Challenges and prospects of plasmonic metasurfaces for photothermal catalysis

Abstract Solar-thermal technologies for converting chemicals using thermochemistry require extreme light concentration. Exploiting plasmonic nanostructures can dramatically increase the reaction rates by providing more efficient solar-to-heat conversion by broadband light absorption. Moreover, hot-carrier and local field enhancement effects can alter the reaction pathways. Such discoveries have boosted the field of photothermal catalysis, which aims at driving industrially-relevant chemical reactions using solar illumination rather than conventional heat sources. Nevertheless, only large arrays of plasmonic nano-units on a substrate, i.e., plasmonic metasurfaces, allow a quasi-unitary and broadband solar light absorption within a limited thickness (hundreds of nanometers) for practical applications. Through moderate light concentration (∼10 Suns), metasurfaces reach the same temperatures as conventional thermochemical reactors, or plasmonic nanoparticle bed reactors reach under ∼100 Suns. Plasmonic metasurfaces, however, have been mostly neglected so far for applications in the field of photothermal catalysis. In this Perspective, we discuss the potentialities of plasmonic metasurfaces in this emerging area of research. We present numerical simulations and experimental case studies illustrating how broadband absorption can be achieved within a limited thickness of these nanostructured materials. The approach highlights the synergy among different enhancement effects related to the ordered array of plasmonic units and the efficient heat transfer promoting faster dynamics than thicker structures (such as powdered catalysts). We foresee that plasmonic metasurfaces can play an important role in developing modular-like structures for the conversion of chemical feedstock into fuels without requiring extreme light concentrations. Customized metasurface-based systems could lead to small-scale and low-cost decentralized reactors instead of large-scale, infrastructure-intensive power plants

Band gap and morphology engineering of hematite nanoflakes from an ex situ Sn doping for enhanced photoelectrochemical water splitting

In this article, we report a simple ex situ Sn-doping method on hematite nanoflakes (coded as MSnO2-H) that can protect the nanoflake (NF) morphology against the 800 degrees C high-temperature annealing process and activate the photoresponse of hematite until 800 nm wavelength excitation. MSnO2-H has been fabricated by dropping SnCl4 ethanol solution on hematite nanoflakes homogeneously grown over the conductive FTO glass substrate and annealed at 500 degrees C to synthesize the SnO2 nanoparticles on hematite NFs. The Sn-treated samples were then placed in a furnace again, and the sintering process was conducted at 800 degrees C for 15 min. During this step, structure deformation of hematite occurs normally due to the grain boundary motion and oriented attachment. However, in the case of MSnO2-H, the outer SnO2 nanoparticles efficiently prevented a shape deformation and maintained the nanoflake shape owing to the encapsulation of hematite NFs. Furthermore, the interface of hematite/SnO2 nanoparticles became the spots for a heavy Sn ion doping. We demonstrated the generation of the newly localized states, resulting in an extension of the photoresponse of hematite until 800 nm wavelength light irradiation. Furthermore, we demonstrated that SnO2 nanoparticles can effectively act as a passivation layer, which can reduce the onset potential of hematite for water splitting redox reactions. The optimized MSnO2-H nanostructures showed a 2.84 times higher photocurrent density and 300 mV reduced onset potential compared with a pristine hematite nanoflake photoanode.Web of Scienc

Surface enamel remineralization: biomimetic apatite nanocrystals and fluoride ions different effects

A new method for altered enamel surface remineralization has been proposed. To this aim carbonate-hydroxyapatite nanocrystals which mimic for composition, structure, nanodimensions, and morphology dentine apatite crystals and resemble closely natural apatite chemical-physical properties have been used. The results underline the differences induced by the use of fluoride ions and hydroxyapatite nanocrystals in contrasting the mechanical abrasions and acid attacks to which tooth enamel is exposed. Fluoride ions generate a surface modification of the natural enamel apatite crystals increasing their crystallinity degree and relative mechanical and acid resistance. On the other hand, the remineralization produced by carbonate-hydroxyapatite consists in a deposition of a new apatitic mineral into the eroded enamel surface scratches. A new biomimetic mineral coating, which progressively fills and shadows surface scratches, covers and safeguards the enamel structure by contrasting the acid and bacteria attacks

Nanoporous Titanium Oxynitride Nanotube Metamaterials with Deep Subwavelength Heat Dissipation for Perfect Solar Absorption

We report a quasi-unitary broadband absorption over the ultraviolet-visible-near-infrared range in spaced high aspect ratio, nanoporous titanium oxynitride nanotubes, an ideal platform for several photothermal applications. We explain such an efficient light-heat conversion in terms of localized field distribution and heat dissipation within the nanopores, whose sparsity can be controlled during fabrication. The extremely large heat dissipation could not be explained in terms of effective medium theories, which are typically used to describe small geometrical features associated with relatively large optical structures. A fabrication-process-inspired numerical model was developed to describe a realistic space-dependent electric permittivity distribution within the nanotubes. The resulting abrupt optical discontinuities favor electromagnetic dissipation in the deep sub-wavelength domains generated and can explain the large broadband absorption measured in samples with different porosities. The potential application of porous titanium oxynitride nanotubes as solar absorbers was explored by photothermal experiments under moderately concentrated white light (1-12 Suns). These findings suggest potential interest in realizing solar-thermal devices based on such simple and scalable metamaterials

Photoelectrochemical abatement of arsenic in water by hematite photoelectrodes

Arsenic is considered as one of the major issues among drinkable water pollutants because of its widespread distribution and its low acceptable limits. The most widely used removal technology involves arsenic adsorption on iron oxides, but this process is more effective for As(V). Since in groundwater arsenic is usually present as As(III), a preliminary oxidation treatment is often required to get high abatement yields. Moreover, despite it is a cheap and effective technology, adsorption generates a contaminated bed that must be disposed as toxic waste or regenerated by expensive techniques. Aiming at solving such problems, we are developing an alternative process involving a one-pot photoelectrochemical in situ oxidation and adsorption. Hematite nanostructured photoelectrodes showed promising performances by achieving almost complete abatement of arsenic from aqueous solutions under simulated solar light irradiation, in the view of economic and environmental sustainable application

Magnetite-free Sn-doped hematite nanoflake layers for enhanced photoelectrochemical water splitting

In the present work, we report a preparation strategy for hematite phase-pure photoanodes consisting of Sn-doped hematite nanoflakes/hematite thin film bilayer nanostructure (Sn-HB). This approach is based on a two-step annealing process of pure iron films deposited on fluorine doped tin oxide (FTO) substrates by advanced magnetron sputtering. While the high density hematite ultrathin nanoflakes (HNs) with detrimental iron oxide layers (Fe3O4 and/or FeO) are generated during the first annealing step at 400 degrees C for two hours, the second thermal treatment at 800 degrees C for 15 minutes oxidises all the undesired iron oxide phases to a photoactive hematite layer as well as is providing efficient Sn doping of a drop-casted SnCl4 in order to increase the conductivity. The optimized Sn-HB shows an around 11 times higher photocurrent density (0.71 mA cm(-2) at 1.23 V-RHE) compared with a reference hematite photoanode produced from iron foil under the same conditions.Web of Science911art. no. E20220006

Nanoscale assembly of BiVO4/CdS/CoOx core-shell heterojunction for enhanced photoelectrochemical water splitting

Porous BiVO4 electrodes were conformally decorated with CdS via a chemical bath deposition process. The highest photocurrent at 1.1 V vs. RHE was achieved for a BiVO4/CdS composite (4.54 mA cm(-2)), compared with CdS (1.19 mA cm(-2)) and bare BiVO4 (2.1 mA cm(-2)), under AM 1.5G illumination. This improvement in the photoefficiency can be ascribed to both the enhanced optical absorption properties and the charge separation due to the heterojunction formation between BiVO4 and CdS. Furthermore, the BiVO4/CdS photoanode was protected with a CoOx layer to substantially increase the photostability of the material. The new BiVO4/CdS/CoOx nanostructure exhibited a highly stable photocurrent density of similar to 5 mA cm(-2). The capability to produce O-2 was locally investigated by scanning photoelectrochemical microscope, which showed a good agreement between photocurrent and O-2 reduction current maps. This work develops an efficient route to improve the photo-electrochemical performance of BiVO4 and its long-term stability.Web of Science116art. no. 68

Mineralisation of surfactants using ultrasound and the Advanced Fenton Process

The destruction of the surfactants, sodium dodecylbenzene sulfonate (DBS) and dodecyl pyridinium chloride (DPC), using an advanced oxidation process is described. The use of zero valent iron (ZVI) and hydrogen peroxide at pH = 2.5 (the advanced Fenton process), with and without, the application of 20 kHz ultrasound leads to extensive mineralisation of both materials as determined by total organic carbon (TOC)measurements. For DBS, merely stirring with ZVI and H2O2 at 20°C leads to a 51% decrease in TOC, but using 20 kHz ultrasound at 40°C, maintaining the pH at 2.5 throughout and adding extra amounts of ZVI and H2O2 during the degradation, then the extent of mineralisation of DBS is substantially increased to 93%. A similar result is seen for DPC where virtually no degradation occurs at 20°C, but if extra amounts of both ZVI and hydrogen peroxide are introduced during the reaction at 40°C and the pH is maintained at 2.5, then an 87% mineralisation of DPC is obtained. The slow latent remediation of both surfactants and the mechanism of degradation are also discussed