The accurate and precise characterisation of disordered, mesoporous solids continues to be an ongoing challenge due to the high level of complexity of such materials. Common, indirect methods, such as gas sorption and mercury porosimetry, still offer relatively cheap, and, most importantly, statistically representative characterisations of macroscopic samples. This work reviews and expands upon recent developments aimed at increasing, and cross-validating, the information obtained from such methods. This involves developing a better understanding of the pore-pore co-operative effects that emerge only in extensive, disordered pore networks to better interpret raw characterisation data, and to use these effects to deliver more information on the void space. This work also describes novel hybrid methods that also greatly increase the information that indirect methods can deliver on complex mesoporous solids.

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