Porphyrin Aggregation under Homogeneous Conditions Inhibits Electrocatalysis: A Case Study on CO2 Reduction DOI Creative Commons
Kaitlin L. Branch, Erin R. Johnson, Eva M. Nichols

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(6), P. 1251 - 1261

Published: June 3, 2024

Metalloporphyrins are widely used as homogeneous electrocatalysts for transformations relevant to clean energy and sustainable organic synthesis. well-known aggregate due π–π stacking, but surprisingly, the influence of aggregation on electrocatalytic performance has not been investigated previously. Herein, we present three structurally related iron meso-phenylporphyrins whose properties different in commonly N,N-dimethylformamide (DMF) electrolyte. Both spectroscopy light scattering provide evidence extensive porphyrin under conventional conditions. Using reduction CO2 CO a test reaction, cyclic voltammetry reveals an inverse dependence kinetics catalyst concentration. The inhibition extends bulk performance, where up 75% at 1 mM is inactive compared 0.25 mM. We additionally report how perturbed by additives, axial ligands, redox state. Periodic boundary calculations additional insights into stability function metalloporphyrin structure. Finally, generalize phenomenon surveying metalloporphyrins with metals substituents. This study demonstrates that can severely well-solubilizing electrolytes, be easily modulated through experimental conditions, extent must considered accurate catalytic benchmarking.

Language: Английский

Phthalocyanine and porphyrin catalysts for electrocatalytic reduction of carbon dioxide: Progress in regulation strategies and applications DOI
Jian Zhao, Honghong Lyu, Zhiqiang Wang

et al.

Separation and Purification Technology, Journal Year: 2023, Volume and Issue: 312, P. 123404 - 123404

Published: Feb. 13, 2023

Language: Английский

Citations

15
CoP2O6-Assisted Copper/Carbon Catalyst for Electrocatalytic Reduction of CO2 to Formate DOI
Juan Du,

Yuxiu Han,

Haobo Zhang

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(11), P. 10055 - 10064

Published: May 9, 2023

Reducing CO2 into value-added chemicals and fuels by electrochemical reduction of (CO2ER) in an aqueous medium is considered a potential way to store intermittent renewable energy alleviate the crisis. Cu-based catalysts are common electrocatalyst used CO2ER. However, selectivity has always been difficult problem solve, especially terms production C1 products. Based on characteristics carbon framework CoP2O6 species, herein, Cu co-anchored N-doped hollow spheres (CoP2O6/HCS-Cu) with precisely controllable copper content were prepared, order produce formate high current density Faraday efficiency from The ratio cobalt strong influence catalytic performance catalyst. In addition, experimental results functional theory calculations show that important factor promoting formation formate.

Language: Английский

Citations

14
Dramatic Improvement of Homogeneous Carbon Dioxide and Bicarbonate Electroreduction Using a Tetracationic Water-Soluble Cobalt Phthalocyanine DOI

Scheryn E. Lawson,

Ryan Roberts, Daniel B. Leznoff

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22306 - 22317

Published: July 31, 2024

Electrochemical conversion of carbon dioxide (CO

Language: Английский

Citations

5
Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors DOI
Luiz F. T. Novaes, Yi Wang, Jinjian Liu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14106 - 14112

Published: Nov. 3, 2022

In this work, we report manganese porphyrin complexes for the electrocatalytic vicinal diazidation of alkenes with sodium azide. This protocol shows improved practicality over our previous work using MnBr2 catalysis in following aspects: (1) it requires substantially lower catalyst loading (as low as 0.3 mol %), which reduces formation metal azide and simplifies product purification; (2) introduction a neutral aqueous buffer prevents generation toxic hydrazoic acid, contributing to safer experimental procedure; (3) catalytic system displays reactivity toward unactivated terminal alkenes. Mechanistic studies support roles second-sphere hydrogen-bond donors stabilizing key reaction intermediates.

Language: Английский

Citations

22
Porphyrin Aggregation under Homogeneous Conditions Inhibits Electrocatalysis: A Case Study on CO2 Reduction DOI Creative Commons
Kaitlin L. Branch, Erin R. Johnson, Eva M. Nichols

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(6), P. 1251 - 1261

Published: June 3, 2024

Metalloporphyrins are widely used as homogeneous electrocatalysts for transformations relevant to clean energy and sustainable organic synthesis. well-known aggregate due π–π stacking, but surprisingly, the influence of aggregation on electrocatalytic performance has not been investigated previously. Herein, we present three structurally related iron meso-phenylporphyrins whose properties different in commonly N,N-dimethylformamide (DMF) electrolyte. Both spectroscopy light scattering provide evidence extensive porphyrin under conventional conditions. Using reduction CO2 CO a test reaction, cyclic voltammetry reveals an inverse dependence kinetics catalyst concentration. The inhibition extends bulk performance, where up 75% at 1 mM is inactive compared 0.25 mM. We additionally report how perturbed by additives, axial ligands, redox state. Periodic boundary calculations additional insights into stability function metalloporphyrin structure. Finally, generalize phenomenon surveying metalloporphyrins with metals substituents. This study demonstrates that can severely well-solubilizing electrolytes, be easily modulated through experimental conditions, extent must considered accurate catalytic benchmarking.

Language: Английский

Citations

4