Direct access to primary amines and particle morphology control in nanoporous CO2 sorbents

N. A. Dogan§, E. Ozdemir§, C. T. Yavuz*
ChemSusChem, accepted. 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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Selective removal of heavy metal ions by disulfide linked polymer networks

D. Ko, J. S. Lee, H. A. Patel, M. H. Jakobsen, Y. Hwang, C. T. Yavuz, H. C. B. Hansen, H. R. Andersen*
J. Hazard. Mater., 332, 140–148, (2017).
DOI: 10.1016/j.jhazmat.2017.03.007.


Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions–copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.
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Enhanced sorption cycle stability and kinetics of CO2 on lithium silicates using lithium ion channeling effect of TiO2 nanotubes

J. S. Lee, C. T. Yavuz*
Ind. Eng. Chem. Res., accepted.
DOI: 10.1021/acs.iecr.6b04918.


Lithium silicate (Li4SiO4) is a promising high temperature CO2 sorbent because of its large CO2 capacity at elevated temperatures with low materials cost. However, the conventional nonporous Li4SiO4 shows very poor CO2 adsorption kinetics. Thus, a Li4SiO4–TiO2 nanotubes complex was synthesized where LiOH and fumed silica would be calcined around TiO2 nanotubes. TiO2 nanotubes in Li4SiO4 structure functioning as open highways, lithium ions were able to channel through the bulky structure and enhance the sorption kinetics, leading the total adsorption capacity to near theoretical values. Furthermore, cyclic studies at 700 °C revealed strong stability over at least 10 cycles. These findings indicate that stability and kinetics of CO2 sorption can be greatly improved by the nanotube composites of known adsorbents.
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Monitoring instability of linear amine impregnated UiO-66 by in-situ temperature resolved powder X-ray diffraction

Y. Song, D. Thirion, S. Subramanian, M. S. Lah, C. T. Yavuz*
Micropor. Mesopor. Mater., 243, 85-90, (2017).
DOI: 10.1016/j.micromeso.2017.02.021.

Carbon dioxide capture requires stable porous solids like zirconium based metal-organic frameworks (MOFs) in order to make sequestration efforts feasible. Because of the weak binding at low CO2 partial pressures, oligomeric amines are commonly loaded on porous supports to maximize CO2 capture while attempting to keep porosity for enhanced diffusion. Here we show the first temperature resolved stability study of linear-amine impregnated UiO-66 by in-situ monitoring of the PXRD pattern. Our findings show that the crystal structure shows a contraction at temperatures as low as 80 °C and deforms considerably above 120 °C, leading to significant doubts about their applicability in CO2 capture from lean feeds. We confirm that all MOFs need to be thoroughly analyzed at least by means of PXRD at the process relevant temperatures, and reinforced before any plausible plans of application in CO2 capture.
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EEWS 2016: Progress and Perspectives of Energy Science and Technology

J. Oh, J. W. Choi, C. T. Yavuz, S. Y. Chung, J. Y. Park, Y. Jung*
ACS Energy Lett., 2, 592–594, (2017).
DOI: 10.1021/acsenergylett.6b00640


Established in 2009, the Graduate School of EEWS (Energy, Environment, Water, and Sustainability) at the Korea Advanced Institute of Science and Technology (KAIST) is the first of its kind, an interdisciplinary department at KAIST collectively addressing with interdisciplinary approaches for the emerging and urgent issues in energy, environment, water, and natural resources of the twenty-first century for sustainable society through science, technology, and education (http://eewseng.kaist.ac.kr). Currently housing 12 research groups with diverse backgrounds in chemistry; physics; chemical, electrical, mechanical, and environmental engineering; and materials science, the EEWS is the culmination of unprecedented collaboration under the same roof with close interaction of students and faculty from unlikely backgrounds (Figure). The output in a relatively short period of time is remarkable; the collaborative research combining basic and applied disciplines of seemingly different subjects have produced many novel concepts and approaches in various energy science and technology fields that are otherwise difficult to conceive in a traditional way. In an effort to critically assess the current status of the energy research, identify major challenges, and further stimulate active interactions among the disciplines to solve the challenges, we held the first EEWS forum, “EEWS 2016: Progress and Perspectives of Energy Science and Technology”, in the KI Fusion Hall of KAIST on October 20, 2016. The meeting featured eight internationally recognized energy experts from around the world introducing their cutting-edge research covering a wide range of topics in energy materials, advanced characterization tools, and catalysis, from both experimental and theoretical viewpoints.
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Haeseong Lim

Haeseong joined ONE Lab as a Master's Student on January 2nd, 2017 to study metal organic
frameworks. He comes from Soongsil University in Seoul with a Bachelor's degree in Organic Materials and Fiber Engineering. He can be reached at sealh7@kaist.ac.kr

Resume:
MS Grad. School of EEWS, KAIST, January 2017 - present
BS Organic Materials and Fiber Engineering, Soongsil University

Click here for his Google Scholar profile.

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Carbon Dioxide Capture Adsorbents: Chemistry and Methods, A Tutorial Review

H. A. Patel, J. Byun, C. T. Yavuz*
ChemSusChem, accepted. DOI: 10.1002/cssc.201601545.

Graphical Art by Ella Marushchenko.

Excess carbon dioxide (CO2) emissions and the inevitable consequences continuing to stimulate hard debate and awareness in both academic and public spaces, despite the clutter on understanding what really is needed to capture and store the unwanted CO2. Capture is the most costly, nearly 70 % of the price tag on the entire carbon capture and storage (CCS) operation. In this tutorial review, we describe and evaluate CO2 capture science and technology based on adsorbents in the context of chemistry and methods, after briefly introducing current status of CO2 emissions. An effective sorbent design is suggested, where six checkpoints are expected to be met: cost, capacity, selectivity, stability, recyclability and fast kinetics.
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Cafer was invited to the advisory board of the new Wiley journal

Cafer was invited to the Advisory Board of the new journal, Advanced Sustainable Systems, scheduled to publish its first issue early 2017. Introduced by Wiley-VCH Verlag GmbH, Adv. Sust. Syst. will follow the tradition of Advanced Materials family in the field of sustainability in materials, systems and their applications.  
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C&EN coverage for Jeehye's paper

Dr. Byun's recent paper on COP-99 was recently highlighted by the Chemical & Engineering News (C&EN). Penned by Stephen K. Ritter, the news piece said "Nanoporous material is the first to selectively pull dyes and other compounds from water based on their charge and size". Please click here to read the full coverage (note: subscription to C&EN or ACS membership required).
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Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

J. Byun, H. A. Patel, D. Thirion, C. T. Yavuz*
Nature Commun., 7, 13377, (2016). OpenAccess
DOI: 10.1038/ncomms13377. ReadCube: rdcu.be/mw1d.
Highlighted in Chemical & Engineering News by Stephen K. Ritter



Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.
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Cafer gave an invited talk at KNU Chemistry

Cafer visited Kyungpook National University, Department of Chemistry and gave a seminar on "Chemistry in Nanopores: Fine tuning chemical interactions". Prof. Jhung kindly hosted him. Here're some photos from his visit:




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Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

D. Thirion, J. S. Lee, E. OzdemirC. T. Yavuz*
Beilstein J. Org. Chem., 12, 2274-2279, (2016). OpenAccess
Invited Paper for the thematic issue on "Organic Porous Materials". DOI: 10.3762/bjoc.12.220.



Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.

Keywords: C–C bond; CO2 capture; microporous materials; porous polymers; postmodification
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Prof. Mohamed Eddaoudi visited our labs


Prof. Mohamed Eddaoudi, the department chair of chemical science at KAUST visited us during the Advisory Board meeting for our department. His talk, insights and discussions taught us a lot. We hope to have him again soon.

More photos from our meeting:



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Covalent organic polymer functionalization of activated carbon surfaces through acyl chloride for environmental clean-up

P. D. Mines*, D. Thirion, B. Uthuppu, Y. Hwang, M. H. Jakobsen, H. R. Andersen, C. T. Yavuz* Chem. Eng. J., 309, 766-771, (2017). DOI: 10.1016/j.cej.2016.10.085.

Nanoporous networks of covalent organic polymers (COPs) are successfully grafted on the surfaces of activated carbons, through a series of surface modification techniques, including acyl chloride formation by thionyl chloride. Hybrid composites of activated carbon functionalized with COPs exhibit a core-shell formation of COP material grafted to the outer layers of activated carbon. This general method brings features of both COPs and porous carbons together for target-specific environmental remediation applications, which was corroborated with successful adsorption tests for organic dyes and metals.
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Congratulations to Sir James Fraser Stoddart for his Nobel Prize in Chemistry

This year's Nobel Prize in Chemistry has a special meaning for us since our mentor, Sir James Fraser Stoddart is one of the laureates. He received the prize for his work on rotaxanes and catenanes towards the discovery of molecular machines.

During his time as a WCU Professor at our department, Graduate School of EEWS, KAIST, he guided us on running research groups, mentoring students and helping to perfect our manuscripts.

In Prof. Yavuz's office after a lively discussion.
Also present is Prof. Mert Atilhan
In particular, I vividly recall his help in Hasmukh's publication at Nature Communications. What makes his help even more special was his refusal to be even acknowledged for his time in editing and discussions. He is truly a remarkable mentor and an exceptional scientist, who needs no prize to be respected.

And my special thanks to my friend, collaborator and colleague, Prof. Ali Coskun for strengthening our relationship with Fraser. I'm also thankful for Prof. Jang Wook Choi, for his efforts to bring him to our department. 
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Jeehye won Humboldt Postdoctoral Fellowship

Dr. Jeehye Byun, the first ever student in ONE Lab, has won a prestigious Humboldt Postdoctoral Fellowship and joining Max Planck Institute for Polymer Research at Mainz, Germany. We congratulate her and wish her the best at her new position.
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Engineered nanoparticles for water treatment application

J. Byun, C. T. Yavuz*
Chapter 2 in Engineered Nanoparticles and the Environment: Biophysicochemical Processes and Toxicity, Edited by B. Xing, C. D. Vecitis, N. Senesi.
WILEY-IUPAC Series in Biophysico-Chemical Processes in Environmental Systems
Published by John Wiley & Sons, Inc.
ISBN: 9781119275824
DOI: 10.1002/9781119275855.ch2


In this chapter, water treatment processes using nanoparticles and studies related to the removal of waterborne contaminants, such as anionic, cationic, and organic pollutants, will be reviewed.
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Aldiar Adishev

Aldiar joined ONE Lab as a Master's Student on September 1st, 2016 to study fluorine mediated porous polymer formations. He comes from UNIST with double majors in Chemical Engineering and Management. He can be reached at aldiar@kaist.ac.kr

Resume:
MS Grad. School of EEWS, KAIST, September 2016 - present
BS Chemical Engineering and Management, UNIST

Click here for his Google Scholar profile.

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Doyun Kim

DoYun joined ONE Lab as a Master's Student on September 1st, 2016. He comes from Kyungpook National University with a Bachelor's degree in Chemistry. He will be studying charged, quaternary ammonium featuring porous polymers for water treatment and catalytic applications. He can be contacted at doyun-kim@kaist.ac.kr.

Resume:
MS Student, Grad. School of EEWS, KAIST, September 2016 - present
BS Kyungpook National University
Major : Chemistry

Email: doyun-kim@kaist.ac.kr

Click here for his Google Scholar profile.
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Farewell lunch for Damien and Jeehye





ONE LAB had a farewell party for Damien and Jeehye at Vesta!
Wish all the best for Damien and Jeehye :)
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Synthesis and Easy Functionalization of Highly Porous Networks through Exchangeable Fluorines for Target Specific Applications

D. Thirion, Y. Kwon, V. Rozyyev, J. Byun, C. T. Yavuz*
Chem. Mater., 28 (16), 5592–5595, (2016). DOI: 10.1021/acs.chemmater.6b02152.


Porous materials as adsorbents with high affinities to target molecules have great potential to facilitate environmentally important separations and remediation. One key challenge is to keep a reactive functionality inert while building a super structure. Protection or post-modification methods are limited because of the incomplete activation, and often require harsh conditions that also compromise the framework integrity. Here, a metal-free, one-pot, RT, deprotection-coupling, regioselective reaction is used for the first time to synthesize a porous network with high specific surface area (1035 m2/g) and easy post-functionalization. The obtained microporous polymer is a robust C-C bonded structure with alkyne and perfluorinated moieties. Aromatic fluorines readily undergo nucleophilic substitutions facilitating numerous post-modification possibilities, a particular feature that was not previously available.



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Investigation of Ester- and Amide-Linker-Based Porous Organic Polymers for Carbon Dioxide Capture and Separation at Wide Temperatures and Pressures

R. Ullah§, M. Atilhan*, B. Anaya, S. Al-Muhtaseb, S. Aparicio, H. A. Patel§, D. Thirion, C. T. Yavuz*
ACS Appl. Mater. Interfaces , 8 (32), 20772–20785, (2016). §: Equal contribution. DOI: 10.1021/acsami.6b05927.
Organic compounds, such as covalent organic framework, metal–organic frameworks, and covalent organic polymers have been under investigation to replace the well-known amine-based solvent sorption technology of CO2 and introduce the most efficient and economical material for CO2 capture and storage. Various organic polymers having different function groups have been under investigation both for low and high pressure CO2 capture. However, search for a promising material to overcome the issues of lower selectivity, less capturing capacity, lower mass transfer coefficient and instability in materials performance at high pressure and various temperatures is still ongoing process. Herein, we report synthesis of six covalent organic polymers (COPs) and their CO2, N2, and CH4 adsorption performances at low and high pressures up to 200 bar. All the presented COPs materials were characterized by using elemental analysis method, Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance (NMR) spectroscopy techniques. Physical properties of the materials such as surface areas, pore volume and pore size were determined through BET analysis at 77 K. All the materials were tested for CO2, CH4, and N2 adsorption using state of the art equipment, magnetic suspension balance (MSB). Results indicated that, amide based material i.e. COP-33 has the largest pore volume of 0.2 cm2/g which can capture up to the maximum of 1.44 mmol/g CO2 at room temperature and at pressure of 10 bar. However, at higher pressure of 200 bar and 308 K ester-based compound, that is, COP-35 adsorb as large as 144 mmol/g, which is the largest gas capturing capacity of any COPs material obtained so far. Importantly, single gas measurement based selectivity of COP-33 was comparatively better than all other COPs materials at all condition. Nevertheless, overall performance of COP-35 rate of adsorption and heat of adsorption has indicated that this material can be considered for further exploration as efficient and cheaply available solid sorbent material for CO2 capture and separation.
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