A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 8012 - 8023

Опубликована: Фев. 18, 2025

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead low activity NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion tailored surface electrostatic potential, allowing asymmetric binding of NO2-. It exhibits outstanding NO2RR performance Faradaic efficiency ∼100% an yield 22 mg h-1 cm-2, among best such process. Theoretical calculations in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated linear polarized [NCN]2- could transform symmetric [Cu-O-N-O-Cu] CuNCN-NO2- [Cu-N-O-Zn] configuration Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption bond cleavage. A paired electro-refinery Cu0.8Zn0.2NCN cathode reaches 2000 mA cm-2 at 2.36 V remains fully operational industrial-level 400 >140 h production rate ∼30 mgNH3 cm-2. Our work opens new avenue tailoring potentials using strategy advanced electrocatalysis.

Язык: Английский

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Maximizing Available Active Hydrogen on FeNi Substitutional Solid-Solution Alloy to Boost Electrosynthesis of Ammonia from Nitrate

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

Electrochemical nitrate reduction reaction (NO3RR) stands out as a promising route for sustainable ammonia synthesis, in which active hydrogen (*H) plays crucial role both the deoxygenation and hydrogenation steps. However, regulation of surface *H is still overlooked, without intervention, competing evolution kinetically more favored over NO3RR, leaving current system far from satisfactory. Herein, based on reverse utilization Sabatier principle, series FexNiy substitutional solid-solution alloys (SSAs) are synthesized to manipulate behavior enhanced NO3RR. Upon precise optimization alloy composition, d-band center HER-active Ni shifts toward Fermi level, endowing catalyst with strong interaction greatly prolonging its lifetime, enables abundant supply facilitate As expected, maximum NH3 yield rate 31.46 mmol h-1 mg-1 delivered optimized Fe3Ni1-SSA, considerably higher than most extensively reported works. Several situ characterizations combined gain in-depth insight. Especially, Fourier transform infrared spectroscopy internal reflection mode directly observes enrichment surface, while accompanied facilitation NO3RR process verified by external mode.

Язык: Английский

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Industrial‐current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm⁻²

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract The electrocatalytic nitrate reduction (NO 3 RR) holds significance in both NH synthesis and contamination remediation. However, achieving industrial‐scale current high stability membrane electrode assembly (MEA) electrolyzer remains challenging due to inherent full‐cell voltage for sluggish NO RR water oxidation. Here, Cu 2 NCN with positive surface electrostatic potential V S (r) is applied as highly efficient electrocatalysts achieve industrial‐current low‐voltage stable production MEA coupled anodic glycerol This paired electro‐refinery (PER) system reaches 4000 mA cm −2 at 2.52 industrial‐level 1000 100 h the rate of 97000 µg NH3 −1 a Faradaic efficiency 83%. Theoretical calculations elucidate that asymmetric electron‐withdrawing [N−C≡N] units enhance polarization (r), promoting robust adsorption * on facilitate O−N bond dissociation. A comprehensive techno‐economic analysis demonstrates profitability commercial viability this system. Our work opens new avenue marks significant advancement systems industrial synthesis.

Язык: Английский

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Enhanced Activity and Stability for Electrocatalytic Nitrate Reduction to Ammonia over Low‐Coordinated Cobalt

Small, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

It is still challenging to develop an effective strategy simultaneously enhance the activity and stability of electrocatalysts for electrocatalytic nitrate reduction reaction (eNO3RR). Herein, taking metallic cobalt as example, it demonstrated that construction low-coordinated nanosheets (L-Co NSs) by H2 plasma etching electrodeposited (Co can greatly eNO3RR. Compared with Co NSs, at -0.4 V versus RHE, removal rate, ammonia partial current density, yield are increased L-Co NSs from 82.14% 98.57%, 476 683 mA cm-2, 2.11 2.54 mmol h-1 respectively. In addition, demonstrate negligible decay after 30 cycles test, while show significant decline. situ electrochemical characterizations theoretical calculations verify abundance vacancies in not only contribute optimized electronic structure enhanced desorption key intermediate boost but also facilitate transformation Co(OH)2 Co0 promote stability. Furthermore, exhibit favorable performance removing simulated wastewater air discharge-electrocatalytic cascade system produce ammonia.

Язык: Английский

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Heteroatom Introduction and Electrochemical Reconstruction on Heterostructured Co‐Based Electrocatalysts for Hydrogenation of Quinolines

Small, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Abstract Electrocatalytic hydrogenation (ECH) of quinoline provides an eco‐friendly and prospective route to achieve the highly value‐added generation 1,2,3,4‐tetrahydroquinoline (THQ). Co element has been proven be efficient catalytic site for ECH quinoline, but rational regulation electronic structure active improve activity is still a challenge. Herein, hierarchical core–shell consisting NiCo‐MOF nanosheets encapsulated Cu(OH) 2 nanorods (Cu(OH) @CoNi‐MOF) constructed. The heterojunction promotes transfer interfacial charge optimizes site. introduction Ni significantly increases binding between Cu, preventing exfoliation sites from core, reducing reaction energy barrier rate‐determining step, thus resulting in superior reactivity durability. Besides, electrochemical reconstruction further modulates by forming multi‐metallic compound with low valence state (NiCoCu), achieving optimal performance conversion 99.5% THQ selectivity 100%. A flow‐cell system assembled, demonstrating prospect industrial application.

Язык: Английский

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Recent Advances in 3d‐Block Transition Metal‐Based Catalysts for Electrochemical Nitrate Reduction to Ammonia

ChemCatChem, Год журнала: 2025, Номер unknown

Опубликована: Май 26, 2025

Abstract Ammonia (NH 3 ) is a crucial chemical in modern industry, serving as key component fertilizers and emerging potential energy carrier. However, traditional NH synthesis via the Haber‐Bosch process highly energy‐intensive contributes significantly to global CO 2 emissions. Electrochemical nitrate reduction reaction (NO RR) has emerged sustainable alternative for production, leveraging renewable electricity reduce −) under ambient conditions. Among various electrocatalysts, 3d‐block transition metal‐based materials have shown remarkable due their low cost, electronic structures, redox flexibility, tunable catalytic properties. This review provides comprehensive analysis of recent advances catalysts NO RR, highlighting catalyst design, performance metrics, mechanistic insights, challenges. Furthermore, strategies such alloying, single‐atom catalysts, high‐entropy alloys are reviewed enhance efficiency selectivity. Finally, we discuss future perspectives on development practical application green aiming bridge gap between fundamental research industrial applications.

Язык: Английский

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Fe₃O₄ Nanoparticles Anchored on Biomass Carbon as Electrocatalysts for Nitrate Reduction

ACS Applied Nano Materials, Год журнала: 2024, Номер 7(24), С. 28693 - 28703

Опубликована: Дек. 12, 2024

The electrocatalysis of nitrate to value-added ammonia is an important strategy address the increasingly pressing problem pollution. Nonetheless, this remains a challenging topic within field catalysis. Iron-based materials are considered promising catalysts for reduction NH3, but they prone agglomeration, with low yields and Faraday efficiencies. In study, Fe3O4 nanoparticles were anchored biomass carbon (BC) through in situ annealing strategy, which can utilize reducing properties BC convert Fe3+ ions. These findings indicate that by modulating temperature BC, ratio Fe2+ on catalyst surface be adjusted, thereby increasing active sites available promoting reduction. Transient photovoltage spectroscopy also indicated introduction contributed increase electron transfer rate. efficiency Fe3O4/BC-700 NH3 presence 100 mM NO3– at −0.5 V vs RHE was 91.10% (±2.36) yield rate 4274.25 (±110.09) mmol gcat–1 h–1. results pave way sustainable ammonium synthesis using low-cost environmentally friendly improved catalytic adjusting structure interface behavior.

Язык: Английский

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A nanoflower-on-nanowire heterogeneous electrocatalyst for enhanced interfacial water activation in nitrate reduction reaction

Nano Research, Год журнала: 2024, Номер 18(2), С. 94907135 - 94907135

Опубликована: Дек. 16, 2024

Язык: Английский

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