Formic acid oxidation reaction on Au(111) electrodes modified with 4-mercaptopyridine SAM

Hermann, Johannes M.; Müller, H.; Daccache, Layal; Adler, Christiane; Keller, Sarah L.; Metzler, Martin; Jacob, Timo; Kibler, Ludwig A.

doi:10.1016/j.electacta.2021.138547

Cited by 8 publications

(10 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…First, the pyridyl group may directly interact with formic acid/formate, helping it to form an active intermediate for FAOR for understanding the role of pyridine (Py) on Au. 35,36 However, in our experiment of FAOR on Pt in the solution containing Py (seen in Figure S2.5 c), and its current measured is lower than that measured on Pt@4MPy. If Pt@4MPy follows the same reason, the FAOR may occur via chemical process followed by electrochemical process (CE).…”

Section: Resultscontrasting

confidence: 54%

Accelerated interfacial proton transfer for promoting electrocatalytic activity

Deng

Sun

et al. 2022

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Section: Resultscontrasting

confidence: 54%

Accelerated interfacial proton transfer for promoting electrocatalytic activity

Deng

Sun

et al. 2022

Chem. Sci.

View full text Add to dashboard Cite

show abstract

“…Studies investigating the effect of thiolate ligands on Au and Pt nanoparticles for ORR have found differences in overpotential, stability, and selectivity depending on particle size and ligand surface coverage. − Evidence has also been shown that ligands can electronically modify the surface and alter the intrinsic ORR activity of the metal sites . Another example of the successful application of SAMs is in the formic acid oxidation reaction, where 4-MPyS SAMs on Au and Pt have been shown to increase activity. , Hermann and co-workers have proposed that surface bound 4-MPyS prevents active Au sites from being poisoned by an unfavorable binding orientation of formates. Deng and colleagues also found a benefit of using 4-MPyS modification on Pt due to the pyridinic nitrogen acting as a proton acceptor.…”

Section: Resultsmentioning

confidence: 99%

“…40,44 Oxidatively, 4-MPyS and BZT are of similar or slightly greater stability than C3 on Au (Figure 5). 4-MPyS has been shown to arrange itself in a striped phase on Au(111), 45 and it has been suggested that BZT forms an adlayer similar to that of alkanethiols on Au(111), oriented perpendicular to the surface. 40 Despite adopting stabilizing configurations that promote π−π (ring-stacking) interactions and most likely having a greater SAM thickness than C3, the surface accessibility (free surface atom density) of these SAMs may be greater than for C3 and offset the stabilizing influence of the SAM thickness.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Stability of Thiolate Self-Assembled Monolayers on Au, Pt, and Cu

Ramos

Medlin

Holewinski

2023

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Self-assembled monolayers (SAMs) of thiolates have increasingly been used for modification of metal surfaces in electrochemical applications including selective catalysis (e.g., CO 2 reduction, nitrogen reduction) and chemical sensing. Here, the stable electrochemical potential window of thiolate SAMs on Au, Pt, and Cu electrodes is systematically studied for a variety of thiols in aqueous electrolyte systems. For fixed tail-group functionality, the reductive stability of thiolate SAMs is found to follow the trend Au < Pt < Cu; this can be understood by considering the combined influences of the binding strength of sulfur and competitive adsorption of hydrogen. The oxidative stability of thiolate SAMs is found to follow the order: Cu < Pt < Au, consistent with each surface's propensity toward surface oxide formation. The stable reductive and oxidative potential limits are both found to vary linearly with pH, except for reduction above pH ∼10, which is independent of pH for most thiol compositions. The electrochemical stability across different functionalized thiols is then revealed to depend on many different factors including SAM defects (accessible surface metal atom sites decrease stability), intermolecular interactions (hydrophilic groups reduce the stability), and SAM thickness (stability increases with alkanethiol carbon chain length) as well as factors such as SAM-induced surface reconstruction and the ability to directly oxidize or reduce the non-sulfur part of the SAM molecule.

show abstract

“…43,46 Oxidatively, 4-MPyS and BZT are of similar stability to C3 on Au (Figure 5). 4-MPyS has been shown to arrange itself in a striped phase on Au(111), 47,48 and it has been suggested that BZT forms an adlayer similar to that of alkanethiols on Au(111). 43 Despite adopting stabilizing configurations that promote pi-pi (ring-stacking) interactions and most likely having a greater SAM thickness than C3, the surface accessibility (free surface atom density) of these SAMs may be greater than for C3 and offset the stabilizing influence of the SAM thickness.…”

Section: Effect Of Thiolmentioning

confidence: 99%

Electrochemical Stability of Thiolate Self-Assembled Monolayers on Au, Pt, and Cu

Ramos

Medlin

Holewinski

2022

Preprint

View full text Add to dashboard Cite

Self-assembled monolayers (SAMs) of thiolates have increasingly been used for modification of metal surfaces in electrochemical applications including selective catalysis (e.g., CO2 reduction, nitrogen reduction) and chemical sensing. Here, the stable electrochemical potential window of thiolate SAMs on Au, Pt, and Cu electrodes is systematically studied for a variety of thiols in aqueous electrolyte systems. For fixed tail-group functionality, the reductive stability of thiolate SAMs is found to follow the trend: Au < Pt < Cu; this can be understood by considering the combined influences of the binding strength of sulfur and competitive adsorption of hydrogen. The oxidative stability of thiolate SAMs is found to follow the order: Cu < Pt < Au, consistent with each surface’s propensity toward surface oxide formation. The stable reductive and oxidative potential limits are both found to vary linearly with pH, except for reduction above pH ~10, which is independent of potential for most thiol compositions. The electrochemical stability across different functionalized thiols is then revealed to depend on many different factors including SAM defects (accessible surface metal atom sites decrease stability), intermolecular interactions (hydrophilic groups reduce the stability), and SAM thickness (stability increases with alkanethiol carbon chain length), as well as factors such as SAM-induced surface reconstruction, and the ability to directly oxidize or reduce the non-sulfur part of the SAM molecule.

show abstract

Formic acid oxidation reaction on Au(111) electrodes modified with 4-mercaptopyridine SAM

Cited by 8 publications

References 66 publications

Accelerated interfacial proton transfer for promoting electrocatalytic activity

Accelerated interfacial proton transfer for promoting electrocatalytic activity

Electrochemical Stability of Thiolate Self-Assembled Monolayers on Au, Pt, and Cu

Electrochemical Stability of Thiolate Self-Assembled Monolayers on Au, Pt, and Cu

Contact Info

Product

Resources

About