Improved Ammonia Synthesis and Energy Output from Zinc-Nitrate Batteries by Spin-State Regulation in Perovskite Oxides

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F25%3A73629161" target="_blank" >RIV/61989592:15640/25:73629161 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989100:27640/25:10258838

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/jacs.4c12240" target="_blank" >https://pubs.acs.org/doi/10.1021/jacs.4c12240</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.4c12240" target="_blank" >10.1021/jacs.4c12240</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Improved Ammonia Synthesis and Energy Output from Zinc-Nitrate Batteries by Spin-State Regulation in Perovskite Oxides

Popis výsledku v původním jazyce

Electrocatalytic nitrate reduction to ammonia (eNRA) is a promising route toward environmental sustainability and clean energy. However, its efficiency is often limited by the slow conversion of intermediates due to spin-forbidden processes. Here, we introduce a novel A-site high-entropy strategy to develop a new perovskite oxide (La0.2Pr0.2Nd0.2Ba0.2Sr0.2)CoO3-delta (LPNBSC) for eNRA. The LPNBSC possesses a higher concentration of high-spin (HS) cobalt-active centers, resulting from an increased concentration of [CoO5] structural motifs compared to conventional LaCoO3. Consequently, this material exhibits a significantly improved electrocatalytic performance toward ammonia (NH3) production, resulting in a 3-fold increase in yield rate (129 mu mol h-1 mgcat. -1) and a 2-fold increase in Faradaic efficiency (FE, 76%) compared to LaCoO3 at the optimal potential. Furthermore, the LPNBSC-based Zn-nitrate battery reaches a maximum FE of 82% and an NH3 yield rate of 57 mu mol h-1 cm-2. Density functional theory calculations reveal that A-site high-entropy management in perovskites facilitates nitrate activation and potentially optimizes the thermodynamic rate-determining step of the eNRA process, namely, *HNO3 + H+ + e- -&gt; *NO2 + H2O. This work presents an efficient concept for modulating the spin state of the B-site metal in perovskites and offers valuable insights for the design of high-performance eNRA catalysts.

Název v anglickém jazyce

Improved Ammonia Synthesis and Energy Output from Zinc-Nitrate Batteries by Spin-State Regulation in Perovskite Oxides

Popis výsledku anglicky

Electrocatalytic nitrate reduction to ammonia (eNRA) is a promising route toward environmental sustainability and clean energy. However, its efficiency is often limited by the slow conversion of intermediates due to spin-forbidden processes. Here, we introduce a novel A-site high-entropy strategy to develop a new perovskite oxide (La0.2Pr0.2Nd0.2Ba0.2Sr0.2)CoO3-delta (LPNBSC) for eNRA. The LPNBSC possesses a higher concentration of high-spin (HS) cobalt-active centers, resulting from an increased concentration of [CoO5] structural motifs compared to conventional LaCoO3. Consequently, this material exhibits a significantly improved electrocatalytic performance toward ammonia (NH3) production, resulting in a 3-fold increase in yield rate (129 mu mol h-1 mgcat. -1) and a 2-fold increase in Faradaic efficiency (FE, 76%) compared to LaCoO3 at the optimal potential. Furthermore, the LPNBSC-based Zn-nitrate battery reaches a maximum FE of 82% and an NH3 yield rate of 57 mu mol h-1 cm-2. Density functional theory calculations reveal that A-site high-entropy management in perovskites facilitates nitrate activation and potentially optimizes the thermodynamic rate-determining step of the eNRA process, namely, *HNO3 + H+ + e- -&gt; *NO2 + H2O. This work presents an efficient concept for modulating the spin state of the B-site metal in perovskites and offers valuable insights for the design of high-performance eNRA catalysts.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

147

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

"3119–3128"

Kód UT WoS článku

001399163600001

EID výsledku v databázi Scopus

2-s2.0-85215837719