Two new heterodinuclear nickel-iron complexes [Ni(pbSmSe)FeCpCO]PF and [Ni(xbSmSe)FeCpCO]PF were synthesized as mimics of the [NiFeSe] hydrogenase active site (HCp = cyclopentadiene; HpbSmSe = 1,9-diselenol-3,7-dithia-2,2,8,8-tetramethylnonane; HxbSmSe = 1,2,-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene). The compounds were characterized by single crystal X-ray diffraction and cyclic voltammetry. X-ray structure determinations showed that in both NiFe complexes the nickel(ii) center is in a square-planar SSe environment; the two selenolate donors are bridging to the iron(ii) center that is further coordinated to an η-cyclopentadienyl group and a carbon monoxide ligand. Electrochemical studies showed that the complex [Ni(pbSmSe)FeCpCO]PF is an electrocatalyst for the production of H in DMF in the presence of acetic acid at -2.1 V vs. Fc/Fc; a foot-of-the-wave (FOWA) analysis of the catalytic currents yielded an estimation of k of 24 s.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c7dt00972k | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Revealing the Potential-Dependent Rate-Determining Step of Oxygen Reduction Reaction on Single-Atom Catalysts.
J Am Chem Soc
January 2025
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China.
Single-atom catalysts (SACs) have attracted widespread attention due to their potential to replace platinum-based catalysts in achieving efficient oxygen reduction reaction (ORR), yet the rational optimization of SACs remains challenging due to their elusive reaction mechanisms. Herein, by employing ab initio molecular dynamics simulations and a thermodynamic integration method, we have constructed the potential-dependent free energetics of ORR on a single iron atom catalyst dispersed on nitrogen-doped graphene (Fe-N/C) and further integrated these parameters into a microkinetic model. We demonstrate that the rate-determining step (RDS) of the ORR on SACs is potential-dependent rather than invariant within the operative potential range.
View Article and Find Full Text PDFIn Situ Spectroscopic Probing of the Hydroxylamine Pathway of Electrocatalytic Nitrate Reduction on Iron-Oxy-Hydroxide.
Small
January 2025
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, Delhi, 110016, India.
Crystalline γ-FeO(OH) dominantly possessing ─OH terminals (𝛾-FeO(OH)), polycrystalline γ-FeO(OH) containing multiple ─O, ─OH, and Fe terminals (𝛾-FeO(OH)), and α-FeO majorly containing ─O surface terminals are used as electrocatalysts to study the effect of surface terminals on electrocatalytic nitrate reduction reaction (eNORR) selectivity and stabilization of reaction intermediates. Brunauer-Emmett-Teller analysis and electrochemically determined surface area suggest a high active surface area of 117.79 m g (ECSA: 0.
View Article and Find Full Text PDFMolecular Photoelectrocatalysis for Radical Reactions.
Acc Chem Res
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, and Discipline of Intelligent Instrument and Equipment, Xiamen University, Xiamen 361005, P. R. China.
ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis.
View Article and Find Full Text PDFEnhanced Electrocatalytic Hydrogen Peroxide Production via a CuWO/WO Heterojunction with High Selectivity and Stability.
ACS Appl Mater Interfaces
January 2025
Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen 518055, China.
The electrocatalytic conversion of oxygen to hydrogen peroxide offers a promising pathway for sustainable energy production. However, the development of catalysts that are highly active, stable, and cost-effective for hydrogen peroxide synthesis remains a significant challenge. In this study, a novel polyacid-based metal-organic coordination compound (Cu-PW) was synthesized using a hydrothermal approach.
View Article and Find Full Text PDFTungsten Carbide/Tungsten Oxide Catalysts for Efficient Electrocatalytic Hydrogen Evolution.
Molecules
December 2024
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
Catalyzing hydrogen evolution reaction (HER) is a key process in high-efficiency proton exchange membrane water electrolysis (PEMWE) devices. To replace the use of Pt-based HER catalyst, tungsten carbide (WC) is one of the most promising non-noble-metal-based catalysts with low cost, replicable catalytic performance, and durability. However, the preparation access to scalable production of WC catalysts is inevitable.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!