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Nanoporous Metal-Organic Frameworks for production

Final Report Summary - NANOMOF (Nanoporous Metal-Organic Frameworks for production)

Executive Summary:

1.1 Executive summary
The nanoMOF-project focused on the development of novel metal-organic frameworks, the formulation and integration of these MOF materials into products and systems. Three high-potential application areas were chosen to demonstrate the applicability and performance of MOFs in industrial applications: 1) MOFs for gas purification, 2) MOFs for safe gas delivery systems, and 3) MOFs for catalysis. A consortium was formed by 17 beneficiaries from 10 European countries, from leading technology developers, through equipment suppliers and major end-users.
For each application area, specific MOFs were developed and evaluated, starting from simple networks leading to more complicated structures in the end (e.g. CPO-27, new MOFs based on isonicotinic acid, Zirconium MOFs, iron MOFs, nickel MOFs, copper MOFs, isoreticular series of Ni-MOFs, DUT-MOFs, HPW/Cu3(BTC)2, ZIF-8, CaBDC-MOF). Cu3(BTC)2 was identified as a valuable compound for gas purification and was selected for upscaling in the demonstrator and prepared as several kg batch. For gas storage well established materials (MIL-100, Cu3(BTC)2) were produced in a kg-scale. For catalytic applications, heteropolyacids in MOFs were established.
The processing of the synthesized MOFs essentially determines the applicability and performance of the MOF material in the final products. For skin and respiratory protection applications, three-dimensionally loaded MOF-functionalized nonwovens were produced and evaluated. The combination of MOF adsorbers with conventional carbon based adsorbents proved to be beneficial. Furthermore, alternative processing routes such as electrospinning, direct fixation by directed growth of MOF on the fibre surface, and simple entrapment of MOFs in the void spaces between the fibres have been performed. Evaluation tests focused on the capacity and the stability of the novel textile air filters and the fulfillment of the ABEK requirements. First large-scaled samples (few square meters) of MOF loaded textiles were produced in upscaling tests and show promising performance data.
For the use of MOFs as a bulk material, spherical granules with satisfactory adsorption properties in a wide variety of sizes are required. Shaping technologies like the oil drop process and the gelation process were developed to achieve required size of MOF granules (< 1 mm). For application in catalysis, encapsulated heteropolyacid MOF (HPW@Cu3(BTC)2) was coated on substrates.
To demonstrate the potential of the novel MOF materials, dedicated demonstrators were developed, equipped with a well-suited MOF-material, synthesized and processed within the nanoMOF frame. The following demonstrators were developed and tested:
- Protective gloves from textile filters with Cu3(BTC)2- impregnated adsorbents
- Filter canisters for respiratory protection by using a stack of nonwoven filters with Cu3(BTC)2 and flat filter media with impregnated carbon adsorbents
- Filter canisters for respiratory protection by using a stack of flat filter media with Cu3(BTC)2 and carbon adsorbents
- Gas purifier unit containing Cu3(BTC)2 coated spheres, equipped with a colorimetric loading sensor and a trace gas analyzer
- High pressure gas cylinder loaded with MOF granules
- A test platform, designed as batch- and continuous tubular reactors, for esterification of oleic acid with glycerol for the selective production of monoglyceride equipped with different MOF catalysts

All activities in the field of MOF synthesis, processing and demonstration were supported by the development and manufacturing of the required equipment for the experiment implementation, production and for test purposes. Dedicated analysis of the adsorption performance of the (processed) MOFs as well modeling and simulation activities, were essential for the nanoMOF progress.
The success of the nanoMOF project can be shown on hand of 24 peer-reviewed papers, the presentation of nanoMOF results at more than 30 conferences and the two well-attended workshops, organized by the nanoMOF consortium.

Project Context and Objectives:
1.2 Summary description of project context and objectives
Metal-Organic Frameworks (MOFs) represent a novel class of nanoporous materials with extremely high specific surface areas surpassing that of traditional adsorbents such as zeolites and activated carbon. The overall objective of this Large-scale integrating collaborative project is to engineer MOFs for industrial applications in catalysis, gas storage, and gas purification using the modular construction principles of MOFs for pore size engineering and functionalization. The project substantially strengthens the position of Europe in the industrial use of Metal-Organic Frameworks, a research area so far dominated by US and Japanese companies and research organizations.
Focussing on environmental applications of MOFs, the integrating project has targeted to establish an internationally leading position for Europe, using the direct integration of MOFs into products. Major efforts in recent years were devoted to the exploration of building principles of MOFs and basic structural characterization demonstrating the outstanding properties of this new class of nanoporous solids. However, for the industrial utilization and commercialization, large-scale production, integration in products such as textile filters for air purification, performance evaluation in catalytic and separation processes under realistic conditions is necessary. The project has explored new MOF materials and their functionalization specifically designed for applications in separation (gas purification), gas storage, and heterogeneous catalysis.

NanoMOF-project has focused beyond discovery and has integrated MOFs into products with industrial impact within a strong cooperation of established MOF research institutions and industrial end users.

Three major impact areas have been selected:
Area 1 focuses on the one hand side on separation processes for downstream feed purification in chemical industry. Highly selective separation processes are crucial for the efficient production of industrial gases. The modular concept allows tailoring MOF materials in pore diameter and pore functionality by introducing functional groups and accessible metal centers in the pore interior. The latter allows adjusting the materials properties and tailor pore sizes for specific molecules to be removed, resulting in increased energy efficiency and lower degree of waste production.
For many industrial downstream applications, hydrocarbon feedstock has to be purified before further processing to prevent poisoning of catalysts. Sulphur in the form of H2S or an organic compound is present in almost all hydrocarbon feed streams, ranging from naphtha to middle distillates. For some downstream applications, such as fuel cell reformer units sulphur reduction to less than 200 ppb wt. sulphur requires hydrogenation to H2S followed by adsorption. Product purity to achieve can be below the limit of commercially available sensing techniques. Selective hydrogenation catalysts, installed downstream have to be perfectly protected to pursue their basic activity and selectivity. MOF materials can be tailor made in pore size, surface functionality, and binding affinity towards small molecules resulting in a unique selectivity and high capacity for separation processes. The concept of accessible metal sites in MOFs is a key technique to achieve a high adsorption selectivity and binding strength for compounds such as H2S. Thus, they are ideally suited for downstream purification.

As a second target in area 1 the high selectivity and capacity for toxic volatile compounds was used for the integration into protective clothing and gas masks. Air permeable protective clothing and gas mask filters require a high adsorption rate and high binding strength for gases like ammonia, but also hydrophobic MOFs for organic toxic volatile compounds. At the same time integration into textiles and immobilization of porous particles is a key target. For a high adsorption rate, MOF nanoparticles are beneficial due to enhanced transport and reduced diffusion limitation. MOF/fibre composites must be designed to guarantee air permeability for protective clothing and selective adsorption of toxic compounds at the same time.

Area 2 focuses on gas storage. In nanoporous solids such as MOFs, gases can be stored in the adsorbed state. Due to the higher density of the adsorbed molecules, the effective storage capacity can be significantly increased by a factor of 2.5-3 as compared to empty cylinders. Not only the capacity is increased but also the pressure needed to store the gases is reduced improving the safety of the storage system. For highly toxic gases used in semiconductor industry, adsorptive storage in MOFs should be used for the first time to reduce handling and contamination risks by reducing the storage pressure needed for operation. Selective removal of contaminants is a key issue in electronic grade gases and air purification. For electronic grade gases, the adsorbent can be designed to act as a getter system for the removal of contaminants in high purity gases. The modular concept of MOFs allows adjusting the chemical functionality to specifically remove the contaminants but release the stored gas. For such a “safe delivery system”, MOFs need to be processed into compact bodies.

Area 3 focuses on catalysis. Catalysis is an ecologically responsible and economically attractive technology that can cope with consumer expectations of ever increasing quality of goods and services, with societal demands for increasing effectiveness to maintain global competitiveness and with the concern of environmental protection. Three extraordinary properties of MOFs are expected to lead to exceptional catalytic performances: (1) the high specific surface area; (2) the well-defined pore size, and (3) the unique coordination chemistry of transition metals and main group elements. These properties should be enabling the development of highly selective catalysts for atom and energy efficient processes. The proposal is focusing on novel MOF materials based on tin and titanium, metals for which only few MOF examples exist so far. The replacement of liquid Lewis acids based on titanium and tin by solid MOF catalysts for (trans)esterification processes in the oleochemical area is targeted. These generic model reactions with a practical scope are particularly relevant to the conversion of fatty acids and triglycerides into a variety of valuable products for cosmetics, foodstuff, detergents, etc. A multidisciplinary approach involving (1) synthesis and evaluation of catalyst materials; (2) characterization and kinetic evaluation; (3) modelling of the catalytic process and (4) pilot scale validation in a balanced industrial-academic partnership was aimed.

The general key targets for nanoMOF project were the development of novel metal-organic frameworks, the formulation and integration of these novel and known MOF materials into products and systems. The industrial research and generic engineering objectives were:
• Exploration of new materials and novel nanoporous structures with customized functionality for industrial processes or products
• Processing technology for MOFs and integration in textiles
• Development of air filter modules
• Protective clothing for personal protection
• Gas purification/adsorption system for removal of minority contaminants in clean industrial processes
• MOF compacts with high packing density
• Safe delivery gas storage system for toxic gases for semiconductor industry
• Lewis type MOF catalysts for monoglyceride production processes
• Simulation and modelling of the gas / MOF interactions
• Crosscutting engineering: equipment and dedicated software for process monitoring and quality assurance
• Evaluation of long term potential strategic value of MOF technology by “road mapping”

Project Results:
Please see the attachment.

Potential Impact:
1.4 Potential impact
The discovery of porous hybrid materials constructed from inorganic nodes and organic multifunctional linkers has established a new area of inorganic-organic hybrids (Metal-Organic Frameworks, MOFs) with extraordinary performance as compared to traditional porous solids such as zeolites and activated carbon. The European joint project “nanoMOF” focused the activities to integrate nanostructured MOFs into products with industrial impact within a strong cooperation of established MOF research institutions and industrial end users. All parts of the development chain, respectively the future value chain, were addressed in the frame of the project: synthesis route of different MOF, up-scaling of MOF synthesis, processing of MOF material, integration of MOF into industrial relevant processes and products. The development of technologies and integration of MOFs are supported by advanced modelling, simulation and process monitoring techniques. The project aimed for a higher integration of MOFs into products with a high added value in order to propel Europe into an internationally leading position in the industrial use of MOFs.

The nanoMOF project was designed in such a way, that different application areas were addressed. All activities starting from the MOF synthesis, processing and up to the integration of MOFs were derived decidedly from the target applications.

Impact area “Gas purification”: The purity of gases has an important economic and environmental relevance. Specific porous materials for selective gas adsorption require an application in advanced filter systems. Industrial feed gases and exhaust gases require a high purity to ensure durable processes and avoid pollution. The integration of MOFs into textile products enables the development of novel filter materials with high air permeability and a high capacity of the elimination of toxic compounds from air and industrial feed gases. For industrial and house-hold applications novel MOF-based gas purification systems can be developed.

Impact area “Safe gas storage and delivery”: Safe and high capacity storage of high purity gases is crucial for tool operation in semiconductor and solar industry. With the aid of porous hybrid materials, the storage capacity of tank systems will be enhanced. Adsorptive gas storage is achieved under reduced pressure will improve handling safety. Furthermore, the adsorption of gaseous impurities results in a purification of the released gases.

Impact area “Catalysis”: Catalysis is an ecologically relevant and economically attractive technology. The replacement of liquid acids by solid state catalysts avoids the production of toxic liquid waste. Decidedly designed MOF catalysts have the potential to support the conversion of natural resources into valuable products for the oleochemical industry.

The nanoMOF project produced significant contributions for all addressed application fields, in the whole MOF process chain. In the frame of the nanoMOF project, 16 exploitable results have been identified. This exploitable foreground has been clustered in different sectors of applications. The potential impact sectors are chemical industry, gas purification, personal protection, gas storage, oleochemical industry, material testing, training.

The exploitable results in the area of chemical industry have been especially focused on the ability to supply industrial quantities of MOF, because the limited availability of MOFs has being addressed as a major obstacle. The synthesis formulation and technologies for up scaling the MOF production, and the delivery of MOF in the kg scale are remarkable. Furthermore, the attention has turned to reduced solvent processes and solvent-free processes to scale up metal organic frameworks. This provides an opportunity to decrease solvent use drastically during the scale up. The nanoMOF project has demonstrated scale up of MOFs up to 20 kg by a reduced solvent method route for the different applications in the consortium. More sustainable processes have been identified as the way forward to scale up this type of material. The impact of this result on potential growth in Europe has been rated as been substantial and the impact will be immediate.

The exploitable results in the sector of gas purification has shown that the development of a MOF material for this application which may be regenerated (in contrast to current products) is possible and could create a niche application in this substantial market.
The application of H2S removal acts as a demonstrator process. The knowledge gained from the work allows estimating the application of MOFs in related field as (ultra)purification, in a moderate volume, high value regime due to their advanced technology. Potential applications are seen in the field of nanotechnology, aerospace, automotive, biotechnology and medical applications.

The exploitable result in the field of personal protection has created foreground in the areas of skin and respiratory protection. The synthesis of porous material with high capacity for removal of toxic gas was demonstrated. A significant higher capacity for the target gases was shown compared to state of the art materials such as activated carbon. Afterwards the application of new gas filter structure with MOFs for respiratory protection was demonstrated in respiratory canisters. Novel air permeable textile material with MOFs for skin protection was demonstrated in special protective clothing. The developments are strongly linked with the dedicated technology developed for MOF–loading to nonwoven materials. A 3D-adsorption system with a very high active surface was created.
The technologies developed show in an exemplary manner the MOF formulation and processing up to a dedicated gas filter. Based on developed technology chain, further target gases are addressable. The technologies developed impact directly the equipment of first responders with an inherent need for skin and respiratory protection from chemicals (fire brigade, technical rescue, and police).
Beyond the personal protection, the activities spread to conventional fields of application of industrial gas filter.

In the area of gas storage the exploitable results are concentrated on the area of expensive gases for electronic industry. The work did show that gas storage in MOF-loaded cylinders is possible and also that loading cycles are possible. The total storage capacity for electronic grade gas increase, resp. the same storage capacity of gases is possible at lower pressure. Furthermore, the predicted effect of gas purification during the gas release was detected. For a successful application of the created foreground, that means for the industrial implementation, the availability of MOFs on a multi ton scale is required. Then, a product with reduce life cycle cost and environmental impact (especially the transportation of more gas per cylinder) may be achieved. In addition, the reduced gas pressure in the cylinder results in a higher safety during cylinder handling procedures. Lower pressure in the gas cylinder also results in lower requirements in gas infrastructure.
Furthermore, the selective gas adsorption on porous materials opens new concepts for gas separation, esp. in the production of rare gases.
The MOFs used in the cylinder has to be tailored processed to granulates, which match the requirements for being applied in gas storage as adsorbents. Developed technology for MOF shaping is essential for any MOF usage as bulk material as in gas separation and filtration processes.

The foreground in the sector of oleochemical industry was created in the area of esterification of fatty acids. The esterification of fatty acids for the food industry is a rather small market, but with high added value which may open perspectives for MOFs. The use of non-toxic metal in MOF catalyst enables the same or better performance of esterification processes at lower cost (regarding energy and by products). Furthermore, it causes a reduced carbon footprint. The improved reactor unit using a MOF catalyst created did work. The applied MOFs show process catalytic properties, which are not found in the classical acid/base catalysts. Regarding the contribution to a sustainable growth, this finding is interesting for the market of catalysts in chemical processing which is much segmented and MOF catalyst will have to find their way through to the special applications.

Although the area of testing is not an area exclusive to MOFs, exploitable results have been created which are especially in the area of laser gas analysers and infrared sensors for toxic gas monitoring. The foreground created in this area will have an impact of growth as devises will be sold also to other industrial areas and will stimulate growth also there. Besides this, a test equipment for analyzing adsorptive and absorptive capacities of MOFs on a very small scale has been created which is applicable very general for porous materials, for any other adsorptive materials or for filter structures.

The last exploitable foreground has been created in the area of training. Within the nanoMOF project two workshops have been held. The workshops brought together experts from the scientific MOF community with potential user of the developed MOF technology from industry.
The material and knowledge created in the frame of project has been used for input into other MOF related conferences. The results of the nanoMOF-project were published in a series of scientific publications in international journals (24 papers). The nanoMOF-researchers participated in 33 conferences and reported on the nanoMOF-results.

But, the nanoMOF project identified the current hurdles for a further spreading of MOF technologies, as well. For all applications and impact areas, a tailored MOF production for suitable sized and physically stable MOF particles is mandatory necessary. The scaling up synthesis of the MOF material is still the limiting step in the progress of the technology. Production of MOF at semi-industrial and industrial scale will definitively open market opportunities. Directly linked to this issue are the cost of the MOF material, which have to be decrease significantly. It seems that there are no technological or scientific limitations but there are still some development steps to take.

The foreground created in the nanoMOF project will stimulate sustainable growth in Europe as the transportation of knowledge will help to find applications and exploitation of the results of the project as well as transfer of this knowledge to other areas of application.
All of the partners in the consortium follow up their exploitable results also after the project and expect, depending on MOF availability and price, to be able to market products in the near and midterm future.

List of Websites: