| 1. |
- Bjerregaard, Joachim, 1996, et al.
(författare)
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Interpretation of H 2 -TPR from Cu-CHA Using First-Principles Calculations
- 2024
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Ingår i: Journal of Physical Chemistry C. - 1932-7447 .- 1932-7455. ; 128:11, s. 4525-4534
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Tidskriftsartikel (refereegranskat)abstract
- Temperature-programmed reduction and oxidation are used to obtain information on the presence and abundance of different species in complex catalytic materials. The interpretation of the temperature-programmed reaction profiles is, however, often challenging. One example is H2 temperature-programmed reduction (H2-TPR) of Cu-chabazite (Cu-CHA), which is a material used for ammonia assisted selective catalytic reduction of NOx (NH3-SCR). The TPR profiles of Cu-CHA consist generally of three main peaks. A peak at 220 °C is commonly assigned to ZCuOH, whereas peaks at 360 and 500 °C generally are assigned to Z2Cu, where Z represents an Al site. Here, we analyze H2-TPR over Cu-CHA by density functional theory calculations, microkinetic modeling, and TPR measurements of samples pretreated to have a dominant Cu species. We find that H2 can react with Cu ions in oxidation state +2, whereas adsorption on Cu ions in +1 is endothermic. Kinetic modeling of the TPR profiles suggests that the 220 °C peak can be assigned to Z2CuOCu and ZCuOH, whereas the peaks at higher temperatures can be assigned to paired Z2Cu and Z2CuHOOHCu species (360 °C) or paired Z2Cu and Z2CuOOCu (500 °C). The results are in good agreement with the experiments and facilitate the interpretation of future TPR experiments.
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| 2. |
- Chaoquan, Hu, 1981, et al.
(författare)
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Catalytic hydrogenation of C=C and C=O in unsaturated fatty acid methyl esters
- 2014
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Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 4:8, s. 2427-2444
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Forskningsöversikt (refereegranskat)abstract
- Biodiesel derived from edible and non-edible oils has received much attention as a chemical feedstock or as a raw fuel alternative to the traditional diesel due to its renewability and biodegradability. However, the crude biodiesel containing large amounts of polyunsaturated fatty acid methyl esters (FAMEs) is susceptible to oxidation upon exposure to heat, light, and oxygen. Catalytic hydro-genation of biodiesel has been considered as a feasible and powerful technique to improve the oxidative stability of biodiesel and hence to provide stable raw materials for industrial applications. The catalytic hydrogenation of FAMEs is a complex process but basically consists of hydrogenation of C=C or C=O, depending on the desirable properties of final products. In this review, we summarize recent developments in hydrogenation of C=C and C=O in FAMEs with focus on catalysts, reaction mechanisms, and reactor conditions. The features of hydrogenation of FAMEs are generalized and the opportunities for future research in the field are outlined.
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| 3. |
- Chaoquan, Hu, 1981, et al.
(författare)
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Methyl crotonate hydrogenation over Pt: Effects of support and metal dispersion
- 2016
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Ingår i: Applied Catalysis A: General. - : Elsevier BV. - 1873-3875 .- 0926-860X. ; 511, s. 106-116
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Tidskriftsartikel (refereegranskat)abstract
- Gas-phase hydrogenation of methyl crotonate (MC) has been studied over Pt supported on Al2O3, C, SiO2,and TiO2. The physicochemical properties of the catalysts were characterized by use of N2 physisorption,transmission electron microscopy and CO chemisorption. The effects of Pt dispersion and nature of the support on the catalytic properties of the catalysts were determined by measurements of the kinetic parameters for MC hydrogenation. The results clearly display MC inhibition effects on the hydrogenation over the catalysts. However, the degree of MC-inhibition is found to depend on both the Pt dispersion and the support used. For alumina a high Pt dispersion can promote the resistance of the catalyst against MC-inhibition, and even allow hydrogen adsorption to become equilibrated on the Pt surface. Compared to SiO2 and C supports, Al2O3 improves the resistance of the Pt surface against MC inhibition, whereas TiO2reduces the resistance. Possible reasons are suggested to understand the positive effect of Al2O3 on Pt against MC inhibition.
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| 4. |
- Chaoquan, Hu, 1981, et al.
(författare)
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Selectivity and kinetics of methyl crotonate hydrogenation over Pt/Al2O3
- 2015
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Ingår i: Catalysis Science and Technology. - 2044-4753 .- 2044-4761. ; 5:3, s. 1716-1730
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Tidskriftsartikel (refereegranskat)abstract
- The hydrogenation of gas-phase methyl crotonate (MC) over Pt/Al2O3 was investigated with the aim to understand C=C hydrogenation in unsaturated methyl esters. Three Pt/Al2O3 catalysts with different Pt dispersions were prepared by varying calcination temperature and evaluated for MC hydrogenation. The main products were found to be methyl butyrate (MB) and methyl 3-butenoate (M3B), resulting from hydrogenation and shift of the C=C bond in MC, respectively. The measured activity for both hydrogenation and shift of the C=C in MC was found to depend on the Pt dispersion where higher Pt dispersion favors the C=C hydrogenation reaction. The effect of reactant concentrations on the activity and selectivity for MC hydrogenation over the Pt/Al2O3 catalyst was examined in detail. Under the investigated conditions, the C=C hydrogenation was found to have a negative reaction order with respect to MC concentration but a positive H2 order. Further understanding of the MC hydrogenation was provided from H2 chemisorption experiments over the catalyst with and without pre-adsorbed MC and from transient experiments using alternating MC and H2 feeds. Based on the present experimental results, a reaction pathway was proposed to describe gas-phase MC hydrogenation over Pt/Al2O3. In order to gain more insight into the reaction, a kinetic analysis of MC hydrogenation was performed by fitting a power-law model to the kinetic data, moreover, dissociative H2 adsorption on the catalyst was found to be the rate-determining step by comparing the power-law model with the overall rate expressions derived from mechanistic considerations.
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| 5. |
- Eliasson, Henrik, et al.
(författare)
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Support-facet-dependent morphology of small Pt particles on ceria
- 2023
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Ingår i: Nanoscale. - 2040-3372 .- 2040-3364. ; 15:47, s. 19091-19098
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Tidskriftsartikel (refereegranskat)abstract
- Direct atomic scale information on how the structure of supported nanoparticles is affected by the metal-support interaction is rare. Using scanning transmission electron microscopy, we provide direct evidence of a facet-dependent support interaction for Pt nanoparticles on CeO2, governing the dimensionality of small platinum particles. Our findings indicate that particles consisting of less than ∼130 atoms prefer a 3D shape on CeO2(111) facets, while 2D raft structures are favored on CeO2(100) facets. Measurements of stationary particles on both surface facets are supplemented by time resolved measurements following a single particle with atomic resolution as it migrates from CeO2(111) to CeO2(100), undergoing a dimensionality change from 3D to 2D. The intricate transformation mechanism reveals how the 3D particle disassembles and completely wets a neighboring CeO2(100) facet. Density functional theory calculations confirm the structure-trend and reveal the thermodynamic driving force for the migration of small particles. Knowledge of the presented metal-support interactions is crucial to establish structure-function relationships in a range of applications based on supported nanostructures.
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| 6. |
- Engedahl, Unni, 1990, et al.
(författare)
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Complete Reaction Cycle for Methane-to-Methanol Conversion over Cu-SSZ-13: First-Principles Calculations and Microkinetic Modeling
- 2021
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:27, s. 14681-14688
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Tidskriftsartikel (refereegranskat)abstract
- The steadily increasing consumption of natural gas imposes a need to facilitate the handling and distribution of the fuel, which presently is compressed or condensed. Alternatively, reduced volatility and increased tractability are achieved by converting the chemical energy of the main component, methane, into liquid methanol. Previous studies have explored direct methane-to-methanol conversion, but suitable catalysts have not yet been identified. Here, the complete reaction cycle for methane-to-methanol conversion over the Cu-SSZ-13 system is studied using density functional theory. The first step in the reaction cycle is the migration of Cu species along the zeolite framework forming the Cu pair, which is necessary for the adsorption of O2. Methane conversion occurs over the CuOOCu and CuOCu sites, consecutively, after which the system is returned to its initial structure with two separate Cu ions. A density functional theory-based kinetic model shows high activity when water is included in the reaction mechanism, for example, even at very low partial pressures of water, the kinetic model results in a turnover frequency of ∼1 at 450 K. The apparent activation energy from the kinetic model (∼1.1 eV) is close to recent measurements. However, experimental studies always observe very small amounts of methanol compared to formation of more energetically preferred products, for example, CO2. This low selectivity to methanol is not described by the current reaction mechanism as it does not consider formation of other species; however, the results suggest that selectivity, rather than inherent kinetic limitations, is an important target for improving methanol yields from humid systems. Moreover, a closed reaction cycle for the partial oxidation of methane has long been sought, and in achieving this over the Cu-SSZ-13, this study contributes one more step toward identifying a suitable catalyst for direct methane-to-methanol conversion.
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| 7. |
- Engedahl, Unni, 1990, et al.
(författare)
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Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion
- 2024
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Ingår i: Journal of Physical Chemistry C. - 1932-7447 .- 1932-7455. ; 128:9, s. 3641-3651
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Tidskriftsartikel (refereegranskat)abstract
- Methanol is a liquid energy carrier that has the potential to reduce the use of fossil fuels. Industrial production of methanol is currently a multistep high-temperature/high-pressure synthesis route. Direct conversion of methane to methanol under low-temperature and low-pressure conditions is an interesting but challenging alternative, which presently lacks suitable catalysts. Here, the complete reaction cycle for direct methane-to-methanol conversion over transition-metal dimers in the chabazite zeolite is studied by using density functional theory calculations and microkinetic modeling. In particular, a reaction mechanism previously identified for the Cu2 dimer is explored under dry and wet conditions for dimers composed of Ag, Au, Pd, Ni, Co, Fe, and Zn and the bimetallic dimers AuCu, PdCu, and AuPd. The density-functional-theory-based microkinetic modeling shows that Cu2, AuPd, and PdCu dimers have reasonable turnover frequencies under technologically relevant conditions. The adsorption energy of atomic oxygen is identified as a descriptor for the reaction landscape as it correlates with the adsorption and transition-state energies of the other reaction intermediates. Using the established scaling relations, a volcano plot of the rate is generated with its apex close to the Cu2, AuPd, and PdCu dimers.
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| 8. |
- Feng, Yingxin, 1994, et al.
(författare)
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Simplified Kinetic Model for NH3‑SCR Over Cu‑CHA Based on First‑Principles Calculations
- 2023
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Ingår i: Topics in Catalysis. - : Springer Science and Business Media LLC. - 1572-9028 .- 1022-5528. ; 66:13-14, s. 743-749
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Tidskriftsartikel (refereegranskat)abstract
- Selective catalytic reduction with ammonia as reducing agent (NH3-SCR) is an efficient technology to control NOx emission during oxygen excess. Catalysts based on Cu-chabazite (Cu-CHA) have shown good performance for NH3-SCR with high activity and selectivity at low temperature and good hydrothermal stability. Here, we explore a first-principles based kinetic model to analyze in detail which reaction steps that control the selectivity for N2 and the light-off temperature. Moreover, a simplified kinetic model is developed by fitting lumped kinetic parameters to the full model. The simplified model describes the reaction with high accuracy using only five reaction steps. The present work provides insight into the governing reaction mechanism and stimulates design of knowledge-based Cu-CHA catalysts for NH3-SCR.
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| 9. |
- Florén, Carl-Robert, 1988, et al.
(författare)
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Modelling complete methane oxidation over palladium oxide in a porous catalyst using first-principles surface kinetics
- 2018
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Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 8:2, s. 508-520
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Tidskriftsartikel (refereegranskat)abstract
- A comprehensive model is developed for complete methane oxidation over supported palladium. The model is based on first-principles microkinetics and accounts for mass and heat transport in a porous catalytic layer. The turnover frequency (TOF) is simulated for wet exhaust gas compositions, exploring the effects of temperature and total pressure on the TOF. Three different temperature regimes are identified each with different dependency on the total pressure. The regimes originate from temperature and pressure dependent coverages of carbon dioxide and water, which are the most abundant surface species hindering methane dissociation at low temperatures. The TOF is controlled by surface kinetics below 400 °C whereas above 500 °C and up to 8 atm, internal mass transport is controlling. A combination of kinetics, external and internal mass transport controls the TOF at other reaction conditions. The physically meaningful model paves the way for extrapolation and optimization of catalyst design parameters for high catalytic efficiency.
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| 10. |
- Florén, Carl-Robert, 1988, et al.
(författare)
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Multiscale reactor modelling of total pressure effects on complete methane oxidation over Pd/Al2O3
- 2019
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Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 9:12, s. 3055-3065
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Tidskriftsartikel (refereegranskat)abstract
- A two-dimensional multiscale model is developed for complete methane oxidation in a continuous flow reactor. The model considers mass and heat transfer for a porous alumina supported palladium catalyst coated on a ceramic monolith substrate and the surface kinetics are described by a first-principles microkinetic model for complete methane oxidation over PdO(101). The temperature dependent conversion for a synthetic exhaust gas composition shows a delayed ignition but a higher conversion at elevated temperatures when the total pressure is increased from 1 to 10 atm. The simulations reveal a temperature and total pressure dependent operating point where the methane conversion is maximized. Analysis of the kinetics shows that the reaction is suppressed by bicarbonates, hydroxyl species and water originating from adsorbed carbon dioxide and water from the gas phase. The reaction order with respect to water and carbon dioxide at 1 atm is -0.94 and -0.99, respectively, and decreases with increasing total pressure. The developed model paves the way for exploring how design parameters and reaction conditions influence the complete methane oxidation reaction.
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