Polymeric coatings for applications in electrocatalytic and photoelectrosynthetic fuel production

Abstract

Polymeric coatings provide opportunities to control matter and energy in complex environments, including applications in artificial photosynthesis and solar fuels.

Stabilization of reactive Co 4 O 4 cubane oxygen-evolution catalysts within porous frameworks

“…Here, we report the greatly improved stability of a [Co 4 O 4 ] molecular cluster by covalent immobilization in a porous metal-organic framework. This strategy has allowed (i) significantly improved stability for a molecular OER catalyst (under practical, high pH conditions), and (ii) observation of a reactive, proposed (and otherwise unstable) intermediate in the OER mechanism (23)(24)(25)(26)(27)(28)(29)(30)(31). The organic linkers of these frameworks were optimized both for protection of the [Co 4 O 4 ] units from aggregation, and to provide electronic and structural tuning of reactivity (32)(33)(34).…”

Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation

“…Sustained heterogeneous electrocatalytic water oxidation by the electrode gave steady-state currents for at least ∼6 h with a Faradaic efficiency of ∼68% for O 2 production. electrocatalytic water oxidation | homogenous and heterogenous | silane surface functionalization | surface electropolymerization | grafting-through C atalytic water oxidation, 2H 2 O → 4H + + 4e -+ O 2 , plays a key role as the "other half-reaction" in artificial photosynthesis (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12). An important factor that hinders the reaction arises from the sluggish kinetics of 4H + /4e − loss and O-O bond formation (1-4, 8, 11, 13).…”

Molecular Cobalt Catalysts Grafted onto Polymers for Efficient Hydrogen Generation Cathodes

“…[ 12 ] Another peak with binding energies of ≈164.0 eV are observed for PTTB‐Cosalen, which corresponds to S 2p. The broad peaks at 168.0 eV is assigned to the shakeup satellites [6e] . The full XPS spectra of PTTB‐Cosalen samples are shown in Figure S4, Supporting Information.…”

“…Although the stability is not comparable with those reported in inorganic materials, [ 17 ] its activity is superior to most of other obtained molecular catalyst‐grafted electrodes ( Table 1 ). [5c,d,f,g,6b,18] …”

“…To this end, the immobilization of soft molecular catalysts on hard electrodes is gaining interest. [ 3 ] Although some versatile strategies have been reported for their immobilization onto metal oxide, [ 4 ] carbon‐based, [ 5 ] and conductive electrode [ 6 ] surfaces for applications in electro‐ and photoelectrocatalytic H 2 production, many systems are confined for implementation at scale due to being designed with synthetically challenging, including costly ligand manifolds (providing good stability and catalytic properties for catalysts), difficult linker design (considering their length, polarity, flexibility, conductivity, etc. ), and necessary anchor components.…”