A new generation of "molecular basket" sorbents (MBS) has been developed by the optimum combination of the nanoporous material and CO(2)/H(2)S-philic polymer sorbent to increase the accessible sorption sites for CO(2) capture from flue gas (Postdecarbonization), and for CO(2) and H(2)S separation from the reduced gases, such as synthesis gas, reformate (Predecarbonization), natural gas, coal/biomass gasification gas, and biogas. The sorption capacity of 140 mg of CO(2)/g of sorb was achieved at 15 kPa CO(2) partial pressure, which shows superior performance in comparison with other known sorbents. In addition, an exceptional dependence of MBS sorption performance on temperature for CO(2) and H(2)S was found and discussed at a molecular level via the computational chemistry approach. On the basis of the fundamental understanding of MBS sorption characteristics, an innovative sorption process was proposed and demonstrated at the laboratory scale for removing and recovering CO(2) and H(2)S, respectively, from a model gas. The present study provides a new approach for development of the novel CO(2)/H(2)S sorbents and may have a major impact on the advance of science and technology for CO(2)/H(2)S capture and separation from various gases.

An infrared study has been conducted on CO 2 sorption into nanoporous CO 2 "molecular basket" sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 °C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO 2 sorption capacity at higher temperatures. CO 2 sorption/desorption behavior studied by in situ transmission FTIR showed that CO 2 is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm -1 with CO 2 flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO 2 species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO 2 exposure time and with raising CO 2 sorption temperature. By comparison of the CO 2 sorption rate at 25 and 75 °C in terms of differential IR intensities, it was found that CO 2 sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO 2 is reversible at 75 °C. Comparative IR examination of the CO 2 sorption/ desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO 2 -amine interaction patterns.