Tailoring the ORR and HER electrocatalytic performances of gold nanoparticles through metal–ligand interfaces

Alba-Molina, David; Santiago, Alain R. Puente; Giner‐Casares, Juan J.; Rodríguez‐Castellón, Enrique; Martín‐Romero, María T.; Camacho, Luis; Luque, Rafael; Cano, Manuel

doi:10.1039/c9ta05492h

Cited by 48 publications

(52 citation statements)

References 53 publications

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“…The presence of the ligands is found to negatively shift the Au 4 f binding energies compared to bulk gold, including gold nanoparticles capped with citrate. The largest shifts are observed for CTAB and MUA . Such an observation suggests a local modification of the electronic properties of the gold surface due to chemical functionalization.…”

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 81%

“…Lead underpotential deposition shows that citrate capped nanoparticles present (100) symmetry while the three other systems display mainly (111) domains. After ORR measurements, significant faceting transformation is observed with the citrate capped nanoparticles that acquire (111) symmetry while the other ligand‐stabilized nanoparticles show almost no difference . It is now established that the most active facets for 4‐electron ORR pathway is the (100) domains .…”

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 96%

“…Due to this effect, the PVP‐capped gold nanoparticles may bind oxygen species too tightly, explaining the lower catalytic activity . In the same context, the effect of the nature of “classical” capping agents (citrate, cetyltrimethylammonium bromide (CTAB), polystyrenesulfonate (PSS) and 11‐mercaptoundecanoic acid (MUA)) has been investigated with nanoparticles having the same core size (15 nm) . The presence of the ligands is found to negatively shift the Au 4 f binding energies compared to bulk gold, including gold nanoparticles capped with citrate.…”

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 99%

“…Such an observation suggests a local modification of the electronic properties of the gold surface due to chemical functionalization. The best catalytic performance for ORR is manifested by citrate capped nanoparticles whereas the lowest one is exhibited by PSS capped nanoparticles . XPS analysis of the stabilized gold nanoparticles is performed after ORR measurements.…”

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 99%

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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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Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 81%

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 96%

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 99%

Section: Surface Functionalization Of Single‐metal Catalystsmentioning

confidence: 99%

See 2 more Smart Citations

Surface Modification for Promoting Durable, Efficient, and Selective Electrocatalysts

2020

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“…Recent works have indeed reported the good activity of citratescapped AuNPs of 15 nm size as electrocatalysts for ORR. [13,43] Citrates are the most classical ligands used for commercially available AuNPs. They stabilize AuNPs through electrostatic adsorption by forming multilayers in a disordered arrangement.…”

Section: Introductionmentioning

confidence: 99%

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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Chemical Tuning of Metal Nanocatalysts Interface for ORR Electrocatalysis

Lenne

Mattiuzzi²,

Jabin

et al. 2023

Adv Materials Inter

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A series of surface-functionalized gold nanocatalysts are synthesized. Through diazonium chemistry, calix[4]arene molecules are grafted at the gold surface. Sharing the same anchoring function and a common backbone, the calix[4]arene ligands possess distinct terminal chemical functions where the length, hydrophobic nature and oxygen affinity are varied. Thanks to the versatility of the calix[4]arene platform, a focused tuning of the solid/liquid interface with tail groups could be achieved. Electrocatalytic tests demonstrate the influence of the tails group on the ORR performances, including efficiency, selectivity and durability. Beyond a pure geometric effect, we show that chemical properties of the ligands could effectively tune the interactions between the metallic catalyst and the electrolyte and reactants.

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Tailoring the ORR and HER electrocatalytic performances of gold nanoparticles through metal–ligand interfaces

Abstract: The oxygen reduction (ORR) and hydrogen evolution (HER) reactions are the most important cathodic processes involved in fuel cell and water splitting, respectively.

Cited by 48 publications

References 53 publications

Surface Modification for Promoting Durable, Efficient, and Selective Electrocatalysts

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

Chemical Tuning of Metal Nanocatalysts Interface for ORR Electrocatalysis

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