| 1. |
- 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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| 2. |
- 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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| 3. |
- 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
-
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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| 4. |
- Abb, Marcel J.S., et al.
(författare)
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Thermal Stability of Single-Crystalline IrO2(110) Layers : Spectroscopic and Adsorption Studies
- 2020
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 124:28, s. 15324-15336
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Tidskriftsartikel (refereegranskat)abstract
- The interaction of ultrathin single-crystalline IrO2(110) films with the gas phase proceeds via the coordinatively unsaturated sites (cus), in particular Ircus, the undercoordinated oxygen species on-top O (Oot) that are coordinated to Ircus, and bridging O (Obr). With the combination of different experimental techniques, such as thermal desorption spectroscopy, scanning tunneling microscopy (STM), high-resolution core-level spectroscopy (HRCLS), infrared spectroscopy, and first-principles studies employing density functional theory calculations, we are able to elucidate surface properties of single-crystalline IrO2(110). We provide spectroscopic fingerprints of the active surface sites of IrO2(110). The freshly prepared IrO2(110) surface is virtually inactive toward gas-phase molecules. The IrO2(110) surface needs to be activated by annealing to 500-600 K under ultrahigh vacuum (UHV) conditions. In the activation step, Ircus sites are liberated from on-top oxygen (Oot) and monoatomic Ir metal islands are formed on the surface, leading to the formation of a bifunctional model catalyst. Vacant Ircus sites of IrO2(110) allow for strong interaction and accommodation of molecules from the gas phase. For instance, CO can adsorb atop on Ircus and water forms a strongly bound water layer on the activated IrO2(110) surface. Single-crystalline IrO2(110) is thermally not very stable although chemically stable. Chemical reduction of IrO2(110) by extensive CO exposure at 473 K is not observed, which is in contrast to the prototypical RuO2(110) system.
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| 5. |
- Abdelgaid, Mona, et al.
(författare)
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Multiscale modeling reveals aluminum nitride as an efficient propane dehydrogenation catalyst
- 2023
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Ingår i: Catalysis Science and Technology. - 2044-4753 .- 2044-4761. ; 13:12, s. 3527-3536
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Tidskriftsartikel (refereegranskat)abstract
- Nonoxidative propane dehydrogenation (PDH) is a promising route to meet the steadily increasing demand for propylene, an important building block in the chemical industry. Wurtzite group-IIIA metal nitrides are potential catalysts for PDH with high chemical, thermal, and mechanical stability alongside inherent Lewis acid-base properties that can activate the C-H bond of alkanes. Herein, we investigate the catalytic behavior of pristine (AlN) and gallium-doped (Ga/AlN) aluminum nitride for PDH via concerted and various stepwise mechanisms using density functional theory (DFT) calculations and microkinetic modeling (MKM). The reaction profiles investigated with DFT calculations are used in MKM, which reveals that the stepwise mechanisms produce >99% of propylene on both AlN and Ga/AlN. AlN has approximately one order of magnitude higher activity than Ga/AlN due to lower barriers along the dominant PDH reaction pathway. In summary, we propose the potential application of AlN as an efficient dehydrogenation catalyst for the conversion of light alkanes into valuable olefins. In addition, we show that multiscale simulations are essential to evaluate the catalytic behavior of complex alkane conversion reaction networks and obtain activity trends for dehydrogenation catalysts.
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| 6. |
- Abrahamsson, Brita, 1989, et al.
(författare)
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NOx Adsorption on ATiO(3)(001) Perovskite Surfaces
- 2015
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:32, s. 18495-18503
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Tidskriftsartikel (refereegranskat)abstract
- Density functional theory calculations have been used to explore NO adsorption on perovskite oxides surfaces ATiO(3)(001) with A = Ca, Sr, Ba. NO adsorbs weakly on all facets with no apparent A-ion dependence, whereas NO2 adsorbs preferably over AO-terminated surfaces with adsorption energies that correlate with the ionization potentials of the alkaline earth atoms. Simultaneous adsorption of NO and NO2 is found to substantially enhance the stability of the adsorbates owing to an oxide mediated electron-pairing mechanism. Stabilization is also predicted for NO/O-2 adsorption, and it is suggested that the presence of oxygen favors the formation of nitrite/nitrate pairs. It is found that the NOx adsorption properties can be modified by mixing alkaline earth cations in the perovskite framework. The results are put in context by comparison with NOx adsorption on the corresponding (001) facets of alkaline earth metal oxides and TiO2(110).
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| 7. |
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| 8. |
- Akola, J., et al.
(författare)
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Thiolate-Protected Au-25 Superatoms as Building Blocks: Dimers and Crystals
- 2010
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 114:38, s. 15986-15994
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Tidskriftsartikel (refereegranskat)abstract
- A particularly stable thiolate-protected gold nanocluster, Au-25(SR)(18), was structurally characterized from X-ray crystallography in 2008, and concomitantly its electronic and optical properties were analyzed via density functional theory. The robust geometry and a well-understood electronic structure of this cluster motivate explorations of properties of extended systems made out of Au-25(SR)(18) building blocks. As a first step in this direction, we analyze here structural, vibrational, electronic, and optical properties of the Au-25 cluster anion as it was observed in the crystalline environment and predict properties of cluster dimers, where the Au-25 units are linked together. via an aromatic dithiolate linker. We show that properties of each Au-25 unit of the dimer can be quite independently modified from the other by doping with a nonmagnetic (Pd) or magnetic (Mn) metal atom. We anticipate that material systems with interesting properties could be made from these building blocks, provided that a suitable chemistry for their controlled linking can be found.
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| 9. |
- Arvidsson, Adam, 1990, et al.
(författare)
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Metal dimer sites in ZSM-5 zeolite for methane-to-methanol conversion from first-principles kinetic modelling: is the [Cu-O-Cu]2+ motif relevant for Ni, Co, Fe, Ag, and Au?
- 2017
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Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 7:7, s. 1470-1477
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Tidskriftsartikel (refereegranskat)abstract
- Direct methane-to-methanol conversion is a desired process whereby natural gas is transformed into an energy-rich liquid. It has been realised at ambient pressure and temperature in metal ion-exchanged zeolites, where especially copper-exchanged ZSM-5 has shown promising results. The nature of the active sites in these systems is, however, still under debate. The activity has been assigned to a [Cu-O-Cu]2+ motif. One remaining question is whether this motif is general and also active in other metal-exchanged zeolites. Herein, we use first-principles microkinetic modelling to analyse the methane-to-methanol reaction on the [Cu-O-Cu]2+ motif, for Cu and other metals. First, we identify the cluster model size needed to accurately describe the dimer motif. Starting from the [Cu-O-Cu]2+ site, the metal ions are then systematically substituted with Ni, Co, Fe, Ag and Au. The results show that activation of Ag and Au dimer sites with oxygen is endothermic and therefore unlikely, whereas for Cu, Ni, Co and Fe, the activation is possible under realistic conditions. According to the kinetic simulations, however, the dimer motif is a plausible candidate for the active site for Cu only. For Ni, Co and Fe, close-to-infinite reaction times or unreasonably high temperatures are required for sufficient methane conversion. As Ni-, Co- and Fe-exchanged ZSM-5 are known to convert methane to methanol, these results indicate that the Cu-based dimer motif is not an appropriate model system for these metals.
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| 10. |
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| 11. |
- Baran, Jakub, 1980, et al.
(författare)
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Analysis of Porphyrines as Catalysts for Electrochemical Reduction of O-2 and Oxidation of H2O
- 2014
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 136:4, s. 1320-1326
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Tidskriftsartikel (refereegranskat)abstract
- Bioinspired structures are promising as improved catalysts for various redox reactions. One example is metal hangman-porphyrines (MHP), which recently have been suggested for oxygen reduction/evolution reaction (ORR/OER). The unique properties of the MHPs are attributed to both the hangman scaffold and the C6F5 side groups. Herein, the OER/ORR over various transition metal MHPs is investigated by density functional theory calculations within an electrochemical framework. A comparison of the reaction landscape for MHP, metal porphyrine (MP) and metaltetrafluorophenyloporphyrines (MTFPP), allow for a disentanglement of the different roles of the hangman motif and the side groups. In agreement with experimental studies, it is found that Fe and Co are the best MHP Metal centers to catalyze these reactions. We find that the addition of the three-dimensional moiety in the form of hangman scaffold does not break the apparently universal energy relation between *OH and *OOH intermediates. However, the hangman motif is found to stabilize the oxygen intermediate, whereas addition of C6F5 groups reduces the binding energy of all reaction intermediates. Our results indicate that the combination of these two effects allow new design possibilities for macromolecular systems with enhanced catalytic OER/ORR activity.
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| 12. |
- Baran, J. D., et al.
(författare)
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Mechanism for Limiting Thickness of Thin Oxide Films on Aluminum
- 2014
-
Ingår i: Physical Review Letters. - 1079-7114 .- 0031-9007. ; 112:14
-
Tidskriftsartikel (refereegranskat)abstract
- A first-principles account of the observed limiting thickness of oxide films formed on aluminum during oxidizing conditions is presented. The results uncover enhanced bonding of oxygen to thin alumina films in contact with metallic aluminum that stems from charge transfer between a reconstructed oxide-metal interface and the adsorbed molecules. The first-principles results are compared with the traditional Cabrera-Mott (CM) model, which is a classical continuum model. Within the CM model, charged surface oxygen species and metal ions generate a (Mott) potential that drives oxidation. An apparent limiting thickness is observed as the oxidation rate decreases rapidly with film growth. The present results support experimental estimates of the Mott potential and film thicknesses. In contrast to the CM model, however, the calculations reveal a real limiting thickness that originates from a diminishing oxygen adsorption energy beyond a certain oxide film thickness.
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| 13. |
- Baumann, S. O., et al.
(författare)
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Size Effects in MgO Cube Dissolution
- 2015
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 1520-5827 .- 0743-7463. ; 31:9, s. 2770-2776
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Tidskriftsartikel (refereegranskat)abstract
- Stability parameters and dissolution behavior of engineered nanomaterials in aqueous systems are critical to assess their functionality and fate under environmental conditions. Using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we investigated the stability of cubic MgO particles in water. MgO dissolution proceeding via water dissociation at the oxide surface, disintegration of Mg2+-O2- surface elements, and their subsequent solvation ultimately leads to precipitation of Mg(OH)(2) nanosheets. At a pH >= 10, MgO nanocubes with a size distribution below 10 nm quantitatively dissolve within few minutes and convert into Mg(OH)(2) nanosheets. This effect is different from MgO cubes originating from magnesium combustion in air. With a size distribution in the range 10 nm
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| 14. |
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| 15. |
- Becker, Elin, 1981, et al.
(författare)
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Methane oxidation over alumina supported platinum investigated by time-resolved in situ XANES spectroscopy
- 2007
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Ingår i: Journal of Catalysis. - : Elsevier BV. - 0021-9517 .- 1090-2694. ; 252:1, s. 11-17
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Tidskriftsartikel (refereegranskat)abstract
- In situ time-resolved X-ray absorption spectroscopy and mass spectrometry were used to correlate changes in catalyst surface composition with catalytic activity for methane oxidation over alumina supported Pt. Different transient experiments (i.e., pulsing of oxygen or hydrogen to an otherwise constant gas composition) were performed to study the methane oxidation kinetics. Changes in the surface O/Pt ratio were monitored by the introduction of a new analysis method of the white line area corresponding to the Pt L-III-edge XANES spectra. The relevance of the method was confirmed by first-principles calculations demonstrating how hydrogen and oxygen adsorbates modify the electronic structure of Pt. The experimental results show that during the gas-phase transients, the surface O/Pt ratio changes, which in turn affects the methane oxidation rate. Activity maxima are observed for an intermediate surface O/Pt ratio. An oxygen-rich surface seems to hinder the dissociative adsorption of methane, leading to low methane oxidation activity at oxygen excess.
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| 16. |
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| 17. |
- Besharat, Zahra, et al.
(författare)
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Se-C Cleavage of Hexane Selenol at Steps on Au(111)
- 2018
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 34:8, s. 2630-2636
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Tidskriftsartikel (refereegranskat)abstract
- Selenols are considered as an alternative to thiols in self-assembled monolayers, but the Se-C bond is one limiting factor for their usefulness. In this study, we address the stability of the Se-C bond by a combined experimental and theoretical investigation of gas phase-deposited hexane selenol (CH3(CH2)(5)SeH) on Au(111) using photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory (DFT). Experimentally, we find that initial adsorption leaves atomic Se on the surface without any carbon left on the surface, whereas further adsorption generates a saturated selenolate layer. The Se 3d component from atomic Se appears at 0.85 eV lower binding energy than the selenolate-related component. DFT calculations show that the most stable structure of selenols on Au(111) is in the form of RSe-Au-SeR complexes adsorbed on the unreconstructed Au(111) surface. This is similar to thiols on Au(111). Calculated Se 3d core-level shifts between elemental Se and selenolate in this structure nicely reproduce the experimentally recorded shifts. Dissociation of RSeH and subsequent formation of RH are found to proceed with high barriers on defect-free Au(111) terraces, with the highest barrier for scissoring R-Se. However, at steps, these barriers are considerably lower, allowing for Se-C bond breaking and hexane desorption, leaving elemental Se at the surface. Hexane is the selenol to selenolate formed by replacing the Se-C bond with a H-C bond by using the hydrogen liberated from transformation.
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| 18. |
- Bjerregaard, Joachim, 1996, et al.
(författare)
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Interpretation of H 2 -TPR from Cu-CHA Using First-Principles Calculations
- 2024
-
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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| 19. |
- Bjerregaard, Joachim, 1996, et al.
(författare)
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Mechanism for SO2 poisoning of Cu-CHA during low temperature NH3-SCR
- 2023
-
Ingår i: Journal of Catalysis. - : Elsevier BV. - 0021-9517 .- 1090-2694. ; 417, s. 497-506
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Tidskriftsartikel (refereegranskat)abstract
- Density Functional Theory (DFT) calculations are used to investigate low temperature SO2 deactivation of Cu-CHA during ammonia assisted selective catalytic reduction of NO (NH3-SCR). SO2 is found to adsorb on [Cu2IINH34O2]2+ forming a copper sulfate complex. NO and NH3 react over the sulfate complex forming N2, H2O and H2SO4. H2SO4 undergoes an acid-base reaction with NH3 yielding SO4(NH4)2 and HSO4(NH4), where HSO4(NH4) is thermodynamically preferred during typical reaction conditions. The SO2-derived species are bulky and have considerable barriers for inter-cage diffusion. Moreover, the presence of HSO4(NH4) species reduces the probability of having two [CuI(NH3)2]+ complexes in one cage, which is a requirement for O2 activation. The results suggest that the key mechanism for low temperature SO2 deactivation is of physical origin and that the catalyst can be regenerated by exposure to high temperatures where HSO4(NH4) decomposes. The suggested mechanism agrees with experimental observations and provides atomistic understanding of sulfur poisoning of Cu-CHA during NH3-SCR.
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| 20. |
- Blomberg, Sara, et al.
(författare)
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Generation and oxidation of aerosol deposited PdAg nanoparticles
- 2013
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028. ; 616, s. 186-191
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Tidskriftsartikel (refereegranskat)abstract
- PdAg nanoparticles with a diameter of 10 nm have been generated by an aerosol particle method, and supported on a silica substrate. By using a combination of X-ray Energy Dispersive Spectroscopy and X-ray Photoelectron Spectroscopy it is shown that the size distribution of the particles is narrow and that the two metals form an alloy with a mixture of 75% Pd and 25% Ag. Under oxidizing conditions, Pd is found to segregate to the surface and a thin PdO like oxide is formed similar to the surface oxide previously reported on extended PdAg and pure Pd surfaces. (C) 2013 Elsevier B.V. All rights reserved.
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| 21. |
- Blomberg, Sara, et al.
(författare)
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Strain Dependent Light-off Temperature in Catalysis Revealed by Planar Laser-Induced Fluorescence
- 2017
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 7:1, s. 110-114
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Tidskriftsartikel (refereegranskat)abstract
- Understanding how specific atom sites on metal surfaces lower the energy barrier for chemical reactions is vital in catalysis. Studies on simplified model systems have shown that atoms arranged as steps on the surface play an important role in catalytic reactions, but a direct comparison of how the light-off temperature is affected by the atom orientation on the step has not yet been possible due to methodological constraints. Here we report in situ spatially resolved measurements of the CO2 production over a cylindrical-shaped Pd catalyst and show that the light-off temperature at different parts of the crystal depends on the step orientation of the two types of steps (named A and B). Our finding is supported by density functional theory calculations, revealing that the steps, in contrast to what has been previously reported in the literature, are not directly involved in the reaction onset but have the role of releasing stress.
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| 22. |
- Borglin, Johan, 1986, et al.
(författare)
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Insights on proximity effect and multiphoton induced luminescence from gold nanospheres in far field optical microscopy
- 2015
-
Ingår i: Applied Physics Letters. - : AIP Publishing. - 0003-6951 .- 1077-3118. ; 107:23
-
Tidskriftsartikel (refereegranskat)abstract
- Goldnanoparticles can be visualized in far-field multiphoton laser-scanning microscopy (MPM) based on the phenomena of multiphoton induced luminescence (MIL). This is of interest for biomedical applications, e.g., for cancer diagnostics, as MPM allows for working in the near-infrared(NIR) optical window of tissue. It is well known that the aggregation of particles causes a redshift of the plasmon resonance, but its implications for MIL applying far-field MPM should be further exploited. Here, we explore MIL from 10nm goldnanospheres that are chemically deposited on glass substrates in controlled coverage gradients using MPM operating in NIR range. The substrates enable studies of MIL as a function of inter-particle distance and clustering. It was shown that MIL was only detected from areas on the substrates where the particle spacing was less than one particle diameter, or where the particles have aggregated. The results are interpreted in the context that the underlying physical phenomenon of MIL is a sequential two-photon absorption process, where the first event is driven by the plasmon resonance. It is evident that goldnanospheres in this size range have to be closely spaced or clustered to exhibit detectable MIL using far-field MPM operating in the NIR region.
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| 23. |
- Bosio, Noemi, 1993, et al.
(författare)
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Can oxygen vacancies in ceria surfaces be measured by O1s photoemission spectroscopy?
- 2022
-
Ingår i: Journal of physics. Condensed matter : an Institute of Physics journal. - 1361-648X .- 0953-8984. ; 34:17
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Tidskriftsartikel (refereegranskat)abstract
- X-ray photoemission spectroscopy is a standard technique for materials characterization and the O 1s binding energy is commonly measured for oxides. Here we use density functional theory calculations to investigate how the O 1s binding energy in CeO2(111) is influenced by the presence of oxygen vacancies. The case with point vacancies in CeO2(111) is compared to complete reduction to Ce2O3. Reduction of CeO2by oxygen vacancies is found to have a minor effect on the O 1s binding energy. The O 1s binding energy is instead clearly changed when the character of the chemical bond for the considered oxygen atom is modified by, for example, the formation of OH-groups or carbonates.
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| 24. |
- Bosio, Noemi, 1993, et al.
(författare)
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Interface Reactions Dominate Low-Temperature CO Oxidation Activity over Pt/CeO 2
- 2022
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 126:38, s. 16164-16171
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Tidskriftsartikel (refereegranskat)abstract
- First-principles-based kinetic Monte Carlo simulations and kinetic experiments are used to explore CO oxidation over Pt/CeO2. The simulations compare CO oxidation over a ceria-supported 1 nm particle with simulations of a free-standing particle and Pt(111). The onset of the CO oxidation over ceria supported Pt is shifted to lower temperatures compared to the unsupported systems thanks to a Mars-van Krevelen mechanism at the Pt/CeO2 interface perimeter, which is not sensitive to CO poisoning. Both the Mars-van Krevelen mechanism and the conventional Langmuir-Hinshelwood mechanism over the Pt nanoparticle are contributing to the conversion after the reaction onset. The reaction orders in CO and O2 are compared experimentally for Pt/CeO2 and Pt/Al2O3. The reaction orders over Pt/CeO2 are close to zero for both CO and O2, whereas the corresponding reaction orders are-0.75 and 0.68 over Pt/Al2O3. The measured zero orders for Pt/CeO2 show the absence of CO/O2 site competition and underline the relevance of interface reactions. The measurements for Pt/Al2O3 indicate that the main reaction path for CO oxidation over Pt is a conventional Langmuir-Hinshelwood reaction. The results elucidate the interplay between condition-dependent reaction mechanisms for CO oxidation over Pt supported on reducible oxides.
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| 25. |
- Bosio, Noemi, 1993, et al.
(författare)
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Scaling-Relation Kinetic Monte Carlo Simulations for CO Oxidation over Dilute Pt@Au Alloys
- 2024
-
Ingår i: Journal of Physical Chemistry C. - 1932-7447 .- 1932-7455. ; 128:21, s. 8621-8627
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Tidskriftsartikel (refereegranskat)abstract
- Catalytic low-temperature CO oxidation continues to be an important materials challenge. Technological catalysts are commonly based on Pd and Pt nanoparticles, which are CO poisoned at low temperatures, hindering O2 adsorption. Using first-principles-based kinetic Monte Carlo simulations, we explore dilute Pt@Au nanoalloys as a possibility to enhance the low-temperature activity by spatially separating CO and O2 adsorption. CO is on these systems absorbed on Pt sites, whereas O2 reacts molecularly from Au sites to form OCOO, which decomposes to CO2 and O. The dilute Pt@Au systems are found to have a higher activity than pure Au systems in a temperature range not accessible to Pt-only catalysts. The results show that dilute Pt@Au alloys in combination with Pt-only catalysts have the potential for CO oxidation in a wide temperature range.
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| 26. |
- Bosio, Noemi, 1993, et al.
(författare)
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Sensitivity of Monte Carlo Simulations to Linear Scaling Relations
- 2020
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 124:22, s. 11952-11959
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Tidskriftsartikel (refereegranskat)abstract
- One approach to study reaction kinetics over metal nanoparticles is to combine linear scaling relations with kinetic Monte Carlo simulations. This methodology is based on the observation that adsorption energies commonly scale linearly with descriptors such as the generalized coordination number and that reaction barriers are related to the adsorption energies via the Brionsted-Evans-Polanyi relation. In this work, the sensitivity of the reaction kinetics on the slopes of the scaling relations is investigated for CO oxidation over Pt-nanoparticles. The obtained trends between the slope and the turnover frequency suggest a modest dependency and that a flat energy landscape with energies corresponding to edge-sites yields a high catalytic activity. We also explore the sensitivity of the O-2 sticking probability on the turnover frequency. This parameter is found to have a minor influence on the kinetics of the studied reaction.
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| 27. |
- Broqvist, Peter, 1975, et al.
(författare)
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Characterization of NOx species adsorbed on BaO: Experiment and theory
- 2004
-
Ingår i: Journal of Physical Chemistry B. - 1520-5207 .- 1520-6106. ; 108:11, s. 3523-3530
-
Tidskriftsartikel (refereegranskat)abstract
- Charged NO, species (x = 1,2,3) formed upon adsorption of NO2 on BaO are characterized by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and theoretical vibrational analysis using the density functional theory (DFT). Experiments at 30degreesC reveal nitrite formation. At T > 250degreesC, shifts associated with formation of nitrates are observed, indicating an interconversion of oxygen atoms among adsorbates. The theoretical study includes single and pairwise NO2 adsorption on (BaO)(9) clusters. As has been reported previously [Broqvist, P.; Panas, I.; Fridell, E.; Persson, H. J. Phys. Chem. B 2002, 106, 137], an additional energy gain is calculated for the second adsorbed NO2. A vibrational analysis of the investigated adsorption configurations supports the interpretation of nitrite to nitrate interconversion on the BaO surface. Moreover, the calculations demonstrate the sensitivity in the NO2 vibrational band splitting with respect to adsorption configuration.
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| 28. |
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| 29. |
- Broqvist, Peter, 1975, et al.
(författare)
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NOx storage on BaO: theory and experiment
- 2004
-
Ingår i: Catalysis Today. - : Elsevier BV. - 0920-5861. ; 96:1-2, s. 71-78
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Tidskriftsartikel (refereegranskat)abstract
- We review our understanding of the NO2 interaction with BaO. The presented picture has evolved from calculations using the density functional theory, reactor measurements and vibrational spectroscopy of surface species during NO2 storage on a BaO/Al2O3 catalyst and BaO powder. The DFT calculations predict nitrite formation on the BaO(1 0 0) surface upon NO2 adsorption. A particular stable adsorption configuration is a nitrate-nitrite pair geometry, with the nitrate bonded to a barium cation and the nitrite involving a surface oxygen anion. This configuration is supported by vibrational spectroscopy. Only nitrite formation is observed for NO exposure to BaO powder at low temperatures, whereas signatures at similar to250degreesC reveal the formation of surface nitrates. Continuous NO2 adsorption at this temperature results in surface Ba(NO3)(2), as well as bulk Ba(NO3)(2), formation.
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| 30. |
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| 31. |
- Broqvist, Peter, 1975, et al.
(författare)
-
Surface properties of alkaline earth metal oxides
- 2004
-
Ingår i: Surface Science. - : Elsevier BV. - 0039-6028. ; 554:2-3, s. 262-271
-
Tidskriftsartikel (refereegranskat)abstract
- Structural and energetic surface properties of the alkaline earth metal oxides MgO, CaO, SrO, and BaO are investigated within the density functional theory. In particular, structural distortions (relaxation and rumpling) and surface energies are studied for the (100) and (110) surfaces. A different sign of the rumpling is calculated for MgO compared to the other oxides. This difference is carefully examined and discussed in terms of differences in electronic properties, as well as nearest and next-nearest neighbor interactions. The stability of the results is investigated with respect to model approximations, such as the finite number of atomic layers used to describe semi-infinite surfaces, and choice of exchange-correlation energy functional.
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| 32. |
- Broqvist, Peter, 1975, et al.
(författare)
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The nature of NOx species on BaO(100): An ab initio molecular dynamics study
- 2005
-
Ingår i: Journal of Physical Chemistry B. - 1520-5207 .- 1520-6106. ; B109, s. 15410-15416
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Tidskriftsartikel (refereegranskat)abstract
- The dynamics of NO., species adsorbed on BaO(100) have been investigated with ab initio molecular dynamics simulations at a temperature of 300 degrees C. Nitrites are found to continuously interconvert between different adsorption configurations. For both nitrites and nitrates, diffusion events between anion sites are observed. These findings support the use of spillover mechanisms often postulated in mechanistic models of catalysts based on the NO, storage and reduction concept. The large number of possible adsorption configurations are reflected in broad calculated vibrational signatures. These results explain the corresponding property observed in experimental infrared measurements of NO, species on BaO. The dynamic response of the BaO(100) surface is found to strongly depend on the nature of the surface- adsorbate interaction. The largest distortions are predicted for nitrite adsorption
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| 33. |
- Broqvist, Peter, 1975, et al.
(författare)
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Toward a Realistic Description of NOxStorage in BaO: The Aspect of BaCO3
- 2005
-
Ingår i: Journal of Physical Chemistry B. ; 109, s. 9613-9621
-
Tidskriftsartikel (refereegranskat)abstract
- NOx storage over hexagonal BaCO3(110) is investigated using first-principles calculations. Special focus is put on the importance of surface decarbonation. Upon decarbonation, supported BaO quasi-molecules are formed and a small drive toward (BaO)(n) cluster formation is predicted. Introduction of NO2 makes the decarbonation energetically relevant, while forming NO2-BaO-NO2 units, on the decarbonated surface. With this configuration, it is possible to replace all surface carbonates with nitrites and nitrates, forming a BaCO3 supported BaNO3NO2 overlayer. Thermodynamic considerations are employed to elaborate on the thermal stability of the formed NOx overlayers.
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| 34. |
- Brown, Rosemary, 1990, et al.
(författare)
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Unraveling the Surface Chemistry and Structure in Highly Active Sputtered Pt3Y Catalyst Films for the Oxygen Reduction Reaction
- 2020
-
Ingår i: ACS Applied Materials & Interfaces. - : American Chemical Society (ACS). - 1944-8252 .- 1944-8244. ; 12:4, s. 4454-4462
-
Tidskriftsartikel (refereegranskat)abstract
- Platinum is the most widely used and best performing sole element for catalyzing the oxygen reduction reaction (ORR) in low-temperature fuel cells. Although recyclable, there is a need to reduce the amount used in current fuel cells for their extensive uptake in society. Alloying platinum with rare-earth elements such as yttrium can provide an increase in activity of more than seven times, reducing the amount of platinum and the total amount of catalyst material required for the ORR. As yttrium is easily oxidized, exposure of the Pt-Y catalyst layer to air causes the formation of an oxide layer that can be removed during acid treatment, leaving behind a highly active pure platinum overlayer. This paper presents an investigation of the overlayer composition and quality of Pt3Y films sputtered from an alloy target. The Pt3Y catalyst surface is investigated using synchrotron radiation X-ray photoelectron spectroscopy before and after acid treatment. A new substoichiometric oxide component is identified. The oxide layer extends into the alloy surface, and although it is not completely removed with acid treatment, the catalyst still achieves the expected high ORR activity. Other surface-sensitive techniques show that the sputtered films are smooth and bulk X-ray diffraction reveals many defects and high microstrain. Nevertheless, sputtered Pt3Y exhibits a very high activity regardless of the film's oxide content and imperfections, highlighting Pt3Y as a promising catalyst. The obtained results will help to support its integration into fuel cell systems.
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| 35. |
- Busch, Michael, 1983, et al.
(författare)
-
Adsorption of NO on Fe3O4(111)
- 2018
-
Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 693, s. 84-87
-
Tidskriftsartikel (refereegranskat)abstract
- Adsorption of NO on Fe 3 O 4 (111) is studied by density functional theory (DFT) calculations. NO is preferably adsorbed atop the octahedral site which has a clearly higher adsorption energy than the tetrahedral site. The difference in adsorption energy correlates with differences in adsorption geometries and N–O stretch vibrations. The results are in good agreement with temperature programmed desorption (TPD) and reflection-adsorption IR spectroscopy (RAIRS) measurements and provide an explanation of the observation of only one vibrational mode despite two distinct TPD features.
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| 36. |
- Busch, Michael, 1983, et al.
(författare)
-
The Influence of Inert Ions on the Reactivity of Manganese Oxides
- 2018
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 122:1, s. 216-226
-
Tidskriftsartikel (refereegranskat)abstract
- Inert ion doping is a possible method to modify electrical conductivity and catalytic activity of transition-metal oxide electrocatalysts. Despite the importance of dopants, little is known about the underlying mechanisms for the change of the system properties. We have performed density functional theory calculations to investigate the influence of different valent ions on the O 2 evolution reaction activity of β-MnO 2 and Mn 2 O 3 . While Mn 2 O 3 is unaffected by dopants, β-MnO 2 is strongly affected by ions placed in a subsurface position. Doping does not affect the ion charge at the active site, but instead it effects the bond character. This is concluded through an analysis of the density overlap regions indicator and the density of states showing that the partially covalent nature of the bonds in β-MnO 2 is responsible for the changes in the adsorbate binding energies. This mechanism is not active in the mostly ionic Mn 2 O 3 . These results highlight the need to explicitly consider the detailed bonding situation and to go beyond simple charge transfer considerations when describing doping of transition metal oxide catalysts.
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| 37. |
- Chaoquan, Hu, 1981, et al.
(författare)
-
Catalytic hydrogenation of C=C and C=O in unsaturated fatty acid methyl esters
- 2014
-
Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 4:8, s. 2427-2444
-
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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| 38. |
- Chaoquan, Hu, 1981, et al.
(författare)
-
Methyl crotonate hydrogenation over Pt: Effects of support and metal dispersion
- 2016
-
Ingår i: Applied Catalysis A: General. - : Elsevier BV. - 1873-3875 .- 0926-860X. ; 511, s. 106-116
-
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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| 39. |
- Chaoquan, Hu, 1981, et al.
(författare)
-
Selectivity and kinetics of methyl crotonate hydrogenation over Pt/Al2O3
- 2015
-
Ingår i: Catalysis Science and Technology. - 2044-4753 .- 2044-4761. ; 5:3, s. 1716-1730
-
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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| 40. |
- Chen, Lin, 1990, et al.
(författare)
-
A comparative test of different density functionals for calculations of NH3-SCR over Cu-Chabazite
- 2019
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 21:21, s. 10923-10930
-
Tidskriftsartikel (refereegranskat)abstract
- A general challenge in density functional theory calculations is to simultaneously account for different types of bonds. One such example is reactions in zeolites where both van der Waals and chemical bonds should be described accurately. Here, we use different exchange-correlation functionals to explore O2 dissociation over pairs of Cu(NH3)2+ complexes in Cu-Chabazite. This is an important part of selective catalytic reduction of NOx using NH3 as a reducing agent. The investigated functionals are PBE, PBE+U, PBE+D, PBE+U+D, PBE-cx, BEEF and HSE06+D. We find that the potential energy landscape for O2 activation and dissociation depends critically on the choice of functional. However, the van der Waals contributions are similarly described by the functionals accounting for this interaction. The discrepancies in the potential energy surface are instead related to different descriptions of the Cu-O chemical bond. By investigating the electronic, structural and energetic properties of reference systems including bulk copper oxides and (Cu2O2)2+ enzymatic crystals, we find that the PBE+U approach together with van der Waals corrections provides a reasonable simultaneous accuracy of the different bonds in the systems.
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| 41. |
- Chen, Lin, 1990, et al.
(författare)
-
A Complete Multisite Reaction Mechanism for Low-Temperature NH3-SCR over Cu-CHA
- 2020
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 10:10, s. 5646-5656
-
Tidskriftsartikel (refereegranskat)abstract
- The dynamic character of the active centers has made it difficult to unravel the reaction path for NH3-assisted selective catalytic reduction (SCR) of nitrogen oxides over Cu-CHA. Herein, we use density functional theory calculations to suggest a complete reaction mechanism for low-temperature NH3-SCR The reaction is found to proceed in a multisite fashion over ammonia-solvated Cu cations Cu(NH3)(2+) and Bronsted acid sites. The activation of oxygen and the formation of the key intermediates HONO and H2NNO occur on the Cu sites, whereas the Bronsted acid sites facilitate the decomposition of HONO and H2NNO to N-2 and H2O. The activation and reaction of NO is found to proceed via the formation of nitrosonium (NO+) or nitrite (NO2-) intermediates. These low-temperature mechanisms take the dynamic character of Cu sites into account where oxygen activation requires pairs of Cu(NH3)(2+) complexes, whereas HO-NO and H3N-NO coupling may occur on single complexes. The formation and separation of Cu pairs is assisted by NH3 solvation. The complete reaction mechanism is consistent with measured kinetic data and provides a solid basis for future improvements of the low-temperature NH3-SCR reaction.
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| 42. |
- Chen, Lin, 1990, et al.
(författare)
-
Activation of oxygen on (NH3–Cu–NH3)+ in NH3-SCR over Cu-CHA
- 2018
-
Ingår i: Journal of Catalysis. - : Elsevier BV. - 0021-9517 .- 1090-2694. ; 358, s. 179-186
-
Tidskriftsartikel (refereegranskat)abstract
- Cu-CHA materials are efficient catalysts for NH 3 –SCR of NO x in oxygen excess. A crucial step in the reaction is oxygen (O 2 ) activation, which still is not well understood. Density functional theory calculations in combination with ab initio thermodynamics and molecular dynamics are here used to study O 2 dissociation on Cu(NH 3 ) 2 + species, which are present under NH 3 –SCR conditions. Direct dissociation of O 2 is found to be facile over a pair of Cu(NH 3 ) 2 + complexes whereas dissociation on a single Cu(NH 3 ) 2 + species is unlikely due to a high activation energy. The presence of NO promotes oxygen dissociation on both single and pairs of Cu(NH 3 ) 2 + complexes. Nitrites and nitrates are easily formed as O 2 dissociates, and NO adsorption over nitrates leads to facile formation of NO 2 . The results stress the importance of ligand-stabilized Cu species in Cu-CHA catalysts for NH 3 –SCR.
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| 43. |
- Chen, Lin, 1990, et al.
(författare)
-
Effect of Al-distribution on oxygen activation over Cu-CHA
- 2018
-
Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 8:8, s. 2131-2136
-
Tidskriftsartikel (refereegranskat)abstract
- Cu(NH 3 ) 2 + -pairs in chabazite (CHA) have been suggested to activate oxygen during lowerature selective catalytic reduction of nitrogen oxides with ammonia (NH 3 -SCR). As charge neutrality requires that each Cu-complex is associated with a framework Al, the Al-distribution may affect Cu(NH 3 ) 2 + -pair formation and subsequent oxygen activation. Here, density functional theory calculations in combination with ab initio molecular dynamics simulations are used to explore Cu(NH 3 ) 2 + -pair formation and oxygen activation in Cu-CHA. The Al-distribution is found to markedly affect the probability for Cu(NH 3 ) 2 + -pair formation. Moreover, the molecular dynamics simulations reveal a low-energy reaction path for O 2 activation and dissociation. The facile O 2 dissociation suggests that Cu-pair formation rather than O 2 activation governs the lowerature NH 3 -SCR activity. The results indicate that precise synthesis of Cu-exchanged chabazite with respect to Al-distribution may enhance the catalytic activity.
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| 44. |
- Chen, Lin, 1990, et al.
(författare)
-
Interpretation of NH 3 -TPD Profiles from Cu-CHA Using First-Principles Calculations
- 2019
-
Ingår i: Topics in Catalysis. - : Springer Science and Business Media LLC. - 1572-9028 .- 1022-5528. ; 62:1-4, s. 93-99
-
Tidskriftsartikel (refereegranskat)abstract
- Temperature-programmed desorption (TPD) with ammonia is widely used for zeolite characterization revealing information on acidity and adsorption sites. The interpretation of TPD measurements is, however, often challenging. One example is the NH 3 -TPD profile from Cu-chabazite (Cu-CHA) which generally is deconvoluted in three peaks with contributions from NH 3 on Lewis acid sites, copper sites and Brønsted acid sites. Here, we use density functional theory calculations combined with kinetic simulations to analyze this case. We find a large number of possible species, giving rise to overlapping features in the NH 3 -TPD. The experimental low-temperature peak (below 200∘C) is assigned to NH 3 desorption from Lewis acid sites together with NH 3 desorption from a [Cu(II)(OH)(NH3)3]+ complex. The intermediate-temperature peak (250-350∘C) is attributed to decomposition of a linear [Cu(I)(NH3)2]+ complex and a residual from [Cu(II)(OH)(NH3)3]+. The high-temperature peak is predicted to have contributions from Brønsted acid sites (NH4+), [Cu(I)NH3]+ and [Cu(II)(NH3)4]2+. The present work shows that NH 3 -TPD from Cu-CHA can be reconciled with copper complexes as NH 3 storage sites.
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| 45. |
- Chen, Lin, 1990, et al.
(författare)
-
Mechanism for Solid-State Ion-Exchange of Cu+ into Zeolites
- 2016
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:51, s. 29182-29189
-
Tidskriftsartikel (refereegranskat)abstract
- Density functional theory calculations are used to investigate solid-state ion-exchange of copper into zeolites. In particular, the energetic conditions for functionalization of Chabazite (CHA) with copper ions from Cu2O(111) via formation of Cu(NH3)2+ is explored. It is found that the diamine complexes form easily on Cu2O(111) and diffuse with low barriers over the surface and in the CHA framework. The charge neutrality of the systems is maintained via counter diffusion of H+ in the form of NH4+ from the zeolite to the Cu2O surface where water can be formed. The efficient solvation of Cu+ and H+ by ammonia renders the ion-exchange process exothermic. The present results highlight the dynamic character of the Cu-ion sites and provide means to understand zeolite functionalization.
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| 46. |
- Chen, Lin, 1990, et al.
(författare)
-
Multiple Roles of Alkanethiolate-Ligands in Direct Formation of H 2 O 2 over Pd Nanoparticles
- 2022
-
Ingår i: Angewandte Chemie - International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:51
-
Tidskriftsartikel (refereegranskat)abstract
- Coadsorbed organic species including thiolates can promote direct synthesis of hydrogen peroxide from H2 and O2 over Pd particles. Here, density functional theory based kinetic modeling, augmented with activity measurements and vibrational spectroscopy are used to provide atomistic understanding of direct H2O2 formation over alkylthiolate(RS) Pd. We find that the RS species are oxidized during reaction conditions yielding RSO2 as the effective ligand. The RSO2 ligand shows superior ability for proton transfer to the intermediate surface species OOH, which accelerates the formation of H2O2. The ligands promote the selectivity also by blocking sites for unselective water formation and by modifying the electronic structure of Pd. The work rationalizes observations of enhanced selectivity of direct H2O2 formation over ligand-funtionalized Pd nanoparticles and shows that engineering of organic surface modifiers can be used to promote desired hydrogen transfer routes.
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| 47. |
- Chen, Lin, 1990, et al.
(författare)
-
On the Reaction Mechanism of Direct H 2 O 2 Formation over Pd Catalysts
- 2021
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 11:5, s. 2735-2745
-
Tidskriftsartikel (refereegranskat)abstract
- Hydrogen peroxide (H2O2) is an effective green oxidant, which is used in many industrial processes. Here, the reaction mechanism for direct formation of H2O2 from H2 and O2 over Pd catalysts is studied using density functional theory calculations and mean-field kinetic modeling. The state of the catalyst as a function of reaction conditions is determined from ab initio thermodynamics. It is found that Pd is in a hydride phase during typical reaction conditions. Reaction landscapes are constructed for the reaction over PdH(111) and PdH(211). Formation of H2O2 instead of H2O requires that O2 adsorbs and that the surface intermediates O2, OOH, and H2O2 do not dissociate. We find that these requirements are fulfilled on the stepped PdH(211) surface. Surface steps are needed for O2 chemisorption as the adsorption on PdH(111) is endothermic. The high H coverage on the surface of the hydride is important to slow down the unwanted scission of the O-O bond and promote the desorption of the products. Comparative calculations for the Pd(111) surface show that this surface is inactive for both H2O2 and H2O formation below room temperature for typical reaction mixtures. Our findings demonstrate the importance of surface steps and high hydrogen coverage for direct synthesis of H2O2 from H2 and O2 over Pd catalysts. The results imply that the selectivity of the reaction toward H2O2 is enhanced by a high partial pressure of H2, which is in agreement with experimental observations.
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| 48. |
- Clayborne, P. A., et al.
(författare)
-
Evidence of superatom electronic shells in ligand-stabilized aluminum clusters
- 2011
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 1089-7690 .- 0021-9606. ; 135:9
-
Tidskriftsartikel (refereegranskat)abstract
- Ligand-stabilized aluminum clusters are investigated by density functional theory calculations. Analysis of Kohn-Sham molecular orbitals and projected density of states uncovers an electronic shell structure that adheres to the superatom complex model for ligand-stabilized aluminum clusters. In this current study, we explain how the superatom complex electron-counting rule is influenced by the electron-withdrawing ligand and a dopant atom in the metallic core. The results may guide the prediction of new stable ligand-stabilized (superatom) complexes, regardless of core and electronwithdrawing ligand composition.
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| 49. |
- Clayborne, P. A., et al.
(författare)
-
The Al50Cp*(12) Cluster - A 138-Electron Closed Shell (L=6) Superatom
- 2011
-
Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-0682. ; :17, s. 2649-2652
-
Tidskriftsartikel (refereegranskat)abstract
- Metal clusters stabilized by a surface ligand shell represent an interesting intermediate state of matter between molecular metal-ligand complexes and bulk metal. Such "metalloid" clusters are characterized by the balance between metal-metal bonds in the core and metal-ligand bonds at the exterior of the cluster. In previous studies, the electronic stability for the Al50Cp*(12) cluster was not fully understood. We show here that the known cluster Al50Cp*(12) can be considered as an analogue to a giant atom ("superatom") with 138 sp electrons organized in concentric angular momentum shells up to L = 6 symmetry.
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| 50. |
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