In situ monitoring of hydrothermal and solvothermal synthesis of molecular sieves

多孔材料，特别是沸石和金属有机骨架（MOF），作为催化剂和吸附剂在化学工业中发挥着关键作用。联合项目的目的是开发新的光谱技术，将其与已知技术相结合，分别对沸石和金属有机框架（MOF）的水热合成和溶剂热合成进行直接比较和互补的原位监测。这将为提高对这两种材料类别的稳健制备及其所需性能的可预测调整的科学理解开辟新的视角。结合使用原位核磁共振、拉曼光谱、FTIR光谱，以及XRD、超声波光谱和动态光散射，可以以时间分辨的方式在同一实时模式下研究原子、分子、纳米和微米水平的晶体形成过程。这种具体的联合研究将产生关于分子筛形成不同阶段的过程的基本新信息，即(1)分子相互作用（核磁共振、拉曼、红外光谱）；（ii）结晶核的形成（NMR, Raman， FTIR）和（iii）晶体生长（US光谱，DLS， XRD）。该项目的具体目标包括：1)制定适合沸石BEA和MFI以及基于mil -53的mof的原位研究的水热和溶剂热合成程序，以联合应用各种原位技术；2)利用MAS NMR开发和优化原位细胞和方法，在原子、分子、纳米和微米尺度上对水热和溶剂热合成进行原位监测；FTIR、拉曼、DLS和US光谱技术；3)阐明了水热合成的主要参数，即合成方法（清液法、溶胶-凝胶法、干凝胶法）、模板类型、矿化剂类型和杂原子类型对沸石BEA和MFI形成机理的影响；4)揭示溶剂热合成mof的主要参数，即溶剂种类和用量、温度、金属源/连接物比对MIL-53形成机理的影响。

Porous materials, esp. zeolites and metal-organic frameworks (MOF), play a key role in chemical industry as catalysts and adsorbents. The joined project aims at the development of novel spectroscopic techniques applied in a specific combination with already known techniques for a direct comparative and complementary in situ monitoring of the hydrothermal and solvothermal synthesis of zeolites and metal-organic frameworks (MOF), respectively. This will open new perspectives for improving the scientific understanding for the robust preparation of both of these material classes and for their predictable tuning of required properties. The combined use of in situ NMR, Raman, FTIR spectroscopy, along with XRD, ultrasonic spectroscopy, and dynamic light scattering will allow to study the crystal formation processes at atomic-, molecular-, nano- and micrometric levels at the same and real time mode in a time-resolved way. Such specifically combined investigation will give rise to obtain fundamentally new information about the processes at the different stages of molecular sieve formation namely (i) molecular interaction (NMR, Raman, FTIR); (ii) the formation of crystallization nuclei (NMR, Raman, FTIR) and (iii) the crystal growth (US spectroscopy, DLS, XRD).Specific goals of the project include: 1) Elaboration of hydrothermal and solvothermal synthetic procedures adapted to the in situ studies of zeolites BEA and MFI as well as MIL-53-based MOFs for combined application of various in situ techniques; 2) Development and optimization of in situ cells and methodological approaches for the in situ monitoring of hydrothermal and solvothermal synthesis at the atomic, molecular, nano- and micrometric scales using MAS NMR; FTIR, Raman, DLS and US spectroscopic techniques; 3) Elucidation of the effect of the main parameters of hydrothermal synthesis, namely, the method of synthesis (clear solution process, sol-gel synthesis, dry-gel conversion), type of template, type of mineralizing agent and type of heteroatom on the mechanism of zeolites BEA and MFI formation; 4) Unravel the effect of the main parameters of solvothermal synthesis of MOFs, namely, type and amount of solvent, temperature and metal source/ linker ratio on the mechanism of MIL-53 formation.