Highly Active Hydrogen Evolution Electrodes via Co-Deposition of Platinum and Polyoxometalates

Abstract

A highly active hydrogen evolution reaction (HER) electrode with low Pt loading on glassy carbon (GC) has been prepared by anodic platinum dissolution and co-deposition of polyoxometalates. TEM, EDS, XPS, CV, and ICP-MS analyses gave a Pt loading of 50-100 ng/cm2, corresponding to a Pt coverage of only 0.08-0.16 monolayer. With an overpotential of 65 mV at 20 mA/cm2, the modified GC has a HER activity comparable to that of the commercial Pt working electrode.

Polyoxometalate‐graphene Electrocatalysts for the Hydrogen Evolution Reaction

“…The first work on HER electrocatalytic activity by POMs was reported in 1985 by Keita and Nadjo . It was also found that co‐deposition of trace amounts of Pt on the working electrode, originating from anodic dissolution of the Pt counter electrode, can be an issue . In 2007, Nadjo's team developed modified surface electrodes for HER based on [H 7 P 8 W 48 O 184 ] 33− , [Co 6 (H 2 O) 30 (Co 9 Cl 2 (OH) 3 (H 2 O) 9 (β‐SiW 8 O 31 ) 3 )] 5− and [(Co 3 ( B ‐β‐SiW 9 O 33 (OH))( B ‐β‐SiW 8 O 29 OH) 2 ) 2 ] 22− .…”

POM & MOF‐based Electrocatalysts for Energy‐related Reactions

“…[105,106] However,the high catalytic performance reported at that time for [SiW 12 O 40 ] 4À was found to be also due to the co-depositiono ft race amountso fP to nt he workinge lectrode, originated from anodic dissolution of the Pt counter electrode. [43,107] In 1992, Rong and Pope also observed the occurrence of hydrogen evolution promoted by aR u-sub-stitutedP OM, a-[PW 11 Ru III (H 2 O)O 39 ] 4À ,i na cidic aqueous solution. [108] Later [104] These POMs were immobilized on carbon black Vulcan XC-72 and deposited on ag lassy carbon electrode (GCE) or confined in poly(vinylpyridine) films on the electrode, which promoted amicroenvironment effect.…”

“…The first POM‐based electrocatalyst for HER was reported in 1985 by Keita and Nadjo . However, the high catalytic performance reported at that time for [SiW 12 O 40 ] 4− was found to be also due to the co‐deposition of trace amounts of Pt on the working electrode, originated from anodic dissolution of the Pt counter electrode . In 1992, Rong and Pope also observed the occurrence of hydrogen evolution promoted by a Ru‐substituted POM, α‐[PW 11 Ru III (H 2 O)O 39 ] 4− , in acidic aqueous solution …”

“…More recently, Zhang et al. have prepared active HER electrodes based on the lacunary SiW 11 and parent SiW 12 and P 2 W 18 POMs, with extremely low Pt loadings in the range of 50–100 ng cm −2 . The authors reported that SiW 11 /Pt‐modified GCE showed best HER performance (in a 0.5 m H 2 SO 4 ), achieving a HER activity similar to Pt working electrode, with an overpotential of η 10 =0.028 V vs. RHE and a TS of 32 mV dec −1 .…”

“…have prepared active HER electrodes based on the lacunary SiW 11 and parent SiW 12 and P 2 W 18 POMs, with extremely low Pt loadings in the range of 50–100 ng cm −2 . The authors reported that SiW 11 /Pt‐modified GCE showed best HER performance (in a 0.5 m H 2 SO 4 ), achieving a HER activity similar to Pt working electrode, with an overpotential of η 10 =0.028 V vs. RHE and a TS of 32 mV dec −1 . Moreover, it was observed that the electrode prepared in the absence of POM resulted in a much reduced HER activity and also that the POM co‐deposition was determinant for the electrode stability …”