A systematic decrease in the DRM catalytic activity of composites from Nd to Eu could be attributed to the basicity reduction of R2O3 components of the composite catalysts. The maximum CH4 conversion in POM reaction was observed for Ni/(Sm2O3,CaO), while the maximum selectivity was demonstrated by Nd2O3-based composite. The possible reasons for the observed difference are discussed.
| S-EPMC9610205 | biostudies-literature
Project description:Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H2 and CO (syngas). CeO2 nanorods, nanocubes, and nanospheres were decorated with 1-4 wt % Ni. The materials were structurally characterized using TEM and in situ XANES/EXAFS. The CO2 activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO2 morphologies expose {111} and {100} terminating facets, varying the strength of the CO2 interaction and redox properties, which influence the CO2 activation. Temperature-programmed CO2 DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to H2O and CO. In excess hydrogen, methane is the preferred reaction product. The CeO2 cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria's surface, resulting in less-abundant surface sites for CO2 dissociation.
| S-EPMC9305712 | biostudies-literature
Project description:Single-atom catalysts often show exceptionally high performance per metal loading. However, the isolated atom sites tend to agglomerate during preparation and/or high-temperature reaction. Here we show that in the case of Rh/Al2O3 this deactivation can be prevented by dissolution/exsolution of metal atoms into/from the support. We design and synthesise a series of single-atom catalysts, characterise them and study the impact of exsolution in the dry reforming of methane at 700-900 °C. The catalysts' performance increases with increasing reaction time, as the rhodium atoms migrate from the subsurface to the surface. Although the oxidation state of rhodium changes from Rh(iii) to Rh(ii) or Rh(0) during catalysis, atom migration is the main factor affecting catalyst performance. The implications of these results for preparing real-life catalysts are discussed.
| S-EPMC10069472 | biostudies-literature
Project description:In a novel process, CO2 and CH4 from the off-gases of the coke oven and blast furnace are used in homogeneous reforming of those greenhouse gases to valuable syngas, a mixture of H2 and CO. Synthetic mixtures of the off-gases from those large apparatuses of steel industry are fed to a high-temperature, high-pressure flow reactor at varying temperature, pressure, residence time, and mixing ratio of coke oven gas (COG) to blast furnace gas (BFG). In this study, a maximal reduction of 78.5 % CO2 and a CH4 conversion of 95 % could be achieved at 1350 °C, 5.5 bar, and a COG/BFG ratio of 0.6. Significant carbonaceous deposits were formed but did not block the reactor tube in the operational time window allowing cyclic operation of the process. These measurements were based on prior thermodynamic analysis and kinetic predictions using an elementary-step reaction mechanism.
| S-EPMC8251717 | biostudies-literature