Shedding Light on Solid Sorbents: Evaluation of Supported Potassium Carbonate Particle Size and Its Effect on CO2 Capture from Air.

Solid sorbents are essential for developing technologies that directly capture CO2 from air. In solid sorbents, metal oxides and/or alkali metal carbonates such as potassium carbonate (K2CO3) are promising active components owing to their high thermal stability, low cost, and ability to chemisorb the CO2 present at low concentrations in air. However, this chemisorption process is likely limited by internal diffusion of CO2 into the bulk of K2CO3. Therefore, the size of the K2CO3 particles is expected to be an important factor in determining the kinetics of the sorption process during CO2 capture. To date, the effects of particle size on supported K2CO3 sorbents are unknown mainly because particle sizes cannot be unambiguously determined. Here, we show that by using a series of techniques, the size of supported K2CO3 particles can be established. We prepared size-tuned carbon-supported K2CO3 particles by tuning the K2CO3 loading. We further used melting point depression of K2CO3 particles to collectively estimate the average K2CO3 particle sizes. Using these obtained average particle sizes, we show that the particle size critically affects the efficiency of the sorbent in CO2 capture from air and directly affects the kinetics of CO2 sorption as well as the energy input needed for the desorption step. By evaluating the mechanisms involved in the diffusion of CO2 and H2O into K2CO3 particles, we relate the microscopic characteristics of sorbents to their macroscopic performance, which is of interest for industrial-scale CO2 capture from air.

Supported Cu Nanoparticles as Selective and Stable Catalysts for the Gas Phase Hydrogenation of 1,3-Butadiene in Alkene-Rich Feeds.

Supported copper nanoparticles are a promising alternative to supported noble metal catalysts, in particular for the selective gas phase hydrogenation of polyunsaturated molecules. In this article, the catalytic performance of copper nanoparticles (3 and 7 nm) supported on either silica gel or graphitic carbon is discussed in the selective hydrogenation of 1,3-butadiene in the presence of a 100-fold excess of propene. We demonstrate that the routinely used temperature ramp-up method is not suitable in this case to reliably measure catalyst activity, and we present an alternative measurement method. The catalysts exhibited selectivity to butenes as high as 99% at nearly complete 1,3-butadiene conversion (95%). Kinetic analysis showed that the high selectivity can be explained by considering H2 activation as the rate-limiting step and the occurrence of a strong adsorption of 1,3-butadiene with respect to mono-olefins on the Cu surface. The 7 nm Cu nanoparticles on SiO2 were found to be a very stable catalyst, with almost full retention of its initial activity over 60 h of time on stream at 140 °C. This remarkable long-term stability and high selectivity toward alkenes indicate that Cu nanoparticles are a promising alternative to replace precious-metal-based catalysts in selective hydrogenation.

Carbon Support Surface Effects in the Gold-Catalyzed Oxidation of 5-Hydroxymethylfurfural.

Oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid is an important transformation for the production of bio-based polymers. Carbon-supported gold catalysts hold great promise for this transformation. Here we demonstrate that the activity, selectivity, and stability of the carbon-supported gold nanoparticles in the oxidation of 5-hydroxymethylfurfural strongly depend on the surface properties of the carbon support. Gold nanoparticles supported on basic carbon materials with a low density of functional groups demonstrate higher activity in 5-hydroxymethylfurfural oxidation (TOFAu up to 1195 h-1), higher selectivity to 2,5-furandicarboxylic acid, and better stability in comparison to gold nanoparticles supported on carbon materials with acidic surface groups. Surface groups of basic carbon supports that are positively charged under the reaction conditions result in a higher adsorption and local concentration of hydroxyl ions, which act as cocatalysts for gold and enhance gold-catalyzed dehydrogenation. Negatively charged surface groups of acidic carbons repel hydroxyls and the intermediate monoacid anions, which leads to lower reaction rates and a high selectivity toward 2,5-hydroxymethylfurancarboxylic acid. Understanding the role of support surface charge and local hydroxyl anion concentration provides a basis for the rational design of the optimal carbon support surface chemistry for highly active, selective, and stable catalysts for the oxidation of 5-hydroxymethylfurfural and related reactions.

Superior Stability of Au/SiO2 Compared to Au/TiO2 Catalysts for the Selective Hydrogenation of Butadiene.

Supported gold nanoparticles are highly selective catalysts for a range of both liquid-phase and gas-phase hydrogenation reactions. However, little is known about their stability during gas-phase catalysis and the influence of the support thereon. We report on the activity, selectivity, and stability of 2-4 nm Au nanoparticulate catalysts, supported on either TiO2 or SiO2, for the hydrogenation of 0.3% butadiene in the presence of 30% propene. Direct comparison of the stability of the Au catalysts was possible as they were prepared via the same method but on different supports. At full conversion of butadiene, only 0.1% of the propene was converted for both supported catalysts, demonstrating their high selectivity. The TiO2-supported catalysts showed a steady loss of activity, which was recovered by heating in air. We demonstrated that the deactivation was not caused by significant metal particle growth or strong metal-support interaction, but rather, it is related to the deposition of carbonaceous species under reaction conditions. In contrast, all the SiO2-supported catalysts were highly stable, with very limited formation of carbonaceous deposits. It shows that SiO2-supported catalysts, despite their 2-3 times lower initial activities, clearly outperform TiO2-supported catalysts within a day of run time.

Silica-Supported Au-Ag Catalysts for the Selective Hydrogenation of Butadiene.

Gold and silver are miscible over the entire composition range, and form an attractive combination for fundamental studies on bimetallic catalysts. Au-Ag catalysts have shown synergistic effects for different oxidation and liquid-phase hydrogenation reactions, but have rarely been studied for gas-phase hydrogenation. In this study 3 nm particles of Au, Ag and Au-Ag supported on silica (SBA-15) were investigated as catalysts for selective hydrogenation of butadiene in an excess of propene. The Au catalyst was over an order of magnitude more active than the Ag catalyst at 120 °C. The initial activity of the Au-Ag catalysts scaled linearly with the Au-content, suggesting a direct correlation between the surface and overall compositions of the nanoparticles and the absence of synergistic effects. All Au-containing catalysts were highly selective to butenes (>99.9 %). The Au catalysts were stable, whereas the Au-Ag catalysts lost about half of their activity during 20 h run time at 200 °C, but the initial activity was restored by a consecutive oxidation-reduction treatment. Near ambient pressure x-ray photoelectron spectroscopy showed that exposure to H2 at elevated temperatures led to a gradual enrichment of the surface of the Au-Ag nanoparticles by Ag. These observations highlight the importance of considering progressive atomic rearrangements in bimetallic nanocatalysts under reaction conditions.