Name: Solvothermal Synthesis and Isolation of the Crystalline Material Al-CAU-60
Uploaded: 2023-10-06T14:20:00
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solvothermal synthesis and isolation of the crystalline material al-cau-60

포스포네이트 기반 MOF의 합성 및 발견: 용융열 접근법

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.

저자 스포트라이트: 미세 다공성 재료 화학의 발견 가속화 

고처리량 방법을 사용한 isoreticular al(III) phosphonate 기반 금속-유기 프레임워크 화합물의 발견 및 합성 최적화

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  

결정질 물질 Al-CAU-60의 용매열 합성 및 분리

시작하려면 링커 H4PMP를 Al-CAU-60용 폴리테트라플루오로에틸렌 또는 PTFE 인서트에 고체로 추가합니다. 그런 다음 피펫을 사용하여 염화 알루미늄 용액, 탈염수 및 첨가제 용액을 삽입물에 첨가하십시오. 디스크를 샘플 플레이트에 삽입하고 채워진 PTFE 인서트를 샘플 플레이트에 넣습니다.PTFE 인서트를 식별할 수 있는 방식으로 반응기의 접지판을 표시하고 s를 삽입합니다.ampPTFE 인서트가 채워진 플레이트가 있는 플레이트를 접지판에 삽입합니다. 두 개의 PTFE 시트를 준비하고 샘플 플레이트에 놓아 전체 커버리지를 보장합니다. PTFE 시트가 올바른 위치에 있고 가이드 핀을 사용하여 헤드 플레이트에 맞는지 확인하십시오.나사를 추가하고 손으로 조입니다. 그런 다음 기계식 또는 유압식 프레스를 사용하여 처음 닫힌 반응기를 밀봉하고 손으로 나사를 다시 조입니다. 멀티클레이브를 프로그래밍 가능한 강제 대류 오븐에 넣습니다.Al-CAU-60의 경우 화면에 표시된 온도 시간 프로그램을 설정합니다. 그런 다음 온도 시간 프로그램을 시작합니다. 오븐에서 멀티클레이브를 꺼냅니다.실온으로 식으면 기계식 또는 유압식 프레스에 놓고 나사가 손으로 풀릴 때까지 부드럽게 압축합니다. 멀티클레이브를 흄 후드 안에 넣고 반응기의 헤드 플레이트를 제거합니다. 그런 다음 반응기의 접지판에서 PTFE 시트와 PTFE 인서트가 있는 샘플 플레이트를 제거합니다.이제 두 개의 세척 병을 통해 필터 블록을 진공 펌프에 연결하여 고처리량 여과 블록을 조립합니다. 필터 블록에 해당 홈이 있는 두 개의 실리콘 밀봉 매트 사이에 두 개의 여과지를 놓습니다. 그런 다음 PTFE 충전 블록을 맨 위에 놓고 적절한 홈이 천장 매트 및 필터 블록과 일치하는지 확인합니다.6개의 스터드 볼트로 제자리에 고정되는 클램핑 프레임을 사용하여 레이어를 조입니다. 장치를 제대로 밀봉하려면 스터드 볼트의 날개 너트를 사용하여 손으로 조입니다. 플러그로 채우지 않는 충전 블록의 홈을 닫습니다.멤브레인 진공 펌프를 켜고 가능한 최상의 진공으로 펌핑하는 모드로 설정합니다. PTFE 삽입물의 내용물을 일회용 피펫을 사용하여 충전 블록의 지정된 웰로 옮깁니다. 모든 인서트가 비워지면 크리스탈을 다시 살펴보고 있는 경우 분리합니다.모든 우물이 배수되면 여과 블록을 조심스럽게 분해하십시오. 이제 필터 용지에서 제품 라이브러리를 사용할 수 있습니다. 흄 후드 내부에서 자연 건조시키십시오.베이스 플레이트와 커버 플레이트 사이에 제품 라이브러리를 배치하여 나중에 분말 X선 회절에 의해 얻은 제품을 특성화합니다. 홈과 플레이트가 제품 위치와 일치하는지 확인하십시오. 플레이트를 정렬한 후 두 개의 나사로 고정합니다.제품 라이브러리를 회절분석기의 샘플 홀더에 삽입합니다. 로드된 샘플 홀더를 회절계의 XY 단계에 조심스럽게 놓습니다. 측정을 시작하기 전에 기기를 닫으십시오.매개변수 공간이 이 그림에 나와 있습니다. 첨가제로 수산화 나트륨을 사용한 합성은 파란색으로 강조 표시되고, 첨가제가없는 합성은 녹색으로 강조 표시되며, 첨가제 염산을 사용한 합성은 주황색과 빨간색으로 강조 표시됩니다. 시약의 몰비는 왼쪽과 상단에 표시됩니다.측정된 모든 분말 X선 회절 패턴의 누적 플롯이 이 그림에 나와 있습니다. 여기서 첨가제 수산화 나트륨은 파란색으로 강조 표시되고 첨가제는 녹색으로 강조 표시되지 않으며 첨가제 염산은 빨간색으로 강조 표시됩니다. 합성 혼합물에 사용된 출발 물질의 몰비와 상관관계가 있는 샘플 이름이 여기에 나와 있습니다.이러한 결과는 수산화 나트륨 대 알루미늄의 몰비가 1 대 1이거나 수산화 나트륨 또는 염산이 존재하지 않는 합성으로부터 낮은 결정성을 갖는 생성물이 얻어 졌음을 시사한다. 더 높은 결정성의 생성물은 염산이 첨가제로 사용 된 합성으로부터 얻어졌다.

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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 ...