TY - JOUR
T1 - Elucidation of Structure–Activity Relations in Proton Electroreduction at Pd Surfaces
T2 - Theoretical and Experimental Study
AU - Schmidt, Thorsten O.
AU - Ngoipala, Apinya
AU - Arevalo, Ryan L.
AU - Watzele, Sebastian A.
AU - Lipin, Raju
AU - Kluge, Regina M.
AU - Hou, Shujin
AU - Haid, Richard W.
AU - Senyshyn, Anatoliy
AU - Gubanova, Elena L.
AU - Bandarenka, Aliaksandr S.
AU - Vandichel, Matthias
N1 - Publisher Copyright:
© 2022 The Authors. Small published by Wiley-VCH GmbH.
PY - 2022/7/27
Y1 - 2022/7/27
N2 - The structure–activity relationship is a cornerstone topic in catalysis, which lays the foundation for the design and functionalization of catalytic materials. Of particular interest is the catalysis of the hydrogen evolution reaction (HER) by palladium (Pd), which is envisioned to play a major role in realizing a hydrogen-based economy. Interestingly, experimentalists observed excess heat generation in such systems, which became known as the debated “cold fusion” phenomenon. Despite the considerable attention on this report, more fundamental knowledge, such as the impact of the formation of bulk Pd hydrides on the nature of active sites and the HER activity, remains largely unexplored. In this work, classical electrochemical experiments performed on model Pd(hkl) surfaces, “noise” electrochemical scanning tunneling microscopy (n-EC-STM), and density functional theory are combined to elucidate the nature of active sites for the HER. Results reveal an activity trend following Pd(111) > Pd(110) > Pd(100) and that the formation of subsurface hydride layers causes morphological changes and strain, which affect the HER activity and the nature of active sites. These findings provide significant insights into the role of subsurface hydride formation on the structure–activity relations toward the design of efficient Pd-based nanocatalysts for the HER.
AB - The structure–activity relationship is a cornerstone topic in catalysis, which lays the foundation for the design and functionalization of catalytic materials. Of particular interest is the catalysis of the hydrogen evolution reaction (HER) by palladium (Pd), which is envisioned to play a major role in realizing a hydrogen-based economy. Interestingly, experimentalists observed excess heat generation in such systems, which became known as the debated “cold fusion” phenomenon. Despite the considerable attention on this report, more fundamental knowledge, such as the impact of the formation of bulk Pd hydrides on the nature of active sites and the HER activity, remains largely unexplored. In this work, classical electrochemical experiments performed on model Pd(hkl) surfaces, “noise” electrochemical scanning tunneling microscopy (n-EC-STM), and density functional theory are combined to elucidate the nature of active sites for the HER. Results reveal an activity trend following Pd(111) > Pd(110) > Pd(100) and that the formation of subsurface hydride layers causes morphological changes and strain, which affect the HER activity and the nature of active sites. These findings provide significant insights into the role of subsurface hydride formation on the structure–activity relations toward the design of efficient Pd-based nanocatalysts for the HER.
KW - active sites
KW - density functional theory
KW - electrochemical scanning tunneling microscopy
KW - hydrogen absorption
KW - hydrogen evolution reaction
KW - palladium
KW - strain effect
UR - http://www.scopus.com/inward/record.url?scp=85132182157&partnerID=8YFLogxK
U2 - 10.1002/smll.202202410
DO - 10.1002/smll.202202410
M3 - Article
AN - SCOPUS:85132182157
SN - 1613-6810
VL - 18
JO - Small
JF - Small
IS - 30
M1 - 2202410
ER -