Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates

Saravanan, S.; Oppenheim, Julius; Kim, Doyun; Nguyen, Thien S.; Silo, Wahyu M.H.; Kim, Byoungkook; Goddard, William A.; Yavuz, Cafer T.

doi:10.1016/j.chempr.2019.10.009

Cited by 77 publications

(46 citation statements)

References 54 publications

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“…Finally, for cyclohexene oxide, low conversion was observed (∼4%), since this substrate usually requires more forcing reaction conditions. 51 , 52 …”

Section: Resultsmentioning

confidence: 99%

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO₂ to Epoxides under Mild Conditions

Pander

Janeta

Bury

2021

ACS Appl. Mater. Interfaces

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We have devised a straightforward tandem postsynthetic modification strategy for Zr-based metal–organic framework (MOF) materials, which resulted in a series of well-defined 2-in-1 heterogeneous catalysts, cat1 – cat8 , exhibiting high catalytic activity in the synthesis of cyclic carbonates under solvent-free and co-catalyst-free conditions. The materials feature precisely located co-catalyst moieties decorating the metal nodes throughout the bulk of the MOF and yield cyclic carbonates with up to 99% efficiency at room temperature. We use diffuse reflectance infrared Fourier transform (DRIFT) and solid-state nuclear magnetic resonance (NMR) measurements to elucidate the role of each component in this model catalytic reaction. Establishing a method to precisely control the co-catalyst loading allowed us to observe the cooperativity between Lewis acid sites and the co-catalyst in the 2-in-1 heterogeneous system.

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“…Finally, for cyclohexene oxide, low conversion was observed (∼4%), since this substrate usually requires more forcing reaction conditions. 51 , 52 …”

Section: Resultsmentioning

confidence: 99%

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO₂ to Epoxides under Mild Conditions

Pander

Janeta

Bury

2021

ACS Appl. Mater. Interfaces

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“…The design, assembly, and utilization of advanced porous materials with precise architectures and prominent features [ 1–4 ] have revolutionized emerging applications in energy and the environment with the development of structures ranging from inorganic silica, [ 5 ] activated carbon, [ 6 ] zeolites, [ 7 ] and metal–organic frameworks [ 8 ] to covalent organic networks. [ 9,10 ] Similarly, an evolving class of porous organic polymers with potential applications in gas capture, separation, water treatment, metal capture, and catalysis have become a major research field in materials chemistry; [ 11–15 ] and the use of rigid building units with multiple covalent connectivities led to tunable surface areas, permanent porosity, and robust nature. The diversity of the building blocks, tied with the extensive availability of linkers allowed the development of new porous materials, such as polymers of intrinsic microporosity, [ 16 ] azo‐linked polymers [ 17,18 ] Schiff base networks, [ 19,20 ] nanoporous benzoxazole networks, [ 21 ] porous aromatic frameworks, [ 22 ] covalent organic frameworks (COFs), [ 23 ] and covalent organic polymers (COPs).…”

Section: Introductionmentioning

confidence: 99%

Asynchronous Double Schiff Base Formation of Pyrazole Porous Polymers for Selective Pd Recovery

et al. 2021

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Pyrazole-linked covalent organic polymer is synthesized using an asynchronous double Schiff base from readily available monomers. The one-pot reaction features no metals as a building block or reagent, hence facilitating the structural purity and industrial scalability of the design. Through a single-crystal study on a model compound, the double Schiff base formation is found to follow syn addition, a kinetically favored product, suggesting that reactivity of the amine and carbonyls dictate the order and geometry of the framework building. The highly porous pyrazole polymer COP-214 is chemically resistant in reactive conditions for over two weeks and thermally stable up to 425°C in air. COP-214 shows well-pronounced gas capture and selectivities, and a high CO 2 /N 2 selectivity of 102. The strongly coordinating pyrazole sites show rapid uptake and quantitative selectivity of Pd (II) over several coordinating metals (especially Pt (II)) at all pH points that are tested, a remarkably rare feature that is best explained by detailed analysis as the size-selective strong coordination of Pd onto pyrazoles. Density functional theory (DFT) calculations show energetically favorable Pd binding between the metal and N-sites of COP-214. The polymer is reusable multiple times without loss of activity, providing great incentives for an industrial prospect.

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“…Various solid sorbents such as petroleum and biomass‐based activated carbon, [7] metal organic frameworks (MOFs), [4a,8] covalent organic polymers (COPs), [4c,9] and other porous materials have been discovered and investigated for CO 2 separation and capture in fossil fuel pre‐combustion and post‐combustion conditions. Porous materials are indeed promising in many areas not just CO 2 capture, [4c,9b,10] but also in methane storage, [11] water treatment, [12] and catalysis [13a] . Although various adsorbents have been developed with varying porosity, they have limited use in CO 2 scrubbing due to the lack of CO 2 ‐philic functionalities.…”

Section: Introductionmentioning

confidence: 99%

Covalent Amine Tethering on Ketone Modified Porous Organic Polymers for Enhanced CO₂ Capture

et al. 2020

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Effective removal of excess greenhouse gas CO 2 necessitates new adsorbents that can overcome the shortcomings of the current capture methods. To achieve that, porous materials are often modified post-synthetically with reactive amine functionalities but suffer from significant surface area losses. Herein, we report a successful amine post-functionalization of a highly porous covalent organic polymer, COP-130, without losing much porosity. By varying the amine substituents, we recorded a remarkable increase in CO 2 uptake and selectivity. Ketone functionality, a rarely accessible functional group for porous polymers, was inserted prior to amination and led to covalent tethering of amines. Interestingly, aminated polymers demonstrated relatively low heats of adsorption, which is useful for the rapid recyclability of materials, due to the formation of suspected intramolecular hydrogen bonding.

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Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates

Cited by 77 publications

References 54 publications

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO₂ to Epoxides under Mild Conditions

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO₂ to Epoxides under Mild Conditions

Asynchronous Double Schiff Base Formation of Pyrazole Porous Polymers for Selective Pd Recovery

Covalent Amine Tethering on Ketone Modified Porous Organic Polymers for Enhanced CO₂ Capture

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Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates

Cited by 77 publications

References 54 publications

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO2 to Epoxides under Mild Conditions

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO2 to Epoxides under Mild Conditions

Asynchronous Double Schiff Base Formation of Pyrazole Porous Polymers for Selective Pd Recovery

Covalent Amine Tethering on Ketone Modified Porous Organic Polymers for Enhanced CO2 Capture

Contact Info

Product

Resources

About

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO₂ to Epoxides under Mild Conditions

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO₂ to Epoxides under Mild Conditions

Covalent Amine Tethering on Ketone Modified Porous Organic Polymers for Enhanced CO₂ Capture