(Closed) COFforH2 – Covalent organic frameworks as artificial metalloenzymes for hydrogen activation


Title Covalent organic frameworks as artificial metalloenzymes for hydrogen activation
Reference UTA-EXPL/NPN/0055/2019
Scientific Area Nanotechnologies
Funding (PT) 49 760,85 EUR
Funding (US) 50 000,00 USD
Leading Institutions International Iberian Nanotechnology Laboratory (INL)
Department of Chemistry, College of Natural Sciences, UT Austin
Duration 12 months 14 months
Start date November 1, 2020
End date  October 31, 2021 December 31, 2021
Keywords Covalent organic framework, Nanozyme, Artificial metalloenzyme, Hydrogen

Hydrogen (H2) is an attractive energy source due to its high enthalpy of combustion and innocuous side products. Nature’s Hydrogen economy solution uses this molecule as an energy source in the form of hydrogenase enzymes, which are involved in the conversion of CO2 to methane and nitrate to nitrogen. To realize these transformations, the enzymes rely on biologically available metal ions, iron, and nickel. However, the industry often depends on critical metals, such as platinum, to catalyze hydrogenation reactions. The COFforH2 project will draw inspiration from nature’s low-carbon solution by developing artificial enzymes from nanomaterials, nanozymes, for H2 activation.

Mimicking such enzymes offers a great opportunity for the replacement of rare and expensive platinum-group metals in catalytic conversions. These innovative nanomaterials will be based on covalent organic frameworks (COFs), crystalline nanoporous networks formed by self-assembly of purely organic building blocks. These materials offer an exceptional opportunity of design with atomic precision combined with high thermal and chemical stability, making them excellent candidates for nanozymatic conversions.

The biomimetic nanozymes could function as stable and recyclable heterogeneous catalysts, which take advantage of natural enzymes’ capacity to realize thermodynamically challenging transformations at ambient temperature and pressure. They can provide breakthrough biomimetic catalysts working at much milder conditions than currently available catalysts while featuring enhanced stability and wider condition-tolerance than natural enzymes. 

Ultimately, the results of this project will be an important milestone in the development of sustainable, biomimetic catalytic nanomaterials for industrially relevant conversions.

Key Outcomes

  • New nanomaterialsbased on COFs that mimic metalloenzyme activity for the activation of hydrogen;
  • Publicationsin peer-reviewed scientific journals;
  • The basis for a larger research project, which will be aimed at enhancing the technology readiness level of nanozymatic COF-based catalysts beyond this exploratory research project.

Papers and Communications

  • Fernandes, S. P. S., Frey, L., Cid-Seara, K. M., Oliveira, O., Guldris, N., Carbó-Argibay, E., Rodríguez-Abreu, C., Kolen’ko, Y. V., Silva, A. M. S., Medina, D. D., & Salonen, L. M. (2022). A post-synthetic modification strategy for the synthesis of pyrene-fused azaacene covalent organic frameworks. In Microporous and Mesoporous Materials (Vol. 343, p. 112162). Elsevier BV. https://doi.org/10.1016/j.micromeso.2022.112162
  • Goralski, S. T., Cid-Seara, K. M., Jarju, J. J., Rodriguez-Lorenzo, L., LaGrow, A. P., Rose, M. J., & Salonen, L. M. (2022). Threefold reactivity of a COF-embedded rhenium catalyst: reductive etherification, oxidative esterification or transfer hydrogenation. In Chemical Communications (Vol. 58, Issue 86, pp. 12074–12077). Royal Society of Chemistry (RSC). https://doi.org/10.1039/d2cc03173f
  • Goralski, S. T., & Rose, M. J. (2022). Emerging artificial metalloenzymes for asymmetric hydrogenation reactions. In Current Opinion in Chemical Biology (Vol. 66, p. 102096). Elsevier BV. https://doi.org/10.1016/j.cbpa.2021.102096
  • Kerns, S. A., Seo, J., Lynch, V. M., Shearer, J., Goralski, S. T., Sullivan, E. R., & Rose, M. J. (2021). Scaffold-based [Fe]-hydrogenase model: H2 activation initiates Fe(0)-hydride extrusion and non-biomimetic hydride transfer. Chemical Science 12(38), 12838–12846. https://doi.org/10.1039/D0SC03154B
  • Frey, L., Jarju, J. J., Salonen, L. M., & Medina, D. D. (2021). Boronic-acid-derived covalent organic frameworks: from synthesis to applications. In New Journal of Chemistry (Vol. 45, Issue 33, pp. 14879–14907). Royal Society of Chemistry (RSC). https://doi.org/10.1039/d1nj01269j
  • Salonen, L. M., Petrovykh, D. Y., & Kolen’ko, Yu. V. (2021). Sustainable catalysts for water electrolysis: Selected strategies for reduction and replacement of platinum-group metals. Materials Today Sustainability, 11–12, 100060. https://doi.org/10.1016/j.mtsust.2021.100060
  • Boucher, D. G., Kearney, K., Ertekin, E., & Rose, M. J. (2021). Tuning p-Si(111) Photovoltage via Molecule|Semiconductor Electronic Coupling. Journal of the American Chemical Society, 143(6), 2567–2580. https://doi.org/10.1021/jacs.0c12075
  • Joseph, C., Shupp, J. P., Cobb, C. R., & Rose, M. J. (2020). Construction of Synthetic Models for Nitrogenase-Relevant NifB Biogenesis Intermediates and Iron-Carbide-Sulfide Clusters. Catalysts, 10(11), 1317. https://doi.org/10.3390/catal10111317


2021 Annual Conference

2021 Annual Conference

Project Team

Laura Salonen

Principal Investigator in Portugal (INL)

Michael J Rose

Principal Investigator in Austin (UT Austin)