Computational Examination of Transition Metal-Salen Complexes for the Reduction of CO2 DOI Creative Commons
Gavin A. McCarver, Taner Yildirim, Wei Zhou

et al.

Published: Sept. 26, 2023

In this comprehensive study, we investigated the catalytic potential of seven transition metal-salen (TM-salen) complexes for reduction CO2 using ab initio methods. Our findings revealed distinct behavior among TM-salen complexes, driven by their electronic and geometric properties. The hydrogen to H2 was most favorable on Mn-salen Cu-salen indicating competition with reduction. Notably, later (Co, Ni, Cu, Zn) exhibited higher energy requirements initial reduction, whereas Mn- Fe-salen demonstrated potential-controlled selectivity, favoring beyond HCOOH at specific thresholds. results highlight Cr-salen as promising candidates CO2RR catalysts due reduced low overpotentials Furthermore, reaction profiles offer valuable insights design development efficient sustainable conversion other chemical transformations. These provide a foundation further exploration optimization viable in environmental energy-related applications.

Language: Английский

Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins DOI

Xinyang Peng,

Mengchun Zhang,

Haonan Qin

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 7, 2024

The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling structures to regulate reaction mechanisms is fundamental interest but has been rarely presented. Herein, we report tuning Cu porphyrins switch pathways the hydrogen evolution (HER). Through controllable and regioselective β-oxidation porphyrin 1, synthesized analogues 2-4 with one or two β-lactone groups either a cis trans configuration. Complexes 1-4 have same Cu-N

Language: Английский

Citations

28
Electrocatalytic hydrogen evolution with a copper porphyrin bearing meso-(o-carborane) substituents DOI

Xinyang Peng,

Jinxiu Han,

Xialiang Li

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(72), P. 10777 - 10780

Published: Jan. 1, 2023

A newly designed copper complex of 5,15-bis(pentafluorophenyl)-10,20-bis(o-carborane)porphyrin (1) was synthesized and tested for the electrocatalytic hydrogen evolution reaction (HER). In acetonitrile, 1 much more efficient than Cu 5,15-bis(pentafluorophenyl)-10,20-diphenylporphyrin (2) HER by shifting catalytic wave to anodic direction 190 mV. aqueous media, also outperformed 2 achieving higher current densities under smaller overpotentials. This enhancement attributed aromatic strong electron-withdrawing properties o-carborane groups. work is significant address crucial effects meso-(o-carborane) substituents metal porphyrins on boosting HER.

Language: Английский

Citations

26
Substituent Effect on Ligand‐Centered Electrocatalytic Hydrogen Evolution of Phosphorus Corroles DOI
Gang Yang, Zakir Ullah, Wu Yang

et al.

ChemSusChem, Journal Year: 2023, Volume and Issue: 16(10)

Published: Feb. 23, 2023

Abstract There have been few reports on the substituent effect of main‐group‐element corrole complexes as ligand‐centered homogeneous electrocatalysts for hydrogen evolution reaction (HER). The key to comprehend catalytic mechanism and develop efficient catalysts is elucidation effects electronic structure performance energy‐related small molecules. In this work, “push‐pull” substituents electrocatalytic HER phosphorus corroles was investigated by using 5,10,15‐tris(phenyl) (1P), 10‐pentafluorophenyl‐5,15‐bis(phenyl) (2P), 10‐phenyl‐5,15‐bis(pentafluorophenyl) (3P), 5,10,15‐tris(pentafluorophenyl) (4P) bearing hydroxyl axial ligands different numbers fluorine atoms meso ‐aryl substituents. results revealed that activity decreased with increasing atom numbers, it follows in order 1P>2P>3P>4P. Density functional theory (DFT) calculations show 1P has lowest free energy barrier HER.

Language: Английский

Citations

14
Sn(iv)-porphyrinoids for photodynamic anticancer and antimicrobial chemotherapy DOI
Balaji Babu, John Mack, Tebello Nyokong

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(16), P. 5000 - 5018

Published: Jan. 1, 2023

Research on recently reported Sn( iv ) porphyrinoids, including corroles, chlorins and N-confused porphyrins, focusing primarily their photodynamic therapy (PDT) antimicrobial chemotherapy (PACT) activity properties is reviewed.

Language: Английский

Citations

12
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
Recent Advances in Main Group Coordination Driven Porphyrins: A Comprehensive Review DOI
Umar Ali Dar,

Mohd Shahnawaz,

Parul Taneja

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(32)

Published: Aug. 22, 2024

Abstract The novel and exciting class of porphyrin‐based compounds are the main group coordination‐driven porphyrins (MGCPs) with a central element into porphyrin macrocycle. MGCPs have unique properties, reactivity, potential applications in catalysis, sensing, biomedicine etc. This comprehensive review article discusses recent advances field coordination driven explores some its uses solar cells, antimicrobial, optoelectronic devices, catalysis. addition elements to systems has resulted production entirely that intriguing qualities including increased stability catalytic activity. Significant modifications these features apparent through analysis their structural properties. It encompasses FTIR, proton NMR, electrical optical characterisation an electrochemical those parameters. They serve as significant building blocks for creation cutting‐edge materials technologies variety scientific technical disciplines because special adaptability. Researchers working domains chemistry, science will find this study be interest since it offers thorough examination current developments prospective applications. Overall, used many different fields, such devices.

Language: Английский

Citations

4
Electrocatalytic Hydrogen Evolution by Binuclear Metal (M=Co, Fe, Mn) Xanthine Bridged Bis-corrole DOI

Shiyin Xu,

Jinghe Cen,

Gang Yang

et al.

Chemical Research in Chinese Universities, Journal Year: 2024, Volume and Issue: 40(6), P. 1106 - 1115

Published: May 15, 2024

Language: Английский

Citations

3
Main group elements in electrochemical hydrogen evolution and carbon dioxide reduction DOI
Soumalya Sinha, Jianbing Jiang

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(79), P. 11767 - 11779

Published: Jan. 1, 2023

Main group elements are promising for developing electrochemical H 2 production or CO reduction catalysts.

Language: Английский

Citations

6
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.

Published: Jan. 25, 2024

Metalloporphyrins are widely used as homogeneous electrocatalysts for transformations relevant to clean energy, environmental remediation, and sustainable organic synthesis. It is common knowledge that metalloporphyrins prone aggregation due π–π stacking of their planar structures, but surprisingly the influence on electrocatalytic performance has not been investigated previously. Herein, we present three structurally related iron meso-phenylporphyrins whose properties expected be 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 all porphyrins. The inhibition at higher concentrations extends bulk performance, where up 75% 1 mM inactive compared 0.25 mM. We additionally report how perturbed by additives, axial ligands, redox state. Periodic boundary calculations gain additional insights into aggregate stability function metalloporphyrin structure. Finally, generalize phenomenon surveying with metals substituents. takeaways this study catalysts can severely even well-solubilizing electrolytes, easily modulated through choice experimental conditions, extent must considered accurate catalytic benchmarking.

Language: Английский

Citations

1
Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins DOI

Xinyang Peng,

Mengchun Zhang,

Haonan Qin

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)

Published: Feb. 7, 2024

Abstract The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling structures to regulate reaction mechanisms is fundamental interest but has been rarely presented. Herein, we report tuning Cu porphyrins switch pathways the hydrogen evolution (HER). Through controllable and regioselective β ‐oxidation porphyrin 1 , synthesized analogues 2–4 with one or two ‐lactone groups either a cis trans configuration. Complexes 1–4 have same Cu‐N 4 core site different structures. Although led large anodic shifts reductions, displayed similar HER activities terms close overpotentials. With electrochemical, chemical theoretical results, show that catalytically active species switches from I for 0 . This work thus significant present mechanism‐controllable via catalysts.

Language: Английский

Citations

1