| 1. |
- Andersson, Viktor, 1994, et al.
(författare)
-
A Novel Method for On-Line Characterization of Alkali Release and Thermal Stability of Materials Used in Thermochemical Conversion Processes
- 2022
-
Ingår i: Energies. - : MDPI AG. - 1996-1073. ; 15:12
-
Tidskriftsartikel (refereegranskat)abstract
- Alkali metal compounds are released during the thermal conversion of biofuels and fossil fuels and have a major impact on the efficiency of conversion processes. Herein, we describe a novel method for the simultaneous characterization of alkali release and mass loss from materials used in combustion and gasification processes including solid fuels, fluidized bed materials, and catalysts for gas reforming. The method combines the thermogravimetric analysis of selected samples with the on-line measurement of alkali release using a surface ionization detector. The technique builds on the careful treatment of alkali processes during transport from a sample to the downstream alkali monitor including the losses of alkali in the molecular form to hot walls, the formation of nanometer-sized alkali-containing particles during the cooling of exhaust gases, aerosol particle growth, and diffusion losses in sampling tubes. The performance of the setup was demonstrated using biomass samples and fluidized bed material from an industrial process. The emissions of alkali compounds during sample heating and isothermal conditions were determined and related to the simultaneous thermogravimetric analysis. The methodology was concluded to provide new evidence regarding the behavior of alkali in key processes including biomass pyrolysis and gasification and ash interactions with fluidized beds. The implications and further improvements of the technique are discussed.
|
|
| 2. |
- Andersson, Viktor, 1983, et al.
(författare)
-
Alkali desorption from ilmenite oxygen carrier particles used in biomass combustion
- 2024
-
Ingår i: Fuel. - 0016-2361 .- 1873-7153. ; 359
-
Tidskriftsartikel (refereegranskat)abstract
- Oxygen-carrying fluidized bed materials are increasingly used in novel technologies for carbon capture and storage, and to improve the efficiency of fuel conversion processes. Potassium- and sodium-containing compounds are released during biomass combustion and may have both negative and positive effects on conversion processes. Ilmenite is an important oxygen carrier material with the ability to capture alkali in the form of titanates. This is a desirable property since it may reduce detrimental alkali effects including fouling, corrosion, and fluidized bed agglomeration. This study investigates the interactions of alkali-containing compounds with ilmenite particles previously used in an industrial scale (115 MWth) oxygen carrier aided combustion system. The ilmenite samples were exposed to temperatures up to 1000 °C under inert and oxidizing conditions while the alkali release kinetics were characterized using online alkali monitoring. Alkali desorption occurs between 630 and 800 °C, which is attributed to loosely bound alkali at or near the surface of the particles. Extensive alkali release is observed above 900 °C and proceeds during extended time periods at 1000 °C. The release above 900 °C is more pronounced under oxidizing conditions and approximately 9.1 and 3.2 wt% of the alkali content is emitted from the ilmenite samples in high and low oxygen activity, respectively. Detailed material analyses using scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy were conducted before and after temperature treatment, which revealed that the concentrations of potassium, sodium and chlorine decrease at the outermost surface of the ilmenite particles during temperature treatment, and Cl is depleted to a deeper level in oxidizing conditions compared to inert. The implications for ilmenite-ash interactions, oxygen carrier aided combustion and chemical looping systems are discussed.
|
|
| 3. |
- Andersson, Viktor, 1983, et al.
(författare)
-
Alkali interactions with a calcium manganite oxygen carrier used in chemical looping combustion
- 2022
-
Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820 .- 1873-7188. ; 227
-
Tidskriftsartikel (refereegranskat)abstract
- Chemical-Looping Combustion (CLC) of biofuels is a promising technology for cost-efficient CO2 separation and can lead to negative CO2 emissions when combined with carbon capture and storage. A potential challenge in developing CLC technology is the effects of alkali metal-containing compounds released during fuel conversion. This study investigates the interactions between alkali and an oxygen carrier (OC), CaMn0.775Ti0.125Mg0.1O3-δ, to better understand the fate of alkali in CLC. A laboratory-scale fluidized bed reactor is operated at 800–900 °C in oxidizing, reducing and inert atmospheres to mimic CLC conditions. Alkali is fed to the reactor as aerosol KCl particles, and alkali in the exhaust is measured online with a surface ionization detector. The alkali concentration changes with gas environment, temperature, and alkali loading, and the concentration profile has excellent reproducibility over repeated redox cycles. Alkali-OC interactions are dominated by alkali uptake under most conditions, except for a release during OC reduction. Uptake is significant during stable reducing conditions, and is limited under oxidizing conditions. The total uptake during a redox cycle is favored by a high alkali loading, while the influence of temperature is weak. The implications for the understanding of alkali behavior in CLC and further development are discussed.
|
|
| 4. |
- Andersson, Viktor, 1983, et al.
(författare)
-
Alkali-wall interactions in a laboratory-scale reactor for chemical looping combustion studies
- 2021
-
Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820 .- 1873-7188. ; 217
-
Tidskriftsartikel (refereegranskat)abstract
- Alkali metal-containing compounds are readily released during thermal conversion of solid fuels, and may have both detrimental and beneficial effects on chemical looping combustion. Here, we characterize alkali interactions with the inner walls of a laboratory-scale reactor under oxidizing, reducing and inert conditions at temperatures up to 900 °C. KCl aerosol particles are continuously introduced to the stainless steel reactor and the alkali concentration is measured on-line with a surface ionization detector. Aerosol particles evaporate at temperatures above 500 °C and KCl molecules rapidly diffuse to the reactor wall. Up to 92% of the alkali reaching the wall below 700 °C remains adsorbed, while re-evaporation is important at higher temperatures, where up to 74% remains adsorbed. Transient changes in alkali concentration are observed during repeated redox cycles, which are associated with changes in chemical composition of the wall material. Metal oxides on the reactor wall are partially depleted under reducing conditions, which allow for the formation of a new potassium-rich phase that is stable in a reducing atmosphere, but not under inert conditions. The observed wall effects are concluded to be extensive and include major transient effects depending on gas composition, and the implications for laboratory studies and improved experimental methodology are discussed.
|
|
| 5. |
- Andersson, Viktor, 1983, et al.
(författare)
-
Design and first application of a novel laboratory reactor for alkali studies in chemical looping applications
- 2023
-
Ingår i: Fuel Processing Technology. - 0378-3820. ; 252
-
Tidskriftsartikel (refereegranskat)abstract
- Alkali compounds are readily released during biomass conversion and their complex interactions with reactor walls and sampling equipment makes detailed investigations challenging. This study evaluates a novel laboratory-scale fluidized bed reactor for chemical looping combustion (CLC) studies. The reactor design is based on detailed consideration of the behavior of alkali-containing molecules and aerosol particles and is guided by computational fluid dynamic simulations. The design allows for interactions between gaseous alkali and a fluidized bed, while minimizing alkali interactions with walls before and after the fluidized bed. The function of the laboratory reactor is demonstrated in experiments using online gas and alkali analysis. Alkali is continuously fed to the reactor as KOH or KCl aerosol with and without a fluidized bed of the oxygen carrier CaMn0.775Ti0.125Mg0.1O3-δ present in inert, reducing and oxidizing conditions at temperatures up to 900 °C. Alkali uptake by the OC is characterized in all conditions, and observed to sensitively depend on gas composition, reactor temperature and type of alkali compound. The experimental setup is concluded to have a significantly improved functionality compared to a previously used reactor, which opens up for detailed studies of interactions between alkali compounds and oxygen carriers used in CLC.
|
|
| 6. |
- Andersson, Viktor, 1983, et al.
(författare)
-
Gaseous alkali interactions with ilmenite, manganese oxide and calcium manganite under chemical looping combustion conditions
- 2024
-
Ingår i: Fuel Processing Technology. - 0378-3820 .- 1873-7188. ; 254
-
Tidskriftsartikel (refereegranskat)abstract
- Alkali species present in biomass pose significant challenges in chemical looping combustion (CLC) processes and other thermal conversion applications. The interactions between different alkali species and three common oxygen carrier (OC) materials that are considered to be state of the art in CLC applications have been investigated. A dedicated fluidized bed laboratory reactor was used to study interactions of KCl, NaCl, KOH, NaOH, K2SO4 and Na2SO4 with manganese oxide, calcium manganite and ilmenite. Alkali vapor was generated by injecting alkali salts under reducing, oxidizing and inert conditions at 900 °C. Gaseous species were measured online downstream of the reactor, and the efficiency of alkali uptake was determined under different conditions. The result show significant alkali uptake by all OCs under the studied conditions. Ilmenite shows near complete alkali uptake in reducing conditions, while manganese oxide and calcium manganite exhibited less effective alkali uptake, but have advantages in terms of fuel conversion and oxidizing efficiency. Alkali chlorides, sulfates and hydroxides show distinctly different behavior, with alkali hydroxides being efficiently captured all three investigate OC materials. The findings contribute to a deeper understanding of alkali behavior and offer valuable guidance for the design and optimization of CLC with biomass.
|
|
| 7. |
- Andersson, Viktor, 1994, et al.
(författare)
-
Online Speciation of Alkali Compounds by Temperature-Modulated Surface Ionization: Method Development and Application to Thermal Conversion
- 2024
-
Ingår i: ENERGY & FUELS. - 0887-0624 .- 1520-5029. ; 38:3, s. 2046-2057
-
Tidskriftsartikel (refereegranskat)abstract
- A novel method for online speciation of potassium- and sodium-containing compounds has been described and demonstrated. The method is based on a temperature-modulated surface ionization (TMSI) technique and may be used to determine the concentrations of alkali chlorides, hydroxides, carbonates, and sulfates in high-temperature processes. The measurement device is a further development of a surface ionization detector (SID) commonly used for online alkali measurements in combustion, gasification, and pyrolysis research. Discrimination between sodium and potassium compounds is made possible by differences in their aerosol evaporation characteristics as a function of temperature combined with the desorption kinetics of alkali on a hot platinum filament. The method is evaluated in laboratory experiments with known alkali salt concentrations. An experimental procedure where the platinum filament in the SID is regularly shifted between three temperatures is concluded to provide sufficient selectivity and time resolution for common applications. The TMSI method is successfully applied to characterize the emission of alkali compounds during pyrolysis of pine wood. The emissions during low-temperature pyrolysis are dominated by KOH, while similar amounts of KOH and NaOH are subsequently emitted from the remaining char and ash. The ability of real-time characterization of individual sodium and potassium compounds opens up new means to understand and optimize solid fuel conversion of common fuels such as low-grade biomass, waste, and coal.
|
|
| 8. |
- Bartels-Rausch, T., et al.
(författare)
-
Interfacial supercooling and the precipitation of hydrohalite in frozen NaCl solutions as seen by X-ray absorption spectroscopy
- 2021
-
Ingår i: Cryosphere. - : Copernicus GmbH. - 1994-0416. ; 15:4, s. 2001-2020
-
Tidskriftsartikel (refereegranskat)abstract
- Laboratory experiments are presented on the phase change at the surface of sodium chloride-water mixtures at temperatures between 259 and 241 K. Chloride is a ubiquitous component of polar coastal surface snow. The chloride embedded in snow is involved in reactions that modify the chemical composition of snow as well as ultimately impact the budget of trace gases and the oxidative capacity of the overlying atmosphere. Multiphase reactions at the snow-air interface have been of particular interest in atmospheric science. Undoubtedly, chemical reactions proceed faster in liquids than in solids; but it is currently unclear when such phase changes occur at the interface of snow with air. In the experiments reported here, a high selectivity to the upper few nanometres of the frozen solution-air interface is achieved by using electron yield near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. We find that sodium chloride at the interface of frozen solutions, which mimic sea-salt deposits in snow, remains as supercooled liquid down to 241 K. At this temperature, hydrohalite exclusively precipitates and anhydrous sodium chloride is not detected. In this work, we present the first NEXAFS spectrum of hydrohalite. The hydrohalite is found to be stable while increasing the temperature towards the eutectic temperature of 252 K. Taken together, this study reveals no differences in the phase changes of sodium chloride at the interface as compared to the bulk. That sodium chloride remains liquid at the interface upon cooling down to 241 K, which spans the most common temperature range in Arctic marine environments, has consequences for interfacial chemistry involving chlorine as well as for any other reactant for which the sodium chloride provides a liquid reservoir at the interface of environmental snow. Implications for the role of surface snow in atmospheric chemistry are discussed. © 2021 BMJ Publishing Group. All rights reserved.
|
|
| 9. |
- Ding, Saiman, et al.
(författare)
-
Time-resolved alkali release during steam gasification of char in a fixed bed reactor
- 2024
-
Ingår i: Fuel. - : Elsevier BV. - 0016-2361 .- 1873-7153. ; 356, s. 129528-
-
Tidskriftsartikel (refereegranskat)abstract
- In this study time-resolved char conversion and alkali release under steam gasification conditions were investigated using a fixed bed reactor. The behaviour of an industrial char and chars produced from straw and furniture waste was investigated. For woody chars, an increase in gasification reactivity is observed together with a notable alkali release as the gasification approaches completion (degree of conversion > 0.8). In contrast, straw char exhibited a decrease in conversion rate and alkali release throughout the gasification process, attributed to the formation of catalytically inactive potassium silicates inhibiting the catalytic role of alkali. Aerosol particles in the 0.01–22 µm size range are emitted during the char conversion. A fraction is formed by nucleation of alkali compounds and other condensable gases. A wide particle distribution that extends over the whole size range is also observed, and the particles are likely to consist of solid char fragments. The study concludes on the importance of alkali release, illustrating the difference in alkali release pattern for high and low ash char.
|
|
| 10. |
|
|
| 11. |
- Ge, Yaxin, 1992, et al.
(författare)
-
Effect of fresh bed materials on alkali release and thermogravimetric behavior during straw gasification
- 2023
-
Ingår i: Fuel. - : Elsevier BV. - 0016-2361 .- 1873-7153. ; 336
-
Tidskriftsartikel (refereegranskat)abstract
- Alkali-associated problems are key issues for the efficient use of straw that is available as a major renewable energy resource worldwide. The effects of six bed materials commonly used in fluidized bed reactors on straw pyrolysis and char gasification were evaluated using online monitoring of alkali release and thermogravimetric analysis. Scanning electron microscopy with energy dispersive spectroscopy was used to determine the elemental composition of the char surface. In the straw pyrolysis stage, alkali release is reduced by the addition of dolomite and silica due to alkali adsorption on the bed materials, and enhanced by the addition of alumina because of its high sodium content. In the char gasification stage, silica, sea sand, olivine, and ilmenite reduce the char reactivity and alkali release, which is attributed to transfer of Si and Ti from the bed materials to the char and reaction with alkali to form stable and catalytically inactive compounds. Alumina also reduces the char conversion rate by transfer of Al to the char and formation of K-Al-Si and Ca-Al-Si compounds, while alkali release from the straw and alumina blend remains high due to the high Na content in alumina. Dolomite initially appears to increase the char gasification reactivity, but the results are affected by conversion of volatile matter that deposited on the dolomite in the straw pyrolysis stage. Dolomite also significantly increases the alkali release, which is attributed to Ca reactions with aluminosilicate compounds that allow potassium to remain in volatile form. Fresh bed materials are concluded to have significant effects on straw conversion depending on their chemical composition, and the results can contribute to the understanding required for efficient use of straw in commercial applications of biomass thermochemical conversion.
|
|
| 12. |
- Ge, Yaxin, et al.
(författare)
-
Effects of used bed materials on char gasification : Investigating the role of element migration using online alkali measurements
- 2022
-
Ingår i: Fuel processing technology. - : Elsevier. - 0378-3820 .- 1873-7188. ; 238
-
Tidskriftsartikel (refereegranskat)abstract
- Online alkali measurements using surface ionization are employed to study alkali release during heating of used industrial fluidized bed materials and gasification of biomass-based char and bed material mixtures. The alkali release from the bed materials starts at 820 °C and increases with temperature, the time a bed material has experienced in an industrial process, and in the presence of CO2. Online alkali measurement during heating of char mixed with used bed material shows significant alkali uptake by the char. Complementary SEM-EDS studies confirm the alkali results and indicate that other important inorganic elements including Si, Mg, and Ca also migrate from the bed material to the char. The migration of elements initially enhances alkali release and char reactivity, but significantly reduces both during the final stage of the gasification. The observed effects on char gasification become more pronounced with increasing amount of bed material and increasing time the material experienced in an industrial process. The ash-layer on the used bed material is concluded to play an important role as a carrier of alkali and other active components. The char and bed material systems are closely connected under operational conditions, and their material exchange has important implications for the thermal conversion.
|
|
| 13. |
- Ge, Yaxin, 1992, et al.
(författare)
-
Impacts of fresh bed materials on alkali release and fuel conversion rate during wood pyrolysis and char gasification
- 2023
-
Ingår i: Fuel. - : Elsevier BV. - 0016-2361 .- 1873-7153. ; 353
-
Tidskriftsartikel (refereegranskat)abstract
- Bed materials provide efficient heat transfer and catalytic function in the thermochemical conversion of biomass, but their interactions with the fuel remain incompletely understood. In this study, the effects of bed materials on alkali release and fuel conversion during wood pyrolysis and CO2 gasification are investigated by online alkali detection combined with thermogravimetric analysis. The investigated bed materials include silica, sea sand, alumina and the natural ores olivine, ilmenite and dolomite. Only dolomite has a significant effect on fuel mass loss and alkali release during wood pyrolysis, while all bed materials influence char reactivity and alkali release during gasification. Sea sand, alumina and dolomite enhance the char gasification during the whole or most of the gasification process, which is related to alkali migration from the bed materials. All bed materials affect char reactivity and alkali release when the conversion approaches completion, and small amounts of some bed materials reduce the alkali release by an order of magnitude. The findings can be understood based on the chemical composition of the different materials. Silicon-rich materials reduce the levels of catalytically active alkali by formation of stable alkali silicates, and a similar explanation applies for ilmenite that captures alkali efficiently. Magnesium and calcium in contrast promote alkali release through their influence on alkali silicate chemistry. Analysis of char surfaces using scanning electron microscopy with energy dispersive spectroscopy indicates that low amounts of several elements are transferred from the bed material to the char where they may be directly involved in the char conversion process. The transferred elements are specific for each bed material and relates to their chemical composition. Mechanisms for material exchange between bed material and char are discussed.
|
|
| 14. |
- Ge, Yaxin, 1992, et al.
(författare)
-
Online monitoring of alkali release during co-pyrolysis/gasification of forest and agricultural waste: Element migration and synergistic effects
- 2023
-
Ingår i: Biomass and Bioenergy. - : Elsevier BV. - 0961-9534 .- 1873-2909. ; 172, s. 106745-106745
-
Tidskriftsartikel (refereegranskat)abstract
- Fuel blends may be used to meet several operational needs in thermal conversion of biomass waste, including optimization of ash properties and fuel conversion efficiency. In this study, online alkali measurements using surface ionization are employed to study synergistic effects produced by inorganic elements during co-pyrolysis/gasification of wood and straw waste. Synergistic effects on the fuel conversion behavior are not observed during co-pyrolysis, while alkali migration from straw to wood is clearly observed above 600 °C by online alkali monitoring. In contrast, synergistic effects on char conversion and alkali release are substantial during co-gasification. Positive effects on char reactivity during most of the gasification process are attributed to alkali migration from the straw to the wood char, and the most pronounced effect occurs at a gasification temperature of 900 °C and a straw content of 25%. Negative effects on char reactivity are observed at the final gasification stage, which is associated with a significantly reduced alkali release from fuel blends compared to pure wood char. The effect is attributed to the migration of silicon, phosphorus, and aluminum to the wood char, as revealed by scanning electron microscopy with energy dispersive spectroscopy, where the elements react with alkali to form catalytically inactive compounds. The mixing of biofuels is concluded to result in substantial effects on the fuel conversion efficiency, which should be taken into consideration in thermochemical conversion of biomass.
|
|
| 15. |
- Ge, Yaxin, 1992, et al.
(författare)
-
Real-time monitoring of alkali release during CO2 gasification of different types of biochar
- 2022
-
Ingår i: Fuel. - : Elsevier BV. - 0016-2361 .- 1873-7153. ; 327
-
Tidskriftsartikel (refereegranskat)abstract
- Potassium and sodium compounds play both positive and negative roles during biomass gasification, but the detailed behavior of alkali metal compounds remain incompletely understood. In this study, alkali release during CO2 gasification of biochar is characterized online with a surface ionization method in combination with thermogravimetric analysis of the char samples undergoing gasification. For wood chars, the alkali release rate follows a slowly decreasing trend as the char conversion proceeds, but increases by up to two orders of magnitude when the conversion approaches completion. In contrast, the alkali release from straw char is 40-50 times higher than observed for wood char and decreases continuously during the whole gasification process. A high temperature and a high CO2 concentration enhance both alkali release and char reactivity. The char preparation method also influences the alkali release from pine char, while the char reactivity is less affected. Alkali release and char reactivity are linked, but other factors including mineral content, surface area and char structure may play important roles for the observed reactivity. The results provide a basis for understanding of alkali behavior during gasification and may help optimize catalytic effects and reduce detrimental issues in biomass gasification.
|
|
| 16. |
- Johansson, Sofia M., 1983, et al.
(författare)
-
A novel gas-vacuum interface for environmental molecular beam studies
- 2017
-
Ingår i: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 88:3
-
Tidskriftsartikel (refereegranskat)abstract
- Molecular beam techniques are commonly used to obtain detailed information about reaction dynamics and kinetics of gas-surface interactions. These experiments are traditionally performed in vacuum and the dynamic state of surfaces under ambient conditions is thereby excluded from detailed studies. Herein we describe the development and demonstration of a new vacuum-gas interface that increases the accessible pressure range in environmental molecular beam (EMB) experiments. The interface consists of a grating close to a macroscopically flat surface, which allows for experiments at pressures above 1 Pa including angularly resolved measurements of the emitted flux. The technique is successfully demonstrated using key molecular beam experiments including elastic helium and inelastic water scattering from graphite, helium and light scattering from condensed adlayers, and water interactions with a liquid 1-butanol surface. The method is concluded to extend the pressure range and flexibility in EMB studies with implications for investigations of high pressure interface phenomena in diverse fields including catalysis, nanotechnology, environmental science, and life science. Potential further improvements of the technique are discussed. Published by AIP Publishing.
|
|
| 17. |
- Johansson, Sofia M., 1983, et al.
(författare)
-
Experimental and Computational Study of Molecular Water Interactions with Condensed Nopinone Surfaces Under Atmospherically Relevant Conditions
- 2020
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 124:18, s. 3652-3661
-
Tidskriftsartikel (refereegranskat)abstract
- Water and organics are omnipresent in the atmosphere, and their interactions influence the properties and lifetime of both aerosols and clouds. Nopinone is one of the major reaction products formed from beta-pinene oxidation, a compound emitted by coniferous trees, and it has been found in both gas and particle phases in the atmosphere. Here, we investigate the interactions between water molecules and nopinone surfaces by combining environmental molecular beam (EMB) experiments and molecular dynamics (MD) simulations. The EMB method enables detailed studies of the dynamics and kinetics of water interacting with solid nopinone at 170-240 K and graphite coated with a molecularly thin nopinone layer at 200-270 K. MD simulations that mimic the experimental conditions have been performed to add insights into the molecular-level processes. Water molecules impinging on nopinone surfaces are efficiently trapped (>= 97%), and only a minor fraction scatters inelastically while maintaining 35-65% of their incident kinetic energy (23.2 +/- 1.0 kJ mol(-1)). A large fraction (60-80%) of the trapped molecules desorbs rapidly, whereas a small fraction (20-40%) remains on the surface for more than 10 ms. The MD calculations confirm both rapid water desorption and the occurrence of strongly bound surface states. A comparison of the experimental and computational results suggests that the formation of surface-bound water clusters enhances water uptake on the investigated surfaces.
|
|
| 18. |
- Johansson, Sofia M., 1983, et al.
(författare)
-
The Dynamics and Kinetics of Water Interactions with a Condensed Nopinone Surface.
- 2017
-
Ingår i: The journal of physical chemistry. A. - : American Chemical Society (ACS). - 1520-5215 .- 1089-5639. ; 121:35, s. 6614-6619
-
Tidskriftsartikel (refereegranskat)abstract
- Water and organic molecules are omnipresent in the environment, and their interactions are of central importance in many Earth system processes. Here we investigate molecular-level interactions between water and a nopinone surface using an environmental molecular beam (EMB) technique. Nopinone is a major reaction product formed during oxidation of β-pinene, a prominent compound emitted by coniferous trees, which has been found in both the gas and particle phases of atmospheric aerosol. The EMB method enables detailed studies of the dynamics and kinetics of D2O molecules interacting with a solid nopinone surface at 202 K. Hyperthermal collisions between water and nopinone result in efficient trapping of water molecules, with a small fraction that scatter inelastically after losing 60-80% of their incident kinetic energy. While the majority of the trapped molecules rapidly desorb with a time constant τ less than 10 μs, a substantial fraction (0.32 ± 0.09) form strong bonds with the nopinone surface and remain in the condensed phase for milliseconds or longer. The interactions between water and nopinone are compared to results for recently studied water-alcohol and water-acetic acid systems, which display similar collision dynamics but differ with respect to the kinetics of accommodated water. The results contribute to an emerging surface science-based view and molecular-level description of organic aerosols in the atmosphere.
|
|
| 19. |
- Johansson, Sofia M., 1983, et al.
(författare)
-
Understanding water interactions with organic surfaces: environmental molecular beam and molecular dynamics studies of the water-butanol system
- 2019
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 21:3, s. 1141-1151
-
Tidskriftsartikel (refereegranskat)abstract
- The interactions between water molecules and condensed n-butanol surfaces are investigated at temperatures from 160 to 240 K using the environmental molecular beam experimental method and complementary molecular dynamics (MD) simulations. In the experiments hyperthermal water molecules are directed onto a condensed n-butanol layer and the flux from the surface is detected in different directions. A small fraction of the water molecules scatters inelastically from the surface while losing 60-90% of their initial kinetic energy in collisions, and the angular distributions of these molecules are broad for both solid and liquid surfaces. The majority of the impinging water molecules are thermalized and trapped on the surface, while subsequent desorption is governed by two different processes: one where molecules bind briefly to the surface (residence time < 10 s), and another where the molecules trap for a longer time = 0.8-2.0 ms before desorbing. Water molecules trapped on a liquid n-butanol surface are substantially less likely to escape from the surface compared to a solid layer. The MD calculations provide detialed insight into surface melting, adsorption, absorption and desorption processes. Calculated angular distributions and kinetic energy of emitted water molecules agree well with the experimental data. In spite of its hydrophobic tail and enhanced surface organization below the melting temperature, butanol's hydrophilic functional groups are concluded to be surprisingly accessible to adsorbed water molecules; a finding that may be explained by rapid diffusion of water away from hydrophobic surface structures towards more strongly bound conformational structures.
|
|
| 20. |
- Kong, Xiangrui, et al.
(författare)
-
A continuous flow diffusion chamber study of sea salt particles acting as cloud nuclei: deliquescence and ice nucleation
- 2018
-
Ingår i: Tellus, Series B: Chemical and Physical Meteorology. - : Stockholm University Press. - 0280-6509 .- 1600-0889. ; 70:1, s. 1-18
-
Tidskriftsartikel (refereegranskat)abstract
- © 2018 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group. Phase changes of sea salt particles alter their physical and chemical properties, which is significant for Earth’s chemistry and energy budget. In this study, continuous flow diffusion chamber is used to investigate deliquescence, homogeneous and heterogeneous ice nucleation between 242K and 215K, of four salts: pure NaCl, pure MgCl 2 , synthetic sea water salt, and salt distilled from sampled sea water. Anhydrous particles, aqueous droplets and ice particles were discriminated using a polarisation-sensitive optical particle counter coupled with a machine learning analysis technique. The measured onset deliquescence relative humidities agree with previous studies, where sea water salts deliquescence at lower humidities than pure NaCl. Deliquesced salt droplets homogenously freeze when the relative humidity reaches a sufficiently high value at temperatures below 233K. From 224K and below, deposition nucleation freezing on a fraction of NaCl particles was observed at humidities lower than the deliquescence relative humidity. At these low temperatures, otherwise unactivated salt particles deliquesced at the expected deliquescence point, followed by homogeneous freezing at temperatures as low as 215K. Thus, the observed sea salt particles exhibit a triad of temperature-dependent behaviours. First, they act as cloud condensation particles (CCNs) > 233K, second they can be homogeneous freezing nuclei (HFNs) < 233K and finally they act as ice nucleating particles (INPs) for heterogeneous nucleation < 224K.
|
|
| 21. |
- Kong, Xiangrui, et al.
(författare)
-
A surface-promoted redox reaction occurs spontaneously on solvating inorganic aerosol surfaces
- 2021
-
Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 374:6568
-
Tidskriftsartikel (refereegranskat)abstract
- A surface-promoted sulfate-reducing ammonium oxidation reaction was discovered to spontaneously take place on common inorganic aerosol surfaces undergoing solvation. Several key intermediate species-including elemental sulfur (S-0), bisulfide (HS-), nitrous acid (HONO), and aqueous ammonia [NH3(aq)]-were identified as reaction components associated with the solvation process. Depth profiles of relative species abundance showed the surface propensity of key species. The species assignments and depth profile features were supported by classical and first-principles molecular dynamics calculations, and a detailed mechanism was proposed to describe the processes that led to unexpected products during salt solvation. This discovery revealed chemistry that is distinctly linked to a solvating surface and has great potential to illuminate current puzzles within heterogeneous chemistry.
|
|
| 22. |
- Kong, Xiangrui, et al.
(författare)
-
Adsorbed Water Promotes Chemically Active Environments on the Surface of Sodium Chloride
- 2023
-
Ingår i: Journal of Physical Chemistry Letters. - 1948-7185. ; 14:26, s. 6151-6156
-
Tidskriftsartikel (refereegranskat)abstract
- Gas-particleinterfaces are chemically active environments.This study investigates the reactivity of SO2 on NaCl surfacesusing advanced experimental and theoretical methods with a NH4Cl substrate also examined for cation effects. Results showthat NaCl surfaces rapidly convert to Na2SO4 with a new chlorine component when exposed to SO2 underlow humidity. In contrast, NH4Cl surfaces have limitedSO(2) uptake and do not change significantly. Depth profilesreveal transformed layers and elemental ratios at the crystal surfaces.The chlorine species detected originates from Cl- expelled from the NaCl crystal structure, as determined by atomisticdensity functional theory calculations. Molecular dynamics simulationshighlight the chemically active NaCl surface environment, driven bya strong interfacial electric field and the presence of sub-monolayerwater coverage. These findings underscore the chemical activity ofsalt surfaces and the unexpected chemistry that arises from theirinteraction with interfacial water, even under very dry conditions.
|
|
| 23. |
|
|
| 24. |
- Kong, Xiangrui, et al.
(författare)
-
Coexistence of Physisorbed and Solvated HCI at Warm Ice Surfaces
- 2017
-
Ingår i: Journal of Physical Chemistry Letters. - 1948-7185. ; 8:19, s. 4757-4762
-
Tidskriftsartikel (refereegranskat)abstract
- The interfacial ionization of strong acids is an essential factor of multiphase and heterogeneous chemistry in environmental science, cryospheric science, catalysis research and material science. Using near ambient pressure core level X-ray photoelectron spectroscopy, we directly detected a low surface coverage of adsorbed HCl at 253 K in both molecular and dissociated states. Depth profiles derived from XPS data indicate the results as physisorbed molecular HCl at the outermost ice surface and dissociation occurring upon solvation deeper in the interfacial region. Complementary X-ray absorption measurements confirm that the presence of ions induces significant changes to the hydrogen bonding network in the interfacial region. This study gives clear evidence for nonuniformity across the air ice interface and questions the use of acid base concepts in interfacial processes.
|
|
| 25. |
- Kong, Xiangrui, et al.
(författare)
-
Dynamics and Kinetics of Methanol-Graphite Interactions at Low Surface Coverage
- 2019
-
Ingår i: Chemphyschem. - : Wiley. - 1439-4235 .- 1439-7641. ; 20:17, s. 2171-2178
-
Tidskriftsartikel (refereegranskat)abstract
- The processes of molecular clustering, condensation, nucleation, and growth of bulk materials on surfaces, represent a spectrum of vapor-surface interactions that are important to a range of physical phenomena. Here, we describe studies of the initial stages of methanol condensation on graphite, which is a simple model system where gas-surface interactions can be described in detail using combined experimental and theoretical methods. Experimental molecular beam methods and computational molecular dynamics simulations are used to investigate collision dynamics and surface accommodation of methanol molecules and clusters at temperatures from 160 K to 240 K. Both single molecules and methanol clusters efficiently trap on graphite, and even in rarified systems methanol-methanol interactions quickly become important. A kinetic model is developed to simulate the observed behavior, including the residence time of trapped molecules and the quantified Arrhenius kinetics. Trapped molecules are concluded to rapidly diffuse on the surface to find and/or form clusters already at surface coverages below 10(-6) monolayers. Conversely, clusters that undergo surface collisions fragment and subsequently lose more loosely bound molecules. Thus, the surface mediates molecular collisions in a manner that minimizes the importance of initial cluster size, but highlights a strong sensitivity to surface diffusion and intermolecular interactions between the hydrogen bonded molecules.
|
|
