The capability of 1 H and 13 C flow magic-angle spinning NMR is demonstrated for monitoring the capture of CO 2 on the surface of mesoporous amine-functionalized silica and the progress of heterogeneously catalyzed CO 2 hydrogenation over the microporous titanosilicate Pt/ETS-10 under in situ conditions. The custom-built gas-handling system allows to maintain a controllable and stable delivery of reaction gases to the sample compartment containing porous material over a period of hours. Using calibration of NMR signals, we obtained the amounts of reactants and products. The presented approach demonstrates a complementary NMR-based in situ method for quantitative investigation of CO 2 capture and conversion over nanoporous solids.
Bifunctional basic-metallic catalysts proved to be efficient for the selective hydrogenation of CO 2 to methanol. The activity of these catalysts depends on the cooperative interaction between the amine groups and metallic sites, which is a function of amine group density, Pd particle perimeter length and the geometric properties of support pores. The pore width has the highest effect on the activity, increasing the methanol yield by about half an order of magnitude. Confining the space leads to a three-dimensional utilization of the available metal surface sites compared to a two-dimensional distribution of the bifunctional sites in larger pores, where the metal particle diameter is the decisive factor for the catalytic properties.
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