Healy Colm, Harvey-Reid Nathan C, Howard Ben I, Kruger Paul E
MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch 8140, New Zealand.
Dalton Trans. 2020 Dec 21;49(47):17433-17439. doi: 10.1039/d0dt03852k. Epub 2020 Nov 23.
Hybrid Ultramicroporous Materials (HUMs) are porous coordination materials with exemplary gas sorption and separation characteristics, but relatively poor thermal stability when compared to other porous coordination polymers or metal-organic frameworks (MOFs). The origin of this poor thermal stability has not yet been experimentally verified. Therefore, we investigate the thermal decomposition mechanisms of representative HUMs with the general formulae [M(SiF)(L)] or [M(SiF)(L)(HO)], where M = Ni(ii), Cu(ii) or Zn(ii) and L = pyrazine or 4,4'-bipyridine. We find that two decomposition mechanisms dominate: (i) the fragmentation of the XF pillar into gaseous XF and fluoride, and (ii) direct sublimation of the N-donor ligand. The former process dictates the overall thermal stability of the material. We also demonstrate that HF is a possible decomposition product from certain hydrated HUM materials.
混合超微孔材料（HUMs）是具有出色气体吸附和分离特性的多孔配位材料，但与其他多孔配位聚合物或金属有机框架（MOF）相比，其热稳定性相对较差。这种热稳定性差的根源尚未得到实验验证。因此，我们研究了通式为[M(SiF)(L)]或[M(SiF)(L)(HO)]的代表性HUMs的热分解机制，其中M = Ni(ii)、Cu(ii)或Zn(ii)，L = 吡嗪或4,4'-联吡啶。我们发现两种分解机制起主导作用：（i）XF柱分解为气态XF和氟化物，以及（ii）含氮供体配体的直接升华。前一过程决定了材料的整体热稳定性。我们还证明HF是某些水合HUM材料可能的分解产物。
