Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas DOI

Shi He,

Samuel R. Bottum, John C. Dickenson

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts perform solar-driven reduction of CO2. Less frequently, molecular employed better control the reactivity toward desired products, yet development robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2-3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and photocurrent density ∼10 mA/cm2 for photoelectrochemical homogeneous catalyst, producing syngas with an ∼2:1 H2 CO ratio. Because low defect density, interface forms electron inversion metal-like at cathodic potentials. This facilitates transfer redox-active molecules via tunneling even if molecule's potential is beyond semiconductor's conduction band edge. Using electrolyte solution composed cobalt bis(terpyridine) catalyst water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting ∼30% Faradaic efficiency similar glassy carbon electrode comparable conditions. The results ultrathin platform aqueous-stable, molecule-driven photoelectrocatalysis.

Language: Английский

Photoelectrocatalytic reduction of CO2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon DOI
Young Hyun Hong, Xiaofan Jia, Eleanor Stewart-Jones

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102462 - 102462

Published: March 1, 2025

Language: Английский

Citations

2
Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas DOI

Shi He,

Samuel R. Bottum, John C. Dickenson

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts perform solar-driven reduction of CO2. Less frequently, molecular employed better control the reactivity toward desired products, yet development robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2-3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and photocurrent density ∼10 mA/cm2 for photoelectrochemical homogeneous catalyst, producing syngas with an ∼2:1 H2 CO ratio. Because low defect density, interface forms electron inversion metal-like at cathodic potentials. This facilitates transfer redox-active molecules via tunneling even if molecule's potential is beyond semiconductor's conduction band edge. Using electrolyte solution composed cobalt bis(terpyridine) catalyst water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting ∼30% Faradaic efficiency similar glassy carbon electrode comparable conditions. The results ultrathin platform aqueous-stable, molecule-driven photoelectrocatalysis.

Language: Английский

Citations

0