Photoelectrochemical operation of a surface-bound, nickel-phosphine H₂ evolution catalyst on p-Si(111): a molecular semiconductor|catalyst construct

Abstract

We demonstrate the covalent attachment and catalytic function of a nickel-phosphine H2 evolution catalyst to a p-Si(111) photoelectrode. The covalently assembled semiconductor|molecular construct achieves a synergistic improvement (ΔVonset = +200 mV) as compared to a solution of [(PNP)2Ni](2+) in contact with a p-Si(111)-CH3 photoelectrode.

Molecular Catalyst Immobilized Photocathodes for Water/Proton and Carbon Dioxide Reduction

“…[55] The immobilization of the catalysto nt he p-type silicon surface was straightforward, as shown in Scheme 8. [55] The immobilization of the catalysto nt he p-type silicon surface was straightforward, as shown in Scheme 8.…”

“…Other semiconductors, such as galliump hosphide (GaP) and nitrogen-doped tantalum pentoxide (N-Ta 2 O 5 ), have also been utilized to cooperate with polymerized Ru complexes, and they also show CO 2 reduction reactivity. [55]with permission from The Royal SocietyofC hemistry. [66] In 2013, Arai and co-workersr eportedacompleteP EC deviceb yu sing SrTiO 3 (STO) as ap hotoanode to performt he light-driven oxidation of water and adopted InP/MCPa saphotocathode to perform the light-driven reduction of CO 2 to formate.…”

“…Comparison of Si-PNP 2 -Ni (c)a nd 2mm [Ni{PNP(C 6 H 4 )Br} 2 ](ClO 4 ) 2 solution on the Si(111)j CH 3 surface(a).Fc + /0 = ferrocenium/ferrocene.R eproduced from Ref [55]. with permission from The Royal Society of Chemistry.…”

Hybrid Photoelectrochemical Water Splitting Systems: From Interface Design to System Assembly

“…Recently, Rose and co‐workers devised a surface PNP linker, for surface binding to p‐Si with a nickel phosphine complex ( Figure 5 ). 28 The covalent link to the surface was verified by electrochemistry and X‐ray photoelectron spectroscopy where the onset potential for the Si‐PNP 2 ‐Ni photocathode was positively shifted by ≈200 mV compared to simple mixture of methyl‐modified p‐Si and the complex [Ni{PNP(C 6 H 4 )Br} 2 ] 2+ . Covalently linked Si‐PNP 2 ‐Ni showed excellent stability for PEC water reduction during PEC‐cyclic voltammetry measurements.…”

Electric and Photoelectric Properties of 3,4–Ethylenedioxythiophene‐Functionalized n‐Si/PEDOT:PSS Junctions

“…[23,51,52] Fast charget ransport has been observed for these surfaces with little to no loss of the attached species. Building off of the aromaticity in these groups,r edox speciess uch as vinylferrocene and electrocatalysts (such as anickel phosphine complexes) could be attached through Heck or Negishic oupling.…”