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

Fosfonat Bazlı MOF'ların Sentezi ve Keşfi: Solvotermal Bir Yaklaşım

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.

Yazar Spotlight: Mikro Gözenekli Malzeme Kimyasında Keşfi Hızlandırma 

İzoretiküler Al(III) Fosfonat Bazlı Metal-Organik Çerçeve Bileşiklerinin Yüksek Verimli Yöntemler Kullanılarak Keşfi ve Sentez Optimizasyonu

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  

Kristal Malzeme Al-CAU-60'ın Solvotermal Sentezi ve İzolasyonu

Başlamak için, bağlayıcı H4PMP'yi Al-CAU-60 için politetrafloroetilen veya PTFE uçlarına katı olarak ekleyin. Ardından, alüminyum klorür çözeltisini, demineralize suyu ve katkı maddesi çözeltisini eklere eklemek için bir pipet kullanın. Diskleri numune plakasına yerleştirin ve doldurulmuş PTFE uçlarını numune plakasına yerleştirin.Reaktörün topraklama plakasını PTFE eklerinin tanımlanmasına izin verecek şekilde işaretleyin ve doldurulmuş PTFE ekleri ile numune plakasını zemin plakasına yerleştirin. İki PTFE tabakası hazırlayın ve tam kapsama sağlayacak şekilde numune plakalarına yerleştirin. PTFE levhanın doğru şekilde yerleştirildiğinden ve kılavuz pimleri kullanarak kafa plakasına oturduğundan emin olun.Vidaları ekleyin ve elle sıkın. Ardından, başlangıçta kapalı olan reaktörü mekanik veya hidrolik bir pres yardımıyla kapatın ve vidaları tekrar elle sıkın. Multiklavı programlanabilir bir cebri konveksiyonlu fırına yerleştirin.Al-CAU-60 için ekranda gösterilen sıcaklık süresi programını ayarlayın. Ardından sıcaklık süresi programını başlatın. Multiklavı fırından çıkarın.Oda sıcaklığına soğuduktan sonra mekanik veya hidrolik bir pres üzerine koyun ve vidalar elle gevşeyene kadar hafifçe sıkıştırın. Multiklavı bir çeker ocak içine yerleştirin ve reaktörün kafa plakasını çıkarın. Ardından PTFE levhalarını ve numune PTFE ekleriyle birlikte reaktörün zemin plakasından çıkarın.Şimdi filtre bloğunu iki yıkama şişesi aracılığıyla bir vakum pompasına bağlayarak yüksek verimli filtreleme bloğunu monte edin. İki silikon sızdırmazlık matı arasına, filtre bloğundaki karşılık gelen girintilere sahip iki filtre kağıdı yerleştirin. Ardından, uygun girintilerin tavan paspasları ve filtre bloğu ile eşleştiğinden emin olarak PTFE doldurma bloğunu üstüne yerleştirin.Altı saplama cıvatası ile yerinde tutulan sıkıştırma çerçevesini kullanarak katmanları sıkın. Üniteyi düzgün bir şekilde kapatmak için saplama cıvatalarındaki kelebek somunları kullanın ve elle sıkın. Doldurma bloğunun tapalarla doldurulmayacak girintilerini kapatın.Membran vakum pompasını açın ve mümkün olan en iyi vakuma pompalayacağı bir moda ayarlayın. PTFE eklerinin içeriğini tek kullanımlık pipetlerle doldurma bloğunun belirlenmiş kuyucuklarına aktarın. Tüm ekler boşaldığında, kristalleri ikinci kez arayın ve varsa izole edin.Tüm kuyucuklar boşaltıldıktan sonra filtrasyon bloğunu dikkatlice sökün. Artık filtre kağıdında bir ürün kütüphanesi mevcuttur. Çeker ocak içinde kurumaya bırakın.Elde edilen ürünü daha sonra toz x-ışını kırınımı ile karakterize etmek için ürün kitaplığını taban plakası ile kapak plakası arasına yerleştirin. Girintilerin ve plakaların ürün konumlarına uygun olduğundan emin olun. Plakaları hizaladıktan sonra iki vidayla sabitleyin.Ürün kitaplığını difraktometrenin numune tutucusuna yerleştirin. Yüklenen numune tutucuyu dikkatlice difraktometrenin XY aşamasına yerleştirin. Ölçümlere başlamadan önce cihazı kapatın.Parametre alanı bu şekilde gösterilmiştir. Katkı maddesi olarak sodyum hidroksit ile sentez mavi renkle, katkı maddesi içermeyen sentez yeşil renkle ve katkı maddesi hidroklorik asit ile sentez turuncu ve kırmızı renkle vurgulanmıştır. Reaktiflerin molar oranları sol tarafta ve üstte gösterilmiştir.Ölçülen tüm toz X-ışını kırınım modellerinin yığılmış grafiği bu şekilde gösterilmiştir. Burada, katkı maddesi sodyum hidroksit mavi renkle vurgulanır, hiçbir katkı maddesi yeşil renkle vurgulanmaz ve katkı maddesi hidroklorik asit kırmızı ile vurgulanır. Sentez karışımında kullanılan başlangıç malzemelerinin molar oranlarıyla ilişkili olan numune adları burada gösterilmiştir.Bu sonuçlar, düşük kristalliğe sahip ürünlerin, sodyum hidroksitin alüminyuma molar oranının bire bir olduğu veya sodyum hidroksit veya hidroklorik asidin bulunmadığı sentezden elde edildiğini göstermektedir. Katkı maddesi olarak hidroklorik asidin kullanıldığı sentezden daha yüksek kristalliğe sahip ürünler elde edildi.

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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 ...