Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates

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

doi:10.1016/j.chempr.2019.10.009

Title: Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates

Full Record
Other Related Research

Abstract

If cycloaddition of CO₂ to epoxides is to become a viable non-redox CO₂ fixation path, it is crucial that researchers develop an active, stable, selective, metal-free, reusable, and cost-effective catalyst. To this end, we report here a new catalyst that is based on imidazolinium functionality and is synthesized from an unprecedented, one-pot reaction of the widely available monomers terephthalaldehyde and ammonium chloride. We show that this covalent organic polymer (COP)-222 exhibits quantitative conversion and selectivity for a range of substrates under ambient conditions and without the need for co-catalysts, metals, solvent, or pressure. COP-222 is recyclable and has been demonstrated to retain complete retention of activity for over 15 cycles. Moreover, it is scalable to at least a kilogram scale. Finally, we determined the reaction mechanism by using quantum mechanics (density functional theory), showing that it involves nucleophilic-attack-driven epoxide ring opening (ND-ERO). This contrasts with the commonly assumed mechanism involving the concerted addition of chemisorbed CO₂.

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

Publication Date:: Sun Dec 01 00:00:00 EST 2019

Research Org.:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC); Saudi Aramco-KAIST CO2 Management Center; National Research Foundation of Korea (NRF)

OSTI Identifier:: 1735664

Alternate Identifier(s):: OSTI ID: 1579269; OSTI ID: 1801622

Grant/Contract Number:: SC0004993; NRF-2016R1A2B4011027; NRF-2017M3A7B4042140; NRF-2017M3A7B4042235

Resource Type:: Published Article

Journal Name:: Chem

Additional Journal Information:: Journal Name: Chem Journal Volume: 5 Journal Issue: 12; Journal ID: ISSN 2451-9294

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; CO2 utilization; Cyclic carbonate; Heterogeneous catalysis; Non-redox carbon fixation; Imidazolinium chloride; Porous polymer; Density functional theory

Citation Formats


                    Subramanian, Saravanan, Oppenheim, Julius, Kim, Doyun, Nguyen, Thien S., Silo, Wahyu M. H., Kim, Byoungkook, Goddard, III, William A., and Yavuz, Cafer T. Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates.  United States: N. p., 2019. 
Web.  doi:10.1016/j.chempr.2019.10.009.

Copy to clipboard


                    Subramanian, Saravanan, Oppenheim, Julius, Kim, Doyun, Nguyen, Thien S., Silo, Wahyu M. H., Kim, Byoungkook, Goddard, III, William A., & Yavuz, Cafer T. Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates.  United States.  https://doi.org/10.1016/j.chempr.2019.10.009

Copy to clipboard


                    Subramanian, Saravanan, Oppenheim, Julius, Kim, Doyun, Nguyen, Thien S., Silo, Wahyu M. H., Kim, Byoungkook, Goddard, III, William A., and Yavuz, Cafer T. Sun .  
"Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates".  United States.  https://doi.org/10.1016/j.chempr.2019.10.009.

Copy to clipboard


                    
@article{osti_1735664,

  title        = {Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates},

  author       = {Subramanian, Saravanan and Oppenheim, Julius and Kim, Doyun and Nguyen, Thien S. and Silo, Wahyu M. H. and Kim, Byoungkook and Goddard, III, William A. and Yavuz, Cafer T.},

  abstractNote = {If cycloaddition of CO2 to epoxides is to become a viable non-redox CO2 fixation path, it is crucial that researchers develop an active, stable, selective, metal-free, reusable, and cost-effective catalyst. To this end, we report here a new catalyst that is based on imidazolinium functionality and is synthesized from an unprecedented, one-pot reaction of the widely available monomers terephthalaldehyde and ammonium chloride. We show that this covalent organic polymer (COP)-222 exhibits quantitative conversion and selectivity for a range of substrates under ambient conditions and without the need for co-catalysts, metals, solvent, or pressure. COP-222 is recyclable and has been demonstrated to retain complete retention of activity for over 15 cycles. Moreover, it is scalable to at least a kilogram scale. Finally, we determined the reaction mechanism by using quantum mechanics (density functional theory), showing that it involves nucleophilic-attack-driven epoxide ring opening (ND-ERO). This contrasts with the commonly assumed mechanism involving the concerted addition of chemisorbed CO2.},

  doi          = {10.1016/j.chempr.2019.10.009},

  journal      = {Chem},

  number       = 12,

  volume       = 5,

  place        = {United States},

  year         = {Sun Dec 01 00:00:00 EST 2019},

  month        = {Sun Dec 01 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1016/j.chempr.2019.10.009

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 63 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Novel Microbial Based Enzymatic CO₂ Fixation Mechanisms

Technical Report Peters, John

The broad, long term goal of the research is to provide insight into the mechanism of novel carboxylation reactions catalyzed by enzymes involved in bacterial alkene, ketone, and epoxide metabolism. Novel convergent pathways in the model microorganism Xanthobacter autotrophicus have been described in which epoxides produced by alkene oxidation and ketones produced by the oxidation of alcohols are further carboxylated and utilized in energy yielding pathways. Both alkene/epoxide and alcohol/ketone pathways involve distinct carboxylases with unique molecular properties and cofactor requirements that represent alternative mechanisms of CO₂ fixation. The main focus and aims of this project is to provide structuralmore »« less
https://doi.org/10.2172/1572716

Full Text Available
A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO₂ Adsorption and Chemical Fixation

Journal Article Zhu, Jie ; Usov, Pavel M. ; Xu, Wenqian ; ... - Journal of the American Chemical Society

Metal–organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr₆ clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintainsmore »« less
Cited by 162
https://doi.org/10.1021/jacs.7b10643

Full Text Available
Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

Thesis/Dissertation Klobukowski, Erik

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallicmore »« less
https://doi.org/10.2172/1048517

Full Text Available
Carbon dioxide fixation: bifunctional complexes containing acidic and basic sites working as reversible carriers

Journal Article Gambarotta, S ; Arena, F., Zanazzi, P. - J. Am. Chem. Soc.; (United States)

Carbon dioxide fixation in its intact form is achieved from ''bifunctional'' complexes containing in their structure a nucleophilic cobalt(I) and an alkali cation: Co(R-salen)M (R-salen = substituted salen ligand; salen = N,N'-ethylenebis(salicylideneaminato); M = Li, Na, K, Cs). The fixation of CO/sub 2/ by such systems displays different degrees of reversibility depending on the reaction solvent and the nature of the alkali cation. The X-ray analysis carried out on (Co(n-Pr-salen)K-(CO)/sub 2/(THF)) shows carbon dioxide anchored to the cobalt through a Co-C sigma bond, while the oxygens interact with the alkali cation, in a polymeric structure. IR spectra are diagnostic formore »« less
https://doi.org/10.1021/ja00383a015
Dramatic differences in carbon dioxide adsorption and initial steps of reduction between silver and copper

Journal Article Ye, Yifan ; Yang, Hao ; Qian, Jin ; ... - Nature Communications

Converting carbon dioxide (CO₂) into liquid fuels and synthesis gas is a world-wide priority. But there is no experimental information on the initial atomic level events for CO₂ electroreduction on the metal catalysts to provide the basis for developing improved catalysts. Here we combine ambient pressure X-ray photoelectron spectroscopy with quantum mechanics to examine the processes as Ag is exposed to CO₂ both alone and in the presence of H₂O at 298 K. We find that CO₂ reacts with surface O on Ag to form a chemisorbed species (O = CO₂^δ-). Adding H₂O and CO₂ then leads to up tomore »« less
Cited by 40
https://doi.org/10.1038/s41467-019-09846-y

Full Text Available

Similar Records