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. 2024 Jan 31;4(2):258-267.
doi: 10.1021/acsorginorgau.3c00064. eCollection 2024 Apr 3.

Biomimetic Frustrated Lewis Pair Catalysts for Hydrogenation of CO to Methanol at Low Temperatures

Jiejing Zhang  1 , Longfei Li  1 , Xiaofeng Xie  1 , Xue-Qing Song  1 , Henry F Schaefer 3rd  2
Affiliations

Biomimetic Frustrated Lewis Pair Catalysts for Hydrogenation of CO to Methanol at Low Temperatures

Jiejing Zhang et al. ACS Org Inorg Au. .

Abstract

The industrial production of methanol through CO hydrogenation using the Cu/ZnO/Al2O3 catalyst requires harsh conditions, and the development of new catalysts with low operating temperatures is highly desirable. In this study, organic biomimetic FLP catalysts with good tolerance to CO poison are theoretically designed. The base-free catalytic reaction contains the 1,1-addition of CO into a formic acid intermediate and the hydrogenation of the formic acid intermediate into methanol. Low-energy spans (25.6, 22.1, and 20.6 kcal/mol) are achieved, indicating that CO can be hydrogenated into methanol at low temperatures. The new extended aromatization-dearomatization effect involving multiple rings is proposed to effectively facilitate the rate-determining CO 1,1-addition step, and a new CO activation model is proposed for organic catalysts.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Catalysts for the Hydrogenation of CO to Methanol
Scheme 2
Scheme 2. Reported Bifunctional Metal Catalysts for the Indirect Hydrogenation of CO to Methanol
Scheme 3
Scheme 3. Nucleic Acid Bases and Bioinspired FLP Catalysts
Figure 1
Figure 1
Structure of bioinspired FLP A1 and the catalyzed hydrogenation of CO to methanol.
Figure 2
Figure 2
Gibbs energy profile for the 1,1-addition of CO to a formic acid intermediate catalyzed by the bioinspired FLP A1. The relative Gibbs energies (ΔG) and potential energies (ΔE) are in kcal/mol.
Figure 3
Figure 3
Atomic charges, bond lengths, and the nucleus-independent chemical shift (NICS) values of the rings in A1, A3, and A7. The −tBu and −C6F5 groups are drawn in a wireframe for simplicity.
Figure 4
Figure 4
Comparisons between the typical traditional FLP catalysts and the new bioinspired FLP catalysts via the Gibbs energy barriers (ΔG‡) of the rate-determining CO 1,1-addition.
Figure 5
Figure 5
(a) Dewar–Chatt–Duncanson model for CO activation based on metal catalysts; (b) dynamic natural localized molecular orbital (NLMO) analysis for the unusual CO 1,1-addition process; and (c) new CO activation model based on organic catalysts.
Figure 6
Figure 6
Hydrogen shuttle mechanism for hydrogen activation by bioinspired FLP A1. The relative Gibbs energies (ΔG) and potential energies (ΔE) are in kcal/mol.
Figure 7
Figure 7
Gibbs energy profile for the hydrogenation of formic acid to methanol catalyzed by the bioinspired FLP. The relative Gibbs energies (ΔG) and potential energies (ΔE) are given in kcal/mol.
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References

    1. Turner J. M. The matter of a clean energy future. Science 2022, 376, 1361.10.1126/science.add5094. - DOI
    1. Slameršak A.; Kallis G.; O’Neill D. W. Energy requirements and carbon emissions for a low-carbon energy transition. Nat. Commun. 2022, 13, 6932.10.1038/s41467-022-33976-5. - DOI - PMC - PubMed
    1. Sen R.; Goeppert A.; Kar S.; Prakash G. K. S. Hydroxide Based Integrated CO2 Capture from Air and Conversion to Methanol. J. Am. Chem. Soc. 2020, 142, 4544–4549. 10.1021/jacs.9b12711. - DOI - PubMed
    1. Zhang Z.; Mao C.; Meira D. M.; Duchesne P. N.; Tountas A. A.; Li Z.; Qiu C.; Tang S.; Song R.; Ding X.; Sun J.; Yu J.; Howe J. Y.; Tu W.; Wang L.; Ozin G. A. New black indium oxide-tandem photothermal CO2-H2 methanol selective catalyst. Nat. Commun. 2022, 13, 1512.10.1038/s41467-022-29222-7. - DOI - PMC - PubMed
    1. Amann P.; Klötzer B.; Degerman D.; Köpfle N.; Götsch T.; Lömker P.; Rameshan C.; Ploner K.; Bikaljevic D.; Wang H. Y.; Soldemo M.; Shipilin M.; Goodwin C. M.; Gladh J.; Halldin Stenlid J.; Börner M.; Schlueter C.; Nilsson A. The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst. Science 2022, 376, 603–608. 10.1126/science.abj7747. - DOI - PubMed

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