Single‐Site Molecular Ruthenium(II) Water‐Oxidation Catalysts Grafted into a Polymer‐Modified Surface for Improved Stability and Efficiency

Badiei, Yosra M.; Annon, Oshane; Maldonado, Christina; Delgado, Emily; Nguyen, Caroline T.; Rivera, Christina G.; Li, Clive; Ortega, Abril Flores

doi:10.1002/celc.202300028

Cited by 2 publications

(1 citation statement)

References 60 publications

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“…Clearly, plexcitonic antenna complexes are promising templates for the design of novel kinds of biomimetic photonic materials. However, further optimization of these materials for solar energy capture, ,− catalysis, , and advanced photonic devices − requires a high degree of programmability to enable the rational design of materials with bespoke optical properties. In the strong coupling regime, the coupling energy E C is proportional to N 1/2 , where N is the number of excitons within the plasmon mode volume. , Moreover, the field strength of the plasmon mode decays with distance from the gold surface.…”

Section: Introductionmentioning

confidence: 99%

XPS Depth-Profiling Studies of Chlorophyll Binding to Poly(cysteine methacrylate) Scaffolds in Pigment–Polymer Antenna Complexes Using a Gas Cluster Ion Source

Csányi,

Hammond,

Bower

et al. 2024

Langmuir

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X-ray photoelectron spectroscopy (XPS) depth-profiling with an argon gas cluster ion source (GCIS) was used to characterize the spatial distribution of chlorophyll a (Chl) within a poly(cysteine methacrylate) (PCysMA) brush grown by surface-initiated atom-transfer radical polymerization (ATRP) from a planar surface. The organization of Chl is controlled by adjusting the brush grafting density and polymerization time. For dense brushes, the C, N, S elemental composition remains constant throughout the 36 nm brush layer until the underlying gold substrate is approached. However, for either reduced density brushes (mean thickness ∼20 nm) or mushrooms grown with reduced grafting densities (mean thickness 6−9 nm), elemental intensities decrease continuously throughout the brush layer, because photoelectrons are less strongly attenuated for such systems. For all brushes, the fraction of positively charged nitrogen atoms (N + /N 0 ) decreases with increasing depth. Chl binding causes a marked reduction in N + /N 0 within the brushes and produces a new feature at 398.1 eV in the N1s core-line spectrum assigned to tetrapyrrole ring nitrogen atoms coordinated to Zn 2+ . For all grafting densities, the N/S atomic ratio remains approximately constant as a function of brush depth, which indicates a uniform distribution of Chl throughout the brush layer. However, a larger fraction of repeat units bound to Chl is observed at lower grafting densities, reflecting a progressive reduction in steric congestion that enables more uniform distribution of the bulky Chl units throughout the brush layer. In summary, XPS depth-profiling using a GCIS is a powerful tool for characterization of these complex materials.

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Section: Introductionmentioning

confidence: 99%

XPS Depth-Profiling Studies of Chlorophyll Binding to Poly(cysteine methacrylate) Scaffolds in Pigment–Polymer Antenna Complexes Using a Gas Cluster Ion Source

Csányi,

Hammond,

Bower

et al. 2024

Langmuir

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Construction of Mesoporous Aluminosilicate Thin Films on ITO Electrodes for Immobilizing a Cationic Ru(II) Water Oxidation Catalyst

Harada,

Yamada,

Nakano

et al. 2024

ChemCatChem

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Aluminosilicate (Al‐SiO2) thin films with vertically aligned mesochannels were successfully synthesized on ITO electrodes and employed for the immobilization of a cationic Ru(II) water oxidation catalyst without requiring linker groups. Optimal synthesis conditions yielded uniform mesoporous Al‐SiO2 films with tunable Al content, high surface area (568 m2/g), 3.94 nm pore size, and 155 nm thickness. Electrochemical studies confirmed the presence of the immobilized Ru complex undergoing diffusion‐controlled Ru(III/II) and Ru(IV/III) electron transfer. The Ru loading reached 4.71 nmol/cm2 at Si/Al = 9.6, with higher Al content enhancing loading amounts via cation exchange. The Ru‐modified electrode exhibited high electrocatalytic water oxidation activity, achieving 75.3% Faradaic efficiency and a turnover number of 298.6 for O2 evolution for 1 hour. This work provides a new approach to construct porous environments on an electrode surface to immobilize positively charged transition‐metal complexes as catalysts, offering potential applications in the development of electrocatalytic systems for energy conversion.

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Single‐Site Molecular Ruthenium(II) Water‐Oxidation Catalysts Grafted into a Polymer‐Modified Surface for Improved Stability and Efficiency

Cited by 2 publications

References 60 publications

XPS Depth-Profiling Studies of Chlorophyll Binding to Poly(cysteine methacrylate) Scaffolds in Pigment–Polymer Antenna Complexes Using a Gas Cluster Ion Source

XPS Depth-Profiling Studies of Chlorophyll Binding to Poly(cysteine methacrylate) Scaffolds in Pigment–Polymer Antenna Complexes Using a Gas Cluster Ion Source

Construction of Mesoporous Aluminosilicate Thin Films on ITO Electrodes for Immobilizing a Cationic Ru(II) Water Oxidation Catalyst

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