Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

An, Lun; Narouz, Mina R.; Smith, Peter T.; De La Torre, Patricia; Chang, Christopher J.

doi:10.1002/anie.202305719

Title: Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

Journal Article · 19 July 2023 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202305719 · OSTI ID:1995549

^[1];

^[1]; De La Torre, Patricia ^[1];

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Department of Chemistry University of California, Berkeley Berkeley CA 94720-1460 USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720-1460 USA
Department of Chemistry University of California, Berkeley Berkeley CA 94720-1460 USA, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720-1460 USA, Department of Molecular and Cell Biology University of California, Berkeley Berkeley CA 94720-1460 USA

Abstract The electrochemical nitrate (NO ₃ ⁻ ) reduction reaction (NO ₃ RR) to ammonia (NH ₃ ) represents a sustainable approach for denitrification to balance global nitrogen cycles and an alternative to traditional thermal Haber‐Bosch processes. Here, we present a supramolecular strategy for promoting NH ₃ production in water from NO ₃ RR by integrating two‐dimensional (2D) molecular cobalt porphyrin ( CoTPP ) units into a three‐dimensional (3D) porous organic cage architecture. The porphyrin box CoPB‐C8 enhances electrochemical active site exposure, facilitates substrate–catalyst interactions, and improves catalyst stability, leading to turnover numbers and frequencies for NH ₃ production exceeding 200,000 and 56 s ⁻¹ , respectively. These values represent a 15‐fold increase in NO ₃ RR activity and 200‐mV improvement in overpotential for the 3D CoPB‐C8 box structure compared to its 2D CoTPP counterpart. Synthetic tuning of peripheral alkyl substituents highlights the importance of supramolecular porosity and cavity size on electrochemical NO ₃ RR activity. These findings establish the incorporation of 2D molecular units into 3D confined space microenvironments as an effective supramolecular design strategy for enhancing electrocatalysis.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1995549

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 35 Vol. 62; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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