The microporous MIL-120(Al) MOF has been tested for CO2/CH4 separation. The material has been synthesised in powder form at the kilogram scale and shaped into spherical beads without significant loss in adsorption capacity (on average, ca. 7% for CO2). MIL-120(Al) is more selective towards CO2 (IAST mean selectivity of 10.6-35 between 0.1-10 bar), showing a good adsorption capacity and a moderate enthalpy of adsorption (-36.7 to -39.1 kJ mol-1 in the low loading regime). Molecular simulation studies have revealed a probable rotation of the & micro;2-OH groups with increasing CO2 pressure altering the CO2 adsorption capacity at higher pressures. Breakthrough experiments have confirmed the CO2/CH4 selectivity of MIL-120(Al) and have shown that the material can retain its original adsorption separation performance after regeneration, following consecutive cycles (10 cycles) and prolonged exposure to high amounts of water vapour, demonstrating the potential of this MOF for biogas upgrading.

Environment-friendly synthesis of metal-organic frameworks (MOFs) is crucial to meet growing industrial demand. Here, we present a generalized and scalable route for the production of the prototypical Al-OH chain-based microporous and flexible MIL-53 (MIL = Materials Institut Lavoisier) with various functional groups. Until recently, the scale-up of these robust and cost-effective Al-MOFs was hindered by challenges associated with their synthesis and purification, restricting their practical deployment. In this work, we optimized a reflux-based aqueous synthesis method and efficient unreacted linker removal process to yield either nano-sized or micron-sized particles. This approach affords high-purity MOFs and enables large-scale production with a high space-time yield (ca. 200 kg/m³/day), paving the way for broader implementation. As a proof of concept, we successfully produced MIL-53(Al)-NH2 up to 300 g scale maintaining high quality and adsorption properties comparable to those achieved at smaller scale. Finally, shaping was performed using wet granulation method and the obtained spherical beads exhibited excellent mechanical strength and adsorption performances. Environmentally friendly synthesis of metal-organic frameworks is essential to meet growing industrial demand. Here, the authors present a generalized and scalable route to produce prototypical aluminum hydroxide chain–based microporous and flexible metal-organic frameworks with various functional groups.

The microporous bioderived MIL-160(Al) MOF has been investigated for CO2/CH4 separation in the context of biogas upgrading, by complementary experimental and computational studies, from the molecular to the industrial process levels. MIL-160(Al) has been synthesised and shaped into beads using silica, without loss of adsorption performance, beyond the expected loss in adsorption capacity due to the presence of nonporous silica. Experimental and GCMC-simulated adsorption isotherms for pure CO2 and CH4 align closely, validating the strategies used. The latter have been extended to binary CO2:CH4 mixtures, with results cross-validated with IAST. A detailed model has been developed in Aspen Adsorption that uses the LDF approach to describe adsorption kinetics, and the Extended Virial isotherm for multicomponent equilibrium, achieving close agreement between simulation and experimental results. Industrial PSA/VPSA process simulations based on the classic 2-bed, 4-step Skarstrom cycle and the validated model have shown the VPSA process offers better CH4 recovery (ca. 82 vs. 52 %) and similar unit energy consumption when compared to the PSA process (ca. 12 vs. 11 Wh & sdot;mol-1 CH4,Prod), despite having higher raw energy requirements due to vacuum regeneration (ca. 92 vs. 33 kWh per cycle). Considering only electricity, a main operation cost factor, the operation cost for the VPSA process is ca. 98 & sdot;t-1Upgraded biogas, which gives an estimated economic return of ca. 725 & sdot;t-1Upgraded biogas, based on the price of natural gas. Consequently, VPSA emerges as a promising industrial-scale process for biogas upgrading with MIL160(Al) as a promising new adsorbent.

A multiscale study was carried out to evaluate the microporous -Ti-bisphosphonate MIL-91-(Ti) sorbent for postcombustion CO2 capture in industrially relevant conditions. The process performance of the MOF was first assessed by using molecular simulated adsorption isotherms, which predicted an energy consumption of 1.65 MJ/kg and a productivity value of 0.42 mol/m3. Subsequently, this Ti-MOF was characterized using several complementary experimental techniques, and the characterization data were supplied to a process simulator to assess energy consumption and productivity values for 95% purity and 90% recovery targets. The experimental adsorption isotherms resulted in a better process performance, with a minimum energy consumption of 1.03 MJ/kg and a maximum productivity of 0.61 mol/m3. Such a discrepancy is likely to be due to the use of a generic force field that does not accurately capture host-guest intermolecular interactions in a highly confined environment of ultramicroporous MOFs like MIL-91. However, the lower energy consumption and higher productivity of this MOF, which are both desirable outcomes for CO2 capture processes, suggest the viability of MIL-91-(Ti) for implications in real CCS applications.

Understanding the impact of MOF synthesis conditions on the production cost is vital in order to have a competitive product in a view of industrial applications. Here, considering the benchmark mesoporous iron(III) trimesate MIL-100(Fe) as a prototypical example, we show that the production cost can reach <30 $/kg if a careful selection of the synthetic route is made. Two routes were considered in the analysis, using sulfate and nitrate as iron sources. A new optimized synthesis protocol in a laboratory pilot-scale reactor of 5 liters based on iron sulfate was developed using optimized sustainable ambient pressure conditions, leading to larger particles and a higher STY. Based on reliable pilot-scale data and established chemical engineering estimation methods, this leads to a significantly low production cost of high quality MIL-100(Fe) achieving a potential competitive product.

Metal–organic frameworks (MOFs) show captivating performances in many large‐scale applications including gas adsorption and separation, heat reallocation, water production, or remediation which can overcome important drawbacks of the conventionally used porous materials in the industry. This raises, therefore, the commercial interest in MOFs which brings the necessity to decrease the cost of their production, calling for the synthesis optimization from small‐scale to large‐scale. However, the commercial availability, yet very limited, is highly dependent on their production cost. Thus, to promote the commercial development and availability of MOFs, many steps can be taken. In this work, the state‐of‐art of the large‐scale production of MOFs can be first outlined, before discussing the criteria of greener MOF synthesis processes. Besides, a critical evaluation of the available synthesis routes for large‐scale production can be given, taking into consideration their cost, environmental impact, safety, and feasibility. Moreover, since there are strong limitations to the use in the powder form, the shaping procedures can thus be discussed briefly to outline the prospects of MOFs for different industrial applications. Finally, yet importantly, the perspective for MOFs commercialization can be highlighted with an emphasis on the necessity of techno‐economic analyses and life‐cycle assessments.

Biogas has been introduced as a sustainable source of energy, which is considered as a promising alternative for conventional fossil fuels. Indeed, biogas requires to be upgraded from the impurities, specifically, carbon dioxide to be commercially utilized. In this study, the potential of shaped form MIL-160(Al) as a water stable Al dicarboxylate microporous MOF has been assessed concerning the biogas upgrading application. To this end, firstly, the dynamic fixed-bed adsorption of carbon dioxide and methane was investigated at 313 K and 4.0 bar. The measured breakthrough outcomes were simulated with a developed mathematical model, which the results confirmed an acceptable potential of model predictions. Afterwards, a pressure swing adsorption (PSA) process with 5-steps was designed relying on dynamic equilibrium results, and experimentally validated by a lab-scale PSA set-up for a 50:50 CO2/CH4 mixture. Finally, an industrial PSA process was designed to have a precise knowledge on the potential of MIL-160(Al) for biogas upgrading for large scale applications. The results demonstrated the purity and recovery of methane around 99 % and 63 %, respectively, which indicated the appealing capacity of this adsorbent for such a purpose.

Indoor air pollution is one of the major threads in developed countries, notably due to high concentrations of formaldehyde, a harmful molecule difficult to eliminate. Addressing this purification challenge while adhering to the principles of sustainable development requires the use of innovative, advanced sustainable materials. Here we show that by combining state-of-the-art spectroscopic techniques with density-functional theory molecular simulations, we have developed an advantageous mild chemisorption synergistic mechanism using porous metal (III or IV) pyrazole- di-carboxylate based metal-organic framework (MOF) to trap formaldehyde in a reversible manner, without incurring significant energy penalties for regeneration. A straightforward, environmentally friendly, and scalable synthesis protocol was established for the porous, water-stable aluminum pyrazole dicarboxylate known as Al-3.5-PDA or MOF-303, capable of functioning as a highly efficient and reusable filter. It demonstrates selectivity and high storage capacity for formaldehyde under conditions typical of severe indoor use, such as in housing or vehicle cockpits, including varying VOC mixtures and concentrations, humidity, and temperature, without any accidental release. Furthermore, we have successfully regenerated this sorbent using a simple domestic protocol, ensuring the material reusability for at least 10 cycles. Indoor air pollution from harmful and carcinogenic formaldehyde is a concern in developed countries. The authors present a sustainable solution using porous Metal-Organic Frameworks (MOFs) for efficient trapping of formaldehyde and regeneration.

Adsorption processes have already been considered as an appealing technology for carbon capture and climate change mitigation. Accordingly, this work investigated the capacity of shaped MIL-160(Al) as a water stable bioderived Al dicarboxylate microporous metal-organic framework for separation of carbon dioxide and nitrogen concerning postcombustion application. First, breakthrough experiments of carbon dioxide and nitrogen were accomplished at 313 K and 4.0 bar. Then, a set of equations/relations were considered to model the dynamic fixed-bed tests, in which the outcomes proved the capacity of the developed model for such a purpose. Next, a pressure swing adsorption (PSA) process with five steps, including pressurization, feed, rinse, blowdown, and purge, was planned and validated using performed experiments in a laboratory-scale PSA setup. In the end, an industrial PSA process was designed to attain a better grasp of the capacity of MIL-160(Al) for postcombustion application. The results indicated an exciting potential of this adsorbent for postcombustion carbon capture, with the purity and recovery of carbon dioxide around 67.3 and 99.1%, respectively.

Herein we report on a robust microporous aluminum tetracarboxylate framework, MIL-120(Al)-AP, (MIL, AP: Institute Lavoisier and Ambient Pressure synthesis, respectively), which exhibits high CO2 uptake (1.9 mmol g-1 at 0.1 bar, 298 K). In situ Synchrotron X-ray diffraction measurements together with Monte Carlo simulations reveal that this structure offers a favorable CO2 capture configuration with the pores being decorated with a high density of µ2-OH groups and accessible aromatic rings. Meanwhile, based on calculations and experimental evidences, moderate host-guest interactions Qst (CO2) value of MIL-120(Al)-AP (~40 kJ mol-1) is deduced, suggesting a relatively low energy penalty for full regeneration. Moreover, an environmentally friendly ambient pressure green route, relying on inexpensive raw materials, is developed to prepare MIL-120(Al)-AP at the kilogram scale with a high yield while the MOF is further shaped with inorganic binders as millimeter-sized mechanically stable beads. First evidences of its efficient CO2/N2 separation ability are validated by breakthrough experiments while IR operando experiments indicate a kinetically favorable CO2 adsorption over water. Finally, a techno-economic analysis gives an estimated production cost of about 13 $/kg, significantly lower than for other benchmark MOFs. These advancements make MIL-120(Al)-AP an excellent candidate as an adsorbent for industrial scale CO2 capture processes.

Low-temperature storage to slow down degradation is accepted by the film conservation community. Still, this solution prohibits public access, is price-sensitive, has high energy costs, and there are concerns about their effects on the physical stability and material lifetime. In this research, a smart solution is developed based on the selective capture of acetic acid produced by the cellulose acetate polymer. This innovative approach is based on Metal-Organic Frameworks (MOFs) for acetic acid adsorption, specifically a highly selective porous iron(III) based MOF, MIL-100(Fe), which was synthesized using a green approach. The stability of MIL-100(Fe), under acetic acid exposure, was demonstrated by accelerated aging experiments, with no noticeable changes in crystallinity and/or porosity as deduced from powder X-ray diffraction analysis, infrared spectroscopy, thermogravimetric analysis, nitrogen porosimetry, and electron microscopy. Compatibility tests with the artefacts were performed to prove the safety of the MIL-100(Fe) to the artefacts. A field application in a demonstration prototype ( smart box ) was performed at Institut Valencia de Cultura. A recently developed hybrid model provided recommendations on the quantity of adsorbents to use in the smart box . Good agreement was observed between the model predictions and the in-field experimental results, which validated the model application. The model predicted that the new adsorbent (5% of the film's weight, replaced every 10 years, at 16 degrees C or 22 degrees C) extends the film's lifetime equivalently to cold storage (5 degrees C). Finally, environmental impact assessment and life cycle analysis were performed to compare the two preservation approaches. The new approach based on this Fe-MOF yielded an average reduction of carbon footprint related to movie film preservation of about 50% considering the current European Union (EU) energy mix and about 40% considering the 2030 EU energy mix (where a transition towards renewable energy is expected). The proposed innovative technology represents a robust solution towards efficient and more sustainable film preservation while significantly contributing to moving toward climate transition objectives in the culture heritage sector.(c) 2023 The Authors. Published by Elsevier Masson SAS on behalf of Consiglio Nazionale delle Ricerche (CNR).This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

Effective capture of polar volatile organic compounds under environmental conditions is a challenge owing to the adsorption competition between polar volatile organic compounds and water.

Effective capture of polar volatile organic compounds under environmental conditions is a chalenge due to the adsorption competition between the polar volatile organic compouinds and water. The best adsorbents exhibit...

The mesoporous iron polycarboxylate MIL-100(Fe) was synthesized in presence of Pseudomonas putida bacteria. The synthesis was performed under green conditions, i.e. pure aqueous media at 30°C that were compatible with the preservation of the cell membrane integrity. Interestingly, the resulting bio-hybrid exhibited a very different microstructure than a physical mixture of the two components, as it led to the formation of a novel living material featuring an exoskeleton encapsulating individual bacteria cell. Interestingly, TEM and STEM on cross-sections revealed that this shell was not directly in contact with the cell wall, suggesting the exo-polysaccharides network promotes strong interactions with the MOF precursors leading to high proximity between the two components.

Owing to their high porosity and tunability, porous solids such as Metal-Organic Frameworks (MOFs), Zeolites and Activated Carbons (ACs) are of great interest in various fields for instance gas separation, catalysis, water and air purification, among others. These materials are usually in powder form and need to be shaped in some practical way that does not modify their intrinsic property (i.e. porosity). Making porous, freestanding and flexible sheets is a relevant shaping strategy. However, achieving high loadings (> 70 wt %) can challenge mechanical properties. We have developed a new green and simple method that combines two cellulosic fibrous structures of different size, i.e. softwood bleached kraft fibres (S) and nano-fibrillated cellulose (NFC), to form a high porous solids loading (>70 wt %) paper sheet. This dual fiber system produces a synergistic effect, where S provides flexibility while NFC acts as a nanostructuring and mechanical strengthening agent with an optimal S:NFC=25:75 ratio. This method can be applied for the preparation of sheets exhibiting the mechanical properties of paper while keeping the adsorption properties of a wide range of porous solids (MOFs, ACs, Zeolites). As an exemple of application, a MOF paper has been considered for the capture of polar volatile organic compounds, showing better performance than other shaping processes such as beads and granules.

Adsorptive separation via scalable and inexpensive adsorbents is now considered among the credible alternative solutions for post-combustion carbon mitigation via selective physisorption of CO2. As industrial gas streams contain many times water vapours, the use of sorbents showing limited detrimental effect of humidity on the working capacity in the operating conditions is considered as a major advantage contributing to lowering the operating costs and/or accelerating the capture process. Here we report on a robust microporous aluminum tetracarboxylate framework, MIL-120(Al)-AP, (MIL and AP refers to Materials from Institute Lavoisier and for Ambient Pressure synthesis, respectively), which possesses high CO2 uptake (1.9 mmol g-1 at 0.1 bar, 298 K) due to a favorable pore architecture combining high density of µ2-OH groups and stacked aromatic rings, close to the performances of the benchmark CO2 physisorbent, CALF-20 (CALF stands for Calgary Frameworks). Advanced in situ synchrotron X-ray diffraction measurement together with GCMC simulations allowed to get deeper insights into the preferential sites that the structure of MIL-120(Al) offers for a favorable CO2 capture, while revealing the importance of the µ2-OH and their accessibility to CO2 for controlling the gas uptakes at low pressure. This supports further the great potential of MIL-120(Al)-AP towards post-combustion capture. Meanwhile, Qst (CO2) value of MIL-120(Al)-AP (44 kJ mol-1) prone to relatively low energy penalty for full regeneration compared to amine-based solutions (90~140 kJ mol-1) and to their stability limitations. Moreover, a phase transition from monoclinic to triclinic occurs due to partial removal of free water molecules, with ca. 40% water molecules still remaining trapped between Al oxo/hydroxo chains, enabling additional interactions with CO2 molecules during adsorption step. Finally, an environmentally friendly ambient pressure green route, relying on the use of inexpensive raw materials, was optimized to prepare the MIL-120(Al)-AP at kg-scale with high yield and high quality. The MOF was further shaped as millimeter (mm)-sized beads with inorganic binders while first evidences of its efficient CO2/N2 separation ability were validated by breakthrough experiments, thus suggesting the high potential of this MOF in a view of integration into an industrial scale CO2 capture process.

Among a plethora of drug nanocarriers, biocompatible nanoscale metal-organic frameworks (nanoMOFs) with a large surface area and an amphiphilic internal microenvironment have emerged as promising drug delivery platforms, mainly for cancer therapy. However, their application in biomedicine still suffers from shortcomings such as a limited chemical and/or colloidal stability and/or toxicity. Here, we report the design of a hierarchically porous nano-object (denoted as USPIO@MIL) combining a benchmark nanoMOF (that is, MIL-100(Fe)) and ultra-small superparamagnetic iron oxide (USPIO) nanoparticles (that is, maghemite) that is synthesized through a one-pot, cost-effective and environmentally friendly protocol. The synergistic coupling of the physico-chemical and functional properties of both nanoparticles confers to these nano-objects valuable features such as high colloidal stability, high biodegradability, low toxicity, high drug loading capacity as well as stimuli-responsive drug release and superparamagnetic properties. This bimodal MIL-100(Fe)/maghemite nanocarrier once loaded with anti-tumoral and anti-inflammatory drugs (doxorubicin and methotrexate) shows high anti-inflammatory and anti-tumoral activities. In addition, the USPIO@MIL nano-object exhibits excellent relaxometric properties and its applicability as an efficient contrast agent for magnetic resonance imaging is herein demonstrated. This highlights the high potential of the maghemite@MOF composite integrating the functions of imaging and therapy as a theranostic anti-inflammatory formulation.

Owing to their high porosity and tunability, porous solids such as metal-organic frameworks (MOFs), zeolites, or activated carbons (ACs) are of great interest in the fields of air purification, gas separation, and catalysis, among others. Nonetheless, these materials are usually synthetized as powders and need to be shaped in a more practical way that does not modify their intrinsic property (i.e., porosity). Elaborating porous, freestanding and flexible sheets is a relevant shaping strategy. However, when high loadings (>70 wt.%) are achieved the mechanical properties are challenged. A new straightforward and green method involving the combination softwood bleached kraft pulp fibers (S) and nano-fibrillated cellulose (NFC) is reported, where S provides flexibility while NFC acts as a micro-structuring and mechanical reinforcement agent to form high loadings porous solids paper sheets (>70 wt.%). The composite has unobstructed porosity and good mechanical strength. The sheets prepared with various fillers (MOFs, ACs, and zeolites) can be rolled, handled, and adapted to different uses, such as air purification. As an example of potential application, a MOF paper composite has been considered for the capture of polar volatile organic compounds exhibiting better performance than beads and granules.

Nanoparticles of biocompatible iron carboxylate metal-organic frameworks (MOFs) or nanoMOFs are of great interest for biomedicine, in particular, for controlled drug release. However, little is known about the impact of their synthesis protocols on their defect content and the possible consequences in terms of physicochemical features and cytotoxicity. Here, we report for the first time how the defect content of the benchmark mesoporous iron trimesate MIL-100-(Fe) (MIL stands for Materials of Institut Lavoisier) nanoparticles, with similar sizes but obtained from three different green synthesis routes, has a significant impact not only on their intrinsic porosity, stability in body fluids, drug loading capacity, and release but also shows a critical difference of in vitro toxicity and inflammatory response depending on the type of cell lines.