We report herein the synthesis and full spectroscopic characterization of two A2B-corrole phosphonic acids. Thanks to the presence of a phosphonic acid functional group at the 10-meso-position, the corroles were covalently linked to the hexanuclear Zr clusters of a PCN-222 metal-organic framework (MOF). After the insertion of cobalt into the corrole macrocycle, the metal complexes are able to bind small volatile molecules such as carbon monoxide (CO). Interestingly, the resulting doped porous materials were used for selective detection of CO, with excellent selectivity for CO vs. CO2, N2, and O2.

Two 3D MOFs based on triphenylcorrole and its cobalt-metalated analog (CoCorr-MOF) are presented. They show a hexagonal structure, a homogeneous particle size, and microporosity with a specific area of 390 and 304 m2 g-1, respectively. The CoCorr-MOF presents a better affinity for CO than for other interferents (N2, CO2 and O2), demonstrating a CO chemisorption capacity of 7.2 cm3 g-1 with high selectivity.

The high risk of CO poisoning justifies the need for indoor air quality control and warning systems based on the detection of low concentrations (ppm‐ppb) of CO. Cobalt corrole complexes selectively bind CO vs. O2, CO2, N2, opening new fields of applications. By combining the CO chemisorption properties of cobalt corroles with the known sorption capacity of MOFs, we hope to obtain high performance sensing materials for CO detection. In addition, the exposed metal sites of MOFs lead to CO2 physisorption, allowing the co‐detection of CO and CO2. In this work, PCN‐222 a stable Zr‐based MOF made from Ni(TCPP) with natural vacancies has been used as a porous matrix for the grafting of electron‐poor metallocorroles. The materials were characterized by powder XRD, SEM and optical microscopy, BET analyses and gas adsorption measurements at 298 K. No degradation of the crystalline structure of PCN‐222 was observed. At 1 atm, the adsorbed CO(g) volumes measured for the best materials were 12.15 cm3 g‐1 and 14.01 cm3 g‐1 for CoCorr2@PCN‐222 and CoCorr3@PCN‐222 respectively, and both materials exhibited high CO chemisorption and selectivity against O2, N2, and CO2 at low pressure due to the highest energy of the chemisorption process vs physisorption. (198 Words)

Detection of carbon monoxide (CO) at few ppm levels is a critical point for quality control of domestic and industrial environment. CO is responsible for thousands of intoxications and hundreds of deaths per year in the world. Moreover, CO is a residual gas found in the industrial dihydrogen used for Proton Exchange Membrane fuel cell, and deactivates the fuel cell prematurely. Corroles have been largely used in sensing applications.[1] Cobalt corroles display high binding affinity for carbon monoxide even in the presence of nitrogen and dioxygen.[2] The affinity of the Co(III) metallocorroles for CO is directly correlated with the Lewis acid character of the metal center. The electrochemistry and spectro-electrochemistry properties have been studied. We have shown that structural modifications on the aromatic ring have a direct influence on the reactivity of the metal complex. We have recently obtained very low CO detection level (ppm) using SAW devices functionalized by cobalt corrole deposited as a film on a silica or a gold surface.[3] Our previous work on the synthesis of porous sol-gel materials functionalized by cobalt corroles gave us encouraging results for CO sorption and detection and prompted us to prepare new porous structured materials functionalized by corrole complexes for gas detection applications. Among all the methods of synthesis of porous architectures, organic materials belonging to the POP (Porous Organic Polymer) family are an appealing and original approach in this research field.[4] The synthesis of new POPs functionalized by cobalt corroles (Fig. 1) will be reported. Their selective sorption properties for CO over N2, O2 and CO2 will be also presented. Preliminary results concerning the design of Molecularly Imprinted Polymers (MIPS) as enzyme mimics for the decontamination of a broad spectrum of pesticides and chemical warfare agents will be also reported. Authors would like to acknowledge the ANR program (MIPEnz-Decontam, 20-CE39-0016-01), the FEDER and the “Région Bourgogne” for financial support (ISITE CO2DECIN) REFERENCES: [1] Di Natale, C.; Gros, C. P.; Paolesse, R., Chem. Soc. Rev. 2022, 000;[2] J.-M. Barbe, G. Canard, S. Brandès, F. Jerôme, G. Dubois, R. Guilard, Dalton Trans. 2004, 1208-1214; [3] Vanotti, M.; Poisson, S.; Soumann, V.; Quesneau, V.; Brandes, S.; Desbois, N.; Yang, J.; Andre, L.; Gros, C. P.; Blondeau-Patissier, V., Sensors and Actuators B: Chemical 2021, (332), 129507. [4] S. Brandès, V. Quesneau, O. Fonquernie, N. Desbois, V. Blondeau-Patissier, C. P. Gros, Dalton Trans. 2019, 48, 11651-11662 (Front Cover). Figure 1

During the last decades, the potential impact of indoor air quality on human health has stimulated an interest in hazardous compounds survey, such as carbon monoxide (CO). The detection of these compounds has consequently become a vital need. To address this issue, we propose a Surface Acoustic Wave (SAW) device functionalized with metallocorroles used for the selective detection of CO. Here, we insist on the necessity to detect CO in the presence of interferents, such as O2 that is obviously present in the air, carbon dioxide (CO2) present in significant quantity in urban area (400 ppm) and humidity (H2O) which is a well-known interferent in the case of SAW-based gas sensors. We will report on the interest of a differential configuration of the sensor that takes advantage of accurate organic layers, to improve the stability of the sensor’s signal and lower the sensitivity to interferents. Acknowledgments: this work was supported by the PIA-Excellence ISITE-BFC (CoMICS program 2019-2022: Chemistry of Molecular Interactions - Catalysis and Sensors) and the ISITE CO2DECIN. REFERENCES: [1] Di Natale, C.; Gros, C. P.; Paolesse, R., Chem. Soc. Rev. 2022, 000;[2] J.-M. Barbe, G. Canard, S. Brandès, F. Jerôme, G. Dubois, R. Guilard, Dalton Trans. 2004, 1208-1214; [3] Vanotti, M.; Poisson, S.; Soumann, V.; Quesneau, V.; Brandes, S.; Desbois, N.; Yang, J.; Andre, L.; Gros, C. P.; Blondeau-Patissier, V., Sensors and Actuators B: Chemical 2021, (332), 129507. [4] S. Brandès, V. Quesneau, O. Fonquernie, N. Desbois, V. Blondeau-Patissier, C. P. Gros, Dalton Trans. 2019, 48, 11651-11662 (Front Cover). Fig. 1.Double delay line SAW-based CO sensor (left) and Open-loop phase measurement (Right) Figure 1

During the last decades, the potential impact of indoor air quality on human health has stimulated an interest in hazardous compounds survey such as carbon monoxide (CO). The detection of this compound has consequently become a vital need. To address this issue, we propose a Surface Acoustic Wave (SAW) device functionalized with metallocorroles used for the selective detection of CO. Here, we insist on the necessity to detect CO in the presence of interferents, such as O-2 that is obviously present in the air, CO2 present in significant quantity in urban area (400 ppm) and humidity (H2O) which is a well-known interferent in the case of SAW-based gas sensors. We report the interest of a differential configuration of the sensor that takes advantage of accurate organic layers, to lower the sensitivity to outer parameters as well as interferents. The sensitivity of the sensor under various conditions and the repeatability of the measurements are finally shown to assess the efficiency of our device.

The potential impact of indoor air quality on human health has become an increasingly important topic of public health and, thus, has stimulated an interest in hazardous compounds survey such as carbon dioxide. To address this issue, we started the development of a Surface Acoustic Wave device functionalized with metal-organic framework for the selective detection of carbon dioxide. Here, we propose preliminary results on the influence of the size of the metal-organic framework crystals on the sensor’s selectivity and on its evolution with the ageing of the sensor. Keywords-Carbon dioxide sensor; SAW device; metalorganique framework.

The quantification of specific gases among thousands of VOCs (Volatile Organic Compounds) present in the human breath at the ppm/ppb level can be used to evidence the presence of diseases in the human body. The detection of these biomarkers in human exhaled breath through a noninvasive approach is an important field of research that is still attracting significant attention to this day. A portable device working at room temperature and usable directly on exhaled breath samples is still a challenge requiring a sensing material with high performances. The rich composition of the human breath implies that the sensing material must be highly selective and sensitive (ppm/ppb) in high relative humidity (RH) conditions and preferably at room temperature. The present work intends to provide a review on recent works in this application field through the use of porous materials and discuss the importance of Metal Organic Frameworks (MOFs) for such application. MOFs are highly porous crystalline materials often used for gas detection and capture, thus raising questions about their potential for detection in exhaled breath.

The exploitation of solar energy, an unlimited and renewable energy resource, is of prime interest to support the replacement of fossil fuels by renewable energy alternatives. Solar energy can be used via concentrated solar power (CSP) combined with thermochemical energy storage (TCES) for the conversion and storage of concentrated solar energy via reversible solid–gas reactions, thus enabling round the clock operation and continuous production. Research is on-going on efficient and economically attractive TCES systems at high temperatures with long-term durability and performance stability. Indeed, the cycling stability with reduced or no loss in capacity over many cycles of heat charge and discharge of the material is pursued. The main thermochemical systems currently investigated are encompassing metal oxide redox pairs (MOx/MOx−1), non-stoichiometric perovskites (ABO3/ABO3−δ), alkaline earth metal carbonates and hydroxides (MCO3/MO, M(OH)2/MO with M = Ca, Sr, Ba). The metal oxides/perovskites can operate in open loop with air as the heat transfer fluid, while carbonates and hydroxides generally require closed loop operation with storage of the fluid (H2O or CO2). Alternative sources of natural components are also attracting interest, such as abundant and low-cost ore minerals or recycling waste. For example, limestone and dolomite are being studied to provide for one of the most promising systems, CaCO3/CaO. Systems based on hydroxides are also progressing, although most of the recent works focused on Ca(OH)2/CaO. Mixed metal oxides and perovskites are also largely developed and attractive materials, thanks to the possible tuning of both their operating temperature and energy storage capacity. The shape of the material and its stabilization are critical to adapt the material for their integration in reactors, such as packed bed and fluidized bed reactors, and assure a smooth transition for commercial use and development. The recent advances in TCES systems since 2016 are reviewed, and their integration in solar processes for continuous operation is particularly emphasized.

Thermochemical energy storage is promising for the long-term storage of solar energy via chemical bonds using reversible redox reactions. The development of thermally-stable and redox-active materials is needed, as single metal oxides (mainly Co and Mn oxides) show important shortcomings that may delay their large-scale implementation in solar power plants. Drawbacks associated with Co oxide concern chiefly cost and toxicity issues while Mn oxide suffers from slow oxidation kinetics and poor reversibility. Mixed metal oxide systems could alleviate the above-mentioned issues, thereby achieving improved materials characteristics. All binary oxide mixtures of the Mn-Co-Fe-Cu-O system are considered in this study, and their properties are evaluated by experimental measurements and/or thermodynamic calculations. The addition of Fe, Cu or Mn to cobalt oxide decreased both the oxygen storage capacity and energy storage density, thus adversely affecting the performance of Co3O4/CoO. Conversely, the addition of Fe, Co or Cu (with added amounts above 15, 40 and 30 mol%, respectively) improved the reversibility, re-oxidation rate and energy storage capacity of manganese oxide. Computational thermodynamics was applied to unravel the governing mechanisms and phase transitions responsible for the materials behavior, which represents a powerful tool for predicting the suitability of mixed oxide systems applied to thermochemical energy storage.

Thermochemical storage of solar heat involves the heat effects of reversible chemical reactions and can be coupled with a solar thermal power plant for continuous electricity generation. A comprehensive study of chemical materials for thermochemical heat storage based on reversible redox reactions was conducted. The evaluation of the selected systems was based on their suitable transition temperatures, chemical conversion rates, reversibility, energy storage density as well as general criteria such as toxicity and cost, and resulted in the selection of metal oxides (based on Co and Mn), perovskites and carbonates/ hydroxides (of Ca, Sr, Ba). For metal oxides processed in air, Co3O4/CoO was cycled as powder bed and porous foam without reactivity loss, whereas Mn2O3/Mn3O4 showed poor reversibility, which can be enhanced via the synthesis of porous microstructure. The potential improvement of their performance was further studied using transition metal addition. The addition of Fe, Cu or Mn to Co3O4/CoO was found to adversely decrease the redox activity and energy storage capacity. In contrast, the reaction rate, oxygen exchange capacity, reversibility and stability of Mn2O3/Mn3O4 were significantly enhanced with added Fe, Co, or Cu amounts above similar to 15, 40 and 30 mol% respectively, while the energy storage capacity was improved accordingly. Perovskites represent another attractive class of thermally-stable redox materials (e.g., energy storage density above 200 kJ/kg for Ca0.5Sr0.5MnO3), but the continuous lattice oxygen transfer may be a barrier for the recovery of the absorbed energy, thus requiring pressure-swing operation with inert gas utilization. Finally, carbonates and hydroxides were identified as promising candidates chiefly because they exhibit the highest energy storage capacities among the considered materials, but they require closed-loop operation. Among these systems, both SrCO3/SrO and Sr(OH)(2)/SrO stabilized with MgO as well as Ca(OH)(2)/CaO showed remarkable cycling stability and energy storage densities. (C) 2018 Elsevier Ltd. All rights reserved.

•A new solar chemical reactor for continuous particles processing was developed.•A rotary tube concept was used for moving bed circulation and uniform tube heating.•Reliable solar reactor operation during limestone (CaCO3) calcination was demonstrated.•Pure lime (CaO) was produced at 1000 °C with suitable tube tilting angle and rotational speed.•The scalable reactor concept can be applied to various solid-gas thermochemical reactions.

Thermochemical energy storage (TCES) can be achieved via reversible redox reactions based on metal oxides for solar energy storage applications in solar power plants. As cobalt oxide (Co3O4/CoO) and manganese oxide (Mn2O3/Mn3O4) appear as attractive candidates for TCES, an experimental study has been conducted to evaluate the potential of mixed oxides from the Co–Cu–O, Mn–Co–O, and Mn–Cu–O systems. The addition of Cu to Co3O4 allows accessing promising materials with good cycling stability and high reaction enthalpy for TCES applications. As for the Mn–Co–O and Mn–Cu–O systems, the role of the hausmannite phase formation at low Co or Cu contents on the irreversibility of Mn-based mixed oxides is made evident, thus demonstrating the interest of the addition of a secondary metal oxide to the Mn-based material. For the Mn–Co–O system, low amounts of Mn should be favored, since both the oxygen storage capacity and the reaction enthalpy significantly increase with decreasing Mn contents, and the reversibility ...

The potential of metal oxides for thermochemical heat storage in solar power plants at high temperature via reversible redox reactions has been largely demonstrated, and cobalt oxide and manganese oxide commonly appear as the most attractive simple oxides. However, drawbacks of pure oxides such as slow reaction kinetics, low reversibility, loss-in-capacity over cycles or sintering, could be tackled by the addition of a secondary oxide This work presents the experimental evaluation of mixed oxides from the Co-Cu-O, Mn-Cu-O, and Co-Mn-O systems. Within the studied series of mixed oxides, the Co-Cu-O system with low amounts of Cu (<= 10 mol%) shows very good cycling stability and high reaction enthalpy (similar to 570 kJ.kg(-1)). Among the mixed oxides studied in the Mn-Cu-O system, the compositions with Cu amounts in the range 40-80 mol% feature promising redox properties with complete reaction reversibility, even though sintering remains an issue. In contrast, compositions with Cu amounts below 30 mol% cannot be cycled because of the formation of the hausmannite phase during reduction, which inhibits further reoxidation. The compositions with less than 40% Mn in the Co-Mn-O system retain an interesting enthalpy for thermochemical energy storage in CSP plants for a cheaper material than pure cobalt oxide, but the reaction enthalpy decreases with the Mn content. In this system, the cycling ability is lost over 70 mol% Mn due to hausmanite phase formation, similarly to the case of Mn-Cu-O system.

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above ~15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

The efficiency and economic competitiveness of thermal storage for concentrating solar power plant can be improved by increasing the operating temperature (above 600 degrees C). Thermochemical energy storage is an attractive way of efficiently storing high-temperature solar heat, in the form of chemical bonds as a stable and safe solid material, when compared with existing sensible and latent heat storage materials. Among the most interesting materials, BaCO3, CaCO3 and SrCO3 show high storage temperatures (typically above 800 degrees C), energy storage densities, and charging and discharging rates. Heat charge corresponds to the calcination (decarbonation) reaction of the carbonates (endothermal step) and heat discharge corresponds to the reverse carbonation of the oxides (exothermal step). A comparative thermodynamic and kinetic study of calcination and carbonation reactions involving commercial and synthesized CaCO3, SrCO3 and BaCO3 powders was performed for application in thermochemical energy storage. An experimental study based on thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) was conducted to study the decomposition and carbonation reactions and to determine the enthalpy of reaction for each metal carbonate. While complete calcination was achieved regardless of the metal carbonate involved, partial carbonation was observed with loss in CO2 capture capacity during cycling. The effect of the addition of a promoting agent such as magnesium oxide on thermal stability for improving chemical and structural cyclability of these three candidate carbonates was also investigated. Beneficial effect of MgO addition was demonstrated and noticeable performance stability was obtained in the case of SrCO3/SrO during successive energy storage cycles. (C) 2017 Elsevier Ltd. All rights reserved.

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Thermochemical redox processes involving novel oxygen ion conducting materials with perovskites structure are studied to evaluate their application potential for solar energy storage in concentrated solar power plants. A series of Ba and Sr containing perovskites was synthesized via modified Pechini method and their crystal structure was characterized by XRD. The thermochemical reduction-oxidation steps of the redox cycle and oxygen exchange capacity of the perovskites were investigated by thermogravimetric (TG) analysis. The results revealed that Co-based perovskites are the most promising candidates for solar thermochemical energy storage application. The O-2 release/absorption of Co-based perovskites is completed in a reversible way when reaching a given temperature. BaCoO3 reduction occurs promptly when the temperature reaches 900 degrees C in Ar atmosphere (pO(2) = 10(-6) atm), and the oxidation proceeds completely as soon as the gas is switched from Ar to 20% O-2 at 600 degrees C. In these conditions, the amount of monatomic oxygen released captured reaches 0.47/0.49 mol per mol BaCoO3. Part substitution in A site improves the O-2 exchange capacity of Ba0.5Sr0.5FeO3-delta but not Ba0.5Sr0.5CoO3-delta, while part substitution in B-site improves the O-2 exchange capacity of SrCo0.8Fe0.2O3-delta and SrCo0.2Fe0.8O3-delta. Part substitution together in A-site and B-site of perovskites does not improve the O-2 exchange capacity of Ba0.5Sr0.5Co0.8Fe0.2O3-delta and Ba0.5Sr0.5Co0.2Fe0.8O3-delta. The Fe-based perovskites generally exhibit continuous non-stoichiometry changes according to the temperature change suggesting continuous topotactic evolution, while the non-stoichiometry of Mn-based systems is almost not changed at the considered temperatures. Ba containing systems (BaCoO3, BaFeO3 and Ba0.5Sr0.5CoO3) show the largest oxygen release ability under inert (pO(2) = 10(-6) atm) or oxidizing atmosphere (pO(2) = 0.2 atm) up to 1050 degrees C, while only BaCoO3 can be fully re-oxidized at 600 degrees C in a 20% O-2 atmosphere, with an energy storage capacity of 292 J/g. (C) 2016 Elsevier Ltd. All rights reserved.

A viable way to manage the inherently intermittent availability of solar energy in concentrated solar power plants is to store solar energy during on-sun hours to be able to use it later during off-sun hours, enabling on-demand electricity delivery. Thermochemical heat storage systems present some noteworthy advantages when compared with latent and sensible heat storage, namely (i) high energy storage density because the storage capacity by unit of mass or volume corresponding to the reaction enthalpy is generally high, (ii) heat storage at room temperature and long term energy storage because the products can be cooled and stored at room temperature without energy losses as heat can be stored indefinitely in chemical bonds, (iii) facility of transport because solid materials can be transferred over long distances, (iv) constant restitution temperature providing constant heat source because exothermic reactions are carried out at sufficiently high temperatures to generate electricity in constant conditions and therefore to produce a constant power. This paper presents an overview of the different potential thermochemical systems based on reversible solid-gas reactions operating at high temperatures and a screening of suitable materials that are interesting candidates in the 400–1200°C range for thermochemical heat storage in concentrated solar power systems. The most promising materials belonging to the metal oxides, hydroxides, and carbonates solid-gas systems are selected for experimental validation and further investigations.