Extremely robust and post-functionalizable gold nanoparticles coated with calix[4]arenes via metal–carbon bonds

Troian‐Gautier, Ludovic; Valkenier, Hennie; Mattiuzzi, Alice; Jabin, Ivan; Brande, Niko Van den; Mele, Bruno Van; Hubert, Julie; Reniers, François; Bruylants, Gilles; Lagrost, Corinne; Leroux, Yann R.

doi:10.1039/c6cc04534k

Cited by 34 publications

(75 citation statements)

References 32 publications

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“…Besides, when R contains a functional group such as COOH, a post‐functionalization of the surface can be readily achieved under mild conditions. Calix[4]arene‐tetradiazonium salts were notably used for the modification and further post‐functionalization of gold, carbon and germanium surfaces,, but also polymers and nanomaterials such as gold nanoparticles . Furthermore, this method allows for controlling the composition of binary mixed monolayers, which is essential for sensing applications , .…”

Section: Introductionmentioning

confidence: 99%

“…Surface modification with calix[4]arene‐tetradiazonium salts X 4 N 4 a – c , . Inset: targeted calix[4]arene‐monodiazonium salt 1 .…”

Section: Introductionmentioning

confidence: 99%

“…Calix [4]arene-tetradiazonium salts were notably used for the modification and further post-functionalization of gold, carbon and germanium surfaces, [7,9] but also polymers [10] and nanomaterials such as gold nanoparticles. [11] Furthermore, this method allows for controlling the composition of binary mixed monolayers, which is essential for sensing applications. [12,13] All in all, calix [4]arene-tetradiazonium salts represent nowadays an established class of compounds that can find various applications in the field of surface modification.…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, such a calix [4]arene-monodiazonium salt would allow us to evaluate the influence of the number of anchoring points on the robustness and compactness of the grafted layer. Moreover, the number of anchoring points may also influence the 3D conformation of the calixarene once anchored onto the sur- [4]arene-tetradiazonium salts X 4 N 4 a-c. [7,[9][10][11][12][13] Inset: targeted calix [4]arene-monodiazonium salt 1. Note that the representation of the grafted calixarene does not necessarily imply that the four aryl units are linked to the surface.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of a Calix[4]arene‐Monodiazonium Salt for Surface Modification

et al. 2018

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Reduction of calix[4]arene‐tetradiazonium salts at the vicinity of a surface, notably a carbon surface, leads to the formation of a dense and robust covalently bound monolayer. To expand the versatility of this unique methodology, the efficient synthesis of a calix[4]arene bearing a single diazonium group and thus a single anchoring point was achieved. The introduction of the diazonium group was developed through an original approach involving a copper‐catalyzed reaction for the preparation of an intermediate azido‐calixarene. The grafting ability of the calix[4]arene‐monodiazonium cation was evaluated by investigating its electrochemical reduction at glassy carbon electrodes. Studies of the blocking properties of the modified surfaces toward redox probes evidenced the formation of compact covalently bound layers at the carbon substrates, opening interesting perspectives in the field of surface modification by calixarene‐based diazonium salts.

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Section: Introductionmentioning

confidence: 99%

“…Surface modification with calix[4]arene‐tetradiazonium salts X 4 N 4 a – c , . Inset: targeted calix[4]arene‐monodiazonium salt 1 .…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of a Calix[4]arene‐Monodiazonium Salt for Surface Modification

et al. 2018

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“…A direct evidence for the formation of Au−C covalent bonds on gold nanoparticles was provided through a surface enhanced Raman scattering (SERS) study . Especially, this method allows the preparation of extremely robust aryl‐stabilized nanoparticles …”

Section: Introductionmentioning

confidence: 99%

Surface Modification for Promoting Durable, Efficient, and Selective Electrocatalysts

2020

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Intensive research into the design of catalysts involved in energy conversion and fuel cell technologies has allowed great progress in the field. However, durable, efficient and selective electrocatalytic systems for the activation of fuel molecules at the lowest cost are still needed. The most developed strategies consist of tailoring the shape, size and composition of metallic nanomaterials. Yet, deliberate surface modification of the catalysts should be considered as a promising alternative approach. The functionalization of metallic catalysts with organic ligands has been recently demonstrated to promote high catalytic activity. This Review focuses on the functionalization of metallic or alloy catalysts with organic ligands, showing the impact of the surface modification for different materials and different reactions. Hybrid systems based on this alternative strategy could contribute to the elaboration of cutting‐edge systems for electrocatalysis.

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Functionalizing Gold Nanoparticles with Calix[4]arenes Monolayers for Enhancing Selectivity and Stability in ORR Electrocatalysis

Lenne

Mattiuzzi²,

Jabin

et al. 2020

Adv Materials Inter

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blocking an important proportion of their active sites and deactivating the catalysts. The removal of ligands from the nanoparticles surface without altering the specific structure that rules their catalytic function, is a major challenge. [5-7] Interestingly, organic ligands are commonly designed and employed in homogeneous catalysis to steer the activity and selectivity of metal centers. [8,9] The presence of organic ligands allows better control of selectivity. In line with this concept, the chemical surface modification of metallic nanostructures has just emerged as a promising strategy to increase their catalytic performances as recently reviewed. [10] Recent reports have highlighted that organic functionalization of metallic nanoparticles can boost their electrocatalytic properties through local interfacial steric or electronic effects. [11,12] Far from having a detrimental impact, the ligands are found to have a beneficial role. The nature of the ligands, [13] and/or the interfacial bonding, [14] promote high electrocatalytic activity, selectivity, and durability. [10] The immobilization of organic molecules to metallic surfaces includes the chemisorption of monomers, polymers or surfactants, the self-assembly, the covalent grafting or the electrostatic adsorption of charged molecules (e.g., citrates, polyelectrolytes). The strength of interaction between surface and ligands depends on the employed procedures. Whereas thiol molecules are known for decades to efficiently bind gold nanoparticles (AuNPs) via AuS bonds, [15,16] more recently, AuC (carbene), [17] AuCC (acetylide), [18] or AuC (through aryl diazonium salts reduction), [19] provide robust interfacial bonds with strong metal-ligands interactions. The aryldiazonium reduction leads to strong interaction between the metallic surfaces and the aryl moieties, with adsorption energies over 200 kJ mol −1. [20] In contrast, electrostatic adsorption, involved for instance in citrate-stabilized gold nanoparticles corresponds to a weaker interaction with binding energy lower than 85 kJ mol −1. [21] We have recently developed a unique strategy to prepare dense and compact monolayers on a wide range of materials including nanomaterials thanks to the reductive grafting of calix[4]arene-tetradiazonium salts. [22,23] The calix[4]arene-tetradiazonium cation exhibits a cone-constrained structure made up of four aromatic units linked by methylene bridges, allowing The deliberate surface modification of nanocatalysts with organic ligands has recently emerged as a promising strategy to boost their efficiency, durability, and/or selectivity in key electrocatalytic processes. The interface between the metallic interface and the immobilized ligands promotes high electrocatalytic activity. Herein, the oxygen reduction reaction activity of gold nanoparticles functionalized with a covalently bound monolayer of calix[4]arenes is compared with commercially available gold nanoparticles, classically stabilized through electrostatic adsorption of citrates onto the gold surfa...

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Extremely robust and post-functionalizable gold nanoparticles coated with calix[4]arenes via metal–carbon bonds

Cited by 34 publications

References 32 publications

Synthesis of a Calix[4]arene‐Monodiazonium Salt for Surface Modification

Synthesis of a Calix[4]arene‐Monodiazonium Salt for Surface Modification

Surface Modification for Promoting Durable, Efficient, and Selective Electrocatalysts

Functionalizing Gold Nanoparticles with Calix[4]arenes Monolayers for Enhancing Selectivity and Stability in ORR Electrocatalysis

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