Regulating the d-Band Center of Metal–Organic Frameworks for Efficient Nitrate Reduction Reaction and Zinc-Nitrate Battery

ACS Catalysis, Год журнала: 2024, Номер 14(21), С. 16205 - 16213

Опубликована: Окт. 18, 2024

The electrochemical reduction of nitrate ions to valuable ammonia enables the recovery pollutants from industrial wastewater, thereby synchronously balancing nitrogen cycle and achieving NH3 production. However, currently reported electrocatalysts still suffer low yield rate, Faradaic inefficiency, partial current density. Herein, a strategy based on regulation d-band center by Ru doping is presented boost Theoretical calculations unravel that dopant in Ni metal–organic framework shifts neighboring sites upward, optimizing adsorption strength N-intermediates, resulting greatly enhanced reaction performance. synthesized Ru-doped rod array electrode delivers rate 1.31 mmol h–1 cm–2 efficiency 91.5% at −0.6 V versus reversible hydrogen electrode, as well good cycling stability. In view multielectron transfer electrocatalytic activity, Zn-NO3– battery assembled this Zn anode, which high open-circuit voltage 1.421 maximum output power density 4.99 mW cm–2, demonstrating potential application value.

Язык: Английский

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Advanced theoretical modeling methodologies for electrocatalyst design in sustainable energy conversion

Applied Physics Reviews, Год журнала: 2025, Номер 12(1)

Опубликована: Фев. 6, 2025

Electrochemical reactions are pivotal for energy conversion and storage to achieve a carbon-neutral sustainable society, optimal electrocatalysts essential their industrial applications. Theoretical modeling methodologies, such as density functional theory (DFT) molecular dynamics (MD), efficiently assess electrochemical reaction mechanisms electrocatalyst performance at atomic levels. However, its intrinsic algorithm limitations high computational costs large-scale systems generate gaps between experimental observations calculation simulation, restricting the accuracy efficiency of design. Combining machine learning (ML) is promising strategy accelerate development electrocatalysts. The ML-DFT frameworks establish accurate property–structure–performance relations predict verify novel electrocatalysts' properties performance, providing deep understanding mechanisms. ML-based methods also solution MD DFT. Moreover, integrating ML experiment characterization techniques represents cutting-edge approach insights into structural, electronic, chemical changes under working conditions. This review will summarize DFT current application status design in various conversions. underlying physical fundaments, advancements, challenges be summarized. Finally, future research directions prospects proposed guide revolution.

Язык: Английский

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Covalent organic frameworks supported geminal-atom catalysts for upcycling nitrate into single-cell protein

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 160681 - 160681

Опубликована: Фев. 1, 2025

Язык: Английский

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A critical review on regulating multi-electron pathways of oxygen reduction reaction on modified carbon-catalysts for organic wastewater treatment

Chemical Engineering Journal, Год журнала: 2024, Номер 488, С. 150967 - 150967

Опубликована: Апрель 3, 2024

Язык: Английский

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Ni_0.25Cu_0.5Sn_0.25 Nanometallic Glasses As Highly Efficient Catalyst for Electrochemical Nitrate Reduction to Ammonia

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 1, 2024

Abstract Electrochemical nitrate reduction to ammonia (NRA) is a promising approach for alleviating energy crisis and water pollution. Current NRA catalysts are challenged simultaneously improve the rate of adsorption desorption processes further increase total activity due Brønsted−Evans−Polanyi (BEP) relationships. Herein, two‐step Joule heating method utilized preparation Ni 0.25 Cu 0.5 Sn nanometallic glass containing synergistic catalytic sites enhance processes. Kelvin probe force microscopy reveals pronounced oscillatory behavior in surface potential glass, which an important feature site, empirical formula proposed quantitatively characterize its characteristic. In situ electrochemical Raman spectroscopy indicates promotion nickel tin atoms processes, respectively. DFT calculations demonstrated that presents wide range distributions favor multisite catalysis. The present work provides new ideas design understanding highly active catalysts.

Язык: Английский

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Manipulating Superexchange Interaction of Ru–O–Fe Sites for Enhanced Electrocatalytic Nitrate-to-Ammonia Selectivity

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12152 - 12162

Опубликована: Июль 30, 2024

Fe-based catalysts are promising for electrochemical nitrate reduction, but their selectivity is limited by the multielectron/proton transfer reaction steps. Here, we propose optimizing eg-orbital electron occupancy regulating superexchange interaction of Fe site to improve NH3 production performance. Our experimental and theoretical prediction results confirmed that Ru–O–Fe sites in double perovskite iron oxides (LaFe0.9Ru0.1O3) have more significant interactions, mainly manifested O-anion-mediated from Ru cations. alters Fe's spin configuration through orbital hybridization, transitioning a high-spin (HS, eg ≈ 2) an intermediate-spin state (eg 1). This transition promotes NO3– adsorption lowers hydrogenation energy barrier *NO intermediate. Consequently, LaFe0.9Ru0.1O3 could efficiently convert NH3, achieving rates 0.75 mmol·h–1·cm–2 with Faraday efficiency 98.5%. Remarkably, was as high 90.7%, which represents almost best catalyst date.

Язык: Английский

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Single Fe atom anchored by N vacancy of C3N4 activates PMS for efficient degradation of refractory organics: The key role of non-radical pathway through 1O2 and Fe(IV)=O

Journal of Environmental Sciences, Год журнала: 2025, Номер unknown

Опубликована: Март 1, 2025

Язык: Английский

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Electronic perturbation of Pd single-atom catalysts on graphdiyne derivatives toward effective electrocatalytic nitrate reduction

ChemPhysMater, Год журнала: 2025, Номер unknown

Опубликована: Март 1, 2025

Язык: Английский

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Emerging strategies for cathode materials toward high-performance microbial fuel cells based on E-Fenton principle

Separation and Purification Technology, Год журнала: 2025, Номер unknown, С. 132662 - 132662

Опубликована: Март 1, 2025

Язык: Английский

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Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis

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

Опубликована: Апрель 15, 2025

Abstract Electro/photocatalytic C-N coupling acts as a key build-block to the next generation of chemicals like amides for wide applications in energy, pharmaceuticals and chemical industries. However, uncontrolled intermediates challenges efficient amide production regarding yield or selectivity. Here we propose photocatalytic radical addition route, where fundamental active species, including oxygen photogenerated electron-hole pairs, are regulated selective acetamide synthesis from mild co-oxidation CH 3 2 OH NH . Sufficient is provided accumulate stable intermediate (CH CHO). Meanwhile, limited concentration ensures controllable fast transient ( ● ) on CHO. Through directed stable-transient intermediates, rate pushed forward hundred-mmol level (105.61 ± 4.86 mmol·g cat −1 ·h with selectivity 99.17% 0.39%, reaching gram-scale (1.82 g) acetamide. These results illuminate valuable opportunities photocatalysis-driven synthetic industry.

Язык: Английский

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