Metal Organic Frameworks for Capture and Neutralisation of NOx and NH3: A Comprehensive EPR Study

金属有机骨架(MOF)是由金属离子和称为配体的有机实体组成的多孔性晶体材料。选择有机配体可以构建具有大孔的功能3D结构，可用于捕获、存储和中和二氧化碳、NO2、NO或NH3，为减少空气污染提供解决方案。此外，MOF的金属中心可以用于催化，通过光或电化学将某些有毒物质转化为有用的化学产品，这也是本项目将探索的一条途径。该项目的目标是开发能够捕获、分离和中和目标空气污染物(如NO、NO2和NH3)的坚固的金属有机骨架(MOF)，并利用先进的电子顺磁共振技术来了解MOF催化剂上发生的气体吸收和催化反应的机理。具体目标可概括如下：i)合成包含不同有机配体和不同金属离子(钛、铁、铜、锆、钯)的坚固的金属有机骨架。Ii)用标准物理技术(X射线衍射、核磁共振、SQUID、XPS、扫描电子显微镜)对化合物进行表征。iii)研究化合物的气体吸收和电子性质，以确定它们作为催化剂的能力。iv)应用EPR来探索材料对腐蚀性气体的吸附稳定性和相关的催化反应。v)用先进的EPR技术探索气体吸附和相关催化反应的机理。vi)用特定的软件记录EPR模型数据，以了解它们的性质，以及如何设计出更好的MOF材料，用于清洁空气应用。研究产生的结构-功能机理信息将有助于设计改进的MOF结构，以实现高效的气体吸附和绿色能源生产。学生将掌握金属有机骨架的合成、电子顺磁共振波谱、X射线衍射谱、X射线光电子能谱、气体吸收和由电子顺磁共振监测的催化，以及使用专门软件模拟电子顺磁共振波谱。

Metal organic frameworks (MOFs) are porous crystalline materials made of metal ions and organic entities called ligands. Choice of organic ligands allows to build functional 3D structures with large pores that can be used to capture, store and neutralise CO2, NO2, NO or NH3, providing solutions for reducing air pollution. Moreover, metal sites of MOFs can be used in catalysis to convert, photo- or electro-chemically, certain toxic substances into useful chemical products, an avenue that will also be explored in this project. The aim of the project is to develop robust metal-organic frameworks (MOFs) that can capture, separate and neutralize targeted air pollutants such as NO, NO2 and NH3, and to use advanced electron paramagnetic resonance techniques to understand the mechanisms involved in gas absorption and catalytic reactions occurring over MOF catalysts.Specific objectives can be summarized as follows: i) Synthesize robust metal-organic frameworks that incorporate varying organic ligands and diverse metal ions (Ti, Fe, Cu, Zr, Pd). ii) Characterize the compounds by standard physical techniques (XRD, NMR, SQUID, XPS, SEM).iii) Study the gas absorption and electronic properties of the compounds to establish their ability as catalysts.iv) Apply EPR to probe material stability versus absorption of corrosive gases.v) Explore the mechanisms of gas adsorption and related catalytic reactions by advanced EPR techniquesvi) Model recorded EPR data with specific software to gain understanding of their properties and how we can design better MOF materials for clean-air applications.The structure-function mechanistic information generated from research will help to design improved MOF structures for efficient gas adsorption and green energy production. The student will gain skills in the synthesis of metal organic frameworks, EPR spectroscopy, XRD, XPS, gas absorption, and catalysis monitored by EPR, as well as modelling of EPR spectra using specialised software.