Structure-sensitive activity and selectivity trends during NO hydrogenation with "catalytic matrices"

Eleonora Romeo^a, María Fernanda Lezana-Muralles^a, Francesc Illas^a, Federico Calle-Vallejo^b

^aUniversitat de Barcelona, Institut de Química Teòrica i Computacional, Departament de Ciència de Materials i Química Física de la Facultat de Química, c/ Martí i Franquès, 1-11, 08028 Barcelona

^bNano-Bio Spectroscopy Group and European Theoretical Spectroscopy Facility (ETSF), Department of Advanced Materials and Polymers: Physics, Chemistry and Technology, University of the Basque Country UPV/EHU, Av. Tolosa 72, 20018 San Sebastián, Spain.

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)

#N2X - Recent advances on nitrogen activation and conversion

Torremolinos, Spain, 2023 October 16th - 20th

Organizers: Victor Mougel, Nella Vargas-Barbosa and Roland Marschall

Oral, Eleonora Romeo, presentation 074
DOI: https://doi.org/10.29363/nanoge.matsus.2023.074
Publication date: 18th July 2023

Electrocatalytic NO_x reduction is a promising way to help restore the natural balance of the nitrogen cycle [1]. Various works agree that nitrate reduction to NH₄⁺/NH₃ involves NO as an intermediate, and NO hydrogenation is the potential-limiting step of NO reduction. However, debates on whether *NO hydrogenation produces *NHO or *NOH hamper catalyst optimization and rational design for NO_x electroreduction [2,3].

In this contribution, I will provide a simple classification of late transition metals for *NO hydrogenation: Cu, Ag, and Au (group 11 of the periodic table) primarily yield *NHO; Ni, Pd, and Pt (group 10) prefer to form *NOH or a combination of *NOH and *NHO. In turn, Co, Rh, and Ir (group 9) predominantly produced *NHO, particularly on adsorption sites with undercoordinated and/or square symmetry. Additionally, Cu and other group 11 elements prove very active for *NO hydrogenation and NO reduction to NH₄⁺/NH₃, while the (100) terraces of various transition metals should display reasonable activities. Statistical analysis enabled qualitative and quantitative conclusions through the use of “catalytic matrices”. These matrices identify that active catalysts for *NO electroreduction statistically favor *NHO over *NOH and possess undercoordinated sites [4].

To conclude, the matrices help uncover that highly active materials for NO reduction should typically contain undercoordinated Cu sites and be mediated by *NHO. The power of the matrices lies in their ability to rapidly extract information and use it to identify active sites with enhanced NO_x electroreduction.

References:

[1] van Langevelde P. H., Katsounaros I., Koper M. T. M., Electrocatalytic Nitrate Reduction for Sustainable Ammonia Production, Joule 2021, 5 (2), 290−294.

[2] Rosca V., Duca M., de Groot M. T., Koper M. T. M., Nitrogen Cycle Electrocatalysis, Chem. Rev. 2009, 109 (6), 2209−2244.

[3] Casey-Stevens C. A., Ásmundsson H., Skúlason E., Garden A. L., A Density Functional Theory Study of the Mechanism and Onset Potentials for the Major Products of NO Electroreduction on Transition Metal Catalysts, Appl. Surf. Sci. 2021, 552, 149063.

[4] Romeo E., Lezana-Muralles M. F., Illas F., Calle-Vallejo F., Extracting Features of Active Transition Metal Electrodes for NO Electroreduction with Catalytic Matrices, ACS Appl. Mater. Interfaces 2023, 15, 22176−22183.

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