Theoretical Insights into the Selectivity of Single-Atom Fe–N–C Catalysts for Electrochemical NO_x Reduction

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

Published: Feb. 2, 2025

Single-atom Fe-N-C catalysts have attracted significant attention in the NOx reduction reaction (NOxRR). However, origin of their selectivity NOxRR remains unclear, impeding further advancements application. Herein, we investigate potential-driven competitive mechanism for NH3 and NH2OH production over single-atom pyridinic-FeN4 pyrrolic-FeN4 sites using constant-potential density functional theory calculations. The is linked to switching Fe 3d orbitals as they interact with intermediates. between determined by applied potentials. predominantly generates at higher potentials (-0.6 -1.2 V, vs SHE), while favored lower (0.6 -0.6 V). shows a similar potential-dependent product distribution, crossover potential -1.0 V. selectivity-determining intermediates (SDIs) are *NH2OH *NH2 + *OH. governed interacting SDIs, from dumbbell-shaped 3dz2 four-leaf clover-like 3dxz, 3dyz, 3dx2-y2, which plays crucial role controlling distribution based on These findings offer new insights into NOxRR.

Language: Английский

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Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime

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

Published: Feb. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Language: Английский

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Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime

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

Published: Feb. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Language: Английский

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Size-effect induced controllable Cu0-Cu+ sites for ampere-level nitrate electroreduction coupled with biomass upgrading

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 10, 2025

The synergistic Cu0-Cu+ sites is regarded as the active species towards NH3 synthesis from nitrate electrochemical reduction reaction (NO3-RR) process. However, mechanistic understanding and roles of Cu0 Cu+ remain exclusive. big obstacle that it challenging to effectively regulate interfacial motifs sites. In this paper, we describe tunable construction structure by modulating size-effect Cu2O nanocube electrocatalysts NO3-RR performance. We elucidate formation mechanism correlating macroscopic particle size with microscopic coordinated properties, identify effect on NO3-RR. Based rational design electrocatalyst, develop an efficient paired-electrolysis system simultaneously achieve production 2,5-furandicarboxylic acid at industrially relevant current densities (2 A cm−2), while maintaining high Faradaic efficiencies, yield rates, long-term operational stability in a 100 cm2 electrolyzers, indicating promising practical applications. It understand for reaction. Here, authors report 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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Bridge‐Oxygen Bond: An Active Group for Energy Electrocatalysis

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

Published: March 20, 2025

Abstract Energy electrocatalytic reactions such as hydrogen evolution reaction, oxygen reduction nitrogen carbon etc., are important to solve the current energy shortage and increasing environmental problems. Developing novel efficient catalyts for these has become an essential urgent issue. Catalysts incorporating bridge‐oxygen bond have received attention due their superior conductivity stability, which favorable optimizing reaction mechanism improving kinetics. This paper provides a comprehensive review encompassing concept of bond, means characterization, activity in electrocatalysis effect on catalytic performance. Through this review, it is expected furnish valuable reference rational design catalysts featuring structure across diverse reactions.

Language: Английский

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Main-Group p-Block Metal-Doped C₃N Monolayers as Efficient Electrocatalysts for NO-to-NH₃ Conversion: A Computational Study

Langmuir, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

The electrochemical NO reduction reaction (NORR) toward NH3 synthesis not only helps address issues of air pollution but also holds significant energy and economic value, making it an innovative method with broad application prospects. However, designing NORR electrocatalysts that are both highly active selective remains a formidable challenge. Herein, we study the main-group p-block metal (M = Al, Ga, In)-doped C3N monolayers as promising single-atom catalysts (SACs) for through spin-polarized first-principles calculations. Our results show Al@VCC, Al@VCN, Ga@VCC, Ga@VCN systems stable exhibit metallic characteristics, ensuring effective charge transfer during process. Moreover, nitric oxide (NO) can be strongly chemisorbed activated on all four candidates adsorption free energies ranging from −0.83 to −1.59 eV then spontaneously converted into without need any applied voltage. More importantly, possesses well-suppressed ability formation H2/N2O/N2 byproducts, indicating excellent selectivity. These findings offer electrocatalyst NO-to-NH3 conversion highlight great potential metals SACs reactions.

Language: Английский

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Strong p–d Orbital Hybridization in Atomically Ordered Intermetallic Pd₃Bi Metallene Enables Energy-Efficient Simultaneous Electrosynthesis of a Nylon-6 Precursor and Glycolic Acid

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6606 - 6617

Published: April 8, 2025

Language: Английский

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Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 6, 2024

Abstract Electrocatalytic reduction of nitric oxide (NO) to ammonia (NH 3 ) represents a potential solution for improving the disrupted nitrogen cycle balance. Unfortunately, designing efficient electrocatalysts NO reaction (NORR) remains notable challenge, especially at low concentrations. Herein, displacement‐alloying strategy is reported successfully induce phase transition Co nanoparticles supported on carbon nanosheets from face‐centered cubic (fcc) hexagonal close‐packed (hcp) structure through Ru incorporation. The obtained RuCo alloy with hcp (hcp‐RuCo) exhibits apparent NORR activity record‐high Faraday efficiency 99.2% and an NH yield 77.76 µg h −1 mg cat −0.1 V versus reversible hydrogen electrode concentration 1 vol %, surpassing fcc most catalysts. Density functional theory calculations reveal that excellent hcp‐RuCo can be attributed optimized electronic site lowered energy barrier rate‐determining step transition. Furthermore, assembled Zn‐NO battery using as cathode achieves power density 2.33 mW cm −2 45.94 . This work provides promising research perspective low‐concentration conversion.

Language: Английский

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Highly Efficient One‐pot Electrosynthesis of Oxime Ethers from NOx over Ultrafine MgO Nanoparticles Derived from Mg‐based Metal–Organic Frameworks

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(26)

Published: April 10, 2024

Abstract Oxime ethers are attractive compounds in medicinal scaffolds due to the biological and pharmaceutical properties, however, crucial widespread step of industrial oxime formation using explosive hydroxylamine (NH 2 OH) is insecure troublesome. Herein, we present a convenient method ether synthesis one‐pot tandem electrochemical system magnesium based metal‐organic framework‐derived oxide anchoring self‐supporting carbon nanofiber membrane catalyst (MgO‐SCM), situ produced NH OH from nitrogen oxides electrocatalytic reduction coupled with aldehyde produce 4‐cyanobenzaldoxime selectivity 93 % Faraday efficiency up 65.1 %, which further reacted benzyl bromide directly give precipitate purity 97 by filtering separation. The high was attributed ultrafine MgO nanoparticles MgO‐SCM, effectively inhibiting hydrogen evolution reaction accelerating production OH, rapidly attacked carbonyl aldehydes form oximes, but hardly crossed hydrogenation barrier forming amines, thus leading yield when coupling nucleophilic reaction. This work highlights importance kinetic control complex electrosynthetic organonitrogen demonstrates green safe alternative for organic drug molecules.

Language: Английский

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