Reversible Angle Distortion-Dependent Electrochemical CO₂ Reduction on Cobalt Phthalocyanine

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

Deducing the local electronic and atomic structural changes in active sites during electrochemical carbon dioxide reduction is essential for elucidating intrinsic mechanisms developing highly catalysts that are stable a long duration. Herein, utilizing operando valence-to-core X-ray emission spectroscopy high energy-resolution fluorescence detected absorption near-edge structure, combined with spectroscopic calculations, structure evolutions of model cobalt phthalocyanine (CoPc) were quantitatively elucidated. Under real reaction conditions, CoPc undergoes reversible angle distortion while maintaining constant metal-ligand bond length, causing energy levels split d orbitals electron density molecular orbitals. The further influences interactions among ligands, intermediates, metal centers. change CO Faraday efficiency was also determined, demonstrating robustness. demonstrated findings serve as an important contribution to determine structure-performance relationship which enlightens rational design atomically dispersed site activity emphasize capabilities resolution toward analyzing metal-implanted N-doped catalysts.

Язык: Английский

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Electrochemical Reduction of CO₂ to CH₃OH Catalyzed by an Iron Porphyrinoid

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 4, 2025

Designing catalysts for the selective reduction of CO2, resulting in products having commercial value, is an important area contemporary research. Several molecular have been reported to facilitate CO2 (both electrochemical and photochemical) yield 2e–/2H+ electron-reduced products, CO HCOOH, beyond rare. This partly because factors that control selectivity 2e– are not yet understood. An iron chlorin complex with a pendent amine functionality its second sphere, known selectively catalyze CO2RR HCOOH very low overpotential from formal Fe(I) state, can Fe(0) state by 6e–/6H+, forming CH3OH as major product Faradaic ∼50%. Mechanistic investigations using situ spectro-electrochemistry indicate reactivity low-spin d7 FeI–COOH intermediate species generated during crucial determining this reaction. In weakly acidic conditions, C-protonation species, which also chemically prepared spectroscopically characterized, leads HCOOH. The O-protonation, leading C–OH bond cleavage eventually CH3OH, ∼3 kcal/mol higher energy be achieved more solutions. Hydrogen bonding catalyst stabilizes reactive intermediates formed enables 6e–/6H+ CH3OH.

Язык: Английский

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Electrochemical CO₂ Reduction on SnO: Insights into C₁ Product Dynamic Distribution and Reaction Mechanisms

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3173 - 3183

Опубликована: Фев. 6, 2025

The precise synthesis of desirable products from the electrochemical CO2 reduction reaction (CO2RR) remains challenging, primarily due to unclear structure–activity relationships under in situ conditions. Recognized by their cost-effectiveness and nontoxic nature, Sn-based materials are extensively utilized CO2RR produce valuable chemicals. Notably, our large-scale data mining experimental literature reveals a significant trend: SnO2-based electrocatalysts generate HCOOH, while SnO-based counterparts demonstrate ability both HCOOH CO comparable quantities. Furthermore, findings indicate that SnO underexplored terms its surface speciation for compared materials. Addressing these issues is crucial field electrocatalysis, as understanding them will not only clarify why uniquely influences distribution C1 but also provide insights into how precisely control electrocatalytic processes targeted product synthesis. Herein, we employed constant-potential method combined with coverage reconstruction analyses simulate energetics intermediates elucidate dynamic on resting typical Our analysis effectively identifies active involved CO2RR. comparative simulations between pristine reconstructed surfaces reveal electrochemistry-induced oxygen vacancies direct distribution. By addressing critical issues, aim advance electrocatalysis contribute chemical production CO2, stimulating future exploration conditions other systems.

Язык: Английский

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Acid-free synthesis of MIL-101(Cr) for enhanced photocatalytic reduction of atmospheric CO2 to methanol in aqueous media using a household light source and TEA as an electron donor source

Inorganic Chemistry Communications, Год журнала: 2025, Номер unknown, С. 114551 - 114551

Опубликована: Апрель 1, 2025

Язык: Английский

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Unveiling Double Layer Effects in Electrocatalytic CO₂ Reduction

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Май 2, 2025

Язык: Английский

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Edge‐Rich Graphene Nanomesh Thermally Self‐Exfoliated From Metal‐Organic Frameworks for Boosting CO₂ Electroreduction

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 15, 2025

Abstract Atomic‐level metal sites at the edges of graphene‐like carbon supports are considered more active for CO 2 electrocatalysis than those in‐plane. However, creating high‐density edge‐dominating sites, particularly in a simple, scalable, and self‐templated fashion, presents significant challenge. Herein, MOF‐mediated self‐exfoliation strategy is reported to preferentially integrate edge‐type FeN 4 onto ultrathin edge‐rich N‐doped graphene nanomesh (e‐Fe‐NGM). Theoretical calculations, finite element method (FEM) simulations, together with series situ spectro‐electrochemical experiments corroborate that can not only optimize electronic structure catalysts, facilitating formation * COOH desorption CO, but also effectively induce strong local electrostatic field, promoting interfacial H O supply thereby accelerating protonation process . Thus‐prepared e‐Fe‐NGM delivers remarkable Faraday efficiency (FE) above 98% over an ultra‐wide potential window 500 mV high turnover frequency 6648 h −1 , much superior controlled sample dominant plane‐type sites. Moreover, this self‐exfoliated, non‐catalyzed approach readily scalable be used produce large‐size industrial levels.

Язык: Английский

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Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 12, 2024

The selective photoreduction of CO

Язык: Английский

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Practical Applications of Grand-canonical Electronic Structure Calculations in Electrochemical Simulation

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 1470 - 1477

Опубликована: Фев. 2, 2025

Modeling electrified interfaces has long been a great challenge in electrochemistry. In recent years, the grand-canonical treatment for electrons gradually developed, and its combination with density functional theory widely used to simulate electrochemical processes on an atomistic scale. this Perspective, we aim discuss several practical applications of powerful technique after short review necessary fundamentals. We will begin capacitor-based parametrization method calculated results. If considering electrodes under different applied potentials as materials, can be viewed kind "quadratic scaling relation", which might reduce overall computational costs by data postanalysis rather than algorithm development. Following example abnormal potential-independent energetic curve within bandgap area, turn topic semiconducting electrodes. Meanwhile, specific behaviors also indicate that besides reaction thermodynamics kinetics, detailed electronic structure system well described electrons. Several possibilities further are proposed correspondingly summarized at end paper. believe calculations greatly enrich our understanding fundamental mechanisms environments.

Язык: Английский

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In situ construction of cobalt phthalocyanine covalent organic polymer on mesoporous graphitic carbon nitride for boosting photocatalytic CO2 reduction

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 160814 - 160814

Опубликована: Фев. 1, 2025

Язык: Английский

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Design Strategies for Coupling CO₂ Reduction Molecular Electrocatalysts to Silicon Photocathodes

ACS Materials Au, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

We explore strategies for enhancing the electronic interaction between silicon nanocrystals (Si NCs) and surface-tethered molecular Re electrocatalysts ([Re]) as models CO2-reducing photocathodes. Using density functional theory (DFT) combined with electrochemical, spectroscopic, photocatalytic measurements, we determine that intrinsic Si (iSi) NC conduction band energy in iSi-[Re] assemblies is below [Re] lowest unoccupied orbital (LUMO) singly occupied energies even strongly quantum-confined 3.0-3.9 nm diameter hydrogen- methyl-terminated iSi NCs, respectively. computationally analyze design to align semiconductor edge electrocatalyst frontier orbitals by varying size, introducing boron a dopant NC, modifying attachment chemistry complex aryl ligand framework. Our DFT analysis identifies target hybrid structure featuring B-doped (B:Si) NCs direct bond surface atom an sp2-hybridized carbon of bipyridine ring (B:Si-CAr[Re]). synthesize B:Si-CAr[Re] assembly find evidence hybridization B:Si LUMO using electrochemical measurements transient absorption spectroscopy. This work provides blueprint new photocathode-molecular hybrids CO2 reduction related fuel-forming conversions.

Язык: Английский

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