Bayesian calibration of thermodynamic models for the uptake of CO2 in supported amine sorbents using ab initio priors

• Published in: Physical chemistry chemical physics : PCCP 2013-01, Vol.15 (12), p.4355-4366
• Main Authors: Mebane, David S, Bhat, K. Sham, Kress, Joel D, Fauth, Daniel J, Gray, McMahan L, Lee, Andrew, Miller, David C
• Format: Article
• Language: English
• Subjects: Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Porous materials; Solid-gas interface; Surface physical chemistry
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c3cp42963f

A statistical methodology was applied to the simultaneous calibration and validation of thermodynamic models for the uptake of CO 2 in mesoporous silica-supported amines. The methodology is Bayesian, and follows the procedure introduced by Kennedy and O'Hagan. One key aspect of the application presented is the use of quantum chemical calculations to define prior probability distributions for physical model parameters. Inclusion of this prior information proved to be crucial to the identifiability of model parameters against experimental thermogravimetric data. Through the statistical analysis, a quantitative assessment of the accuracy of various quantum chemical methods is produced. Another important aspect of the current approach is the conditioning of the model form discrepancy - a critical component of the Kennedy and O'Hagan methodology - to the experimental data in such a mannner that it becomes an implicit function of the model parameters and thereby connected with the posterior distribution. It is shown that the inclusion of prior information in the analysis leads to a shifting of uncertainty from the posterior distribution for model parameters to this conditioned model form discrepancy. Prospects for more accurate model predictions and propagation of uncertainty in upscaling and extrapolation through a "model-plus-discrepancy" approach are discussed. The synthesis methods and thermogravimetric characterization of hybrid grafted/impregnated mesoporous silica-supported amine sorbents are presented, along with the details of the quantum chemical study, which shows that a carbamic acid-base acceptor complex is the most stable form of adsorbed CO 2 in both alkanol- and ethyleneamines. Experimental and theoretical methods combine in a Bayesian predictive framework for chemical systems.