Improved Ammonia Synthesis and Energy Output from Zinc-Nitrate Batteries by Spin-State Regulation in Perovskite Oxides DOI Creative Commons
Hele Guo, Yazhou Zhou, Kaibin Chu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

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

Language: Английский

Unveiling Cutting‐Edge Developments in Electrocatalytic Nitrate‐to‐Ammonia Conversion DOI
Haoran Zhang, Haijian Wang, X. P. Cao

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 11, 2024

The excessive enrichment of nitrate in the environment can be converted into ammonia (NH

Language: Английский

Citations

166
Unveiling the Reaction Mechanism of Nitrate Reduction to Ammonia Over Cobalt-Based Electrocatalysts DOI

Kaiwen Yang,

Shuhe Han, Chuanqi Cheng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 12976 - 12983

Published: April 3, 2024

Electrocatalytic reduction of nitrate to ammonia (NRA) has emerged as an alternative strategy for sewage treatment and generation. Despite excellent performances having been achieved over cobalt-based electrocatalysts, the reaction mechanism well veritable active species across a wide potential range are still full controversy. Here, we adopt CoP, Co, Co3O4 model materials solve these issues. CoP evolves into core@shell structured CoP@Co before NRA. For Co catalysts, three-step relay is carried out superficial dynamical Coδ+ under low overpotential, while continuous hydrogenation from unveiled high overpotential. In comparison, stable steadily catalyze range. As result, exhibit much higher NRA activity than especially Moreover, performance although they experience same mechanism. A series characterizations clarify reason enhancement highlighting that core donates abundant electrons species, leading generation more hydrogen nitrogen-containing intermediates.

Language: Английский

Citations

73
Relay Catalysis of Fe and Co with Multi‐Active Sites for Specialized Division of Labor in Electrocatalytic Nitrate Reduction Reaction DOI
Hongxia Luo, Shuangjun Li, Ziyang Wu

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: April 8, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) driven by renewable energy is a promising technology for the removal of nitrate‐containing wastewater. However, sluggish kinetics resulted from complex proton‐coupled electron transfer and various intermediates remain key barriers large‐scale application NO RR. Herein, tactic reported to raise rate RR increase selectivity N 2 using bimetal catalyst: Co inclined act on steps needed in process, rate‐determining step (RDS: *NO , asterisk means intermediates) subsequent *N hydrogenation as well Fe exhibits efficient activity selectivity‐ determining (SDS: then ) via relay catalysis mechanism. A efficiency 78.5% an ultra‐long cycle stability 60 cycles (12 h per cycle) are achieved FeCo alloy confined with nitrogen‐doped porous carbon nanofibers (FeCo‐NPCNFs). DFT calculations unveil that introduction active site not only regulates d‐band center alloy, optimizes adsorption intermediates, but also has strong capacity supply hydrogen species. Clearly, this study elucidates effects bimetallic performance electrocatalytic offers avenues designing Fe‐based catalysts realize nitrogen‐neutral cycle.

Language: Английский

Citations

43
Mott–Schottky contact synergistically boosts the electroreduction of nitrate to ammonia under low-nitrate concentration DOI
Xiaojuan Zhu, Chaoqun Ma, Yi‐Chi Wang

et al.

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(8), P. 2908 - 2920

Published: Jan. 1, 2024

A Mott–Schottky electrocatalyst composed of amorphous Co–B nanochain embedded in CoO x nanosheets was developed for highly efficient conversion NO 3 − -to-NH .

Language: Английский

Citations

37
Composition-engineered FeCo nanoalloys with lattice expansion and optimized electron structure boosting electrocatalytic Nitrate reduction DOI
Yang Liu,

Xiu Zhong,

Mengting Liu

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 355, P. 124205 - 124205

Published: May 16, 2024

Language: Английский

Citations

23
Enhancing Compatibility of Two‐Step Tandem Catalytic Nitrate Reduction to Ammonia Over P‐Cu/Co(OH)2 DOI

Qiuyu Yan,

Rundong Zhao, Lihong Yu

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 11, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO − NH involves multiple proton‐coupled electron transfer processes by‐products 2 , H etc.), making high selectivity challenge. Herein, two‐phase nanoflower P‐Cu/Co(OH) electrocatalyst consisting of P‐Cu clusters P‐Co(OH) nanosheets designed match two‐step tandem process ) more compatible, avoiding excessive accumulation optimizing whole reaction. Focusing on initial 2e process, inhibited * desorption Cu sites in gives rise appropriate released electrolyte. Subsequently, exhibits superior capacity for trapping transforming desorbed during latter 6e due thermodynamic advantage contributions active hydrogen. In 1 m KOH + 0.1 leads yield rate 42.63 mg h cm Faradaic efficiency 97.04% at −0.4 V versus reversible hydrogen electrode. Such well‐matched achieves remarkable synthesis performance perspective catalytic reaction, offering novel guideline design RR electrocatalysts.

Language: Английский

Citations

23
Enhancing nitrate reduction to ammonia by synergistic and interface coupling effects of binary metal sites DOI

Qiao Gou,

Yini Mao,

Shengmei Lv

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 348, P. 123810 - 123810

Published: April 24, 2024

Language: Английский

Citations

22
The synergistic catalysis effect on electrochemical nitrate reduction at the dual-function active sites of the heterostructure DOI
Yuxiang Li,

Zhenjie Lu,

Lei Zheng

et al.

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(13), P. 4582 - 4593

Published: Jan. 1, 2024

The synergistic catalysis effect based on CoP and Cu 3 P dual-function active sites is proposed to understand the mechanism of hydrogen (*H) adsorbed intermediates (*NO x ) during water-splitting nitrate reduction.

Language: Английский

Citations

21
π‐d Conjugated Copper Chloranilate with Distorted Cu‐O4 Site for Efficient Electrocatalytic Ammonia Production DOI
Chengyong Xing, Jiali Ren, Longlong Fan

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 9, 2024

Abstract Understanding the relationship between electrocatalytic performance and local structure at molecular level is of great significance. Herein, a bifunctional electrocatalyst CuCA (CA = chloranilate) constructed for both nitrogen reduction reaction (NRR) nitrate (NO 3 RR). Combined structural analyses using Rietveld refinement, extended X‐ray adsorption fine (EXAFS), pair distribution function (PDF) revealed significant distortion Cu‐O 4 structure. Benefitting from unique structure, Cu‐CA shows an impressive NH yield rate 286.00 ug h −1 mg (FE 18.25%, ‐0.85 V vs RHE), 3180.00 90.3%, ‐0.9 RHE) NRR NO RR, respectively. In contrast, pyrazine (Pyz) decorated compound Cu‐CA‐Pyz with less distorted fewer active sites show much lower activity. Density functional theory (DFT) calculations shed light on that nature can effectively regulate electron density distribution, which energy barrier activation intermediate species, leading to enhanced These findings may give new insight into structural‐property open up opportunities exploration efficient electrocatalysts.

Language: Английский

Citations

21
Matched Kinetics Process Over Fe2O3‐Co/NiO Heterostructure Enables Highly Efficient Nitrate Electroreduction to Ammonia DOI
Qiang Yang,

Yongguang Bu,

Shuailei Pu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 31, 2024

Abstract Tandem nitrate electroreduction reaction (NO 3 − RR) is a promising method for green ammonia (NH ) synthesis. However, the mismatched kinetics processes between NO ‐to‐NO 2 and ‐to‐NH results in poor selectivity NH excess evolution electrolyte solution. Herein, Ni 2+ substitution strategy developing oxide heterostructure Co/Fe layered double oxides (LDOs) was designed employed as tandem electrocataltysts RR. (Co 0.83 0.16 Fe exhibited high yield rate of 50.4 mg ⋅ cm −2 h −1 with Faradaic efficiency 97.8 % at −0.42 V vs. reversible hydrogen electrode (RHE) pulsed electrolysis test. By combining situ / operando characterization technologies theoretical calculations, we observed strong over Fe, playing dual role RR by i) modifying electronic behavior Co, ii) serving complementary site active (*H) supply. Therefore, adsorption capacity *NO its subsequent hydrogenation on Co sites became more thermodynamically feasible. This study shows that promotes provides insights into design electrocatalysts evolution.

Language: Английский

Citations

20