TY - JOUR

T1 - Catalysis of C-N Coupling on High-Entropy Alloys

AU - Plenge, Mads K.

AU - Pedersen, Jack K.

AU - Bagger, Alexander

AU - Rossmeisl, Jan

N1 - Funding Information: The Center for High Entropy Alloy Catalysis (CHEAC) is supported by the Danish National Research Foundation [grant number DNRF149 ]. The Authors also acknowledges the Pioneer Center for Accelerating P2X Materials Discovery, CAPeX [DNRF grant number P3]. A. Bagger acknowledges the Novo Nordisk Foundation Start Package grant [grant number NNF23OC0084996 ]. Publisher Copyright: © 2024 The Authors

PY - 2024

Y1 - 2024

N2 - Catalyzing carbon–nitrogen (C-N) coupling using small abundant nitrogenous molecules is of growing interest to lessen the environmental impact of the industrial process. High-entropy alloys hold the potential to have surface sites optimized for each of the coupling intermediates and by varying the alloy composition of the catalyst it provides tunability to the adsorption energy distribution. We model the C-N coupling using adsorption energies of CO and NO and assume that *CO couples with an *NO-reduced intermediate. As more mechanistic insight is needed, we limit the model to the coverage of pairs of *CO and *NO, providing a necessary but not sufficient condition for catalytic activity. Two limiting cases for simulating the adsorption process are presented: one considering thermodynamic equilibrium and one considering out-of-equilibrium conditions. A Monte Carlo method connecting the two limits is suggested which reproduce trends observed in experiments. By varying the partial pressure of NO, the shape of the pair coverage function in the composition space, as well as its optima, are altered. Our method finds a ternary AuCuPd optimum at equal CO/NO partial pressures and copper to be the optimum at low NO partial pressures.

AB - Catalyzing carbon–nitrogen (C-N) coupling using small abundant nitrogenous molecules is of growing interest to lessen the environmental impact of the industrial process. High-entropy alloys hold the potential to have surface sites optimized for each of the coupling intermediates and by varying the alloy composition of the catalyst it provides tunability to the adsorption energy distribution. We model the C-N coupling using adsorption energies of CO and NO and assume that *CO couples with an *NO-reduced intermediate. As more mechanistic insight is needed, we limit the model to the coverage of pairs of *CO and *NO, providing a necessary but not sufficient condition for catalytic activity. Two limiting cases for simulating the adsorption process are presented: one considering thermodynamic equilibrium and one considering out-of-equilibrium conditions. A Monte Carlo method connecting the two limits is suggested which reproduce trends observed in experiments. By varying the partial pressure of NO, the shape of the pair coverage function in the composition space, as well as its optima, are altered. Our method finds a ternary AuCuPd optimum at equal CO/NO partial pressures and copper to be the optimum at low NO partial pressures.

KW - C-N coupling

KW - Catalysis

KW - Catalyst discovery

KW - High-entropy alloys

KW - Urea

U2 - 10.1016/j.jcat.2024.115322

DO - 10.1016/j.jcat.2024.115322

M3 - Journal article

AN - SCOPUS:85184920143

VL - 430

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

M1 - 115322

ER -