Periodic Reporting for period 1 - ATMOS (Pollutants and greenhouse gases in the atmosphere - understanding gas-gas and gas-solid interactions towards a cleaner atmosphere)
Okres sprawozdawczy: 2020-04-01 do 2024-01-31
ATMOS designates an international network of 12 scientific groups (Figure 1), whose main objective is the study of atmosphere pollutants, with an emphasis on training students in atmospheric sciences. It aims to enhance the academic prospects of the participants, in particular, of female researchers from third countries. The objectives are intended to be achieved through 194 secondments and 4 networking activities. The school ATMOS2022 and the workshop ATMOS2023 were organized during the 1 period.
Atmosphere pollution is a serious problem both for developed countries and developing countries. A great deal of research effort is devoted to understand the effects of the proliferation of pollutants and greenhouse effect gases (GHG) and to design air pollution strategies. Earth’s atmosphere is a system very rich in chemical species, some of them uncharacterized. ATMOS tries to provide scientific exchange fostering a fast and efficient study of not fully cataloged species.
Volatile organic compounds (VOCs) and radicals are widely present in the atmosphere. Their structural and spectroscopic parameters are needed for species that are not fully characterized. The study of the chemical evolution, the photochemical processes and radical cycles, are objective of the project. Another is the design of strategies for the elimination of pollutants for which gas–gas and gas-solid interaction studies are fundamental. ATMOS focuses on abundant species (GHG) and on oxygenated VOCs (OVOCs) containing internal rotation groups. The main novelties are: a) The spectroscopic description of uncharacterized OVOCs focused to their detection; b) The study of reactive processes to understand in detail the connection between VOCs and atmospheric radicals; c) The exploitation of GHG as reagents towards the preparation of innovative materials, contributing to the reduction of their presence in the environment.
ATMOS is organized into six working packages (WP). WP1, WP2 and WP3 are scientific packages, WP4 and WP5 deal with the project administration and dissemination and WP6 with the training activities. WP1 pursues both the theoretical and the experimental spectroscopic characterization of OVOC’s, atmosphere radicals and abundant atmosphere components. WP2 deals with reactive processes, with the photodissociation pathways of radicals and with the organic peroxy radical reactions; WP3 deals with non-reactive interactions, such as rotationally-inelastic collisions of pairs of small atmosphere components and gas-solid interactions towards the design of new materials for gas sequestration.
Atmosphere pollution is a serious problem both for developed countries and developing countries. A great deal of research effort is devoted to understand the effects of the proliferation of pollutants and greenhouse effect gases (GHG) and to design air pollution strategies. Earth’s atmosphere is a system very rich in chemical species, some of them uncharacterized. ATMOS tries to provide scientific exchange fostering a fast and efficient study of not fully cataloged species.
Volatile organic compounds (VOCs) and radicals are widely present in the atmosphere. Their structural and spectroscopic parameters are needed for species that are not fully characterized. The study of the chemical evolution, the photochemical processes and radical cycles, are objective of the project. Another is the design of strategies for the elimination of pollutants for which gas–gas and gas-solid interaction studies are fundamental. ATMOS focuses on abundant species (GHG) and on oxygenated VOCs (OVOCs) containing internal rotation groups. The main novelties are: a) The spectroscopic description of uncharacterized OVOCs focused to their detection; b) The study of reactive processes to understand in detail the connection between VOCs and atmospheric radicals; c) The exploitation of GHG as reagents towards the preparation of innovative materials, contributing to the reduction of their presence in the environment.
ATMOS is organized into six working packages (WP). WP1, WP2 and WP3 are scientific packages, WP4 and WP5 deal with the project administration and dissemination and WP6 with the training activities. WP1 pursues both the theoretical and the experimental spectroscopic characterization of OVOC’s, atmosphere radicals and abundant atmosphere components. WP2 deals with reactive processes, with the photodissociation pathways of radicals and with the organic peroxy radical reactions; WP3 deals with non-reactive interactions, such as rotationally-inelastic collisions of pairs of small atmosphere components and gas-solid interactions towards the design of new materials for gas sequestration.
During the 1 period, two networking activities, the school ATMOS2022 and the workshop ATMOS2023, have been successfully organized. The aim of the school was to announce the project and motivate north African students for participation in ATMOS. Senior and young participants in ATMOS and six external scientists were invited to present talks concerning the advance of their scientific work in the workshop.
The scientific working groups have been achieved the following activities:
1-Participants in WP1 have tackled different spectroscopic studies combining experimental (FIR, MW, Raman, THz) and molecular fluid dynamics) and theoretical techniques (quantum chemical calculations and theoretical developments) emphasizing species whose studies also concern groups WP2 and WP3.
The spectroscopic characterization of OVOCs and its radicals is a key objective. Studies of neutral species such as CH3COCH3, CH3COCOOH, CH3COCOH, CH3COCHCH3, (CH3CO)2, CH3CHOHCH3, CH3COOOH, CH3OCH2OH, CH3COCH2OH, CH3OOCH3, HCOH, and radicals such as CH3CO, CH2COH, and CH3COCH2, have been achieved.
Studies of CF4 and CHN are in progress but the main attention has been given to CO2, one of the main GHG responsible for the global warning, which has been studied theoretically and through Raman spectroscopy. A theoretical model (UHU) has been applied to CO2. The rotational and vibrational relaxation of CO2 were studied producing a series of supersonic jets at different temperatures.
Aromatic species (see Figure 2) such as el 2-furfural, methylfuran, nitroguaiacol, methyl catechol, methyl thiophene C5H6S and methyl pyrrole have been studied by the groups of ULCO, CNRS, UMV, CAPSHIPS and CQU using as experimental THz spectroscopy, a high-resolution Fourier transform spectrometer IR spectroscopy (JET-AILES-SOLEIL synchrotron), and a pulsed jet coupled to a mid-IR tunable quantum cascade laser spectrometer (SPIRALES)
2- Participants in WP2 have tackled 2 types of problems combining experimental and theoretical techniques:
a) The photodissociation of organic radicals produces additional atmosphere pollutants following radical cycles that are not fully understood. During the first period in collaboration with external laboratories in Madrid, studies of vinyl radical, methanimine, fragments of acetaldehyde and acetone, and the CH2Br radical, have been achieved (see Figure 3). The study of acetaldehyde is part of a PhD Thesis co-supervised in the frame of ATMOS.
Studies of organic peroxy radical reactions in atmospheric degradation of volatile organic compounds VOC’s in simulation chambers are in progress in ULCO.
3-Whitin WP3, 2 lines of research are in progress: studies of gas-gas collisions applied to atmospheric species and the capture of gas pollutants by solids.
In the CSIC, the combination of Raman spectroscopy with supersonic jets has allowed to obtain for the first time a set of self-consistent rate coefficients for inelastic rotational collisions of CO2 over the broad thermal range.
In UHULL, the utilisation of CO2 as a reagent for the modification of the crystal structure of solids, has been explored. Selected mixed metal oxides were reacted with CO2 and led to the formation of oxide-carbonates with modified crystal structures (see Figure 4).
The capture and storage by activated carbon with and without the presence of water, of nitro polycyclic aromatic hydrocarbons, pollutants derived from vehicles, have been studied using theoretical procedure at the molecular level. Gas-solid interactions are also contemplated. The behavior of adsorbed Nitrogen-VOCs s with and without water in ZIF-8 has been studied in the CSIC using solid state simulations.
The scientific working groups have been achieved the following activities:
1-Participants in WP1 have tackled different spectroscopic studies combining experimental (FIR, MW, Raman, THz) and molecular fluid dynamics) and theoretical techniques (quantum chemical calculations and theoretical developments) emphasizing species whose studies also concern groups WP2 and WP3.
The spectroscopic characterization of OVOCs and its radicals is a key objective. Studies of neutral species such as CH3COCH3, CH3COCOOH, CH3COCOH, CH3COCHCH3, (CH3CO)2, CH3CHOHCH3, CH3COOOH, CH3OCH2OH, CH3COCH2OH, CH3OOCH3, HCOH, and radicals such as CH3CO, CH2COH, and CH3COCH2, have been achieved.
Studies of CF4 and CHN are in progress but the main attention has been given to CO2, one of the main GHG responsible for the global warning, which has been studied theoretically and through Raman spectroscopy. A theoretical model (UHU) has been applied to CO2. The rotational and vibrational relaxation of CO2 were studied producing a series of supersonic jets at different temperatures.
Aromatic species (see Figure 2) such as el 2-furfural, methylfuran, nitroguaiacol, methyl catechol, methyl thiophene C5H6S and methyl pyrrole have been studied by the groups of ULCO, CNRS, UMV, CAPSHIPS and CQU using as experimental THz spectroscopy, a high-resolution Fourier transform spectrometer IR spectroscopy (JET-AILES-SOLEIL synchrotron), and a pulsed jet coupled to a mid-IR tunable quantum cascade laser spectrometer (SPIRALES)
2- Participants in WP2 have tackled 2 types of problems combining experimental and theoretical techniques:
a) The photodissociation of organic radicals produces additional atmosphere pollutants following radical cycles that are not fully understood. During the first period in collaboration with external laboratories in Madrid, studies of vinyl radical, methanimine, fragments of acetaldehyde and acetone, and the CH2Br radical, have been achieved (see Figure 3). The study of acetaldehyde is part of a PhD Thesis co-supervised in the frame of ATMOS.
Studies of organic peroxy radical reactions in atmospheric degradation of volatile organic compounds VOC’s in simulation chambers are in progress in ULCO.
3-Whitin WP3, 2 lines of research are in progress: studies of gas-gas collisions applied to atmospheric species and the capture of gas pollutants by solids.
In the CSIC, the combination of Raman spectroscopy with supersonic jets has allowed to obtain for the first time a set of self-consistent rate coefficients for inelastic rotational collisions of CO2 over the broad thermal range.
In UHULL, the utilisation of CO2 as a reagent for the modification of the crystal structure of solids, has been explored. Selected mixed metal oxides were reacted with CO2 and led to the formation of oxide-carbonates with modified crystal structures (see Figure 4).
The capture and storage by activated carbon with and without the presence of water, of nitro polycyclic aromatic hydrocarbons, pollutants derived from vehicles, have been studied using theoretical procedure at the molecular level. Gas-solid interactions are also contemplated. The behavior of adsorbed Nitrogen-VOCs s with and without water in ZIF-8 has been studied in the CSIC using solid state simulations.
During the 1 period, ATMOS was suspended and reactivated due to the pandemic. ATMOS researchers wish the second period to be friendlier than the first, and to be able to organize the ATMOS2024 workshop and the ATMOS2025 Congress.
The study of pollutants has social applications because pollution is a serious problem both for developed and developing countries. Since training activities are also objectives of ATMOS, 4 co-supervised PhD Thesis are in progress. We expect 4-5 more students for the 2 period.
WP1 has been the most active group during the first period. A long list of VOCs has already been studied. Extensive studies of CO2 and 2-furfural are in progress. During the 2 period, we will try to extend studies to other species such as unsaturated hydrocarbons. Within WP2, studies in the simulation chamber are expected. The abundant photodissociation work will be extended to more species. Within WP3, relevant for studies of gas capture by solids, such as the characterization of adsorption on Cu squarate and MOFs, will be achieved.
The study of pollutants has social applications because pollution is a serious problem both for developed and developing countries. Since training activities are also objectives of ATMOS, 4 co-supervised PhD Thesis are in progress. We expect 4-5 more students for the 2 period.
WP1 has been the most active group during the first period. A long list of VOCs has already been studied. Extensive studies of CO2 and 2-furfural are in progress. During the 2 period, we will try to extend studies to other species such as unsaturated hydrocarbons. Within WP2, studies in the simulation chamber are expected. The abundant photodissociation work will be extended to more species. Within WP3, relevant for studies of gas capture by solids, such as the characterization of adsorption on Cu squarate and MOFs, will be achieved.