Ambient temperature CO2 fixation to pyruvate and subsequently to citramalate over iron and nickel nanoparticles
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The chemical reactions that formed the building blocks of life at origins required catalysts, whereby the nature of those catalysts influenced the type of products that accumulated. Recent investigations have shown that at 100 °C awaruite, a Ni 3 Fe alloy that naturally occurs in serpentinizing systems, is an efficient catalyst for CO 2 conversion to formate, acetate, and pyruvate. These products are identical with the intermediates and products of the acetyl-CoA pathway, the most ancient CO 2 fixation pathway and the backbone of carbon metabolism in H 2 -dependent autotrophic microbes. Here, we show that Ni 3 Fe nanoparticles prepared via the hard-templating method catalyze the conversion of H 2 and CO 2 to formate, acetate and pyruvate at 25 °C under 25 bar. Furthermore, the 13 C-labeled pyruvate can be further converted to acetate, parapyruvate, and citramalate over Ni, Fe, and Ni 3 Fe nanoparticles at room temperature within one hour. These findings strongly suggest that awaruite can catalyze both the formation of citramalate, the C5 product of pyruvate condensation with acetyl-CoA in microbial carbon metabolism, from pyruvate and the formation of pyruvate from CO 2 at very moderate reaction conditions without organic catalysts. These results align well with theories for an autotrophic origin of microbial metabolism under hydrothermal vent conditions.
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Only the acetyl-CoA pathway operates in vitro to form formate, acetate and pyruvate from H2 and CO2 without enzymes or cofactors, using only metals or minerals that occur in hydrothermal vents as catalysts.
“Moreover, only one of those seven, again only the acetyl CoA pathway, operates in vitro to form its main products – formate, acetate and pyruvate [49, 90] – from H2 and CO2 without enzymes or cofactors, using only metals or minerals that occur in hydrothermal vents as catalysts [60, 61, 62, 63, 64, 125].”
From Evidence for corrin biosynthesis in the last universal common ancestor (2025) · cites this paper as [125]
The products produced are similar to the intermediates formed in the Acetyl-CoA pathway of autotrophic microbes, such as formate and acetate.
“The products produced are similar to the intermediates formed in the Acetyl-CoA pathway of autotrophic microbes, such as formate and acetate [9,103].”
From Opinion: The Key Steps in the Origin of Life to the Formation of the Eukaryotic Cell (2024) · cites this paper as [103]
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Self-citationMetal ions turn on a stereoselective nonenzymatic reduction of keto acids by the coenzyme NADH
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Self-citationZhang, L., Jiang, H., Tang, M., Jiang, Y. Y., Tang, B., Tan, H., Kong, Y., & Hu, H. (2024) · Applied Catalysis B: Environmental · doi:10.1016/j.apcatb.2024.124151 · Cited by 29 · see citing works
GTP before ATP: The energy currency at the origin of genes
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Self-citationQuantifying Catalysis at the Origin of Life**
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Prebiotic Synthesis of Aspartate Using Life’s Metabolism as a Guide
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Chemical Antiquity in Metabolism
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Self-citationEvidence for corrin biosynthesis in the last universal common ancestor
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“4.”
Self-citationCO2 Fixation to Prebiotic Intermediates over Heterogeneous Catalysts
Song, Y., & Tüysüz, H. (2024) · Accounts of Chemical Research · doi:10.1021/acs.accounts.4c00151 · Cited by 9 · see citing works
Self-citationWeingart, M., Chen, S., Donat, C., Helmbrecht, V., Orsi, W., Braun, D., & Alim, K. (2023) · Science Advances · doi:10.1126/sciadv.adi1884 · Cited by 11 · see citing works
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Self-citationBuilding complex biochemicals from one-carbon compounds
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The Moon‐Forming Impact and the Autotrophic Origin of Life
Mrnjavac, N., Wimmer, J. L. E., Brabender, M., Schwander, L., & Martin, W. F. (2023) · ChemPlusChem · doi:10.1002/cplu.202300270 · Cited by 13 · see citing works
Self-citationPrebiotic Synthesis of Microdroplets from Formate over a Bimetallic Cobalt–Nickel Nanomotif
Zhu, P., Wang, C., Lang, J., He, D., & Jin, F. (2024) · Journal of the American Chemical Society · doi:10.1021/jacs.4c06989 · Cited by 14 · see citing works
Biophysical Interactions Underpin the Emergence of Information in the Genetic Code
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Belthle, K. S., Martin, W. F., & Tüysüz, H. (2024) · ChemCatChem · doi:10.1002/cctc.202301218 · Cited by 12 · see citing works
Self-citationSchlikker, M. L., Brabender, M., Schwander, L., Garcia, C. G., Burmeister, M., Metzger, S. U., Moran, J., & Martin, W. F. (2024) · FEBS Journal · doi:10.1111/febs.17357 · Cited by 11 · see citing works
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Self-citationEnceladus: Astrobiology Revisited
Dávila, A. F., & Eigenbrode, J. L. (2024) · Journal of Geophysical Research Biogeosciences · doi:10.1029/2023jg007677 · Cited by 10 · see citing works
Zimmermann, J., Basar, A. B., & Moran, J. (2024) · Angewandte Chemie International Edition · doi:10.1002/anie.202410698 · Cited by 9 · see citing works
Self-citationSelf-Oxidation of the Atmospheres of Rocky Planets with Implications for the Origin of Life
Johansen, A., Camprubí, E., van Kooten, E. M. M. E., & Hoeijmakers, H. J. (2024) · Astrobiology · doi:10.1089/ast.2023.0104 · Cited by 9 · see citing works
Hädrich, M., Scheuchenegger, C., Vital, S.-T., Gunkel, C., Müller, S., Hoff, J., Borger, J., Glawischnig, E., Thoma, F., & Blombach, B. (2025) · Microbial Cell Factories · doi:10.1186/s12934-025-02693-1 · Cited by 7 · see citing works
Kitadai, N., Shibuya, T., Ueda, H., Tasumi, E., Okada, S., & Takai, K. (2024) · Communications Earth & Environment · doi:10.1038/s43247-024-01689-w · Cited by 6 · see citing works
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The early evolution of the glycolytic pathway from autotrophic origins to glycogen and back
Modjewski, L. D., Johnsen, U., Schönheit, P., & Martin, W. F. (2025) · FEMS Microbiology Reviews · doi:10.1093/femsre/fuaf049 · Cited by 6 · see citing works
Self-citationRedox chemistry of early Earth and the origin of life
Moldogazieva, N. T., Terentiev, A. A., Mokhosoev, I. M., & Astakhov, D. V. (2026) · Communications Chemistry · doi:10.1038/s42004-026-01969-w · Cited by 8 · see citing works
Intermediate stages in the origin of metabolism at a phosphorylating hydrothermal vent
Mrnjavac, N., Hoffmann, N. K., Schlikker, M. L., Burmeister, M., Schwander, L., Garcia, C. G., Brabender, M., Steel, M., Huson, D., Metzger, S., et al. (2025) · Science Advances · doi:10.1126/sciadv.aef3128 · Cited by 4 · see citing works
Self-citationOpinion: The Key Steps in the Origin of Life to the Formation of the Eukaryotic Cell
Brunk, C. F., & Marshall, C. R. (2024) · Life · doi:10.3390/life14020226 · Cited by 5 · see citing works
BioIron: Origin, Chemical Properties, and Biological Functions
Pantopoulos, K. (2025) · Advances in experimental medicine and biology · doi:10.1007/978-3-031-92033-2_1 · Cited by 4 · see citing works
Chen, P., Liu, X., He, D., Liao, Y., Li, H.-Z., Cheng, J., Lu, Y., Yang, Z.-M., Yang, Y., & Jin, F.-M. (2026) · Nature Communications · doi:10.1038/s41467-026-69255-w · Cited by 4 · see citing works
Thermodynamic Constraints on the Citric Acid Cycle and Related Reactions in Ocean World Interiors
Işık, S., Daswani, M. M., Işık, E., Weber, J. M., & Olgun, N. (2025) · ACS Earth and Space Chemistry · doi:10.1021/acsearthspacechem.4c00371 · Cited by 2 · see citing works
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Li, J., & Guo, L. (2026) · Journal of Solid State Chemistry · doi:10.1016/j.jssc.2026.125882 · Cited by 2 · see citing works
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Prebiotic aqueous reactions catalyzed by native nickel without hydrogen
Garcia, C. G., Brabender, M., & Martin, W. F. (2026) · bioRxiv · doi:10.1111/febs.70556 · Cited by 4 · see citing works
Self-citationProtein folds and catalytic strategies at the origin of biological CO2 fixation
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Self-citationThangamuthu, M., Kohlrausch, E. C., Lilonfe, S., LeMercier, T. M., Burwell, T., Young, M., Dimitriou, I., Taresco, V., Fernandes, J. A., & Khlobystov, A. N. (2026) · Communications Materials · doi:10.1038/s43246-026-01189-8 · Cited by 2 · see citing works
A Prebiotic Route to Lactate from Acetaldehyde, Cyanide and Carbon Dioxide
Sharma, S., Yang, Y., & Lee, J. (2024) · Chemistry - A European Journal · doi:10.1002/chem.202403763 · Cited by 3 · see citing works
Prebiotic Interconversion of Pyruvate and Lactate over Zeolite‐Supported Ni Catalyst
Song, Y., Budiyanto, E., Kumar, A., Landrot, G., & Tüysüz, H. (2025) · Angewandte Chemie · doi:10.1002/ange.202503747 · Cited by 1 · see citing works
Self-citationLiu, Y., Jiang, J., Ju, Y., He, J., Zhang, H., Zhao, J., & Qiao, L.-N. (2025) · Colloids and Surfaces A: Physicochemical and Engineering Aspects · doi:10.1016/j.colsurfa.2025.138671 · Cited by 2 · see citing works
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Camprubí, E., Pearce, B. K. D., & Preiner, M. (2026) · Astrobiology · doi:10.1177/15311074261454245 · Cited by 1 · see citing works
Self-citationHydrocarbon Basis of Emerging Chemoautotrophic Metabolism (Thermodynamic Justification)
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Exploration of extraterrestrial biosignatures and planetary habitability: A prospect
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Shiny metal catalysts at the origin of metabolism
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Self-citationThe Abiotic Background: Challenges and Opportunities in the Search for Evidence of Life Beyond Earth
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Self-citationLUCA and the Origins of Cellular Life
Mrnjavac, N., Schwander, L., & Martin, W. F. (2024) · Elsevier eBooks · doi:10.1016/b978-0-443-15750-9.00050-1
Self-citationThe dinucleotide structure of NAD enables specific reduction on mineral surfacesPreprint
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Self-citationPrebiotic Interconversion of Pyruvate and Lactate over Zeolite‐Supported Ni Catalyst
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Self-citationPräbiotische Chemie – vom Stoffwechsel aus gedacht/Trendbericht Biochemie 2026 3/4
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Self-citationProgress toward a Nonenzymatic Gluconeogenesis: One-Pot Reactions and Model Systems
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Thermodynamic ontogeny: From hydrothermal thioesters to a protein world
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Metal-catalyzed phosphorylation by phosphite and energy at origins.
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Self-citationEnceladus: Exploring a Habitable Ocean Beyond Earth
Dávila, A. F., Neveu, M. F., Kang, W., Hoehler, T. M., MacKenzie, S., German, C. R., Hurford, T. A., & Eigenbrode, J. L. (2026) · Geosciences · doi:10.3390/geosciences16100405
Approaching life in a test tube with prebiotic chemistry
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- Authors
- Beyazay, T., Belthle, K. S., Farès, C., Preiner, M., Moran, J., Martin, W. F., & Tüysüz, H.
- Affiliations
- Max-Planck-Institut für Kohlenforschung (DE)
- Utrecht University (NL)
- Centre National de la Recherche Scientifique (FR)
- Heinrich Heine University Düsseldorf (DE)
- Corresponding author
- Martin, William F.
- Tüysüz, Harun
- ORCID
- Venue
- Nature Communications
- Published
- 2023-02-02
- Volume
- 14
- Issue
- 1
- Pages
- 570-570
- ISSN
- 2041-1723 (ISSN-L)
- PMC
- PMC9894855
- OpenAlex
- W4319062307
- Cited by
- 72
- References
- 91
- Citations by year
- 2026: 24 · 2025: 12 · 2024: 22 · 2023: 14
- FWCI
- 8.38
- Type
- journal article
- Language
- en
- Open access
- gold
- doi.org
- Locations
- Nature Communications (publishedVersion, cc-by)
- PubMed Central (publishedVersion, cc-by)
- PubMed (publishedVersion)
- NIOZ Publications (Royal Netherlands Institute for Sea Research) (acceptedVersion, cc-by)
- Flanders Marine Institute (Flanders Marine Institute) (submittedVersion, other-oa)
- HAL (submittedVersion, cc-by)
- RePEc: Research Papers in Economics (submittedVersion)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- Funders
- Deutsche Forschungsgemeinschaft (MA-1426/21-1 / TU 315/8-1)
- Volkswagen Foundation (96_742)
- Max-Planck-Gesellschaft
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Keywords
- CO2 fixation, pyruvate, citramalate, awaruite, iron nanoparticles, nickel nanoparticles, origin of life, acetyl-CoA pathway, formate, acetate, serpentinization, hydrothermal vents, autotrophic metabolism
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