Electrografting of Phenyl Phosphate Layers onto Glassy Carbon for Tuning Catalytic Activity toward the Hydrogen Evolution Reaction.

In this study, we explored the surface modification of a glassy carbon electrode through the electrografting of 4-Aminophenyl phosphate, which features heteroatoms and ionic properties. The electrochemical grafting process involves reducing in situ-generated diazonium derivatives. The primary objective of this research was to immobilize organic layers and assess their electrochemical and surface properties. Subsequently, the generated surface serves as a template for the electrochemical growth of Pd and Co nanoparticles on functionalized electrodes. The electrocatalytic performances of these hybrid electrodes in driving the hydrogen evolution reaction were investigated. The obtained results indicate an enhancement in the electrocatalytic activity of the modified electrodes, where lower overpotential and higher stability were observed when the catalyst was electrodeposited onto the attached ionic layer. These findings highlight the synergistic effect between the attached phenyl phosphate moieties and electrocatalysts.

Competition of CO and Acetaldehyde Adsorption and Reduction on Copper Electrodes and Its Impact on n-Propanol Formation.

Selective synthesis of n-propanol from electrocatalytic CO2/CO reduction on copper remains challenging and the impact of the local interfacial effects on the production of n-propanol is not yet fully understood. Here, we investigate the competition between CO and acetaldehyde adsorption and reduction on copper electrodes and how it affects the n-propanol formation. We show that n-propanol formation can be effectively enhanced by modulating the CO partial pressure or acetaldehyde concentration in solution. Upon successive additions of acetaldehyde in CO-saturated phosphate buffer electrolytes, n-propanol formation was increased. Oppositely, n-propanol formation was the most active at lower CO flow rates in a 50 mM acetaldehyde phosphate buffer electrolyte. In a conventional carbon monoxide reduction reaction (CORR) test in KOH, we show that, in the absence of acetaldehyde in solution, an optimum ratio of n-propanol/ethylene formation is found at intermediate CO partial pressure. From these observations, we can assume that the highest n-propanol formation rate from CO2RR is reached when a suitable ratio of CO and acetaldehyde intermediates is adsorbed. An optimum ratio was also found for n-propanol/ethanol formation but with a clear decrease in the formation rate for ethanol at this optimum, while the n-propanol formation rate was the highest. As this trend was not observed for ethylene formation, this finding suggests that adsorbed methylcarbonyl (adsorbed dehydrogenated acetaldehyde) is an intermediate for the formation of ethanol and n-propanol but not for ethylene. Finally, this work may explain why it is challenging to reach high faradaic efficiencies for n-propanol, as CO and the intermediates for n-propanol synthesis (like adsorbed methylcarbonyl) compete for active sites on the surface, where CO adsorption is favored.

Chemical Surface Grafting of Pt Nanocatalysts for Reconciling Methanol Tolerance with Methanol Oxidation Activity.

A conceptual challenge toward more versatile direct methanol fuel cells (DMFCs) is the design of a single material electrocatalyst with high activity and durability for both oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). This requires to conciliate methanol tolerance not to hinder ORR at the cathode with a good MOR activity at the anode. This is especially incompatible with Pt materials. We tackled this challenge by deriving a supramolecular concept where surface-grafted molecular ligands regulate the Pt-catalyst reactivity. ORR and MOR activities of newly reported Pt-calix[4]arenes nanocatalysts (Pt CF 3 ${{_{{\rm CF}{_{3}}}}}$ NPs/C) are compared to commercial benchmark PtNPs/C. Pt CF 3 ${{_{{\rm CF}{_{3}}}}}$ NPs/C exhibit a remarkable methanol tolerance without losing the MOR reactivity along with outstanding durability and chemical stability. Beyond designing single-catalyst material, operable in DMFC cathodic and anodic compartments, the results highlight a promising strategy for tuning interfacial properties.

Highly stable silver nanohybrid electrocatalysts for the oxygen reduction reaction.

Silver nanoparticles (AgNPs) were deliberately functionalized via aryl diazonium chemistry with a monolayer of calix[4]arenes. The resulting nanohybrids show high efficiency and high selectivity toward the ORR in alkaline media along with an exceptional durability and a high methanol tolerance.

Strategies for the Formation of Monolayers From Diazonium Salts: Unconventional Grafting Media, Unconventional Building Blocks.

Pioneered by J. Pinson and coll. in 1990s, the reductive grafting of aryldiazonium salts has become a powerful method for surface functionalization. Highly robust interfaces result from this surface attachment, resistant to heat, chemical degradation and ultrasonication. Importantly, this approach can be applied to many materials, ranging from conducting, semi-conducting, oxides to insulating substrates. In addition, either massive, flat surfaces or nanomaterials can be functionalized. The method is easy to process and fast. The grafting process involves the formation of highly reactive aryl radicals able to attack the substrate. However, the generated radicals can also react with already-grafted aryl species, leading to the formation of loosely-packed polyaryl multilayer films, typically of 10-15 nm thick. It is thus highly challenging to control the vertical extension of the deposited layer and to form well-ordered monolayers from aryldiazonium salts. In this mini review, we briefly describe the different strategies that have been developed to prepare well-ordered monolayers. We especially focus on two strategies successfully used in our laboratories, namely the use of unconventional solvents, i.e., room temperature ionic liquids (RTILs), as grafting media and the use of calixarene macrocycles by taking benefit of their pre-organized structure. These strategies give large possibilities for the structuring of interfaces with the widest choice of materials and highlight the potential of aryldiazonium grafting as a competitive alternative to self-assembled monolayers (SAMs) of alkyl thiols.

Robust hydrophobic gold, glass and polypropylene surfaces obtained through a nanometric covalently bound organic layer.

The (electro)chemical grafting of a polyfluorinated calix[4]arene on gold, polypropylene and glass is reported. The modified surfaces were characterized by ellipsometry, atomic force microscopy (AFM), and by X-ray photoelectron spectroscopy (XPS). A nanometric, robust and uniform monolayer of covalently surface-bound calix[4]arenes was obtained on the three different materials. For all surfaces, contact angles higher than 110° were recorded, highlighting the hydrophobic character given by this ∼2 nm thin organic monolayer. Remarkably, the contact angle values remained unchanged after 18 months under a laboratory atmosphere. The results presented herein thus present an attractive and sustainable strategy for bringing hydrophobic properties to the interface of a wide range of materials.