Biomimetic [MFe3S4]3+ Cubanes (M = V/Mo) as Catalysts for a Fischer–Tropsch-like Hydrocarbon Synthesis─A Computational Study DOI Creative Commons
Maxim Barchenko, Thomas Malcomson, Patrick J. O’Malley

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 479 - 494

Published: Dec. 27, 2024

Nitrogenase is the enzyme primarily responsible for reducing atmospheric nitrogen to ammonia. There are three general forms of nitrogenase based on metal ion present in cofactor binding site, namely, molybdenum-dependent nitrogenases with iron–molybdenum (FeMoco), vanadium-dependent FeVco, and iron-only nitrogenases. It has been shown that tend have a lesser efficacy dinitrogen but higher carbon monoxide. In biomimetic chemistry, [MFe3S4] (M = Mo/V) cubanes synthesized, studied, be promising mimics some geometric electronic properties cofactors. this work, density functional theory (DFT) study presented Fischer–Tropsch catalysis by these cubane complexes studying CO reduction hydrocarbons. Our work implies molybdenum stronger interactions iron–sulfur framework cubane, which results easier substrates like N2H4. However, inhibits activation CO, hence, molybdenum-containing less suitable than vanadium-containing complexes.

Language: Английский

Tuning Bro̷nsted Acidity by up to 12 pKa Units in a Redox-Active Nanopore Lined with Multifunctional Metal Sites DOI
Taro J. Jones, Kaitlyn G. Dutton, Harender S. Dhattarwal

et al.

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

Published: Jan. 2, 2025

Electrostatic interactions, hydrogen bonding, and solvation effects can alter the free energies of ionizable functional groups in proteins other nanoporous architectures, allowing such structures to tune acid-base chemistry support specific functions. Herein, we expand on this theme examine how metal sites (

Language: Английский

Citations

0
CO2 Adsorption in Natural Deep Eutectic Solvents: Insights from Quantum Mechanics and Molecular Dynamics DOI Creative Commons
Chengxu Zhu, Hannah Wood, Paola Carbone

et al.

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

CO2 capture is an important process for mitigating emissions in the atmosphere. Recently, ionic liquids have been identified as possible systems processes. Major drawbacks of such are mostly high cost synthesis and poor biodegradability. Natural deep eutectic solvents, a class solvents using materials natural origin, developed, which compared to low-cost more environmentally benign. However, very little known on details at molecular level that govern adsorption these what limits features. Elucidating aspects would represent step forward design implementation promising emissions. Herein, we report computational study mechanisms characteristics containing arginine/glycerol mixtures. We establish hydrogen bonding effects drive carbon dioxide composed L-arginine glycerol dynamics quantum mechanics simulations. Our findings indicate that, although both arginine contain multiple atoms capable acting bond donors acceptors, primarily functions acceptor while serves donor most interactions. Furthermore, compounds contribute participate binding. This provides valuable insights into behaviour enhances our understanding from perspective

Language: Английский

Citations

0
CO2 Reduction to CO on an Iron-Porphyrin Complex with Crown-Ether Appended Cation-Binding Site DOI Creative Commons
Chengxu Zhu, Adarsh Koovakattil Surendran, Carmine D’Agostino

et al.

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this work a novel CO 2 reduction catalyst is discussed that contains an iron-porphyrin complex with K + ion bound in the second coordination sphere, which assists efficient proton delivery.

Language: Английский

Citations

0
Theoretical Study on the Mechanism of the Electrocatalytic CO2 Reduction to Formate by an Iron Schiff Base Complex DOI

Ya-Qiong Zhang,

Jiayi Chen, Man Li

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The iron(III) chloride compound 6,6'-di(3,5-ditert-butyl-2-hydroxybenzene)-2,2'-bipyridine (Fe(tbudhbpy)Cl) can effectively catalyze the electrochemical CO2 reduction in N,N-dimethylformamide. Density functional calculations were conducted to investigate mechanism and unravel governing factors of product selectivity. results suggest that initial catalyst, Fe(tbudhbpy)Cl (formally FeIII-Cl), undergoes two steps, accompanied by dissociation Cl-, leading formation active ferrous radical intermediate 2 FeI). Without phenol, attacks generate FeIII-carboxylate FeIII-CO2, followed a one-electron FeII-CO2, which reacts with another produce CO. This aligns experimental result CO is main when phenol absent. In contrast, presented, triple reduced species 3 protonated at its ligand N site yield 3pt(N) Fe0-NH), subsequently performs nucleophilic attack on afford formate. process occurs via an orthogonal electron/proton transfer mechanism, where electrons one proton are transferred from moiety. redox noninnocent nature thus crucial for formate formation, as it facilitates electron shuttling, enabling through this unusual effectively.

Language: Английский

Citations

0
Origins of HCOOH Selectivity Over CO Mediated by an Unusual Fe(I)-Porphyrin Bearing a β-Substituted Cation DOI
Bing Bai, Ying Pan, Jingwen Zhao

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Molecular metalloporphyrins have been commonly reported to efficiently catalyze electrochemical CO2-to-CO conversion. Unconventionally, Dey and coworkers that an iron-porphyrin analogue bearing a pendant amine binds with CO2 at the Fe(I) state reduces into formic acid using water molecules as proton sources. However, origins of HCOOH selectivity over conventional CO product, well fundamental mechanistic details, are lacking. In work, theoretical computations were employed fundamentally investigate reaction mechanisms. Our calculations reconfirmed formal Fe(I)-porphyrin would proceed direct CO2-binding step, this behavior could be ascribed significant hydrogen bonding through-space electrostatic interactions between cationic N-H [CO22-]-coordinated species. A two-electron transfer process in key step is found, which estimated consecutively protonation 1e-reduction give rise Fe(III)-COOH Fe(II)-COOH intermediate, respectively. The plays vital roles stabilization C-protonation species yield HCOOH. Moreover, terminal hinder dissociation CO. computational results consistent experimental observations. elucidated, insightful understanding cooperative second-sphere effects provided.

Language: Английский

Citations

0
Mechanistic insight into electrocatalytic CO2 reduction to formate by the iron(I) porphyrin complex: A DFT study DOI
Yaqing Wang, Wenzhen Lai

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 566, P. 114430 - 114430

Published: Aug. 7, 2024

Language: Английский

Citations

2
CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere DOI Open Access

Xiangming Liang,

Zhijun Ruan,

Gui‐Quan Guo

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

Abstract Homogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO 2 reduction. Primary coordination sphere of plays a key role regulating its intrinsic redox properties catalytic activity. However, the overall reduction efficiency is also bound up substrate activation process. Transition‐metal are hoped to exhibit reasonable potential, reactive activity, stability, while binding activating molecules achieve Construction second sphere, especially hydrogen‐bonding network complexes, reported be “kill two birds one stone” strategy realize via systematic catalyst modulation activation. Herein, we present recent progress on construction ligand modification or introduction exogenous organic ligand, resulted productive enhancement performance improvement adsorption capacity , proton transfer rate, stability reaction intermediates, so forth.

Language: Английский

Citations

2
Interface Properties of Hydroxyapatite in Ternary Composites Cathodes for Electromethanogenesis DOI Creative Commons
Michele Bigica, Giorgia Ghiara, Pierangela Cristiani

et al.

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(22), P. 9909 - 9919

Published: Jan. 1, 2024

Hydroxyapatite (HAP) is a key modifier in biochar-based cathode materials electromethanogenesis systems. It enhances the adsorption of reagents, promotes adhesion microorganisms, and stabilizes pH at interface.

Language: Английский

Citations

0
Mechanistic Insight into Electrocatalytic Co2 Reduction to Formate by the Iron(I) Porphyrin Complex DOI
Yaqing Wang, Wenzhen Lai

Published: Jan. 1, 2024

Electrocatalytic reduction of CO2 into value-added chemicals has been considered as a promising pathway to alleviate the energy crisis and global warming. Iron porphyrins have extensively studied for electrocatalytic reaction (CO2RR) are well documented promote CO2-to-CO conversion. However, mechanism CO2-to-HCOO- conversion by Fe porphyrin remains unclear. Here, means density functional theory (DFT) calculations, we investigated detailed novel catalyst HCOO- in its Fe(I) state. Our results demonstrated that proceeds through C-protonation an FeII-OCO·- complex rather than hydrolysis FeIII-COOH or insertion Fe-H bond. Moreover, is not stable intermediate. The protonation hydroxyl group with concomitant C-OH bond cleavage produce CO thermodynamically kinetically unfeasible. Instead, can undergo coordination switch followed conformational change form active production HCOO-. single-electron gives FeII-COOH, which leads formation insights gained from this work may be useful designing electrocatalysts selective formate.

Language: Английский

Citations

0
Biomimetic [MFe3S4]3+ Cubanes (M = V/Mo) as Catalysts for a Fischer–Tropsch-like Hydrocarbon Synthesis─A Computational Study DOI Creative Commons
Maxim Barchenko, Thomas Malcomson, Patrick J. O’Malley

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 479 - 494

Published: Dec. 27, 2024

Nitrogenase is the enzyme primarily responsible for reducing atmospheric nitrogen to ammonia. There are three general forms of nitrogenase based on metal ion present in cofactor binding site, namely, molybdenum-dependent nitrogenases with iron–molybdenum (FeMoco), vanadium-dependent FeVco, and iron-only nitrogenases. It has been shown that tend have a lesser efficacy dinitrogen but higher carbon monoxide. In biomimetic chemistry, [MFe3S4] (M = Mo/V) cubanes synthesized, studied, be promising mimics some geometric electronic properties cofactors. this work, density functional theory (DFT) study presented Fischer–Tropsch catalysis by these cubane complexes studying CO reduction hydrocarbons. Our work implies molybdenum stronger interactions iron–sulfur framework cubane, which results easier substrates like N2H4. However, inhibits activation CO, hence, molybdenum-containing less suitable than vanadium-containing complexes.

Language: Английский

Citations

0