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Energies 2020, 13, 420 29 of 96 The photocatalyst efficiency could be enhanced with the introduction of transition-metal cations Energies 2020, 13, x FOR PEER REVIEW 28 of 95 (W [340], Cr [341], Zr [342], Mn [343–345], Fe [346], Ni [341,347,348], Mo [340,349,350]) or anions (N [351], C [352], S [353,354], B [355]). Doping ions are functional in the modification of electronic and or anions (N [351], C [352], S [353,354], B [355]). Doping ions are functional in the modification of optical properties of semiconductors and improve photoelectrical conductivity and charge-carriers electronic and optical properties of semiconductors and improve photoelectrical conductivity and transport and separation [356]. However, high quantities of doping elements could act as recombination charge-carriers transport and separation [356]. However, high quantities of doping elements could centers for photo-generated charges that limit the photocatalytic activity [357]. Further, substituting Ti act as recombination centers for photo-generated charges that limit the photocatalytic activity [357]. sites of the TiO2 semiconductor, the conduction band of the photocatalyst could shift below the water Further, substituting Ti sites of the TiO2 semiconductor, the conduction band of the photocatalyst redox potential requiring an external bias for the water splitting [351]. could shift below the water redox potential requiring an external bias for the water splitting [351]. Plasmonic metallic nanostructures such as Au, Ag, Al and Cu actively interact with resonant Plasmonic metallic nanostructures such as Au, Ag, Al and Cu actively interact with resonant photons through the interaction of surface plasmon resonance (SPR) that is an oscillation of valence photons through the interaction of surface plasmon resonance (SPR) that is an oscillation of valence electrons due to resonant photons [358]. Plasmons are introduced in the photocatalyst to enhance electrons due to resonant photons [358]. Plasmons are introduced in the photocatalyst to enhance the the light-harvesting of photoelectrodes and the photocatalytic efficiency. Furthermore, plasmonic light-harvesting of photoelectrodes and the photocatalytic efficiency. Furthermore, plasmonic metal metal nanostructures ensure a good photostability in comparison with dye-sensitizers or quantum nanostructures ensure a good photostability in comparison with dye-sensitizers or quantum dots that dots that are usually subjected to photo-corrosion [359]. Strong light absorption, huge light scattering, are usually subjected to photo-corrosion [359]. Strong light absorption, huge light scattering, strong strong electromagnetic field, numerous hot carrier generation are the main properties of plasmons and electromagnetic field, numerous hot carrier generation are the main properties of plasmons and modify the physical and chemical characteristics of the semiconductor [360]. Light absorption and modify the physical and chemical characteristics of the semiconductor [360]. Light absorption and scattering are strongly dependent on the size and morphology of the nanoparticles improve the solar scattering are strongly dependent on the size and morphology of the nanoparticles improve the solar radiation harvesting, the electromagnetic field reduces the charge-carriers recombination, and the hot radiation harvesting, the electromagnetic field reduces the charge-carriers recombination, and the hot electron injection increases the photocatalytic efficiency [361]. electron injection increases the photocatalytic efficiency [361]. Dye-sensitized photocatalyst consists of dye molecules anchored to the wide bandgap photoelectrode. Dye-sensitized photocatalyst consists of dye molecules anchored to the wide bandgap Photosensitizer should be characterized by efficient light absorption in a wide solar spectrum and photoelectrode. Photosensitizer should be characterized by efficient light absorption in a wide solar anchoring groups for the linkages to the semiconductor [362]. The solar irradiation of dye molecules spectrum and anchoring groups for the linkages to the semiconductor [362]. The solar irradiation of induces the injection of an excited electron in the lowest unoccupied molecular orbital (LUMO) level dye molecules induces the injection of an excited electron in the lowest unoccupied molecular orbital of the photosensitizer into the conduction band of the photoelectrode [363]. The photosensitizer is (LUMO) level of the photosensitizer into the conduction band of the photoelectrode [363]. The coupled with a water oxidation catalyst (WOC) that oxidize and regenerate the oxidized dye (see photosensitizer is coupled with a water oxidation catalyst (WOC) that oxidize and regenerate the Figure 13) [364]. The interface between semiconductor and dye molecules ensures the charge-carriers oxidized dye (see Figure 13) [364]. The interface between semiconductor and dye molecules ensures separation [365]. The most studied photosensitizers are based on ruthenium polypyridine [366,367] or the charge-carriers separation [365]. The most studied photosensitizers are based on ruthenium porphyrin [365,368]. polypyridine [366,367] or porphyrin [365,368]. Figure 13. Energy scheme of a dye-sensitized photoelectrochemical cell (DS-PEC). Reproduced with Figure 13. Energy scheme of a dye-sensitized photoelectrochemical cell (DS-PEC). Reproduced with permission from [362]. permission from [362]. Cocatalyst deeppoossititioionnisisa faeafseiabsliebmleetmhoetdhtodentohaenncheatnhceeeftfhiceieenfficyciaendcythaenpdhotthoecaptahloytoicatcatilvyittiyc a[3c6ti9v]i.tyC[o3c6a9t]a.lyCsotscarteadlyusctes rtehdeuocveetrhpeootevnertipaoltreenqtuiailreremqeunirte,mthenet,lethcteroelne–chtrolne–phaoilrespraeicrosmrebcionmatbioinatainond athnedptheoptoh-octoor-rcosrironsiwonhiwlehinlecirnecarseinasginthgethkeinkeintiectsicosfothftehreeraecatciotino,nt,htehelilgighhttaabbssoorrpptitoionnandthenumber of active sites [370]. Cocatalysts are employed both for the hydrogen evolution reaction (HER) and the oxygen evolutiionrreaccttiion((OEERR))[3[37711].].NNobolbelme meteatla(le.(ge.,gP.,tP[3t7[23]7)2c]o) caotcaalytasltyasrteauresuaslulyalulyseudsfeodr HER and noble metal oxides (e.g., IrO2 [373,374], RuO2 [374,375]) are used for water oxidation reactions [376]. However, due to the high cost and rarity of noble metals, researchers focus on noble metal-free cocatalyst, including cobalt [370,377–379] and nickel-based compounds [380–384].PDF Image | Green Synthetic Fuels
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