Reversibly Modulating the Selectivity of Carbon Dioxide Reduction via Ligand-Driven Spin Crossover DOI

Yuan Tang,

Xiangyu Zhu, Qiquan Luo

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 8

Published: Dec. 17, 2024

Selectivity is an essential aspect in catalysis. At present, the improvement of selectivity for complex reactions with multiple pathways/products, example carbon dioxide reduction reaction (CO2RR), can usually be achieved only one pathway/product. It still a challenge to reversibly modulate between two pathways or products CO2RR by catalyst. Here, we propose reversible modulation via spin crossover. By employing first-principles calculations, six crossover molecular catalysts are found among 17 kinds transition metal embedded porphyrin derivatives (ppy_TM), where changes axial ligand configurations switch state high and low spin. For ppy_Os ppy_Ru, alteration effectively influence CO2 into either formic acid monoxide changing relative stability key intermediates *COOH *HCOO.

Language: Английский

Electrocatalytic hydrogenation of unsaturated organic compounds with molecular complexes: Mechanistic views DOI Creative Commons
Gabriel Durin, Nicolas Kaeffer, Walter Leitner

et al.

Current Opinion in Electrochemistry, Journal Year: 2023, Volume and Issue: 41, P. 101371 - 101371

Published: Aug. 10, 2023

Electrocatalytic hydrogenation of π-bonds in unsaturated organic compounds is a promising strategy for electrifying chemical synthesis using renewable energies. This approach not only offers an alternative to the use molecular hydrogen but also has potential unlock original reaction pathways with higher efficiencies or featuring distinct selectivities functional group tolerances. In this emerging field, such reactivity engineering can be ideally explored complexes based on fundamental understanding underlying mechanisms. Recent developments via electrocatalysis and related key mechanistic features are presented viewpoint. Perspectives drawn highlight less areas catalytic space point way improved systems.

Language: Английский

Citations

5
Unusual Ligand Assistance in Molecular Electrocatalysis via Interfacial Proton Charge Assembly DOI

Sanchayita Mukhopadhyay,

Alagar Raja Kottaichamy,

Pallavi Vyankuram Chame

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(23), P. 5377 - 5385

Published: June 6, 2023

We show that the ability of ligand to reorganize electric double layer (EDL) often dominates electrocatalysis contrary their inductive effect in spectrochemical series, leading counterintuitive electrocatalysis. With water oxidation and chlorine evolution as probe reactions, same catalytic entity with carboxy functionalized exhibited surprisingly higher electrochemical activity comparison aggressively electron-withdrawing nitro ligands, which is actual location series. Spectroscopic analyses suggest enrichment catalytically active species substituted via proton charge assembly EDL turn enhances kinetics overall process. This demonstration less obvious ligands becoming indispensable suggests a blind designing solely based on should be reconsidered it will prevent utilization maximum potential molecule

Language: Английский

Citations

4
Suppressing H2 Evolution with Sterically Encumbered Proton Sources to Improve the Faradaic Efficiency for CO2 Reduction to Formate DOI
Andrew D. Cypcar,

Kathleen M. Bui,

Jenny Y. Yang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14517 - 14523

Published: Sept. 16, 2024

Language: Английский

Citations

1
Electrohydrogenation of Unsaturated Bonds Catalyzed by Earth‐Abundant Metal Complexes DOI Creative Commons
Ying Hua,

Huihua Bi,

Jie Liu

et al.

ChemElectroChem, Journal Year: 2024, Volume and Issue: 11(21)

Published: Oct. 21, 2024

Abstract Catalytic hydrogenation is one of the most important transformations in both academia and industry. Compared with direct molecular hydrogen or transfer hydrogenations hydrides, electrohydrogenation provides an alternative practical pathway using proton as source. In this review, we have summarized recent advances electrohydrogenations polar non‐polar unsaturated compounds catalyzed by earth‐aubundant metal complexes. addition, also present a detailed discussion scope limitations, plausible mechanisms opportunities for further development.

Language: Английский

Citations

1
Reversibly Modulating the Selectivity of Carbon Dioxide Reduction via Ligand-Driven Spin Crossover DOI

Yuan Tang,

Xiangyu Zhu, Qiquan Luo

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 8

Published: Dec. 17, 2024

Selectivity is an essential aspect in catalysis. At present, the improvement of selectivity for complex reactions with multiple pathways/products, example carbon dioxide reduction reaction (CO2RR), can usually be achieved only one pathway/product. It still a challenge to reversibly modulate between two pathways or products CO2RR by catalyst. Here, we propose reversible modulation via spin crossover. By employing first-principles calculations, six crossover molecular catalysts are found among 17 kinds transition metal embedded porphyrin derivatives (ppy_TM), where changes axial ligand configurations switch state high and low spin. For ppy_Os ppy_Ru, alteration effectively influence CO2 into either formic acid monoxide changing relative stability key intermediates *COOH *HCOO.

Language: Английский

Citations

1