• Programmable Single-Stranded DNA Layers as Modulators of Nanoscale pH at Electrocatalytic Interfaces
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  • 2026-06-09 16:37:44|
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ㅇ [Title]         Programmable Single-Stranded DNA Layers as Modulators of Nanoscale pH at Electrocatalytic Interfaces

  

ㅇ [Journal]    Journal of the American Chemical Society


                                                                         
ㅇ [Author]     Sang Yeon Oh†, Tae Kyoung Lee†, Jaeyeon Jun, Jinse Woo, Changho Lee, Yongha Kim, Jimin Park*




 


ㅇ [Abstrct]


Control of the local reaction environment at electrocatalytic interfaces is crucial for determining the activity and selectivity of many electrochemical reactions. Here, we

demonstrate that single-stranded DNA (ssDNA) layers with anionic phosphate backbones can serve as ionomer-like coatings that modulate local pH. On gold nanoparticle

(AuNP) electrocatalysts, ssDNA layers enable nanoscale control of the interfacial environment by independently controlling coating thickness through strand-length

variation and internal phosphate backbone networking through sequence-encoded base-pairing interactions. We find that ssDNA layers modulate the activity and

selectivity of hydroxide ion (OH-)-involving reactions in a sequence-dependent manner on AuNPs, as exemplified by the hydrogen evolution and glycerol oxidation

reactions. Through structure-activity analysis, temperature-dependent experiments, and ssDNA constructs with systematically varied base-pairing, we identify base-

pairing interactions within ssDNA layers as the key determinant governing the catalytic behavior. Operando surface-enhanced Raman spectroscopy reveals an ssDNA-

mediated regulation mechanism in which the anionic phosphate backbones induce Donnan exclusion of OH- at the nanoscale interface, with the extent of OH- buildup or

replenishment strongly dependent on base-pairing interactions. Our results suggest ssDNA as a programmable platform for engineering nanoscale reaction environments

and propose design principles for ionomer-like architectures in electrocatalysis.









 
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