GC-DFT-Based Dynamic Product Distribution Reveals Enhanced CO2-to-Methanol Electrocatalysis Durability by Heterogeneous CoPc DOI
Zhiyuan Xu, Chao Ma, Beibei Tang

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 16(1), P. 294 - 307

Published: Dec. 26, 2024

Heterogeneous cobalt phthalocyanine has emerged as a promising molecular catalyst for electrochemical reduction of CO2 to methanol. Boosting both electrocatalytic durability and selectivity remains great challenge, which is more difficult with unknown regulation factors the HER side reaction. Herein, discover key balancing selectivity, well regulation, we carried out GC-DFT calculations, based on dynamic product distribution modeling was conducted visually present variation within applied voltage range. The strongly electron-donating NMe2-substituted CoPc found be an excellent candidate. reveals that balance regulate potential highest methanol Faradaic efficiency corresponding energy barrier selectivity-determining step hydrogenated CoPc. pivotal factor in stems from hindered H adsorption due ligand hydrogenation, arising decreased Co-to-H charge transfer. analysis provides intuitive theoretical guidance highly selective durable electroreduction.

Language: Английский

Electrochemical Reduction of CO2 to CH3OH Catalyzed by an Iron Porphyrinoid DOI
Paramita Saha, Sk Amanullah, Sudip Barman

et al.

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

Published: Jan. 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.

Language: Английский

Citations

1
Practical Applications of Grand-canonical Electronic Structure Calculations in Electrochemical Simulation DOI
Gaomou Xu, Tao Wang

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 1470 - 1477

Published: Feb. 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.

Language: Английский

Citations

0
Electrochemical CO2 Reduction on SnO: Insights into C1 Product Dynamic Distribution and Reaction Mechanisms DOI Creative Commons
Zhongyuan Guo, Tianyi Wang,

Heng Liu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3173 - 3183

Published: Feb. 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.

Language: Английский

Citations

0
Reversible Angle Distortion-Dependent Electrochemical CO2 Reduction on Cobalt Phthalocyanine DOI
Bingbao Mei, Jianing Mao,

Zhaofeng Liang

et al.

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

Published: Feb. 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.

Language: Английский

Citations

0
In situ construction of cobalt phthalocyanine covalent organic polymer on mesoporous graphitic carbon nitride for boosting photocatalytic CO2 reduction DOI

Jiaxin Rong,

Qiang Xu,

Jingwei Han

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160814 - 160814

Published: Feb. 1, 2025

Language: Английский

Citations

0
Design Strategies for Coupling CO2 Reduction Molecular Electrocatalysts to Silicon Photocathodes DOI Creative Commons
Simran S. Saund, Melissa K. Gish, Jeremiah C. Choate

et al.

ACS Materials Au, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Language: Английский

Citations

0
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 DOI
Dara Muhammed Aziz, Sangar Ali Hassan

Inorganic Chemistry Communications, Journal Year: 2025, Volume and Issue: unknown, P. 114551 - 114551

Published: April 1, 2025

Language: Английский

Citations

0
Unveiling Double Layer Effects in Electrocatalytic CO2 Reduction DOI

Jikai Sun,

Jianzhong Wu

The Journal of Physical Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: May 2, 2025

Language: Английский

Citations

0
Dynamic CO2 Adsorption Reconfiguration Directs Product Branching on Heterogeneous Dual-Atom Catalysts DOI
Tianyang Liu, Zeyu Yang, Zifan Wang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8479 - 8488

Published: May 6, 2025

Language: Английский

Citations

0
Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water DOI Creative Commons
Jia‐Wei Wang, Fengyi Zhao, Lucía Velasco

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 12, 2024

The selective photoreduction of CO

Language: Английский

Citations

1