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

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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


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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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


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


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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


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.
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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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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Interviewed by Hankook Ilbo

Cafer was interviewed by Hankook Ilbo for his naturalization and contributions to Korea. The story appeared as a cover story on March 3, 2018 and was part of the national discussion on naturalizing foreign nationals based on their talents. Please click here to view the entire story (Korean). 
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Highly efficient catalytic cyclic carbonate formation by pyridyl salicylimines

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
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Dr. Thien Nguyen

Dr. Thien Nguyen joins our lab as a Postdoctoral Scholar. He received his PhD from the University of Houston at Jeremy May's lab. He is an expert on synthetic organic chemistry and will take responsibility in our Porous Polymers projects.

Postdoctoral Scholar
January 2018 - present

PhD University of Houston, Houston, TX
BSc University of Science, Vietnam

Publications before joining ONE Lab:
1. Nguyen, T.S.; Le, P.Q.; May, J.A., “A general method for the enantioselective synthesis of α-chiral heterocycles”, Org. Lett. 2012, 14, 6104—6107
2. Nguyen, T.S.; Yang, M.S.; May, J.A., “Experimental mechanistic insight into the BINOL-catalyzed enantioselective conjugate addition of boronates to enones”, Tetrahedron Letters 2015, 56, 3337—3341.
3. Shih, J-L; Nguyen, T.S.; May, J. A., “Organocatalyzed Asymmetric Conjugate Addition of Heteroaryl & Aryl Trifluoroborates: a Synthetic Strategy for Discoipyrrole D”, Angew. Chem. Int. Ed. 2015, 54, 9931—9935.
4. Shih, J-L; Nguyen, T.S.; May, J.A., “Asymmetric Organocatalytic Conjugate Addition of Trifluoroborates”, Synfacts 2015, 11, 1102.
5. May, J.A.; Shih, J-L; Nguyen, T.S.; Le, P.; Vallakati, R.; Huynh, C.; Tran, T.; Jansone-Popova, S.; Lundy, B.J., “Synthetic Discoveries from Polycyclic Natural Products”, Planta Med 2015, 81, IL6.
6. Nguyen, T.N.; Nguyen, T.S.; May, J.A., “Brønsted Acid Catalyzed Homoconjugate Addition of Organotrifluoroborates to Arylated Cyclopropyl Ketones”, Org. Lett. 2016, 18, 3786—3789
7. Nguyen, T.N.; Nguyen, T.S.; May, J.A., “Addition of Organotrifluoroborates to Arylated Cyclopropyl Ketones”, Synfacts 2016, 12, 1069.

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An all-purpose porous cleaner for acid gas removal and dehydration of natural gas

V. RozyyevC. T. Yavuz*
Chem, 3, 5, 719-721, (2017).
DOI: 10.1016/j.chempr.2017.10.014

Raw natural gas is predominantly methane (up to 95%) but also contains larger hydrocarbons such as ethane and propane, acidic gases such as H2S and CO2, and considerable amounts of water. In some reserves, H2S can reach up to 20%, and water content can be as much as 5%. CO2 in natural gas, from ppm levels up to 0.5%, is less significant but noteworthy. Natural gas treatment starts with the removal of sludge and gas condensate, followed by acid gas removal (mostly H2S) by amine scrubbing. Regenerated H2S is converted to elemental sulfur via the Claus process or sulfuric acid by the wet sulfuric acid process. Sweet (H2S and CO2-free) natural gas is then dehydrated with the use of glycols and then separated from higher alkanes.
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Dr. Mousumi Garai

Dr. Mousumi Garai joins our lab as a BK21 Plus Postdoctoral Scholar. She received her PhD from IIT Kharagpur at Prof. Kumar Biradha's lab. She is an expert on crystalline porous materials and will take responsibility of our Metal Organic Frameworks and Covalent Organic Framework projects.

Postdoctoral Scholar
September 2017 - present

PhD Indian Institute of Technology Kharagpur, India
MSc Indian Institute of Technology Kharagpur, India
BSc The University of Burdwan, India

Publications before joining ONE Lab:
1. R. Santra, M. Garai, D. Mondal, K. Biradha, Anion Influence in Directing and Altering the Stereochemistry of the Double [2+2] Reaction of Bis-Pyridyl Dienes in their Silver Complexes: A Green Synthetic Route, Chem. Eur. J. 2013, 19, 489–493.
2. M. Garai, R. Santra, K. Biradha, Tunable Plastic Films of a Crystalline Polymer by Single-Crystal-to-Single-Crystal Photopolymerization of a Diene: Self-Templating and Shock-Absorbing Two-Dimensional Hydrogen-Bonding Layers, Angew. Chem. Int. Ed. 2013, 52, 5548-5551.
3. M. Garai, K. Biradha, Coordination Polymers of Organic Polymers Synthesized via Photopolymerization of Single Crystals: Two-Dimensional Hydrogen Bonding Layers with Amazing Shock Absorbing Nature, Chem. Commun. 2014, 50, 3568-3570.
4. M. Garai, K. Biradha, Exploration and Exploitation of Homologues Series of Bis-(acrylamido)alkanes Containing Pyridyl and Phenyl Groups: β-sheet vs 2D-layers in Solid State Photo Chemical [2+2] Reactions, IUCrJ. 2015, 2, 523-533.
5. M. Garai, K. Maji, V. V. Chernyshev , K. Biradha, Interplay of Pyridine Substitution and Ag(I)···Ag(I) and Ag(I)···π Interactions in Templating Photochemical Solid State [2+2] Reactions of Unsymmetrical Olefins Containing Amides: Single-Crystal-to-Single-Crystal Transformations of Coordination Polymers, Cryst. Growth Des., 2016, 16(2), 550-554.
6. M. Garai, Biradha, K. Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid State [2+2] Photopolymerization. Chem. Eur. J. 2016, 23, 273-277.
7. M. Garai, Biradha, K. One-dimensional Coordination Polymers of Bis-(3-pyridyl-acrylamido)ethane: Influence of Anions and Metal Ions on Their Solid State [2+2] Photochemical Polymerization and Dimerization Reactions. Cryst. Growth Des. 2017, 17, 925-932.
8. R. Mandal, M. Garai, K. Biradha. Hydrogen-bonded Two-fold Interpenetrated Diamondoid Networks for Solid State [2+2] Polymerizations of Criss-crossed Olefins: Molecular Connections vs Supramolecular Connections. Cryst. Growth Des. 2017, DOI: 10.1021/acs.cgd.7b01114.

Please click here for Google Scholar profile:

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Sustainable nanoporous benzoxazole networks as metal-free catalysts for one-pot oxidative self-coupling of amines by air oxygen

S. Subramanian, H. A. Patel, Y. Song, C. T. Yavuz*
Adv. Sustain. Syst., 1, 1700089, (2017).
DOI: 10.1002/adsu.201700089

The development of sustainable organocatalysts with porosity, high stability, and excellent catalytic activity offers a clean and green alternative to precious metal catalysts. Here, an efficient, nanoporous, heterogeneous benzoxazole catalyst is reported for aerobic oxidative coupling of amines. A molecular design strategy is presented to functionalize primary amines to produce valuable products under one-pot, open-air reaction conditions. Unprecedented and previously unknown, the stable imine intermediate catalyzes its own formation, also known as autocatalysis, enabling a direct and favorable access to amino acids, even if the catalysts are absent. The biomimetic benzoxazole catalysts developed here provide quantitative catalytic activity over 50 cycles with favorable kinetics with no degradation. This work also marks the first use of benzoxazoles for oxidative catalytic reactions.
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Sungyoon Kim

Sungyoon Kim joins our lab as a Ph.D. student. He finished his undergraduate studies at KAIST Chemistry department and will be taking on projects related to fluorine substituent effect on chemistry of small molecules and porous polymers.

Ph.D. Student
September 2017 - March 2019

BS Chemistry and Biological Sciences, KAIST, 2014
High School Korea Science Academy of KAIST, 2010


ORCID: 0000-0002-8434-9167
ResearcherID: L-5593-2016

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Reversible water capture by a charged metal-free porous polymer

J. Byun, H. A. Patel, D. ThirionC. T. Yavuz*
Polymer, 126, 308-313, (2017).
Invited paper for the special issue on Porous Polymers
DOI: 10.1016/j.polymer.2017.05.071

Climate change and industrial pollution threatens the availability of clean water. Although established protocols of water treatment exist, water capture by porous materials has emerged as a viable alternative to energy intensive processes. Here we introduce a new charged porous polymer that is capable of capturing and releasing water by simple humidity or temperature swings. The quaternary amines on the framework structure attract water molecules and further solvate by coordination. The porosity of the network structure also provides enough void where water can diffuse throughout the solid. Water uptake capacity of the porous polymer surpasses common desiccants like silica gel and molecular sieves, and has the potential to act as an organic desiccant in applications like electronics or food packaging.
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Nesibe and Ercan's paper was selected for the back cover of ChemSusChem

Nesibe and Ercan's paper on "Direct access to primary amines and particle morphology control in nanoporous CO2 sorbents" got selected for the back cover of ChemSusChem! Congratulations!

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Selective removal of cationic micro-pollutants using disulfide-linked network structures

M. S. Atas, S. Dursun, H. Akyildiz, M. Citir, C. T. Yavuz*, M. S. Yavuz*
RSC Adv., 7, 25969-25977, (2017). Open Access
DOI: 10.1039/C7RA04775D

Micropollutants are found in all water sources, even after thorough treatments that include membrane filtration. New ones emerge as complex molecules are continuously produced and discarded after used. Treatment methods and sorbent designs are mainly based on non-specific interactions and, therefore, have been elusive. Here, we developed swellable covalent organic polymers (COP) with great affinity towards micropollutants, such as textile industry dyes. Surprisingly, only cationic dyes in aqueous solution were selectively and completely removed. Studies of the COPs surfaces led to a gating capture, where negatively charged layer attracts cationic dyes and moves them inside the swollen gel through diffusive and hydrophobic interaction of the hydrocarbon fragments. Despite its larger molecular size, crystal violet has been taken the most, 13.4 mg g−1, surpassing all competing sorbents. The maximum adsorption capacity increased from 12.4 to 14.6 mg and from 8.9 to 11.4 mg when the temperature of dye solution was increased from 20 to 70 °C. The results indicated that disulfide-linked COPs are attractive candidates for selectively eliminating cationic dyes from industrial wastewater due to exceptional swelling behaviour, low-cost and easy synthesis.
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Jason's paper is selected for the cover of I&EC

Jason's paper on the enhanced cyclic stability of lithium silicates for CO2 sorption by using TiO2 nanotubes was selected for the cover image of the current issue of Industrial & Engineering Chemistry Research
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Interviewed at KAIST Podcast for Jeehye's work

Mik Fanguy interviewed Cafer for Jeehye's paper on the water treatment by COP-99. The interview is now online at KAIST Podcast with additional coverage by Professor Mik Fanguy of the College of Liberal Arts and Convergence Science, and Scientific Communicator Dan Kopperud. You can listen to the podcast here or you can visit the KAIST Podcast page to view all. You should also subscribe the feed on your mobile phone!
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Direct access to primary amines and particle morphology control in nanoporous CO2 sorbents

N. A. Dogan§, E. Ozdemir§, C. T. Yavuz*
ChemSusChem10, 2130-2134, (2017). DOI: 10.1002/cssc.201700190. §: Equal contribution

Chemical tuning of nanoporous, solid sorbents for an ideal CO2 binding requires unhindered amine functional groups on the pore walls. Although common for soluble organics, post-synthetic reduction of nitriles in porous networks often fail due to the insufficient and irreversible metal hydride penetration. Here, we synthesized a nanoporous network with pendant nitrile groups, microsphere morphology and in large scale. The hollow microspheres were easily decorated with primary amines through in situ reduction by widely available boranes. CO2 capture capacity of the modified sorbent was increased up to an eight times of the starting nanoporous network with a high heat of adsorption (98 kJ/mol). Surface area can be easily tuned between 1 and 354 m2/g. Average particle size (~50 µm) is also quite suitable for CO2 capture applications where processes like fluidized bed require spheres of micron sizes.
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