Subnanometric Nickel Phosphide Heteroclusters with Highly Active Ni^δ+–P^δ− Pairs for Nitrate Reduction toward Ammonia

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

Опубликована: Март 26, 2025

The development of efficient electrocatalysts for the neutral nitrate reduction reaction (NO3–RR) toward ammonia (NH3) is essential to address environmental issues caused by NO3– but remains considerably challenging owing sluggish kinetics NO3–RR in media. Herein, we report subnanometric heteroclusters with strongly coupled nickel–phosphorus (Ni–P) dual-active sites as boost NO3–RR. Experimental and theoretical results reveal that feature Ni–P promotes electron transfer from Ni P, generating Niδ+–Pδ− active pairs, which Niδ+ species are highly Pδ− tunes interfacial water hydrogen bonding network promote dissociation step accelerate proton during Consequently, NO3–RR, exhibit a large NH3 yield rate 0.61 mmol h–1 cm–2 at −0.8 V versus reversible electrode, 2.8- 3.3-fold larger than those on nanoparticles clusters, respectively, generated exists NH4+ electrolytes. This study offers an approach boosting electrocatalytic reactions multiple intermediates designing sites.

Язык: Английский

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Manipulating the Electronic Properties of an Fe Single Atom Catalyst via Secondary Coordination Sphere Engineering to Provide Enhanced Oxygen Electrocatalytic Activity in Zinc‐Air Batteries

Advanced Materials, Год журнала: 2024, Номер 36(44)

Опубликована: Сен. 16, 2024

Abstract Oxygen reduction and evolution reactions are two key processes in electrochemical energy conversion technologies. Synthesis of nonprecious metal, carbon‐based electrocatalysts with high oxygen bifunctional activity stability is a crucial, yet challenging step to achieving conversion. Here, an approach address this issue: synthesis atomically dispersed Fe electrocatalyst (Fe 1 /NCP) over porous, defect‐containing nitrogen‐doped carbon support, described. Through incorporation phosphorus atom into the second coordination sphere iron, durability boundaries catalyst pushed unprecedented level alkaline environments, such as those found zinc‐air battery. The rationale delicately incorporate P heteroatoms defects close central metal sites (FeN 4 ‐OH) order break local symmetry electronic distribution. This enables suitable binding strength oxygenated intermediates. In situ characterizations theoretical studies demonstrate that these synergetic interactions responsible for stability. These intrinsic advantages /NCP enable potential gap mere 0.65 V power density 263.8 mW cm −2 when incorporated findings underscore importance design principles access high‐performance green

Язык: Английский

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Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Июль 12, 2024

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C

Язык: Английский

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Boosting Amino Acid Synthesis with WO_x Sub‐Nanoclusters

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 12, 2025

Abstract The conversion of nitrate‐rich wastewater and biomass‐derived blocks into high‐value products using renewably generated electricity is a promising approach to modulate the artificial carbon nitrogen cycle. Here, new synthetic strategy WO x sub‐nanoclusters reported supported on materials as novel efficient electrocatalysts for nitrate reduction its coupling with α‐keto acids. In acidic solutions, NH 3 ‐NH 2 OH selectivity can also optimized by adjusting potential, total FE exceeding 80% over wide potential range. After introducing acids, /D‐CB electrode achieves remarkable activity toward C ‐C 6 amino For glycine alanine, impressive FEs 49.34% 38.22% based transitional metal oxides be obtained, surpassing those nanoclusters larger size. situ analysis mechanistic studies reveal critical role in reducing energy barriers key steps alanine synthesis. This work opens up insights rational design cluster catalysts promote electrochemical acid

Язык: Английский

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Research Progress of Coordination Materials for Electrocatalytic Nitrogen Oxides Species Conversion into High-Value Chemicals

EnergyChem, Год журнала: 2025, Номер unknown, С. 100146 - 100146

Опубликована: Фев. 1, 2025

Язык: Английский

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Cu–Bi Bimetallic Catalysts Derived from Metal–Organic Framework Arrays on Copper Foam for Efficient Glycine Electrosynthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

Abstract Glycine as one of the most abundant amino acids in human proteins, with extensive applications both life and industry, is conventionally synthesized through complex procedures or toxic feedstocks. In this study, we present a facile benign electrochemical pathway for synthesis glycine reductive coupling glyoxylic acid nitrate over copper‐bismuth bimetal catalyst derived from metal–organic framework (MOF) array on copper foam (Cu/Bi−C@CF). Remarkably, Cu/Bi−C@CF achieves fantastic selectivity 89 %, corresponding high Faraday efficiency 65.9 %. From control experiments, introduction Bi caused binding energy Cu shift to lower state, which leads towards formation key intermediate hydroxylamine rather than ammonia product, facilitating oxime providing additional sites subsequent hydrogenation reaction way glycine. Moreover, derivation MOF arrays ensures effective dispersion enhances stability Cu/Bi−C@CF. This innovative approach not only presents sustainable pathways production value‐added organonitrogen compounds utilizing readily available carbon nitrogen sources, but also provides novel insights into design multistage structural catalysts sequential reactions.

Язык: Английский

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Enhanced nitrite electroreduction to ammonia via interfacial dual-site adsorption

Journal of Energy Chemistry, Год журнала: 2024, Номер 96, С. 328 - 335

Опубликована: Май 13, 2024

Язык: Английский

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Oriented Synthesis of Glycine from CO2, N2, and H2O via a Cascade Process

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(50)

Опубликована: Авг. 28, 2024

Abstract Air contains carbon, hydrogen, oxygen, and nitrogen elements that are essential for the constitution of amino acids. Converting air into acids, powered with renewable electricity, provides a green sustainable alternative to petrochemical‐based methods produce waste pollution. Here, taking glycine as an example, we demonstrated complete production chain electrorefining acids directly from CO 2 , N H O. Such prospective Scheme was composed three modules, linked by spontaneous C−N bond formation process. The high‐purity bridging intermediates, separated stepwise synthesis, boosted both carbon selectivity 91.7 % 98.7 %. Under optimum condition, obtained partial current density 160.8 mA cm −2 . solid product acquired separation efficiency 98.4 This work unveils method abiotic creation components.

Язык: Английский

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Advances and perspectives on photochemical/electrochemical synthesis of nitrogen, sulfur, and phosphorus heteroatom containing compounds from biomass-based feedstocks

Industrial Crops and Products, Год журнала: 2024, Номер 222, С. 119738 - 119738

Опубликована: Сен. 27, 2024

Язык: Английский

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Theoretical study on the synthesis of glycine via electrocatalytic reduction over tandem catalysts based on two-dimensional carbon-rich conjugated metalloporphyrin frameworks

New Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

FeY-Cr(Zr)-BPor COF catalysts not only maintain the advantages of bimetallic but also utilize role B atoms to fully activate NO and CO 2 , thereby exhibiting good catalytic activity with a very low limiting potential (−0.20 V).

Язык: Английский

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