We report herein on the use of two binuclear cobalt complexes with the ,'-bis(salicylidene)-phenylmethanediamine ligand as catalysts for the H evolution in DMF solution with acetic acid as proton source. Both experimental analyses (electrochemical analysis, spectroscopy analysis) and theoretical analysis (foot-of-the wave analysis) were employed. These catalysts required an overpotential of 470 mV to catalyze the H evolution and generated H gas with a faradaic efficiency of 85-95% as calculated on the basis of after 5 hour bulk electrolysis. The kinetic investigation showed the maximal TOF value of 50 s on the basis of an ECEC mechanism. Two cobalt centers, standing at a long distance of 4.175 Å, operated independently during catalysis without a synergetic effect or cooperation capability.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9479770 | PMC |
| http://dx.doi.org/10.1039/d2ra05109e | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Densely populated macrocyclic dicobalt sites in ladder polymers for low-overpotential oxygen reduction catalysis.
Nat Commun
January 2025
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, 610065 Chengdu, China.
Dual-atom catalysts featuring synergetic dinuclear active sites, have the potential of breaking the linear scaling relationship of the well-established single-atom catalysts for oxygen reduction reaction; however, the design of dual-atom catalysts with rationalized local microenvironment for high activity and selectivity remains a great challenge. Here we design a bisalphen ladder polymer with well-defined densely populated binuclear cobalt sites on Ketjenblack substrates. The strong electron coupling effect between the fully-conjugated ladder structure and carbon substrates enhances the electron transfer between the cobalt center and oxygen intermediates, inducing the low-to-high spin transition for the 3d electron of Co(II).
View Article and Find Full Text PDFIncorporation of a Binuclear Cobalt Complex into MOFs for Photocatalytic CO Reduction with HO as an Electron Donor.
Inorg Chem
November 2024
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China.
The development of molecular composite photocatalysts for cost-effective, sacrificial-reagent-free CO reduction is desirable but challenging. Herein, we employed an encapsulation strategy to encapsulate the binuclear cobalt complex (CoL) within NH-MIL-125 and synthesized a range of MOF-based composites with varying cobalt content for photocatalytic CO reduction. The photocatalytic results showed that the catalytic performance increased with the increase in CoL content, reaching a rapid CO generation rate of 27.
View Article and Find Full Text PDFBridge vs Terminal Cyano-coordination in Binuclear Cobalt Porphyrin Dimers: Interplay of Electrons between Metal and Ligand and Spin-Coupling via Bridge.
Inorg Chem
August 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Three cyano-coordinated cobalt porphyrin dimers were synthesized and thoroughly characterized. The X-ray structure of the complexes reveals that cyanide binds in a terminal fashion in both the and isomers of ethane- and ethylene-bridged cobalt porphyrin dimers, while in the ethylene-bridged dimer, cyanides bind in both terminal and bridging modes. The nonconjugated ethane-bridged complex stabilizes exclusively a diamagnetic metal-centered oxidation of type Co(por)(CN) both in the solid and in solution.
View Article and Find Full Text PDFElectrochemical Synthesis of Urea: Co-Reduction of Nitrite and Carbon Dioxide on Binuclear Cobalt Phthalocyanine.
Small
October 2024
International Joint Laboratory of Catalytic Chemistry, Department of Chemistry, Institute for Sustainable Energy, College of Sciences, Shanghai University, No. 99 Shangda Road, Shanghai, 200444, China.
Article Synopsis
- The study focuses on developing molecular catalysts with customizable atomic structures to enhance the electrochemical co-reduction of CO₂ and nitrite into urea.
- A binuclear cobalt phthalocyanine (biCoPc) catalyst was synthesized and showed a high Faradaic efficiency of 47.4% for urea production, surpassing many existing molecular catalysts.
- The research combines advanced spectroscopic methods and computational modeling to show how CO acts as an essential intermediate in the reduction process, highlighting the significance of molecular design in optimizing catalytic efficiency.
MOF-derived CoCuS nanoparticles with gold-decorated reduced graphene oxide for electrochemical determination of chloramphenicol in real samples.
Food Chem
November 2024
Faculty of Chemistry, University of Mazandaran, Babolsar, Iran.
Despite the beneficial effects of antibiotics such as chloramphenicol (CAP), they exert some destructive impacts on human health. We designed an electrochemical sensor based on reduced graphene oxide (rGO)/Au/CoCuS nanohybrid for determination of CAP in food and biological samples. The CoCuS was synthesized from binuclear metal-organic framework (CoCu-BDC) through a two-step process.
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!