Name: Solvothermal Synthesis and Isolation of the Crystalline Material Al-CAU-60
Uploaded: 2023-10-06T14:20:00
Description: Watch this Scientific Journal Video about Solvothermal Synthesis and Isolation of the Crystalline Material Al-CAU-60 at JoVE.com

solvothermal synthesis and isolation of the crystalline material al-cau-60

Síntesis y descubrimiento de MOF basados en fosfonatos: un enfoque solvotérmico

Metal-organic frameworks (MOFs) are porous, crystalline compounds whose structures consist of metal-containing nodes, like metal ions or metal-oxygen clusters, which are connected by organic molecules (linkers)1. By varying the metal-containing nodes as well as the linker, a variety of compounds can be obtained that exhibit a wide range of properties and therefore have potential applications in different fields1.
The stability of a material is important for its application1,2,3. Therefore, MOFs containing tri- or tetravalent metal ions, such as Al3+, Cr3+, Ti4+, or Zr4+, with carboxylate2 or phosphonate4 linker molecules have been the focus of many investigations5,6,7. In addition to the direct synthesis of stable MOFs, the enhancement of stability through post-synthetic modifications as well as the formation of composites is a field of interest2. Phosphonate-based MOFs have been less often reported compared to carboxylate-based MOFs8. One reason is the higher coordination flexibility of the CPO32- group compared to the -CO2- group, which often leads to the formation of dense structures and greater structural diversity8,9,10,11. In addition, phosphonic acids often must be synthesized, as they are rarely available on the market. While some metal phosphonates exhibit exceptional chemical stability10, systematic access to isoreticular metal phosphonate MOFs, which allows the tuning of properties, is still a topic of high relevance12,13. Different strategies for the synthesis of porous metal phosphonates have been investigated, such as incorporating defects into otherwise dense layers, for example, by partially replacing phosphonate with phosphate ligands4,14. However, as defective structures are poorly reproducible, and the pores are not uniform, other strategies have been developed. In recent years, the use of sterically demanding or orthogonalized phosphonic acids as linker molecules have emerged as a suitable strategy for the preparation of porous metal phosphonates4,8,10,11,13,15,16,17,18. However, a universal synthesis route for porous metal phosphonates has not yet been discovered. As a result, the synthesis of metal phosphonates is often a process of trial and error, requiring the investigation of many synthesis parameters.
The parameter space of a reaction system includes chemical and process parameters and can be vast19. It consists of parameters such as the type of starting material (metal salt), molar ratios of starting materials, additives for pH adjustment, modulators, type of solvent, solvent mixtures, volumes, reaction temperatures, times, etc.19,20. A moderate number of parameter variations can easily result in several hundred individual reactions, making a carefully considered synthesis plan and well-chosen parameter space necessary. For example, a simple study using six molar ratios of the linker to the metal (e.g., M:L = 1:1, 1:2, ... to 1:6) and four different concentrations of an additive and keeping the other parameter constant, leads already to 6 x 4 = 24 experiments. Using four concentrations, five solvents, and three reaction temperatures would necessitate carrying out the 24 experiments 60 times, resulting in 1,440 individual reactions.
High-throughput (HT) methods are based on the concepts of miniaturization, parallelization, and automation, to varying degrees depending on the scientific question being addressed19,20. As such, they can be used to accelerate the investigation of multi-parameter systems and are an ideal tool for the discovery of new compounds, as well as synthesis optimization19,20. HT methods have been used successfully in different fields, ranging from drug discovery to materials science20. They have also been used for the investigation of porous materials such as zeolites and MOFs in solvothermal reactions, as recently summarized20. A typical HT workflow for solvothermal synthesis consists of six steps (Figure 1)19,20,21: a) selection of the parameter space of interest (i.e., the design of experiment [DOE]), which can be done manually or by using software; b) dosing of the reagents into the vessels; c) solvothermal synthesis; d) isolation and workup; e) characterization, which is typically done with powder X-ray diffraction (PXRD); and f) data evaluation, which is followed by step one again.
Parallelization and miniaturization are achieved in solvothermal reactions through the use of multiclaves, often based on the well-established 96-well plate format most commonly used in biochemistry and pharmacy19,20,22,23. Various reactor designs have been reported and several groups have constructed their own reactors19,20. Reactor choice depends on the chemical system of interest, especially the reaction temperature, (autogenous) pressure, and reactor stability19,20. For example, in a systematic study of zeolitic imidazolate frameworks (ZIFs), Banerjee et al.25 used the 96-well glass plate format to perform over 9600 reactions24. For reactions under solvothermal conditions, customized polytetrafluoroethylene (PTFE) blocks, or multiclaves with 24 or 48 individual PTFE inserts, have been described among others by the Stock group19,20.&#160;They are routinely employed, for example, in the synthesis of metal carboxylates and phosphonates. As such, Reinsch et al.25 reported the advantages of the methodology in the field of porous aluminum MOFs25. The in-house made HT reactor systems (Figure 2), which allow 24 or 48 reactions to be studied simultaneously, contain PTFE inserts with a total volume of 2.655 mL and 0.404 mL, respectively (Figure 2A,B). Usually, no more than 1 mL or 0.1 mL, respectively, is used. While these reactors are used in conventional ovens, microwave-assisted heating using SiC blocks and small glass vessels has also been reported26.
The automation of studies leads to time savings and improved reproducibility, as influence of the human factor is minimized20. The degree to which automation has been used varies strongly19,20. Fully automated commercial systems, including pipetting20 or weighting capabilities20, are known. A recent example is the use of a liquid-handling robot to study ZrMOFs, reported by the group of Rosseinsky27. Automated analysis can be performed by PXRD using a diffractometer equipped with an xy stage. In another example, a plate reader was used to screen solid-state catalysts, mainly MOFs, for HT screening of nerve agent degradation28. Samples can be characterized in a single run without the need for manual sample or position changes. Automation does not eliminate human error, but it reduces the possibility of its occurring19,20.
Ideally, all steps in a HT workflow should be adapted in terms of parallelization, miniaturization, and automation to eliminate possible bottlenecks and maximize efficiency. However, if it is not possible to establish a HT workflow in its entirety, it may be helpful to adopt selected steps/tools for one&#39;s own research. The use of multiclaves for 24 reactions is particularly useful here. The technical drawings of the in-house made equipment used in this study (as well as others) are published for the first time and can be found in Supplementary File 1, Supplementary File 2, Supplementary File 3, and Supplementary File 4.

Autor destacado: Acelerando el descubrimiento en química de materiales microporosos 

Descubrimiento y optimización de la síntesis de compuestos metal-orgánicos basados en fosfonato de Al(III) isorreticular utilizando métodos de alto rendimiento

I see the periodic table as a huge playground, and in our research, we focus on the synthesis of new materials, porous materials, such as this here. That's a structural model, and we see holes in the framework. and that can be used to store molecules or also to separate molecules based on the size of these.And in addition to that kind of studies, we also develop new reactor systems in order to accelerate the discovery process. The current experimental challenges are to further accelerate the synthesis and characterization process with additional high throughput instrumentation, such as high throughput absorption characterization device. The lack of detail in publications regarding the synthesis and characterization procedure affecting reproducibility is a well-known problem in chemistry.By providing a thorough description of our method and setup, we aim to encourage other groups to adopt the described methodology, thereby increasing the reproducibility of experimental studies. We do not know what the future will bring since we work on the discovery of new materials, and we never know what kind of properties these materials will have. Nevertheless, I think that the use of linker molecules from renewable feedstocks will play a major role.And regarding the application, the use in sensing and the separation of gas molecules will be very important.

Watch this Scientific Journal Video about Solvothermal Synthesis and Isolation of the Crystalline Material Al-CAU-60 at JoVE.com

Solvothermal Synthesis and Isolation of the Crystalline Material Al-CAU-60  

Síntesis solvotérmica y aislamiento del material cristalino Al-CAU-60

Para comenzar, agregue el enlazador H4PMP como sólido a los insertos de politetrafluoroetileno, o PTFE, para Al-CAU-60. Luego use una pipeta para agregar la solución de cloruro de aluminio, agua desmineralizada y la solución de aditivos a los insertos. Inserte los discos en la placa de muestra y coloque los insertos de PTFE llenos en la placa de muestra.Marque la placa de tierra del reactor de manera que permita la identificación de los insertos de PTFE e inserte la placa de muestra con los insertos de PTFE llenos en la placa de tierra. Prepare dos láminas de PTFE y colóquelas en las placas de muestra asegurando una cobertura total. Asegúrese de que la lámina de PTFE esté colocada correctamente y se ajuste a la placa principal utilizando los pasadores guía.Añade los tornillos y apriétalos con la mano. A continuación, selle el reactor inicialmente cerrado con la ayuda de una prensa mecánica o hidráulica y vuelva a apretar los tornillos a mano. Coloque el multiclave en un horno de convección forzada programable.Para Al-CAU-60, configure el programa de tiempo de temperatura que se muestra en la pantalla. A continuación, inicie el programa de tiempo de temperatura. Retira el multiclave del horno.Una vez que se enfríe a temperatura ambiente, colóquelo en una prensa mecánica o hidráulica y comprímalo suavemente hasta que los tornillos se puedan aflojar con la mano. Coloque el multiclave dentro de una campana extractora y retire la placa principal del reactor. A continuación, retire las láminas de PTFE y la placa de muestra con los insertos de PTFE de la placa de tierra del reactor.A continuación, monte el bloque de filtración de alto rendimiento conectando el bloque de filtro a una bomba de vacío a través de dos botellas de lavado. Coloque dos papeles de filtro entre dos esteras de sellado de silicona con los huecos correspondientes en el bloque de filtro. A continuación, coloque el bloque de llenado de PTFE en la parte superior, asegurándose de que los huecos adecuados coincidan con las alfombrillas del techo y el bloque filtrante.Apriete las capas con el marco de sujeción, que se mantiene en su lugar mediante seis espárragos. Para sellar correctamente la unidad, use tuercas de mariposa en los pernos y apriételos con la mano. Cierre los huecos del bloque de llenado que no se van a llenar con tapones.Encienda la bomba de vacío de membrana y configúrela en un modo en el que bombee hasta el mejor vacío posible. Transfiera el contenido de los insertos de PTFE a los pocillos designados del bloque de llenado con pipetas desechables. Una vez que todos los insertos estén vacíos, busque por segunda vez los cristales y aíslelos si están presentes.Desmonte con cuidado el bloque de filtración una vez que se hayan drenado todos los pozos. Ahora hay disponible una biblioteca de productos en papel de filtro. Deje que se seque al aire dentro de la campana extractora.Coloque la biblioteca de productos entre la placa base y la placa de cubierta para caracterizar el producto obtenido mediante difracción de rayos X de polvo posteriormente. Asegúrese de que los huecos y las placas coincidan con las ubicaciones de los productos. Después de alinear las placas, asegúrelas con dos tornillos.Inserte la biblioteca de productos en el portamuestras del difractómetro. Coloque con cuidado el portamuestras cargado en la etapa XY del difractómetro. Cierre el instrumento antes de comenzar las mediciones.El espacio de parámetros se muestra en esta figura. La síntesis con hidróxido de sodio como aditivo se resalta en azul, la síntesis sin aditivo se resalta en verde y la síntesis con el aditivo ácido clorhídrico se resalta en naranja y rojo. Las proporciones molares de los reactivos se muestran en el lado izquierdo y en la parte superior.En esta figura se muestra el gráfico apilado de todos los patrones de difracción de rayos X de polvo medidos. Aquí, el aditivo hidróxido de sodio se resalta en azul, ningún aditivo se resalta en verde y el aditivo ácido clorhídrico se resalta en rojo. Aquí se muestran los nombres de las muestras, que se correlacionan con las proporciones molares de los materiales de partida utilizados en la mezcla de síntesis.Estos resultados sugieren que los productos con baja cristalinidad se obtuvieron a partir de la síntesis donde la relación molar de hidróxido de sodio a aluminio fue de uno a uno, o no hubo hidróxido de sodio ni ácido clorhídrico. Los productos de mayor cristalinidad se obtuvieron a partir de la síntesis donde se utilizó ácido clorhídrico como aditivo.

Research

JoVE Journal

Chemistry

Solvothermal Synthesis and Isolation of the Crystalline Material Al-CAU-60

Discovery and Synthesis Optimization of Isoreticular Al(III) Phosphonate-Based Metal-Organic Framework Compounds Using High-Throughput Methods

High-throughput (HT) methods are an important tool for the fast and efficient screening of synthesis parameters and the discovery of new materials. This ...