Micellar Transfer Hydrogenation Catalysis in Water with Monocarbonyl Ruthenium(II)-poly(vinylphosphonate)-Containing Polymers: Achieving Reduction of Biomass-Derived Aldehydes DOI Creative Commons
Denise Lovison,

Philipp Weingarten,

Alexandra Sebeschuk

et al.

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(22), P. 13855 - 13864

Published: Nov. 7, 2024

With the aim to build a supramolecular organometallic catalyst for transfer hydrogenation (TH) reactions of hydrophobic substrates, micellar architectures different sizes were obtained using amphiphilic diblock copolymers (BCPs) tethered Ru(II) monocarbonyl complex. An end-group functionalization strategy was employed incorporate bipyridyl end-group, used further coordinate cationic ruthenium fragment, poly(2-vinylpyridine)-b-poly(diethyl vinylphosphonate). Owing their character, polymers form spherical micelles in water, which characterized by spectroscopic and analytical methods at pH values temperatures. The most suitable core–shell system could level catalytic activity complex toward biomass-derived aldehydes, be successfully reduced corresponding alcohols water potassium formate as hydride source. Depending on substrate's hydrophobicity concentration, varied significantly. In addition, polymer's properties hardly changed during catalysis, facilitating effective recycling until third cycle.

Language: Английский

Facet-Engineered Copper Electrocatalysts Enable Sustainable NADH Regeneration with High Efficiency DOI
Shuo Sun, Yizhou Wu,

Yunxuan Ding

et al.

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

Published: April 30, 2025

Electrochemical regeneration of the nicotinamide cofactor (NADH) provides a sustainable approach to enzymatic reactions. However, low productivity and selectivity bioactive 1,4-NADH limit its broad applications. The hydrogenation NAD+ at electrode surface is strongly coupled conformation adsorbed NAD*, formation hydrogen (Had), Had transfer NAD*. Therefore, searching for materials with suitable NAD* conformation, energy, rapid becomes key task research. In this study, (111) facet Cu was found exhibit higher 86.4%, compared 50.4% 57.4% (100) (110) facets, respectively. Density functional theory (DFT) calculations revealed that high Cu(111) stemmed from favorable reduced barrier. Subsequently, nanowire (111)-dominant abundant grain boundaries, Cugb(111), constructed. kinetic analysis DFT demonstrated boundaries reduce reaction barrier formation. A record-high 73.5 μmol h-1 cm-2 achieved by while well-maintained 84.7%. This study elucidates effects crystal facets on regulating 1,4-NADH, providing pathway renewable energy-powered, high-efficiency green biomanufacturing.

Language: Английский

Citations

0
Electricity-driven organic hydrogenation using water as the hydrogen source DOI Creative Commons
Bidyut Kumar Kundu, Yujie Sun

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Employing water as a hydrogen source is an attractive and sustainable option in electricity-driven organic hydrogenation, which can overcome the drawbacks associated with traditional sources like H 2 .

Language: Английский

Citations

3
Rh-functionalized Imino-pyridine Covalent Organic Framework Assembled on Ti3C2Tx (MXene) for Efficient NADH Regeneration and Photoenzymatic CO2 Reduction DOI

Hailong Zheng,

Zhipeng Huang,

Ping Wei

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: March 4, 2025

Nicotinamide adenine dinucleotide (NADH) regeneration is crucial for sustainable enzymatic CO2 reduction. In this study, Ti3C2Tx (MXene) and [Cp*Rh(bpy)(H2O)]2+ (labeled as [Cp*Rh]) were sequentially assembled onto imino-pyridine structured covalent organic frameworks (TD-COF) to construct Rh@TDM photocatalysts with dual cocatalyst. The photoelectrochemical tests temperature-dependent photoluminescence spectra suggest that the synergistic effect of incorporation [Cp*Rh] immobilization enables a reduction in exciton binding energy promotes carrier transfer. Consequently, optimized [email protected] photocatalyst achieves 95.0% NADH yield, significantly higher than TD-COF free (32.7%). Additionally, modification strategy applied also enhances selectivity 1,4-NADH. Therefore, turnover frequency 1,4-NADH 1.06 h–1, which 7.1 times (0.15 h–1). Subsequently, photoenzymatic cascade catalytic system, obtained remarkable formate generation rate 2137.7 μmol g–1 h–1. This work not only provides novel example using COF containing an structure immobilize but reveals synergetic MXene facilitates These findings offer new insights opportunities design application artificial systems

Language: Английский

Citations

0
Reversible Electrocatalytic NAD+/NADH Interconversion Mediated by a Pyrazine-Amidate Iridium Complex DOI
Gabriel Menendez Rodriguez, Caterina Trotta, Leonardo Tensi

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 3, 2024

Herein, we report reversible electrocatalytic NAD+/NADH interconversion mediated by [Cp*Ir(pyza)Cl] (1, pyza = pyrazine amidate). 1 was designed through a rational approach aimed at lowering the overpotential of NAD+ to NADH reduction with respect that observed for electrocatalyst [Cp*Ir(pica)Cl] (2, pica picolinamidate). The peculiar properties pyza, which is substantially less σ electron-donator and more π electron-acceptor than pica, resulted in an easier bielectronic process occurring −0.29 V (instead ca. −0.65 2), very close equilibrium potential redox couple (E°eq −0.32 vs NHE, 298 K, pH 7). catalyzes both oxidation response even small departure from potential, catalytic bias former (|ipred/ipox| 6.2, 333 K). reversibility ascertained 1H EXSY NMR spectroscopy clearly demonstrated rapid establishment 1_H + ⇌ (Keq 3, ΔG −0.6 kcal/mol, K) similar hydridicity (28.9 (28.3

Language: Английский

Citations

1
Acceptorless dehydrogenation of glycerol catalysed by Ir(III) complexes with carbohydrate‐functionalised ligands: a sweet pathway to produce hydrogen and lactic acid DOI Creative Commons
Alceo Macchioni, Elisa Boccalon,

Gabriel Menendez Rodriguez

et al.

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Glycerol, a by‐product of biodiesel production, has gained prominence as precious platform chemical. To enhance the economic viability production process and address surplus glycerol it is essential to transform into value‐added products. In this context, homogeneous catalysis offers promising avenue for valorisation. study, we introduce family iridium complexes bearing picolineamidate ligands with glucose‐functionalised substituents novel catalysts hydrogen lactic acid conversion. These exhibit high activity (conversion up 53.3 %) 99 % selectivity after 24 hours reaction (TOF MAX =159 h −1 , TON 24h =2498). Notably, occurs under ambient air at milder temperature conditions (120 °C) compared other catalysts. efforts in valorisation contribute reducing costs, increasing competitiveness biofuels against petroleum‐based liquid fuels, giving rise H 2 through global negative carbon dioxide emission, utilizable, among other, monomer synthesis biodegradable plastics.

Language: Английский

Citations

0
Micellar Transfer Hydrogenation Catalysis in Water with Monocarbonyl Ruthenium(II)-poly(vinylphosphonate)-Containing Polymers: Achieving Reduction of Biomass-Derived Aldehydes DOI Creative Commons
Denise Lovison,

Philipp Weingarten,

Alexandra Sebeschuk

et al.

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(22), P. 13855 - 13864

Published: Nov. 7, 2024

With the aim to build a supramolecular organometallic catalyst for transfer hydrogenation (TH) reactions of hydrophobic substrates, micellar architectures different sizes were obtained using amphiphilic diblock copolymers (BCPs) tethered Ru(II) monocarbonyl complex. An end-group functionalization strategy was employed incorporate bipyridyl end-group, used further coordinate cationic ruthenium fragment, poly(2-vinylpyridine)-b-poly(diethyl vinylphosphonate). Owing their character, polymers form spherical micelles in water, which characterized by spectroscopic and analytical methods at pH values temperatures. The most suitable core–shell system could level catalytic activity complex toward biomass-derived aldehydes, be successfully reduced corresponding alcohols water potassium formate as hydride source. Depending on substrate's hydrophobicity concentration, varied significantly. In addition, polymer's properties hardly changed during catalysis, facilitating effective recycling until third cycle.

Language: Английский

Citations

0