Endowing Cu-Based Oxide with a Self-Healing Feature via High-Entropy Doping toward Ampere-Level Electrochemical Nitrate Reduction to Ammonia

ACS Materials Letters, Год журнала: 2025, Номер unknown, С. 938 - 946

Опубликована: Фев. 10, 2025

Язык: Английский

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Quaternary Medium-Entropy Alloy Metallene with Strong Charge Polarization for Highly Selective Urea Electrosynthesis from Carbon Dioxide and Nitrate

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Фев. 14, 2025

Electrochemical urea synthesis via the coreduction of CO2 and NO3- is a sustainable alternative to traditional Bosch-Meiser process. However, sluggish reaction kinetics usually result in low efficiency. Herein, we designed kind quaternary PdCuCoZn medium-entropy alloy (MEA) metallene for highly selective electrosynthesis. The random occupation Cu, Co, Zn with lower electronegativity face-centered cubic lattice Pd-based enables abundant electron donation from transition metals adjacent Pd atoms, leading formation charge-polarized Pdδ--Cu/Co/Znδ+ sites. Considering that pivotal C- N-intermediates, namely, *CO *NH2, are electrophilic nucleophilic, respectively, such strong charge polarization would greatly benefit their respective stabilization. stable adsorption bonded electron-rich sites *NH2 electron-deficient Cu/Co/Zn-based demonstrated by combination situ characterizations theoretical calculations. proof-of-concept MEA achieves maximum yield rate 1840 μg h-1 mg-1 high Faradaic efficiency 70.2%, surpassing most reported state-of-the-arts. Our strategy proposed this work believed enlighten design an effective catalyst used multistep reactions.

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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Sulfur Defect Tuning of CuS/BiVO₄ and Understanding the Function of Hydrogen Radicals for Photoelectrochemical Ammonia Production

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Photoelectrochemical nitrate reduction has been a promising method for ammonia (NH3) production under normal temperatures and neutral conditions. However, hydrogenation is key process in the selective of NH3 during reduction; therefore, inducing active hydrogen inhibiting are noteworthy problem. In this study, BiVO4/CuS (BVO/CS) heterostructure constructed photoelectrochemical reaction (PEC NIRR). The introduction CuS optimizes electron-transfer ability enhances surface catalytic kinetics BVO/CS. At same time, presence sulfur vacancies on promotes adsorption activation nitrate, realizes splitting H2O, successfully generates abundant radicals (H*). generated H* effectively utilized NIRR. yield selectivity optimal BVO/CS reach 30.55 μg h-1 cm-2 43.8%, respectively, which 2.65 2.39 times that bare BVO. Therefore, work determines role hydrogenation, providing novel strategy boosting PEC CuS/BiVO4 was fabricated reduction. Sulfur defects enabled generation radicals, promoted production.

Язык: Английский

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Bidirectional Nitrogen Neutralization via Coupled Electrocatalytic Processes of Nitrate Reduction and Hydrazine Oxidation

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

Abstract The electrocatalytic coupling of the nitrate reduction reaction (NO 3 − RR) and hydrazine oxidation (HzOR), denoted as NO RR||HzOR, not only holds promise for synthesis high‐value‐added products (such NH ) but also facilitates bidirectional nitrogen neutralization. Here, sponge‐like porous nitrogen‐doped carbon encapsulated Cu nanoparticles electrocatalysts is presented electrochemical RR||HzOR. Substituting traditional oxygen evolution (OER) with HzOR anode notably accelerates kinetic process via RR. Moreover, spatial confinement within a (NDC) structure addresses aggregation detachment issues NPs from catalyst support surface effectively modulates electronic through interactions between NDC NPs. This, in turn, enhances adsorption activation ions. Consequently, combined advantages optimized significantly improve activity stability RR to . This work offers significant reference value sustainable neutrality development by leveraging mild, energy‐efficient, environmentally friendly that concurrently eliminates pollutants both high low states.

Язык: Английский

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Conjugated Cobalt Porphyrin Polymer for Highly Active and Selective Electrocatalytic Nitrite Reduction to Ammonia

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 15, 2025

Abstract Electrocatalytic nitrite (NO 2 − ) reduction RR) to ammonia (NH 3 is a promising green technology for producing NH with high efficiency. Cobalt macrocyclic complexes have attracted great interest because of their ability selectively convert NO , but suffer from low yields. Herein, cobalt porphyrin conjugated polymer on carbon nanotubes (CoPCOP@CNT) reported display exceptional RR performance large yield 133.39 mg h −1 CoP at −1.0 V and Faradaic efficiency (FE) 98.0% −0.8 V. Utilizing CoPCOP@CNT as the catalyst cathode, Zn‐NO battery exhibits remarkable power density (5.34 mW cm −2 ), open‐circuit voltage (≈1.45 V), FE (94.6%), (29.15 ). The active intermediates reaction pathways CoPCOP in process are revealed by differential electrochemical mass spectroscopy theory calculations. This work highlights potential electrocatalysts based metal porphyrins conversion nitrogenous pollutant into .

Язык: Английский

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Multivariate covalent organic frameworks with tailored electrostatic potential promote nitrate electroreduction to ammonia in acid

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 19, 2025

The direct synthesis of ammonia from nitrate (NO3-) reduction in acid is a promising approach for industrialization. However, the difficulty arises intense competition with inevitable hydrogen evolution reaction, which favoured due to overwhelming protons (H+). Here, we systematically explore and rationally optimize microenvironment using multivariate covalent organic frameworks (COFs) as catalyst adlayers promote nitrate-to-ammonia conversion acid. With application tailored positive electrostatic potential generated over COFs, both mass transfer NO3- H+ are regulated via appropriate interactions, thus realizing priority NO3RR respect HER or NO3--to-NO2-. As result, an NH3 yield rate 11.01 mmol h-1 mg-1 corresponding Faradaic efficiency 91.0% attained, solid NH4Cl high purity 96.2% directly collected acid; therefore, this method provides practical economically valorising wastewater into valuable ammonia.

Язык: Английский

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Mechanical and Covalent Tailoring of Copper Catenanes for Selective Aqueous Nitrate-to-Ammonia Electrocatalysis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

Electrocatalytic nitrate reduction reaction (NO3RR) for the selective generation of ammonia (NH3) enables removal deleterious pollutants while simultaneously upcycling them into a value-added fertilizer. The development nonprecious metal-derived catalysts such as those featuring copper (Cu) earth-abundant alternatives state-of-the-art precious metal is urgent need yet suffering from activity-selectivity-durability trilemma. Rational design molecular Cu complexes with well-defined coordination structures permitting systematic structure-activity relationship (SAR) investigations key to addressing challenge. Here, series Cu(I) [2]catenane ligands are developed NO3RR electrocatalysts first time. By engineering multiple cationic ammoniums on catenane backbone, acceptance anionic substrate well release ammonium product promoted, thereby facilitating higher Faradaic efficiency and selectivity toward via an 8e- pathway. Of note, mutual Coulombic repulsion between multiply charged overcome by mechanical interlocking that catalyst integrity can be maintained under practical conditions. This report highlights promise employing mechanically interlocked platform customizing redox processes involving proton-coupled electron transfer steps.

Язык: Английский

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Recent advances in electrocatalytic conversion of nitrates into high-value products

Journal of Energy Chemistry, Год журнала: 2024, Номер 99, С. 50 - 65

Опубликована: Июль 26, 2024

Язык: Английский

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CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

Inorganic Chemistry, Год журнала: 2024, Номер 63(30), С. 14093 - 14102

Опубликована: Июль 12, 2024

Electrochemical nitrate reduction (NO

Язык: Английский

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