High-capacity methane storage in flexible alkane-linked porous aromatic network polymers

V. Rozyyev, D. Thirion, R. Ullah, J. Lee, M. Jung, H. Oh, M. Atilhan*, C. T. Yavuz*
Nat. Energy, accepted, (2019).
DOI: 10.1038/s41560-019-0427-x
Readcube link to read for free

Adsorbed natural gas (ANG) technology is a viable alternative to conventional liquefied or compressed natural-gas storage. Many different porous materials have been considered for adsorptive, reversible methane storage, but fall short of the US Department of Energy targets (0.5 g g−1, 263 l l−1). Here we prepare a flexible porous polymer, made from benzene and 1,2-dichloroethane in kilogram batches, that has a high methane working capacity of 0.625 g g−1 and 294 l l−1 when cycled between 5 and 100 bar pressure. We suggest that the flexibility provides rapid desorption and thermal management, while the hydrophobicity and the nature of the covalently bonded framework allow the material to tolerate harsh conditions. The polymer also shows an adsorbate memory effect, where a less adsorptive gas (N2) follows the isotherm profile of a high-capacity adsorbate (CO2), which is attributed to the thermal expansion caused by the adsorption enthalpy. The high methane capacity and memory effect make flexible porous polymers promising candidates for ANG technology.
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Farewell lunch for Dr. Dogan

We bid farewell to Dr. Nesibe A. Dogan with a group lunch. She joined our lab in September 2014 as a PhD student and worked on morphology control of porous polymers and their applications. Please click here to read her publications. She is moving to Paris, France for a postdoc at CNRS. We wish her all the best!
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Sustainable synthesis of superhydrophobic perfluorinated nanoporous networks for small molecule separation

S. Kim§, D. Thirion§, T. S. Nguyen, B. Kim, N. A. Dogan, C. T. Yavuz* 
Chem. Mater., accepted, (2019). §: Equal contribution
DOI: 10.1021/acs.chemmater.9b01447

Nanoporous polymers offer great promise in chemical capture and separations because of their versatility, scalability, and robust nature. Here, we report a general methodology for one-pot, metal-free, and room-temperature synthesis of nanoporous polymers by highly stable carbon–carbon bond formation. Three new polymers, namely, COP-177, COP-178, and COP-179, are derived from widely available perfluoroarenes and found to be superhydrophobic, microporous, and highly stable against heat, acid, base, and organic solvents. Nitrile, amine, and ether functionalities were successfully installed by SNAr-type postfunctionalization and were shown to increase CO2 uptake twice and CO2/N2 selectivity 4-fold. Due to its inherent superhydrophobicity, COP-177 showed high organic solvent uptake both in liquid and vapor form. Furthermore, in a first of its kind, by combining microporosity and hydrophobicity, COP-177 separated two small molecules with the same boiling point in a continuous column setting.
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Polypyrrole decorated mechanically robust conductive nanocomposites via solution blending and in-situ polymerization techniques

M. Zahra, S. Zulfiqar, C. T. Yavuz, H. S. Kweon, M. I. Sarwar*
Ind. Eng. Chem. Res., 58, 25, 10886-10893 (2019).
DOI: 10.1021/acs.iecr.9b01187

Polypyrrole grafted polystyrene-b-poly(ethylene-ran-butylene)-b-polystyrene (SEBS-g-PPy)/multiwall carbon nanotubes (MWCNTs) conductive nanocomposites were fabricated using two different approaches. The approach of system-I involved primarily the grafting of PPy on SEBS and its subsequent composites with nanotubes. In system-II in situ polymerization/grafting of PPy on SEBS was carried out along with MWCNTs yielding nanomaterials. Presynthesized SEBS-g-PPy and nanocomposites were characterized by Fourier transform infrared spectroscopy, NMR, field emission scanning electron microscopy, transmission electron microscopy, and electrical, mechanical, and thermal properties. The π–π stacking interactions between PPy of SEBS-g-PPy and MWCNTs rendered ample dispersion of the nanotubes in system-II relative to system-I. The electrical conductivity and tensile data showed improvement in these properties of nanocomposites and that system-II nanocomposites can sustain higher stresses, is stiffer, and can absorb more energy before breaking. Thermal stability of both the systems was improved relative to the matrices, and decomposition temperatures were found to increase from 437 to 568 °C. Relative improvement in electrical, thermal and tensile properties were observed for system-II nanocomposites rather than for system-I nanocomposites.
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Inversion of dispersion: Colloidal stability of calixarene modified metal-organic framework nanoparticles in non-polar media

U. Jeong, N. A. Dogan, M. Garai, T. S. Nguyen, J. F. Stoddart, C. T. Yavuz* 
J. Am. Chem. Soc., accepted, (2019).
DOI: 10.1021/jacs.9b04198

Making metal-organic frameworks (MOFs) which are stabilized in non-polar media is not as straightforward as their inorganic nanoparticle counterparts, since surfactants penetrate through the porous structures or dissolve the secondary building units (SBUs) through ligand-exchange linker modulator mechanisms. Herein we report that calixarenes stabilize UIO-66 nanoparticles effectively by remaining outside the grains through size exclusion, without pores becoming blocked, all the while providing amphiphilicity that permits the formation of stable colloidal dispersions with much narrower size distributions. Using the UIO-66 dispersed solutions, we showed that smooth films from an otherwise immiscible polystyrene can be made feasibly.
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Photochemically-enhanced Selective Adsorption of Gold Ions on Tannin-coated Porous Polymer Microspheres

J. Kim, K. R. Kim, Y. Hong, S. Choi, C. T. Yavuz, J. W. Kim*, Y. S. Nam*
ACS Appl. Mater. Interfaces, 11, 24, 21915-21925 (2019).
DOI: 10.1021/acsami.9b05197

Metal recovery from electronic waste and industrial wastewater has attracted increasing attention to recycle precious metals and inhibit the emission of hazardous heavy metals. However, the selective recovery of precious metals with a large quantity is still very challenging because wastewater contains a variety of different cations while precious metal ions are relatively scarce. Here, we introduce a simple method to selectively increase the adsorption of gold ions using tannin-coated porous polymer microspheres through photochemical reduction. Mesoporous poly(ethylene glycol dimethacrylate-co-acrylonitrile) microspheres with an average pore diameter of 13.8 nm were synthesized and used as an adsorbent matrix. Tannic acid (TA) was deposited onto the internal pores of the polymer matrix by simple immersion in an aqueous milieu. TA coatings increased the maximum number of adsorbed gold ions by 1.3 times because of the well-known metal ion chelation of TA. Under light illumination, the maximum number of adsorbed gold ions dramatically increased by 6.1 times. We examined two distinct mechanisms presumably involved in the enhanced adsorption: the photooxidation of TA and plasmon-induced hot electrons. Moreover, TA-coated microspheres exhibited remarkable selectivity for gold ions among competing metal ions commonly found in waste resources. This work suggests that the photochemically activated TA can serve as an excellent adsorbent for the selective and efficient recovery of gold ions from wastewater.
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Sustainable porous polymer catalyst for size-selective cross-coupling reactions

S. Kim, B. Kim, N. A. Dogan, C. T. Yavuz*
ACS Sustain. Chem. Eng., 7, 10865-10872 (2019).
DOI: 10.1021/acssuschemeng.9b01729

A new, high surface area, nanoporous polymer (COP-220) was synthesized using sustainable building blocks, namely, a food coloring dye (erythrosine B) and a commercial alkyne. During the Sonogashira coupling, it is observed that Pd and Cu ions and triphenylphosphine ligands of the catalyst get trapped inside the pores. The remnant synthesis catalyst components were characterized in detail and were tested as a new catalyst for Suzuki–Miyaura coupling reactions. COP-220 showed conversion yields comparable to the commercial homogeneous catalyst Pd(PPh3)2Cl2 with an additional advantage of size-dependent catalytic activity when bulkier substrates were used. COP-220 was highly stable under thermal and chemical treatments and recyclable with no loss of activity. These findings show a clear need for extensive characterization of nanoporous polymers made through cross-coupling reactions and the potential of the trapped catalysts for new catalytic activity without additional loading.
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Radioactive Strontium Removal from Seawater by a MOF via Two-Step Ion Exchange

M. Garai, C. T. Yavuz*
Chem, 5 (4), 750-752 (2019). Preview 
DOI: 10.1016/j.chempr.2019.03.020

Radioactive waste, such as 90Sr, 134Cs, and 131I, from the Fukushima nuclear spill highlighted the need to find effective adsorbents for scrubbing radioactive ions from seawater. In this issue of Chem, Wang and colleagues report a remarkably 90Sr-selective metal-organic framework (SZ-4) that operates with a two-step ion-exchange mechanism and at a wide pH range while being active and intact when tested in actual seawater.

Link to the journal website
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Wonki Lim

Mr. Wonki 임원기 Lim joins us as a Masters degree student from the Chemical & Biomolecular Engineering (CBE) department of KAIST. He will be working on catalyst development for cyclic carbonate formation from CO2 and epoxides.

MS Student
March 2019 - present

BS in CBE, KAIST, Korea

Email: wonki0123@kaist.ac.kr
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Intizar Tashov

Mr. Intizar Tashov joins us as an Undergraduate Intern while studying for his degree in Chemistry and Chemical & Biomolecular Engineering at KAIST. He will be picking up the Friedel-Crafts based porous polymer project and develop more materials with suitable functionalities towards gas capture and conversion.

Undergraduate Intern
February 2019 - present

High School degree from 57th Secondary School, Ashgabat, Turkmenistan

Email: intizar.tashov@kaist.ac.kr

2017 Bronze Medal in 49th International Chemistry Olympiad (IChO), Kingdom of Thailand
2017 Bronze Medal in 50th International Mendeleev Chemistry Olympiad, Kazakhstan
2017 Silver Medal in National Chemistry Olympiad, Turkmenistan
2016 Bronze Medal in 49th International Chemistry Olympiad (IChO), Georgia
2016 Bronze Medal in 50th International Mendeleev Chemistry Olympiad, Russia
2016 Gold Medal in National Chemistry Olympiad, Turkmenistan
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Cafer gave a plenary lecture at the APM 2019

Cafer visited Chennai, India for the 10th International Conference on Advancements in Polymeric Materials (APM-2019) organized by Central Institute of Plastics Engineering and Technology (CIPET), the largest plastics research institution in India. He gave a plenary lecture on Sustainable Porous Polymers. 
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A combined experimental and theoretical study on gas adsorption performance of amine and amide porous polymers

R. Ullah, H. A. Patel, S. Aparicio, C. T. Yavuz*, M. Atilhan*
Micropor. Mesopor. Mater., 279, 61-72 (2019).
DOI: 10.1016/j.micromeso.2018.12.011

In this manuscript, we report synthesis, characterization and application of amine and amide type covalent organic frameworks as CO2 adsorbent materials at various isotherms and wide pressure conditions. Furthermore, we also report a detailed density functional theory investigation of the studied adsorbents in order to explain their adsorption behaviors and provide comparisons with experimental results. The objective of this work was to investigate custom design porous polymers by building amine and amide functionalities in the final structures, whether they have efficient CO2 capturing performances at wide process conditions that covers both low and high pressure end applications to cover either pre- or post-combustion processes. On the other hand, energy storage performances of these materials were tested by performing H2 sorption experiments as well. Two porous polymers, namely COP-9 and COP-10, were characterized with BET, TGA and FTIR to evaluate the physical properties of studied porous polymers and then were tested for CO2, N2 and H2 adsorption both at low and high pressures. Studied materials were found to have compelling adsorption capacity mostly at high pressures and have very good selectivity for CO2/N2 and CO2/H2 respectively.
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Nanoporous Polymer Microspheres with Nitrile and Amidoxime Functionalities for Gas Capture and Precious Metal Recovery from E-Waste

N. A. Dogan, Y. Hong, E. Ozdemir, C. T. Yavuz*
ACS Sustain. Chem. Eng., 7 (1), 123–128 (2019).
Invited paper for the special issue on advanced porous materials
DOI: 10.1021/acssuschemeng.8b05490 

Nanoporous materials could offer sustainable solutions to gas capture and precious metal recovery from electronic waste. Despite this potential, few reports combine target functionalities with physical properties such as morphology control. Here, we report a nanoporous polymer with microspherical morphology that could selectively capture gold from a mixture of 15 common transition metals. When its nitriles are converted into amidoxime, the capacity increases more than 20-fold. Amidoximes are also very effective in CO2 binding and show a record high CO2/CH4 selectivity of 24 for potential use in natural gas sweetening. The polymer is successfully synthesized in 1 kg batches starting from sustainable inexpensive building blocks without the need for costly catalysts. Because the morphology is controlled from the beginning, the nanoporous materials studied in lab scale could easily be moved into respective industries.

Link to the journal webpage
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Dr. Sreerangappa Ramesh

Dr. Sreerangappa Ramesh joins us from Belgium as a Postdoctoral Scholar. He is an expert in heterogeneous catalysis and will be working on the nano-catalysis projects.

Postdoctoral Scholar
September 2018 - present

PhD in Chemistry from Visveswaraya Technological University, India
MS in Chemistry from Bangalore University, India
BS in Chemistry from Bangalore University, India

Email: rameshs@kaist.ac.kr

Publications prior to joining ONE Lab:
1. Citric acid-assisted synthesis of nanoparticle copper catalyst supported on oxide system for the reduction of furfural to furfuryl alcohol in the vapor phase. N.J. Venkatesha and Sreerangappa Ramesh, Ind & Eng. Chem. Res, 2018, 57, 1506-1515.
2. Hydrotalcite promoted by NaAlO2 as strongly basic catalysts with record activity in glycerol carbonate synthesis Sreerangappa Ramesh, François Devred, Ludivine van den Biggelaar and Damien P. Debecker Chem Cat Chem, Article in press
3. Sodium aluminate nano spheres made by aerosol processing catalyse the room temperature synthesis of glycerol carbonate Sreerangappa Ramesh, Damien P. Debecker Catalysis communications, 2017, 97,102-105.
4. Template free synthesis of Ni-Pervoskite: an efficient catalyst for hydrogen production by steam reforming of Bio-glycerol S. Ramesh, Venkatesh ACS sustainable chemistry and Engineering, 2017, 5, 1339-1346.
5. Copper decorated Pervoskite an efficient catalyst for low temperature hydrogen production by steam reforming of glycerol S. Ramesh, Eun-Hyeok Yang, Jae-Sun Jung, Dong Ju Moon International Journal of Hydrogen Energy, 2015, 40, 11428- 11435.
6. The effect of promoters in La0.9M0.1Ni0.5Fe0.5O3(M= Sr, Ca) perovskite catalysts on dry reforming of methane Eun-Hyeok Yang, Young Su Nho, S. Ramesh, Sung Soo Lim, Dong Ju Moon , Fuel Processing Technology, 2015, 134,404-413.
7. Nanoporous montmorillonite catalysed condensation reactions under microwave irradiation: A Green approach S. Ramesh, B.S. Jai Prakash, Y.S. Bhat Current Organo Catalysis, 2015, 2, 51-57.
8. Microstructure of FTS over spherical Co/γ-Al2O3 Jae-Sun Jung, Garam Choi, Jae-Suk Lee, S. Ramesh, Dong Ju Moon Catalysis Today, 2014, 250,102-114.
9. The Characterization of microstructure of Co on γ-Al2O3 for FTS: Effect of pretreatment on Ru- Co/γ-Al2O3 Jae-Sun Jung, Garam Choi, Jae-Suk Lee, S. Ramesh, Dong Ju Moon Fuel, 2014, 149,118-129.
10. Microwave activated p-TSA dealuminated montmorillonite - a new material with improved catalytic activity S. Ramesh, B.S. Jai Prakash, Y.S. Bhat Clay minerals 47,231-242. 2012.
11. Highly active and selective C-alkylation of p-cresol with cyclohexanol using p-TSA treated clays under microwave irradiation. S. Ramesh, B.S. Jai Prakash, Y.S. Bhat Applied Catalysis, A, 2012, 414-415,157-161
12. Synthesis of p-cresylpropionate over Mn+- montmorillonite catalysts: aspect of catalyst solvent interactions by DRIFTS study C. Ravindra Reddy, S. Ramesh, Y. S. Bhat, G. Nagendrappa, B. S. Jai Prakash, Reaction kinetics, Mechanism and Catalysis.2010, 100,289-30
13. Enhancing Brønsted acid site activity of ion exchanged montmorillonite by microwave irradiation for ester synthesis S. Ramesh, B.S. Jai Prakash, Y.S. Bhat Applied Clay Science, 2010, 48, 159-163.
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Sirinapa Wongwilawan

Ms. Srinapa "Mai" Wongwilawan joins our lab from Thailand as a Ph.D. student. She will be studying Polymers of Intrinsic Microporosity and their applications in gas capture and separations.

PhD Student
September 2018 - present

MS in Polymer Science from Chulalongkorn University
BS in Chemistry from Naresuan University

Email: sirinapa.w@kaist.ac.kr

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Dr. Manmatha Mahato

Dr. Manmatha Mahato joins us as a BK21 Plus Postdoctoral Scholar. He received his PhD from IIT Kharagpur, India. His research will include membrane applications of porous polymers and new COF structures.

Postdoctoral Scholar
Aug 2018 - Mar 2019

PhD IIT Kharagpur, India
MS IIT Kanpur, India
BS Burdwan University

Email: manmatha@kaist.ac.kr

Publications before joining ONE Lab:
1. Monitoring of Drinking Water Quality: A Preliminary Approach by an Electronic Tongue based on Functionalized Polymer Membrane Electrodes, M. Mahato and B. Adhikari, Analytical Methods, 2017, Accepted, DOI: 10.1039/C7AY01756A.
2. Poly (N-[4H-1, 2, 4-triazol-4-yl] acrylamide) with different ratio of poly (vinyl chloride) composite membrane for liquid phase sensing of alcohol, M. Mahato, A. Ghosh, H. Roy, N. Bhattacharyya, B. Adhikari, Journal of Applied Polymer Science, 2017, 134, 15. Selected as cover page image, DOI: 10.1002/app.44675.
3. Vapor phase sensing response of doped polyaniline-poly (vinyl alcohol) composite membrane to different aliphatic alcohols, M. Mahato, B. Adhikari, Synthetic Metals, 2016, 220, 410-420.
4. A mesoporous WN co-doped titania nanomaterial with enhanced photocatalytic aqueous nitrate removal activity under visible light. T. Mishra, M. Mahato, Noor Aman, J. N. Patel, R. K. Sahu; Catalysis Science and Technology, 2011, 1, 609–615 (This article has been identified as suitable for inclusion in weekly RSC Publishing press pack, which is published in the RSC blog. http://blogs.rsc.org/cy/2011/05/11/lights-on-denitrification)
5. Synthesis and photocatalytic activity of mesoporous cerium doped TiO2 as visible light sensitive photocatalyst. Noor Aman, P.K. Satapathy, T. Mishra, M. Mahato, N.N. Das; Materials Research Bulletin, 2012, 47, 2, 179-183.
6. Taste sensing with HDTC modified polyvinyl alcohol-polyacrylic acid membrane. M. Mahato, T. Sinha, A. Halder, B. Adhikari, J.K. Mukherjee, D. Ghosh, Sensing Technology (ICST), 2012, 775-780.
7. Development of novel polymeric sensors for taste sensing: Electronic tongue. B. Adhikari, M. Mahato, T. Sinha, A. Halder, N. Bhattacharya, Sensors, 2013 IEEE, 1-4.
8. Polymer membrane electrode based potentiometric taste sensor: A new sensor to distinguish five basic tastes. A. Halder, M. Mahato, T. Sinha, B. Adhikari, S. Mukherjee, N. Bhattacharyya, Sensing Technology (ICST), 2012, 785-789.
9. Discrimination of tea quality by polymer membrane electrode based potentiometric taste sensor. T. Sinha, A. Halder, M. Mahato, B. Adhikari, S. Sarkar, N. Bhattacharyya, Sensing Technology (ICST), 2012, 781-784.
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Structural Elucidation of Covalent Organic Polymers (COP) and Their Linker Effect on Gas Adsorption Performance via Density Functional Theory Approach

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.
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Wiley Interview

The Wiley Network interviewed Cafer along with the other panel speakers at the Wiley Impact Forum. The topic was "What Is Research Impact?". You can read the blog post by Jen Cheng here. Also, the video is posted online at Youtube, as well as on Twitter, Facebook and Linkedin.

The Wiley Network is an online community designed to offer advice, ideas, and collaboration opportunities for researchers, learners, and professionals as they pursue their goals. Read more and participate!
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Applicability of disulfide-polymer particles surface embedded on alginate beads for cadmium removal from airport derived stormwater

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.
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Disulfide polymer grafted porous carbon composites for heavy metal removal from stormwater runoff

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.
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A catalytic role of surface silanol groups in CO2 capture on the amine-anchored silica support

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.
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Molecular Insights into Benzimidazole-linked Polymer Interactions with Carbon Dioxide and Nitrogen

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.
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