Related Experiment Video
Updated: Jul 30, 2025
10:57
Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
18.3K
Mechanistic insights into CO2 conversion to CO using cyano manganese complexes
Kailyn Y Cohen1, Delaan G Nedd1, Rebecca Evans1
1Department of Chemistry, Frick Laboratory, Princeton University, Princeton, New Jersey, USA. bocarsly@princeton.edu.
Dalton Transactions (Cambridge, England : 2003)
|May 15, 2023
Summary
The manganese complex MnCN can photochemically reduce carbon dioxide (CO2) by forming an active species without a photosensitizer. Steric hindrance in MnCN(mesbpy) prevents photochemical CO2 reduction but enables electrocatalytic CO2 reduction to CO.
Area of Science:
- Inorganic Chemistry
- Photochemistry
- Electrocatalysis
Background:
- Manganese complexes of the type fac-[M(N-N)(CO)3X] are known to undergo axial ligand dissociation upon irradiation.
- The behavior of the cyanide ligand in similar manganese complexes under photochemical conditions is less understood.
- Carbon dioxide (CO2) reduction is a critical area for sustainable chemistry.
Purpose of the Study:
- To investigate the photochemical behavior of [Mn(bpy)(CO)3(CN)] (MnCN) and its derivatives for CO2 reduction.
- To elucidate the mechanism of CO2 reduction initiated by MnCN.
- To compare the photochemical and electrochemical activity of related manganese complexes.
Main Methods:
- Anaerobic irradiation of MnCN and MnCN(mesbpy).
- Infrared (IR) and UV-vis spectroscopy to identify reaction products.
- Electrochemical analysis of MnCN(mesbpy) for CO2 reduction.
Main Results:
- Irradiation of MnCN leads to the formation of [Mn(bpy)(CO)2(MeCN)(CN)] (s-MnCN), indicating retention of the cyanide ligand.
- The cyanide ligand is retained during photochemical reactions of MnCN, unlike halide or pseudohalogen ligands.
- MnCN(mesbpy), due to steric hindrance, does not follow the same photochemical pathway but is catalytically active for electrochemical CO2 reduction to CO.
Conclusions:
- The cyanide ligand in MnCN is stable under photochemical conditions relevant to CO2 reduction.
- A distinct photochemical pathway is observed for MnCN compared to other fac-[M(N-N)(CO)3X] complexes.
- MnCN(mesbpy) demonstrates a difference between photochemical and electrochemical charge transfer mechanisms in CO2 reduction.
More Related Videos
Related Concept Videos
03:45Formation of Complex Ions
23.8K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
23.8K
01:43Electron Transport Chain: Complex III and IV
7.7K
During the electron transport chain, electrons from NADH and FADH2 are first transferred to complexes I and II, respectively. These two complexes then transfer the electrons to ubiquinol, which carries them further to complex III. Complex III passes the electrons across the intermembrane space to Cyt c, which carries them further to complex IV. Complex IV donates electrons to oxygen and reduces it to water. As electrons pass through complexes I, III, and IV, the energy released aids the pumping...
7.7K
01:28Carbon-dioxide Fixation
43
Carbon dioxide fixation in prokaryotes enables the assimilation of inorganic carbon into organic molecules, supporting biosynthetic pathways, sustaining ecosystems, and contributing to the global carbon cycle. It also has industrial applications in carbon capture and bioproduct synthesis. Autotrophic organisms rely on this process to utilize CO₂ as a carbon source in diverse environments.The Calvin CycleThe Calvin cycle is the most widespread carbon fixation mechanism, primarily used by...
43
01:10Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
3.3K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
3.3K
01:23Properties of Organometallic Compounds
1.1K
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
1.1K
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.1K