Understanding the Dynamic Evolution of Active Sites among Single Atoms, Clusters, and Nanoparticles

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Abstract Catalysis remains a cornerstone of chemical research, with the active sites catalysts being crucial for their functionality. Identifying sites, particularly during reaction process, is elucidating relationship between catalyst's structure and its catalytic property. However, dynamic evolution within heterogeneous metal presents substantial challenge accurately pinpointing real sites. The advent in situ operando characterization techniques has illuminated path toward understanding changes offering robust scientific evidence to support rational design catalysts. There pressing need comprehensive review that systematically explores among single atoms, clusters, nanoparticles as utilizing techniques. This aims delineate effects various factors on nanoparticles. Moreover, several are elaborated emphases tracking linking them properties. Finally, it discusses challenges future perspectives identifying process advancing

Язык: Английский

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Potential Dependence and Substituent Effect in CO₂ Electroreduction on a Cobalt Phthalocyanine Catalyst

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9575 - 9585

Опубликована: Июнь 11, 2024

Cobalt phthalocyanine molecules combined with carbon materials (CoPc@NC) have been reported to exhibit prominent electrocatalytic performance toward the CO2 reduction reaction (CO2RR). However, molecular-scale insights into mechanisms regarding its high activity or Faraday efficiency remain limited due great challenge in modeling electrochemical interface. Herein, an explicit computational model inclusion of solvation and electrode potential was employed explore mechanistic nature CO2RR at graphene-supported CoPc It is suggested that on molecular catalyst can be remarkably affected by potential. The DFT-based constrained ab initio dynamics simulations thermodynamic integration method support notion frontier orbitals easily modulated potentials thus influence redox during CO2RR. adsorption step involving partial charge transfer from strongly potential-dependent. Once absorbed, subsequent protonation, as rate-determining step, not significantly Moreover, overall catalytic enhanced introducing electron-donating substituent such a cyano group (−CN), which attributed redistribution between substrate catalyst. Our work only provides deep electronic structure CoPc@NC system but also illustrates critical role substituents catalyst, paving promising way for advancing efficient transformation.

Язык: Английский

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First-Principles Insights into Tungsten Semicarbide-Based Single-Atom Catalysts: Single-Atom Migration and Mechanisms in Oxygen Reduction

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(10), С. 2815 - 2824

Опубликована: Март 5, 2024

Understanding the structural evolution of single-atom catalysts (SACs) in catalytic reactions is crucial for unraveling their mechanisms. In this study, we utilize density functional theory calculations to delve into active phase and oxygen reduction reaction (ORR) mechanism tungsten semicarbide-based transition metal SACs (TM1/W2C). The stable crystal phases optimal surface exposures W2C are identified by using ab initio atomistic thermodynamics simulations. Focusing on W-terminated (001) surface, screen 13 TM1/W2C variants, ultimately selecting Pt1/W2C(001) as our primary model. Pourbaix diagram, mapped model under ORR conditions, reveals dynamic Pt1 migration triggered oxidation. This discovery suggests a novel pathway. Remarkably, behavior also discerned seven other group VIII SACs, enhancing both activity stability. Our findings offer insights considering substrate arrangement, incorporation, self-optimization various conditions.

Язык: Английский

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Enhancing d Electrons’ Delocalization of the Single-Atom Ni–N₄ Site to Boost Electrochemical CO₂ Reduction to CO by Axial d–d Orbital Coupling

The Journal of Physical Chemistry C, Год журнала: 2024, Номер 128(14), С. 5909 - 5918

Опубликована: Апрель 1, 2024

Atomically dispersed nitrogen-coordinated transition metal (TM) anchored on graphene (TM–Nx–C) provides a promising potential for an electrochemical CO2 reduction reaction (CO2RR). However, it is still challenge to precisely control the electronic structures of TM single-atom catalysts (SACs) optimizing catalytic performance. Using first-principles calculations, we propose novel strategy regulate structure Ni–N4–C site by vertically coupling 3-fold N atom-coordinated atom (TM–N3–C) promoting CO. In contrast traditional TM–N4–C substrate that weakly coupled with N–N4–C site, raised atoms TM–N3–C relative basal plane shorten distance from Ni and strengthen d orbital hybridization between them, thus leading more delocalized charge distribution active site. As result, improved axial d–d largely enhances adsorption key *COOH intermediate SACs and, importantly, maintains facile desorption adsorbed *CO. particular, these Tc– Ru–N3–C substrates not only exhibit high activity toward CO production, low limiting potentials −0.68 −0.61 V, respectively, but also effectively suppress competing hydrogen evolution (HER).

Язык: Английский

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Electrochemical Ammonia Synthesis at p-Block Active Sites Using Various Nitrogen Sources: Theoretical Insights

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 889 - 903

Опубликована: Янв. 18, 2025

Electrochemical nitrogen conversion for ammonia (NH3) synthesis, driven by renewable electricity, offers a sustainable alternative to the traditional Haber-Bosch process. However, this process remains limited low Faradaic efficiency (FE) and NH3 yield. Although transition metals have been widely studied as catalysts synthesis through effective electron donation/back-donation mechanisms, there are challenges in electrochemical environments, including competitive hydrogen evolution reaction (HER) catalyst stability issues. In contrast, p-block elements show unique advantages light of higher selectivity activation chemical stability. The present article explores potential element-based active sites discussing their performance modulation strategies, future research directions from theoretical perspective.

Язык: Английский

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Applications of machine learning in surfaces and interfaces

Chemical Physics Reviews, Год журнала: 2025, Номер 6(1)

Опубликована: Март 1, 2025

Surfaces and interfaces play key roles in chemical material science. Understanding physical processes at complex surfaces is a challenging task. Machine learning provides powerful tool to help analyze accelerate simulations. This comprehensive review affords an overview of the applications machine study systems materials. We categorize into following broad categories: solid–solid interface, solid–liquid liquid–liquid surface solid, liquid, three-phase interfaces. High-throughput screening, combined first-principles calculations, force field accelerated molecular dynamics simulations are used rational design such as all-solid-state batteries, solar cells, heterogeneous catalysis. detailed information on for

Язык: Английский

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Reaction-Driven Varieties of Active Sites on Cu(100) in Electrochemical CO₂ Reduction Reaction

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6497 - 6506

Опубликована: Апрель 6, 2025

Язык: Английский

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Deactivation Mechanism and Mitigation Strategies of Single‐Atom Site Electrocatalysts

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Abstract Single‐atom site electrocatalysts (SACs), with maximum atom efficiency, fine‐tuned coordination structure, and exceptional reactivity toward catalysis, energy, environmental purification, have become the emerging frontier in recent decade. Along significant breakthroughs activity selectivity, limited stability durability of SACs are often underemphasized, posing a grand challenge meeting practical requirements. One pivotal obstacle to construction highly stable is heavy reliance on empirical rather than rational design methods. A comprehensive review urgently needed offer concise overview progress stability/durability, encompassing both deactivation mechanism mitigation strategies. Herein, this first critically summarizes degradation induction factors at atomic‐, meso‐ nanoscale, mainly based but not oxygen reduction reaction. Subsequently, potential stability/durability improvement strategies by tuning catalyst composition, morphology surface delineated, including robust substrate metal‐support interaction, optimization active stability, fabrication porosity modification. Finally, challenges prospects for discussed. This facilitates fundamental understanding provides efficient principles aimed overcoming difficulties beyond.

Язык: Английский

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Surface coverage and reconstruction analyses bridge the correlation between structure and activity for electrocatalysis

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Electrocatalysis is key to realizing a sustainable future for our society. However, the complex interface between electrocatalysts and electrolytes presents an ongoing challenge in electrocatalysis, hindering accurate identification of effective/authentic structure-activity relationships determination favourable reaction mechanisms. Surface coverage reconstruction analyses are important address each conjecture and/or conflicting viewpoint on surface-active phases their corresponding electrocatalytic origin,

Язык: Английский

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Origin of copper dissolution under electrocatalytic reduction conditions involving amines

Chemical Science, Год журнала: 2024, Номер 15(35), С. 14485 - 14496

Опубликована: Янв. 1, 2024

Copper electrodes corrode using mixtures of acetone and methylamine even under reductive potential conditions. Simulations explain this dynamical process from a microscopic perspective through the formation surface Cu–amine complex.

Язык: Английский

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