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, Journal Year: 2024, Volume and Issue: 36(44)

Published: Sept. 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

Language: Английский

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

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

Published: March 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.

Language: 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, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 12, 2024

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C

Language: 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, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 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.

Language: Английский

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Boosting Amino Acid Synthesis with WO_x Sub‐Nanoclusters

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

Published: Jan. 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

Language: Английский

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Enhanced nitrite electroreduction to ammonia via interfacial dual-site adsorption

Journal of Energy Chemistry, Journal Year: 2024, Volume and Issue: 96, P. 328 - 335

Published: May 13, 2024

Language: Английский

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

EnergyChem, Journal Year: 2025, Volume and Issue: unknown, P. 100146 - 100146

Published: Feb. 1, 2025

Language: Английский

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Single-atom catalysts for electrocatalytic conversion of biomass-derived small molecules

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 534, P. 216576 - 216576

Published: March 6, 2025

Language: Английский

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Electronic Structure Modulated by B-Doped Cu Promotes Electrocatalytic Nitrate Reduction for Ammonia Production

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 156 - 166

Published: Dec. 16, 2024

Electrocatalytic nitrate reduction for ammonia (eNIRR) is an production process that simultaneously removes contaminants from water. However, the lack of activity cathode catalysts used as eNIRR main limiting factor its development. Motivated by this fact, born-doped copper (BDCu) was obtained using ZnO, which easily removed at high temperature, a dispersant, combined with weakly reducing boron clusters (closo-[B12H12]2–) agent and B source during high-temperature pyrolysis. Impressively, BDCu demonstrated Faradaic efficiency 96.58% yield rate 25741.51 μg h–1 mgcat–1 toward −1.8 V (vs saturated calomel electrode). The twice in case undoped B. Evolutionary behavior NO3– to NH3 conversion detected situ Fourier-transform infrared (in FT-IR) electrochemical mass spectrometry DEMS). Experimental density functional theory (DFT) calculations explained activation water enhanced B-doped Cu, adsorption proton *H weakened, made it easy migrate away catalyst required reduction. In addition, electron-deficient provides conditions electron transfer between Cu. Cu led decrease center d-band modulated electronic properties altered transition on surface. Compared well unreduced CuO, lowered energy barrier rate-determining step (*NO → *N), allowing smoother NH3. This study strategy change structure metals B-modification thus improve performance synthesis.

Language: Английский

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Efficient electrochemical coupling of nitrate and biomass-derived acetone to acetoxime at a high current density over a Zn/Cu hexagonal nanosheet catalyst

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 5286 - 5298

Published: Jan. 1, 2024

Efficient electrosynthesis of acetoxime from nitrate and acetone at a high current density over novel Zn/Cu hexagonal nanosheet electrocatalyst.

Language: Английский

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