التفاصيل البيبلوغرافية
| العنوان: |
Increasing the CO2 Reduction Activity of Cobalt Phthalocyanine by Modulating the σ-donor Strength of Axially Coordinating Ligands |
| المؤلفون: |
Kevin Rivera Cruz (10526882), Yingshuo Liu (10765151), Taylor L. Soucy (10871619), Paul M. Zimmerman (5788046), Charles McCrory (10867854) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Electrochemistry, Kinetics and Mechanism - Inorganic Reactions, Small Molecule Activation (Inorg.), Theory - Inorganic, Electrocatalysis, Redox Catalysis, cobalt phthalocyanine, ALMO-CTA, density functional theory, CO2 Reduction Reaction |
| الوصف: |
Axial coordination of a pyridyl moieties to CoPc (either exogenous or within poly-4-vinylpyridine polymer) dramatically increases the complex’s activity for CO 2 RR. It has been hypothesized that axial coordination to the Co active site leads to an increase in the Co dz 2 orbital energy, which increases the complex’s nucleophilicity and facilitates CO 2 coordination compared to the parent CoPc complex. The magnitude of the energy increase in the Co dz 2 orbital should depend on the σ-donor strength of the axial ligand—a stronger σ-donating ligand (L) will increase the overall CO 2 RR activity of axially coordinated CoPc(L) and vice versa. To test this, we have studied a series of CoPc(L) complexes where the σ-donor strength of L is varied. We show that CoPc(L) reduces CO 2 with an increased activity as the σ-donor ability of L is increased. These observed electrochemical activity trends are correlated with computationally-derived CO 2 binding energy and charge transfer terms as a function of σ-donor strength. The findings of this study supports our hypothesis that the increased CO 2 RR activity observed upon axial coordination to CoPc is due to the increased energy of the dz 2 orbital, and highlight an important design consideration for macrocyclic MN 4 -based electrocatalysts. |
| نوع الوثيقة: |
report |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/preprint/Increasing_the_CO2_Reduction_Activity_of_Cobalt_Phthalocyanine_by_Modulating_the_-donor_Strength_of_Axially_Coordinating_Ligands/14555841 |
| DOI: |
10.26434/chemrxiv.14555841.v2 |
| الاتاحة: |
https://doi.org/10.26434/chemrxiv.14555841.v2 |
| Rights: |
CC BY-NC-ND 4.0 |
| رقم الانضمام: |
edsbas.EAD4EC8E |
| قاعدة البيانات: |
BASE |