Controlling the Metal–Ligand Coordination Environment of Manganese Phthalocyanine in 1D–2D Heterostructure for Enhancing Nitrate Reduction to Ammonia

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13516 - 13527

Опубликована: Окт. 6, 2023

Eight-electron nitrate reduction (NO3RR) offers a cost-effective and environmentally friendly route of ammonia production wastewater remediation. However, identification reinforcement the metal–ligand interaction responsible for catalytic activity in transition-metal phthalocyanine-based heterostructures still remain unclear due to their complexity. Herein, directed by computation, we present heterostructure approach couple 2D graphene sheets with 1D manganese (II) phthalocyanine produce pyrrolic-N coordinated electron-deficient Mn center that interacts generate vital intermediates NO3RR process. The catalyst system delivers an yield rate 20,316 μg h–1 mgcat–1, faradaic efficiency (FE) 98.3%, electrocatalytic stability 50 h. Mechanistic investigations verified FTIR spectroscopy theoretical calculations identify as active sites MnPc RGO reinforce orbital enhancing charge transfer formation *NOH @ while suppressing competitive hydrogen evolution reaction (HER), resulting high selectivity FE.

Язык: Английский

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Iron phthalocyanine hollow architecture enabled ammonia production via nitrate reduction to achieve 100 % Faradaic efficiency

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 343, С. 123580 - 123580

Опубликована: Ноя. 29, 2023

Язык: Английский

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Fe(TCNQ)₂ nanorod arrays: an efficient electrocatalyst for electrochemical ammonia synthesis via the nitrate reduction reaction

Journal of Materials Chemistry A, Год журнала: 2023, Номер 12(6), С. 3352 - 3361

Опубликована: Дек. 2, 2023

Nitrate, a water-pollutant, is converted to valuable product ammonia electrochemically using Fe(TCNQ) 2 /CF nanorod arrays with yield rate 11351.6 μg h –1 cm –2 and faradaic efficiency 85.2% under ambient conditions.

Язык: Английский

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Enhancing Electrochemical Reactivity with Magnetic Fields: Unraveling the Role of Magneto‐Electrochemistry

Small Methods, Год журнала: 2024, Номер 8(7)

Опубликована: Янв. 14, 2024

Abstract Electrocatalysis performs a vital role in numerous energy transformation and repository mechanics, including power cells, Electric field‐assisted catalysis, batteries. It is crucial to investigate new methods improve electrocatalytic performance if effective long‐lasting systems are developed. The modulation of catalytic activity selectivity by external magnetic fields over electrochemical processes has received lot interest lately. How the use various electrocatalysis great promise for building selective catalysts, opening door advancement sophisticated conversion discussed. Furthermore, challenges possibilities incorporating into suggestions future research areas

Язык: Английский

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High-Entropy Perovskite Oxides as a Family of Electrocatalysts for Efficient and Selective Nitrogen Oxidation

ACS Nano, Год журнала: 2024, Номер 18(27), С. 17642 - 17650

Опубликована: Июнь 24, 2024

Electrocatalytic nitrogen oxidation reaction (NOR) can convert (N2) into nitrate (NO3–) under ambient conditions, providing an attractive approach for synthesis of NO3–, alternative to the current involving harsh Haber–Bosch and Ostwald processes that necessitate high temperature, pressure, substantial carbon emission. Developing efficient NOR catalysts is a prerequisite, which remains formidable challenge, owing weak activation/dissociation N2. A variety electrocatalysts have been developed, but their kinetics are still extremely sluggish, resulting in inferior Faradaic Efficiencies. Here, we report high-entropy Ru-based perovskite oxide (denoted as Ru-HEP) function high-performance catalyst exhibit NO3– yield rate 39.0 μmol mg–1 h–1 with Efficiency 32.8%. Both our experimental results theoretical calculations suggest configuration Ru-HEP markedly enhance oxygen-vacancy concentration, where Ru sites neighboring oxygen vacancies serve unsaturated centers decrease overall energy barrier N2 electrooxidation, thereby leading promoted kinetics. This work presents avenue promoting catalysis on oxides through engineering strategy.

Язык: Английский

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Controlling electrocatalytic nitrate reduction efficiency by utilizing dπ–pπ interactions in parallel stacking molecular systems

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The orientation of β-CuPc favours the overlap central Cu with N parallel molecules, which is reason behind high electrical conductivity and selectivity in NH 3 production via nitrate reduction, impossible other polymorphs.

Язык: Английский

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Boosting Selective Nitrogen Oxidation to Nitric Acid by Synergizing Cobalt Phthalocyanine on Carbon Nitride Surface

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Июнь 14, 2024

Abstract The Ostwald process, which is producing HNO 3 for commercial use, involves the catalytic oxidation of NH and a series chemical reactions conducted under severe operating conditions. Due to their energy‐intensive nature, these activities play major role in greenhouse gas emissions global energy consumption. In response urgent requirements environmental sectors, there an increasingly critical need develop novel, highly efficient, environmentally sustainable methods. Herein, CoPc/C N 4 electrocatalyst, integrating CoPc nanotubes with C nanosheets, shown. electrocatalyst demonstrates yield rate 871.8 µmol h −1 g cat at 2.2 V, corresponding Faradaic efficiency (FE) 46.4% 2.1 notably surpasses that CoPc. Through combination experimental investigations density functional theory (DFT) calculations, this study shows anchored on effectively simplifies adsorption activation chemically inactive nitrogen molecules. improved activity composite system may be reason re‐distribution charges over CoPc, tuning valence orbital Co center due presence 2D layer . This mechanism significantly lowers barrier required breaking inert 2 , ultimately leading significant improvement efficiency.

Язык: Английский

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A Simple Descriptor toward Optimizing Electrocatalytic N₂ Oxidation to HNO₃ Performance over Graphene-Based Single-Atom Catalysts

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 2742 - 2751

Опубликована: Март 7, 2025

Single-atom catalysts (SACs) exhibit tremendous advantages in the electrochemical N2 oxidation reaction (EN2OR) to HNO3, which is an eco-friendly alternative synthesis of conventional industrial nitric acid and nitrates, but methods rationally design rapidly screen high-efficiency EN2OR SACs are unclear. Herein, taking pyridinic nitrogen-doped graphene-supported as example, a simple descriptor has been proposed evaluate performance through systematically constructing surface phase diagram. This comprised merely geometric information inherent atomic properties (occupied d electron number, electronegativity, coordinate number) that can accurately predict activity selectivity EN2OR, independent DFT simulations. Based on this descriptor, high-throughput screening executed partially N/C/O coordinated SACs, including 160 candidates; 13 candidates with overpotential less than 1.0 V selected then validated by calculations mean absolute error (MAE) low 0.09 V, indicating reliability descriptor. Meanwhile, screened CoO2N2-G RhO2N2-G lower 0.64 0.68 more negative UL(EN2OR) - UL(OER) values -0.34 -0.44 comparison other candidates, respectively, demonstrating excellent EN2OR. work offers route rapid discovery high-performance for

Язык: Английский

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Dynamic Restructuring of Electrocatalysts in the Activation of Small Molecules: Challenges and Opportunities

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Structural transformation of electrocatalyst contributes to its catalytic activity and selectivity. Properly guided stabilized offers enhanced catalyst performance, while unregulated surface reconstruction may lead deactivation.

Язык: Английский

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The •OH-induced direct ammonia oxidation pathway for nitric acid photosynthesis

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 160522 - 160522

Опубликована: Фев. 1, 2025

Язык: Английский

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