Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Oct 26;8(10):1457-1463.
doi: 10.1021/acscentsci.2c00723. Epub 2022 Oct 19.

Manganese Promoted (Bi)carbonate Hydrogenation and Formate Dehydrogenation: Toward a Circular Carbon and Hydrogen Economy

Duo Wei  1 , Xinzhe Shi  1 , Peter Sponholz  2 , Henrik Junge  1 , Matthias Beller  1
Affiliations

Manganese Promoted (Bi)carbonate Hydrogenation and Formate Dehydrogenation: Toward a Circular Carbon and Hydrogen Economy

Duo Wei et al. ACS Cent Sci. .

Abstract

We report here a feasible hydrogen storage and release process by interconversion of readily available (bi)carbonate and formate salts in the presence of naturally occurring α-amino acids. These transformations are of interest for the concept of a circular carbon economy. The use of inorganic carbonate salts for hydrogen storage and release is also described for the first time. Hydrogenation of these substrates proceeds with high formate yields in the presence of specific manganese pincer catalysts and glutamic acid. Based on this, cyclic hydrogen storage and release processes with carbonate salts succeed with good H2 yields.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Different concepts of chemical hydrogen storage and release based on the interconversion of CO2/formic acid (left) and (bi)carbonate/formate (right).
Figure 2
Figure 2
Hydrogenation of potassium bicarbonate to potassium formate catalyzed by base metal complexes. Standard conditions: KHCO3 (10 mmol), catalyst (0.1 mg), H2O/THF (5/5 mL), H2 (60 bar), 90 °C, 12 h. Yield of formate is calculated by (mmol formate)/(mmol KHCO3) × 100%.
Figure 3
Figure 3
Catalytic hydrogenation of potassium carbonate to potassium formate. Conditions: K2CO3 (10 mmol), Mn-2 (0.18 μmol), H2O/THF (5/5 mL), H2 (60 bar), additive, 90 °C, 12 h. Yield of formate is calculated by (mmol formate)/(mmol K2CO3) × 100%.
Figure 4
Figure 4
Catalytic hydrogen production from formates. Conditions: formate (5.0 mmol), Mn-2 (5 μmol), additive (5.0 mmol), H2O/THF (5/5 mL), 90 °C, 12 h. Yield of H2 is calculated by (mmol H2)/(mmol formate) × 100%. The dotted lines serve as guides to the eye.
Figure 5
Figure 5
H2 storage-release cycles via interconversion of (a) bicarbonate/formate and (b) carbonate/formate. Standard conditions: (a) formate/Lys (5.0/5.0 mmol); (b) carbonate/Glu (5.0/5.0 mmol), Mn-2 (5 μmol), H2O/THF (5/5 mL), 90 °C, 12 h. H2 (60 bar) was applied in the hydrogenation step. H2 storage-release cycles start with (a) dehydrogenation and (b) hydrogenation. H2 yields of each cycle are calculated based on the initial loading of formate or carbonate salts, respectively (each 5 mmol).
See this image and copyright information in PMC

References

    1. Stahel W. R. The circular economy. Nature 2016, 531, 435–438. 10.1038/531435a. - DOI - PubMed
    1. Meys R.; Kätelhön A.; Bachmann M.; Winter B.; Zibunas C.; Suh S.; Bardow A. Achieving net-zero greenhouse gas emission plastics by a circular carbon economy. Science 2021, 374, 71–76. 10.1126/science.abg9853. - DOI - PubMed
    1. Sanz-Pérez E. S.; Murdock C. R.; Didas S. A.; Jones C. W. Direct Capture of CO2 from Ambient Air. Chem. Rev. 2016, 116, 11840–11876. 10.1021/acs.chemrev.6b00173. - DOI - PubMed
    1. Brethomé F. M.; Williams N. J.; Seipp C. A.; Kidder M. K.; Custelcean R. Direct air capture of CO2 via aqueous-phase absorption and crystalline-phase release using concentrated solar power. Nat. Energy 2018, 3, 553–559. 10.1038/s41560-018-0150-z. - DOI
    1. Chatterjee S.; Huang K.-W. Unrealistic energy and materials requirement for direct air capture in deep mitigation pathways. Nat. Commun. 2020, 11, 3287.10.1038/s41467-020-17203-7. - DOI - PMC - PubMed

LinkOut - more resources