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

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

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

Hematene: A sustainable 2D conductive platform for visible-light-driven photocatalytic ammonia decomposition

The emerging class of 2D non-van der Waals (n-vdW) materials, including 2D iron oxides, possesses unique properties and high applicability, making them attractive for various technological applications. However, the synthesis of these materials through a scalable and eco-friendly method remains a challenge, as most known chemical exfoliation processes require toxic organic solvents. In this study, we report a green synthesis of 2D hematene (α-Fe2O3) using an ultrasound-supported exfoliation method of earth-abundant iron oxide ore in a pure aqueous solution. The resulting hematene sheets, only a few nanometers thick, exhibit superior electrochemical performance in terms of charge transfer processes, making them ideal for photocatalytic applications. By doping a conductive hematene substrate with ruthenium, we demonstrate a synergistic effect for generating electrons and holes under visible light irradiation. Using this approach, we successfully decomposed ammonia into hydrogen and nitrogen, highlighting the potential of this novel class of environmentally-friendly photocatalysts for clean energy production. Overall, our water-assisted scalable synthesis of hematene offers a promising strategy for producing efficient and sustainable photocatalysts.Web of Science34art. no. 10188

Graphene-based metal-organic framework hybrids for applications in catalysis, environmental, and energy technologies

Current energy and environmental challenges demand the development and design of multifunctional porous materials with tunable properties for catalysis, water purification, and energy conversion and storage. Because of their amenability to de novo reticular chemistry, metal-organic frameworks (MOFs) have become key materials in this area. However, their usefulness is often limited by low chemical stability, conductivity and inappropriate pore sizes. Conductive two-dimensional (2D) materials with robust structural skeletons and/or functionalized surfaces can form stabilizing interactions with MOF components, enabling the fabrication of MOF nanocomposites with tunable pore characteristics. Graphene and its functional derivatives are the largest class of 2D materials and possess remarkable compositional versatility, structural diversity, and controllable surface chemistry. Here, we critically review current knowledge concerning the growth, structure, and properties of graphene derivatives, MOFs, and their graphene@MOF composites as well as the associated structure- property-performance relationships. Synthetic strategies for preparing graphene@MOF composites and tuning their properties are also comprehensively reviewed together with their applications in gas storage/separation, water purification, catalysis (organo-, electro-, and photocatalysis), and electrochemical energy storage and conversion. Current challenges in the development of graphene@MOF hybrids and their practical applications are addressed, revealing areas for future investigation. We hope that this review will inspire further exploration of new graphene@MOF hybrids for energy, electronic, biomedical, and photocatalysis applications as well as studies on previously unreported properties of known hybrids to reveal potential "diamonds in the rough".Web of Science12224173381724

Magnetic polaron states in photoluminescent carbon dots enable hydrogen peroxide photoproduction

Photoactivation of aspartic acid-based carbon dots (Asp-CDs) induces the generation of spin-separated species, including electron/hole (e−/h+) polarons and spin-coupled triplet states, as uniquely confirmed by the light-induced electron paramagnetic resonance spectroscopy. The relative population of the e−/h+ pairs and triplet species depends on the solvent polarity, featuring a substantial stabilization of the triplet state in a non-polar environment (benzene). The electronic properties of the photoexcited Asp-CDs emerge from their spatial organization being interpreted as multi-layer assemblies containing a hydrophobic carbonaceous core and a hydrophilic oxygen and nitrogen functionalized surface. The system properties are dissected theoreti cally by density functional theory in combination with molecular dynamics simulations on quasi-spherical assemblies of size-variant flakelike model sys tems, revealing the importance of size dependence and interlayer effects. The formation of the spin-separated states in Asp-CDs enables the photoproduc tion of hydrogen peroxide (H2O2) from water and water/2-propanol mixture via a water oxidation reaction.Web of Science1932art. no. 220658

Nanostruktury a nanohybridy na bázi TiO2 a α-Fe2O3 pro fotokatalytické a fotoelektrochemické aplikace

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Interfacial states in Au/reduced TiO2 plasmonic photocatalysts quench hot-carrier photoactivity

Understanding the interface of plasmonic nanostructures is essential for improving the performance of photocatalysts. Surface defects in semiconductors modify the dynamics of charge carriers, which are not well understood yet. Here, we take advantage of scanning photoelectrochemical microscopy (SPECM) as a fast and effective tool for detecting the impact of surface defects on the photoactivity of plasmonic hybrid nanostructures. We evidenced a significant photoactivity activation of TiO2 ultrathin films under visible light upon mild reduction treatment. Through Au nanoparticle (NP) arrays deposited on different reduced TiO2 films, the plasmonic photoactivity mapping revealed the effect of interfacial defects on hot charge carriers, which quenched the plasmonic activity by (i) increasing the recombination rate between hot charge carriers and (ii) leaking electrons (injected and generated in TiO2) into the Au NPs. Our results show that the catalyst’s photoactivity depends on the concentration of surface defects and the population distribution of Au NPs. The present study unlocks the fast and simple detection of the surface engineering effect on the photocatalytic activity of plasmonic semiconductor systems.Web of Science12732158701586

Determining the role of Pd catalyst morphology and deposition criteria over large area plasmonic metasurfaces during light-enhanced electrochemical oxidation of formic acid

The use of metal composites based on plasmonic nanostructures partnered with catalytic counterparts has recently emerged as a promising approach in the field of plasmon-enhanced electrocatalysis. Here, we report on the role of the surface morphology, size, and anchored site of Pd catalysts coupled to plasmonic metasurfaces formed by periodic arrays of multimetallic Ni/Au nanopillars for formic acid electro-oxidation reaction (FAOR). We compare the activity of two kinds of metasurfaces differing in the positioning of the catalytic Pd nanoparticles. In the first case, the Pd nanoparticles have a polyhedron crystal morphology with exposed (200) facets and were deposited over the Ni/Au metasurfaces in a site-selective fashion by limiting their growth at the electromagnetic hot spots (Ni/Au-Pd@W). In contrast, the second case consists of spherical Pd nanoparticles grown in solution, which are homogeneously deposited onto the Ni/Au metasurface (Ni/Au-Pd@M). Ni/Au-Pd@W catalytic metasurfaces demonstrated higher light-enhanced FAOR activity (61%) in comparison to the Ni/Au-Pd@M sample (42%) for the direct dehydrogenation pathway. Moreover, the site-selective Pd deposition promotes the growth of nanoparticles favoring a more selective catalytic behavior and a lower degree of CO poisoning on Pd surface. The use of cyclic voltammetry, energy-resolved incident photon to current conversion efficiency, open circuit potential, and electrochemical impedance spectroscopy highlights the role of plasmonic near fields and hot holes in driving the catalytic enhancement under light conditions.Web of Science15711art. no. 11470