Recent Progress and Future Outlook on Catalysts for Ammonia Electrosynthesis: Materials, Structural Design, and Reaction Efficiency

Energy & Fuels, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

With the increasing demand for downstream ammonia products, research on fuel has received growing attention. Therefore, under "dual carbon" context, it is crucial to develop an energy-efficient and environmentally friendly method synthesis. Current indicates that electrocatalytic synthesis one of most promising methods. This study systematically summarizes three major factors influencing nitrogen reduction reaction (eNRR) catalysts synthesis: material optimization, structural design, engineering. In terms materials, precious-metal-based, non-precious-metal-based, metal-free eNRR are classified listed. By examination properties catalytic effects various metals non-metals in synthesis, materials with highest activity can be further identified. To enhance efficiency, strategies, such as vacancy creation, doping, interface engineering, facet changes size morphology active sites, have been summarized. integration reactions, including microscale activation, proton transfer, electron efficiency was discussed depth. Finally, urgent issues need addressed current were discussed, unique insights future development provided. review aims provide innovative ideas design improve rate selectivity catalysts.

Language: Английский

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In@Mn₃O₄ with Rich Interface Low‐Coordination Mn Active Sites for Boosting Electrocatalytic Nitrogen Reduction

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract Electrocatalytic nitrogen reduction reaction (NRR) is a potential strategy for green synthesis of ammonia. However, the lack efficient catalysts with both high activity and selectivity restricts development electrocatalytic NRR. In this study, simple water‐based redox method used to synthesize core–shell nanoparticle catalyst 2D Mn 3 O 4 as shell core. The rich interface low‐coordination helps provide more active sites At same time, nucleus gives electrons shell, jointly promotes adsorption activation nitrogen, well enhancement NRR activity. Moreover, designed hydrophobicity, which effectively reduces side hydrogen evolution H proton generated from water dissociation, improved. 0.1 m Na 2 SO , ammonia yield In@Mn 89.44 µg h −1 mg cat (−0.9 V vs RHE) maximum Faradaic efficiency 27.01% at −0.7 (vs RHE), superior most reported catalysts. unique structure design low coordination insights regulation nitrogen–water environment rational advanced electrocatalysts.

Language: Английский

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Interfacial Engineering Boosting the Activity and Stability of MIL-53(Fe) toward Electrocatalytic Nitrogen Reduction

Langmuir, Journal Year: 2024, Volume and Issue: 40(10), P. 5469 - 5478

Published: March 4, 2024

The electrochemical nitrogen reduction reaction (eNRR) has emerged as a promising strategy for green ammonia synthesis. However, it suffers unsatisfactory performance owing to the low aqueous solubility of N2 in solution, high dissociation energy N≡N, and unavoidable competing hydrogen evolution (HER). Herein, MIL-53(Fe)@TiO2 catalyst is designed synthesized highly efficient eNRR. Relative simple MIL-53(Fe), achieves 2-fold enhancement Faradaic efficiency (FE) with an improved yield rate by 76.5% at −0.1 V versus reversible electrode (RHE). After four cycles electrocatalysis, can maintain good catalytic activity, while MIL-53(Fe) exhibits significant decrease NH3 FE 79.8 82.3%, respectively. Benefiting from synergetic effect between TiO2 composites, Fe3+ ions be greatly stabilized during eNRR process, which hinders deactivation caused ions. Further, charge transfer ability interface composites improved, thus, activity significantly boosted. These findings provide insight into preparation composite electrocatalysts.

Language: Английский

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Role of synergies of Cu/Fe3O4 electrocatalyst for nitric oxide reduction to ammonia

Journal of Colloid and Interface Science, Journal Year: 2025, Volume and Issue: unknown, P. 137376 - 137376

Published: March 1, 2025

Language: Английский

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Enabling Unconventional “Alternating‐Distal” N₂ Reduction Pathway for Efficient Ammonia Electrosynthesis

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

The general understanding on the reaction path is that electrocatalytic N2 reduction follows either individual associative alternating or distal pathways, where efficient activation and selective NH3 production are very challenging. Herein, an unconventional "alternating-distal" pathway was achieved by shifting "*NHNH2→*NH2NH2" to "*NHNH2→*NH + NH3" step boost synthesis with amorphous CeMnOx electrocatalyst. In this process, realized through π back donation Mn site, while Mn/Ce dual active sites could regulate intermediate configurations avoid nitrogen-containing by-product formation. Such affirmed in situ spectroscopic analyses theoretical calculations. a neutral media, average ammonia rate of 82.8 µg h-1 mg-1 outstanding Faradaic efficiency 37.3% were attained. This work validated mechanism synthesis, which might be extended other catalytic process multiple possible paths.

Language: Английский

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Enabling Unconventional “Alternating‐Distal” N₂ Reduction Pathway for Efficient Ammonia Electrosynthesis

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Abstract The general understanding on the reaction path is that electrocatalytic N 2 reduction follows either individual associative alternating or distal pathways, where efficient activation and selective NH 3 production are very challenging. Herein, an unconventional “alternating‐distal” pathway was achieved by shifting “*NHNH →*NH ” to + step boost synthesis with amorphous CeMnO x electrocatalyst. In this process, realized through π back donation Mn site, while Mn/Ce dual active sites could regulate intermediate configurations avoid nitrogen‐containing by‐product formation. Such affirmed in situ spectroscopic analyses theoretical calculations. a neutral media, average ammonia rate of 82.8 µg h −1 mg outstanding Faradaic efficiency 37.3% were attained. This work validated mechanism synthesis, which might be extended other catalytic process multiple possible paths.

Language: Английский

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MXene Jacketed Amorphous Ga₂O₃ Nanofibers Modulate the Fiber Surface-Rich Electron for Boosted Electrocatalytic Ammonia Synthesis

Nano Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 13, 2025

Nitrogen (N2) activation and the hydrogen evolution reaction pose significant limitations on electrocatalytic nitrogen reduction (NRR) performance. The exclusive electronic structure of main group elements has advantage inhibiting generation in electrochemical NRR. However, poor conductivity activity remain obstacles to its application. Herein, we report a combination strategy cation-induced amorphous Ga2O3 nanofibers heterostructure engineering, thereby effectively enhancing amorphization generates more oxygen vacancies that enhance N2 electron transfer ability. Additionally, by constructing heterogeneous structures drive charge transfer, enrich electronics surface a-Ga2O3 increase their catalytic activity. Thus, a-Ga2O3/MXene deliver NH3 yield 50.00 μg h-1 mg-1 FE 19.13% at -0.35 V. We anticipate these findings will offer new reference value for further ammonia synthesis research materials.

Language: Английский

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Promoting Mn³⁺ Spin-State Transitions from t_2g to e_g through Ni Doping in Antiperovskite CuNMn₃ for Highly Efficient Ammonia Synthesis

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 5025 - 5033

Published: May 13, 2025

The electrochemical nitrogen reduction reaction (e-NRR) offers a sustainable approach to ammonia synthesis under ambient conditions, with the potential replace energy-intensive Haber-Bosch process. Despite significant progress in this promising field, low NH3 yield rate and limited Faradaic efficiency (FE) remain formidable challenges. Here, we introduce antiperovskite Cu1-xNixNMn3, where partial substitution of Cu by Ni CuNMn3 is developed as an effective robust e-NRR electrocatalyst. Notably, Cu0.7Ni0.3NMn3 demonstrates outstanding performance, achieving 33.9 ± 1.1 μg h-1 mg-1, FE 19.2 0.62% at -0.4 V versus RHE, excellent long-term stability over 50 h electrolysis. In-depth mechanistic studies reveal that Ni/Cu exchange process Cu1-xNixNMn3 maintains structural integrity stabilizes valence states. atoms corner sites interact adjacent Mn face centers via antiferromagnetic interactions, altering original magnetic interactions. This modification triggers spin-state transition some Mn3+ ions from low-spin (t2g4eg0) high-spin (t2g3eg1) configuration. Density functional theory (DFT) calculations confirm improved eg orbital electronic configuration enhances N2 adsorption energy catalytic promotes hydrogenation form *NNH intermediates, thereby accounting for high activity Cu0.3Ni0.7NMn3 e-NRR.

Language: Английский

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Light Entrapment by Plasmonic Chiral Lock for Enhancement of 2D Flakes Catalytic Activity

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: May 21, 2025

Plasmon-based triggering leads to an effective increase of material catalytic activity in a number relevant photoelectrochemical transformations, including nitrogen reduction for the production ammonia. The efficiency plasmon assistance can be significantly increased through rational design hybrid photoelectrodes, e.g., by placing redox-active at plasmonic hot spots that may arise between two coupled nanostructures. In this work, we describe creation and utilization chiral plasmon-active structures (based on so-called gold helicoids) with 2H-MoS2. nanoparticles (with same or opposite chirality) were spatially separated thin two-dimensional (2D) flakes reach mutual coupling them. Using numerical simulations SERS measurements, dependence local enhancement electric field (EF) inside created diastereomer consisting Au helicoid-2D MoS2-Au helicoid "sandwich structure", chirality is demonstrated. It found energy more efficiently "concentrated" MoS2 space using "chiral trap" light (i.e., lock), even case where handedness matching. subsequently used ammonia proceeding surface. A clear matching mismatching chiralities (and related value EF) observed. particular, two-time yield obtained chirality, compared mismatched configuration control experiments performed nonchiral nanocubes. Hence, their dimers (or multimers) provides additional opportunity photosensibilization materials.

Language: Английский

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Low-dimensional lateral heterojunctions made of hexagonal boron nitride and carbon materials as efficient electrocatalysts for the chlorine evolution reaction: a study of DFT and machine learning

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(7), P. 4258 - 4267

Published: Jan. 1, 2024

The reduction of the catalyst's dimension is conducive to facilitating CER. increase Cl − concentration helpful for accelerating oxygen evolution reaction promotes selectivity 2 generation.

Language: Английский

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