Home » Posts filed under 2018
S. Aparicio*,
C. T. Yavuz, M. Atilhan*
ChemistrySelect, 3, 8294– 8305 (2018).
DOI:
10.1002/slct.201801849
Investigation of the binding affinity gases on porous adsorbents are important for establishing understanding of effective carbon dioxide adsorption and design target specific sorbents for capturing hazardous gases for environmental protection and fuel upgrading. A Density Functional Theory (DFT) study that highlights the impact of covalent organic polymer (COP) design has been conducted to explain the molecular and electronic structure, investigate the interaction sites and elucidate the experimental findings on carbon dioxide (CO2) and nitrogen (N2) sorption on these porous structures. DFT calculations were used to infer the details of the type and the strength of the polymer – gas interaction modes at various interaction sites as well as to quantify short‐range interactions between the polymer – gas via topological characteristics analysis of intermolecular forces. Results obtained in this study were used to shed light on CO2 and N2 affinity of the studied polymer structures; interpretations regarding to the macroscopic behaviors were discussed and conclusions were attained on the characteristics of the adsorption type and mechanism.
D. Ko, H. Kim, H. Lee,
C. T. Yavuz, H. R. Andersen, Y. Hwang*
J. Environ. Chem. Eng., 6, 4124–4129 (2018).
DOI:
10.1016/j.jece.2018.06.007
Stormwater runoff derived from airports causes severe cadmium contamination in excess of the maximum limit level and is difficult to treat due to the irregular contamination levels from scattered rainfall. To overcome this and remove cadmium from runoff, a new reactive filtration column is introduced. Sulfur functionalized polymer particles were successfully embedded onto the surface of alginate bead (DiS-algi) and simulated a real stormwater treatment filtration column. The DiS-algi shows 22.3 mg/g of batch and 877 μg/g of continuous flow sorption capacity. Also, the results for the new sorption material show that within 6 mins half of the cadmium was removed with 31 L/mg of Langmuir sorption affinity, outperforming an activated carbon filter. From a breakthrough test the reactive column shows complete uptake of cadmium from a contaminated flow, lasting two hours until reaching the breakthrough point. Furthermore, regeneration tests of the column verified its reusability. DiS-algi appears to be a viable new cadmium sorption material for airport derived stormwater runoff filtration systems.
D. Ko*, P. D. Mines, M. H. Jakobsen,
C. T. Yavuz, H. C. B. Hansen, H. R. Andersen
Chem. Eng. J., 348, 685–692 (2018).
DOI:
10.1016/j.cej.2018.04.192
The emerging concern of heavy metal pollution derived from stormwater runoff has triggered a demand for effective heavy metal sorbents. To be an effective sorbent, high affinity along with rapid sorption kinetics for environmental relevant concentrations of heavy metals is important. Herein, we have introduced a new composite suitable for trace metal concentration removal, which consists of cheap and common granular activated carbon covered with polymers containing soft bases, thiols, through acyl chlorination (DiS-AC). Material characterization demonstrated that the polymer was successfully grafted and grown onto the surface of the carbon substrate. The distribution coefficient for Cd2+ bonding was 89·103 L/kg at a solution concentration of 0.35 mg/L, which is notably higher than sorption affinities for Cd2+ seen in conventional sorbents. The sorption isotherm is well described by the Freundlich isotherm and within an hour, half of the initial trace (0.2 mg/L) concentration of Cd2+ was removed by the DiS-AC at a sorbent loading of 2 g/L. Therefore, the novel material DiS-AC promises to be an ideal candidate for filters treating stormwater runoff.
M. Cho, J. Park,
C. T. Yavuz, Y. Jung*
Phys. Chem. Chem. Phys., 20, 12149-12156 (2018).
DOI:
10.1039/C7CP07973G
A new mechanism of CO2 capture on the amine-functionalized silica support is demonstrated using density functional theory calculations, in which the silica surface not only acts as a support to anchor amines, but also can actively participate in the CO2 capture process through a facile proton transfer reaction with the amine groups. The surface-mediated proton transfer mechanism in forming a carbamate–ammonium product has lower kinetic barrier (8.1 kcal mol−1) than the generally accepted intermolecular mechanism (12.7 kcal mol−1) under dry conditions, and comparable to that of the water-assisted intermolecular mechanism (6.0 kcal mol−1) under humid conditions. These findings suggest that the CO2 adsorption on the amine-anchored silica surface would mostly occur via the rate-determining proton transfer step that is catalyzed by the surface silanol groups.
S. Aparicio*,
C. T. Yavuz, M. Atilhan*
ChemistrySelect, 3, 3691 – 3701 (2018).
DOI:
10.1002/slct.201800253
Investigation of the binding affinity gases on porous adsorbents are important for establishing understanding of effective carbon dioxide adsorption and design target specific sorbents for capturing hazardous gases for environmental protection and fuel upgrading. A density functional theory (DFT) study that highlights the impact of benzimidazole‐linked polymer structure design has been conducted to explain the molecular and electronic structure, investigate the interaction sites and elucidate the experimental results on carbon dioxide and nitrogen sorption on these porous structures. DFT calculations were used to infer the strength of the polymer – gas interaction modes as well as to quantify short‐range interactions between the polymer – gas via topological characteristics analysis of intermolecular forces. Obtained results shed light on the carbon dioxide and nitrogen affinity as well as the selectivity during the adsorption process, and yet conclusions were attained on the characteristics of the adsorption type and mechanism in this study.
S. Subramanian, J. Park,
J. Byun, Y. Jung,
C. T. Yavuz*
ACS Appl. Mater. Interfaces, accepted.
DOI:
10.1021/acsami.8b00485
Cyclic carbonates as industrial commodities offer a viable non-redox carbon dioxide fixation, and suitable heterogeneous catalysts are vital for their widespread implementation. Here we report a highly efficient heterogeneous catalyst for CO2 addition to epoxides based on a newly identified active catalytic pocket consisting of pyridine, imine and phenol moieties. The polymeric, metal-free catalyst derived from this active site converts less reactive styrene oxide under atmospheric pressure in quantitative yield and selectivity to the corresponding carbonate. The catalyst doesn’t need additives, solvents, metals or co-catalysts, can be reused at least 10 cycles without loss of activity, and scaled up easily to a kg scale. DFT calculations reveal that the nucleophilicity of pyridine base gets stronger due to the conjugated imines and H-bonding from phenol accelerates the reaction forward by stabilizing the intermediate.
Link to the journal page
P. D. Mines, B. Uthuppu,
D. Thirion, M. H. Jakobsen,
C. T. Yavuz, H. R. Andersen, Y. Hwang*
Chem. Eng. J., 339, 22-31 (2018).
DOI: 10.1016/j.cej.2018.01.102
Granular activated carbon was customized with a chemical grafting procedure of a nanoporous polymeric network for the purpose of nanoscale zero-valent iron impregnation and subsequent water contaminant remediation. Characterization of the prepared composite material revealed that not only was the polymer attachment and iron impregnation successful, but also that the polymeric shell acted as a protective barrier against the effects of oxidation from the surrounding environment, nearly 99% of total iron content was in the form of zero-valent iron. When applied towards the remediation of two common water contaminants, nitrobenzene and nitrate, the composite material exploited the qualities of both the activated carbon and the polymeric network to work together in a synergistic manner. In that the increased protection from oxidation allowed for increased reactivity of the nanoscale zero-valent iron, and that the adsorption abilities of both the carbon and the polymer achieved a higher amount of total removal of the contaminants.
