Design Criteria for Active and Selective Catalysts in the Nitrogen Oxidation Reaction DOI Creative Commons

Muhammad Usama,

Samad Razzaq, Kai S. Exner

et al.

ACS Physical Chemistry Au, Journal Year: 2024, Volume and Issue: 5(1), P. 38 - 46

Published: Dec. 24, 2024

The direct conversion of dinitrogen to nitrate is a dream reaction combine the Haber–Bosch and Ostwald processes as well steam reforming using electrochemistry in single process. Regrettably, corresponding nitrogen oxidation (NOR) hampered by selectivity problem, since oxygen evolution (OER) both thermodynamically kinetically favored same potential range. This opens search for identification active selective NOR catalysts enable production under anodic conditions. While theoretical considerations computational hydrogen electrode approach have helped identifying material motifs electrocatalytic reactions over last decades, inherent complexity NOR, which consists ten proton-coupled electron transfer steps thus at least nine intermediate states, poses challenge electronic structure theory calculations realm materials screening. To this end, we present different strategy capture competing OER atomic scale. Using data-driven method, provide framework derive generalized design criteria with toward NOR. leads significant reduction costs, only two free-energy changes need be evaluated draw first conclusion on selectivity.

Language: Английский

Understanding Free-Energy Landscapes in Electrocatalysis: A Case Study on Nitrate Reduction over Au(111) DOI Creative Commons
Ebrahim Tayyebi, Kai S. Exner

ACS electrochemistry., Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Free-energy landscapes are essential tools in electrocatalysis for assessing catalyst activity and selectivity of proton-coupled electron transfer steps. It is a common approach to focus on the thermodynamic part free-energy landscape refer only reaction intermediates, which turn leads results being highly dependent accuracy calculated binding energies adsorbed intermediates. Since evaluation electrocatalytic processes solid surfaces usually requires density functional theory calculations (DFT) with periodic boundary conditions, free energy reference molecules relevant binding-energy determination subject an inherent error. For this purpose, gas-phase error corrections have been introduced recent years, allow correction DFT error, based assessment formation enthalpies, by assigning double or triple bonds molecules. In contribution, we present simple unbiased errors: do not distinguish between bond order but correct all single, double, referring atomization compounds. We employ our nitrate reduction Au(111) as case study, using different levels exchange–correlation functionals generalized gradient meta-generalized approximation. shown that inclusion well solvation ion significantly affects energetics predictions descriptor-based analysis, highlighting importance correcting DFT-based gaining reliable insights into systems.

Language: Английский

Citations

1
Data-driven discovery of single-atom catalysts for CO2 reduction considering the pH-dependency at the reversible hydrogen electrode scale DOI

Yue Chu,

Yuhang Wang, Di Zhang

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(17)

Published: May 2, 2025

The electrochemical carbon dioxide reduction reaction (CO2RR) represents a promising approach to mitigating climate change and addressing energy challenges by converting CO2 into value-added chemicals. Among various CO2RR products, CO is attractive due its economic viability industrial relevance. By integrating large-scale data mining (with 939 experimental performance data), we reveal that the catalytic of d-block transition metal-based single-atom catalysts (SACs) for influenced not only coordination environment but also significantly pH. However, unified model could accurately depict pH-dependent activity SACs urgently needed. Herein, conducted microkinetic modeling based upon density functional theory calculations pH-electric field coupled analyze 101 SACs. Our data-driven screening identifies 12 high-performance with selectivity across different pH conditions, primarily on Fe, Cu, Ni centers. We establish scaling relation between key intermediates (*COOH *CO) their adsorption behaviors under varying conditions. Furthermore, our reveals critical role electric effects in determining performance, aligning well turnover frequency values. Most importantly, theoretical captures CO2RR-to-CO SACs, which experimentally validated serves as general framework rational design catalysts. Based this model, identify series M–N–C catalysts, providing universal principle optimizing CO2-to-CO conversion.

Language: Английский

Citations

0
Aromaticity monitoring during the donor-acceptor coordination of pyrosilicate, pyrophosphate, and pyrosulfate anions to a new designed anion receptor DOI

Ferdos Ariafard,

Morteza Rouhani, Seyed Amin Mirmohammadi

et al.

Phosphorus, sulfur, and silicon and the related elements, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 10

Published: April 16, 2025

Language: Английский

Citations

0
Divergent Activity Shifts of Tin‐Based Catalysts for Electrochemical CO2 Reduction: pH‐Dependent Behavior of Single‐Atom versus Polyatomic Structures DOI Creative Commons
Yuhang Wang, Di Zhang, Bin Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Tin (Sn)-based catalysts have been widely studied for electrochemical CO

Language: Английский

Citations

1
Divergent Activity Shifts of Tin‐Based Catalysts for Electrochemical CO2 Reduction: pH‐Dependent Behavior of Single‐Atom versus Polyatomic Structures DOI
Yuhang Wang, Di Zhang, Bin Sun

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Abstract Tin (Sn)‐based catalysts have been widely studied for electrochemical CO 2 reduction reaction (CO RR) to produce formic acid, but the intricate influence of structural sensitivity in single‐atom Sn (e.g., Sn−N−C) and polyatomic SnO x SnS ; =1,2) on their pH‐dependent performance remains enigmatic. Herein, we integrate large‐scale data mining (with >2,300 RR from available experimental literature during past decade), ab initio computations, machine learning force field accelerated molecular dynamic simulations, pH‐field coupled modelling unravel pH dependence. We reveal a fascinating contrast: electric response binding strength *OCHO Sn−N 4 −C exhibits opposite behaviors due differing dipole moment changes upon formation. Such leads an intriguing volcano evolution Sn. Subsequent validations turnover frequency current density under both neutral alkaline conditions well aligned with our theoretical predictions. Most importantly, analysis suggests necessity distinct optimization strategies energy different types Sn‐based catalysts.

Language: Английский

Citations

1
Design Criteria for Active and Selective Catalysts in the Nitrogen Oxidation Reaction DOI Creative Commons

Muhammad Usama,

Samad Razzaq, Kai S. Exner

et al.

ACS Physical Chemistry Au, Journal Year: 2024, Volume and Issue: 5(1), P. 38 - 46

Published: Dec. 24, 2024

The direct conversion of dinitrogen to nitrate is a dream reaction combine the Haber–Bosch and Ostwald processes as well steam reforming using electrochemistry in single process. Regrettably, corresponding nitrogen oxidation (NOR) hampered by selectivity problem, since oxygen evolution (OER) both thermodynamically kinetically favored same potential range. This opens search for identification active selective NOR catalysts enable production under anodic conditions. While theoretical considerations computational hydrogen electrode approach have helped identifying material motifs electrocatalytic reactions over last decades, inherent complexity NOR, which consists ten proton-coupled electron transfer steps thus at least nine intermediate states, poses challenge electronic structure theory calculations realm materials screening. To this end, we present different strategy capture competing OER atomic scale. Using data-driven method, provide framework derive generalized design criteria with toward NOR. leads significant reduction costs, only two free-energy changes need be evaluated draw first conclusion on selectivity.

Language: Английский

Citations

1