Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO

Y. Song, E. Ozdemir, S. Ramesh, A. Adishev, S. Subramanian, A. Harale, M. Albuali, B. A. Fadhel, A. Jamal, D. Moon, S. H. Choi, C. T. Yavuz*
Science, 367, 6479, 777-781 (2020).
DOI: 10.1126/science.aav2412

Large-scale carbon fixation requires high-volume chemicals production from carbon dioxide. Dry reforming of methane could provide an economically feasible route if coke- and sintering-resistant catalysts were developed. Here, we report a molybdenum-doped nickel nanocatalyst that is stabilized at the edges of a single-crystalline magnesium oxide (MgO) support and show quantitative production of synthesis gas from dry reforming of methane. The catalyst runs more than 850 hours of continuous operation under 60 liters per unit mass of catalyst per hour reactive gas flow with no detectable coking. Synchrotron studies also show no sintering and reveal that during activation, 2.9 nanometers as synthesized crystallites move to combine into stable 17-nanometer grains at the edges of MgO crystals above the Tammann temperature. Our findings enable an industrially and economically viable path for carbon reclamation, and the “Nanocatalysts On Single Crystal Edges” technique could lead to stable catalyst designs for many challenging reactions.

Perspective: Liyu Chen, Qiang Xu*, "Fewer defects, better catalysis?", p. 737
Research summary by Phil Szuromi, "Overcoming surface defects", p. 752-753
Highlighted in Chemistry World, C&EN, Nature Asia
Korean press release, English press release

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

N. A. Dogan§, E. Ozdemir§, C. T. Yavuz*
ChemSusChem, 10, 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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Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

D. Thirion, J. S. Lee, E. Ozdemir, C. 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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Covalent organic polymer framework with C-C bonds as a fluorescent probe for selective iron detection

E. Ozdemir, D. Thirion, C. T. Yavuz*
RSC Adv., 5, 69010-69015, (2015). DOI: 10.1039/C5RA10697D.

A new carbon–carbon bonded nanoporous polymer network was synthesized via efficient and catalyst free Knoevenagel-like condensation polymerization in near quantitative yields. The obtained polymer network, Covalent Organic Polymer – COP-100 possesses strong fluorescent properties and designed solubility in polar aprotic solvents, which shows promise for use as a metal-sensing material in solution. COP-100 exhibited high selectivity towards Fe2+ and Fe3+ in the presence of other common metal cations (Al3+, Ag+, Cd2+, Co2+, Cr3+, Cu2+, Hg2+, Mg2+, Mn2+, Na+, Ni2+, Zn2+) as the fluorescence of the polymer was significantly quenched even at very low concentrations. In the range from 2.5 × 10−6 to 2 × 10−4 M, a linear fluorescence emission response with equipment limited detection minimum of 2.13 × 10−7 M and 2.45 × 10−7 M for Fe2+ and Fe3+, respectively, was observed. These results suggest that COP-100 is a promising material as a selective fluorescence sensor for iron ions.

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