Single Atom Catalysts Based on Earth-Abundant Metals for Energy-Related Applications.

Anthropogenic activities related to population growth, economic development, technological advances, and changes in lifestyle and climate patterns result in a continuous increase in energy consumption. At the same time, the rare metal elements frequently deployed as catalysts in energy related processes are not only costly in view of their low natural abundance, but their availability is often further limited due to geopolitical reasons. Thus, electrochemical energy storage and conversion with earth-abundant metals, mainly in the form of single-atom catalysts (SACs), are highly relevant and timely technologies. In this review the application of earth-abundant SACs in electrochemical energy storage and electrocatalytic conversion of chemicals to fuels or products with high energy content is discussed. The oxygen reduction reaction is also appraised, which is primarily harnessed in fuel cell technologies and metal-air batteries. The coordination, active sites, and mechanistic aspects of transition metal SACs are analyzed for two-electron and four-electron reaction pathways. Further, the electrochemical water splitting with SACs toward green hydrogen fuel is discussed in terms of not only hydrogen evolution reaction but also oxygen evolution reaction. Similarly, the production of ammonia as a clean fuel via electrocatalytic nitrogen reduction reaction is portrayed, highlighting the potential of earth-abundant single metal species.

Mass Transport Limitations in Plasmonic Photocatalysis.

The interpretation of mechanisms governing hot carrier reactivity on metallic nanostructures is critical, yet elusive, for advancing plasmonic photocatalysis. In this work, we explored the influence of the diffusion of molecules on the hot carrier extraction rate at the solid-liquid interface, which is of fundamental interest for increasing the efficiency of photodevices. Through a spatially defined scanning photoelectrochemical microscopy investigation, we identified a diffusion-controlled regime hindering the plasmon-driven photochemical activity of metallic nanostructures. Using low-power monochromatic illumination (<2 W cm-2), we unveiled the hidden influence of mass transport on the quantum efficiency of plasmonic photocatalysts. The availability of molecules at the solid-liquid interface directly limits the extraction of hot holes, according to their nature and energy, at the reactive spots in Au nanoislands on an ultrathin TiO2 substrate. An intriguing question arises: does the mass transport enhancement caused by thermal effects unlock the reactivity of nonthermal carriers under steady state?

Plasmonic titanium nitride nanomaterials prepared by physical vapor deposition methods.

Titanium nitride (TiN) has recently emerged as an alternative to coinage metals to enable the development of integrated plasmonic devices at visible and medium-infrared wavelengths. In this regard, its optical performance can be conveniently tuned by tailoring the process parameters of physical vapor deposition methods, such as magnetron sputtering and pulsed laser deposition (PLD). This review first introduces the fundamental features of TiN and a description on its optical properties, including insights on the main experimental techniques to measure them. Afterwards, magnetron sputtering and PLD are selected as fabrication techniques for TiN nanomaterials. The fundamental mechanistic aspects of both techniques are discussed in parallel with selected case studies from the recent literature, which elucidate the critical advantages of such techniques to engineer the nanostructure and the plasmonic performance of TiN.

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.

Solar Thermoplasmonic Nanofurnace for High-Temperature Heterogeneous Catalysis.

Most of existing solar thermal technologies require highly concentrated solar power to operate in the temperature range 300-600 °C. Here, thin films of refractory plasmonic TiN cylindrical nanocavities manufactured via flexible and scalable process are presented. The fabricated TiN films show polarization-insensitive 95% broadband absorption in the visible and near-infrared spectral ranges and act as plasmonic "nanofurnaces" capable of reaching temperatures above 600 °C under moderately concentrated solar irradiation (∼20 Suns). The demonstrated structures can be used to control nanometer-scale chemistry with zeptoliter (10-21 L) volumetric precision, catalyzing C-C bond formation and melting inorganic deposits. Also shown is the possibility to perform solar thermal CO oxidation at rates of 16 mol h-1 m-2 and with a solar-to-heat thermoplasmonic efficiency of 63%. Access to scalable, cost-effective refractory plasmonic nanofurnaces opens the way to the development of modular solar thermal devices for sustainable catalytic processes.

Operando X-ray Absorption Spectroscopy (XAS) Observation of Photoinduced Oxidation in FeNi (Oxy)hydroxide Overlayers on Hematite (α-Fe2O3) Photoanodes for Solar Water Splitting.

An FeNi (oxy)hydroxide cocatalyst overlayer was photoelectrochemically deposited on a thin-film hematite (α-Fe2O3) photoanode, leading to a cathodic shift of ∼100 mV in the photocurrent onset potential. Operando X-ray absorption spectroscopy (XAS) at the Fe and Ni K-edges was used to study the changes in the overlayer with potential in the dark and under illumination conditions. Potential or illumination only had a minor effect on the Fe oxidation state, suggesting that Fe atoms do not accumulate significant amount of charge over the whole potential range. In contrast, the Ni K-edge spectra showed pronounced dependence on potential in the dark and under illumination. The effect of illumination is to shift the onset for the Ni oxidation because of the generated photovoltage and suggests that holes that are photogenerated in hematite are transferred mainly to the Ni atoms in the overlayer. The increase in the oxidation state of Ni proceeds at potentials corresponding to the redox wave of Ni, which occurs immediately prior to the onset of the oxygen evolution reaction (OER). Linear combination fitting analysis of the obtained spectra suggests that the overlayer does not have to be fully oxidized to promote oxygen evolution. Cathodic discharge measurements show that the photogenerated charge is stored almost exclusively in the Ni atoms within the volume of the overlayer.

Gap-plasmon enhanced water splitting with ultrathin hematite films: the role of plasmonic-based light trapping and hot electrons.

Hydrogen is a promising alternative renewable fuel for meeting the growing energy demands of the world. Over the past few decades, photoelectrochemical water splitting has been widely studied as a viable technology for the production of hydrogen utilizing solar energy. A solar-to-hydrogen (STH) efficiency of 10% is considered to be sufficient for practical applications. Amongst the wide class of semiconductors that have been studied for their application in solar water splitting, iron oxide (α-Fe2O3), or hematite, is one of the more promising candidate materials, with a theoretical STH efficiency of 15%. In this work, we show experimentally that by utilizing gold nanostructures that support gap-plasmon resonances together with a hematite layer, we can increase the water oxidation photocurrent by two times over that demonstrated by a bare hematite film at wavelengths above the hematite bandgap. Moreover, we achieve a six-fold increase in the oxidation photocurrent at near-infrared wavelengths, which is attributed to hot electron generation and decay in the gap-plasmon nanostructures. Theoretical simulations confirmed that the metamaterial geometry with gap plasmons that was used allows us to confine electromagnetic fields inside the hematite semiconductor and to enhance the surface photochemistry.

Sb-Doped SnO2 Nanorods Underlayer Effect to the α-Fe2 O3 Nanorods Sheathed with TiO2 for Enhanced Photoelectrochemical Water Splitting.

Here, a Sb-doped SnO2 (ATO) nanorod underneath an α-Fe2 O3 nanorod sheathed with TiO2 for photoelectrochemical (PEC) water splitting is reported. The experimental results, corroborated with theoretical analysis, demonstrate that the ATO nanorod underlayer effect on the α-Fe2 O3 nanorod sheathed with TiO2 enhances the PEC water splitting performance. The growth of the well-defined ATO nanorods is reported as a conductive underlayer to improve α-Fe2 O3 PEC water oxidation performance. The α-Fe2 O3 nanorods grown on the ATO nanorods exhibit improved performance for PEC water oxidation compared to α-Fe2 O3 grown on flat fluorine-doped tin oxide glass. Furthermore, a simple and facile TiCl4 chemical treatment further introduces TiO2 passivation layer formation on the α-Fe2 O3 to reduce surface recombination. As a result, these unique nanostructures show dramatically improved photocurrent density (139% higher than that of the pure hematite nanorods).

Observation of charge transfer cascades in α-Fe2O3/IrOx photoanodes by operando X-ray absorption spectroscopy.

Electrochemical devices for energy conversion and storage are central for a sustainable economy. The performance of electrodes is driven by charge transfer across different layer materials and an understanding of the mechanistics is pivotal to gain improved efficiency. Here, we directly observe the transfer of photogenerated charge carriers in a photoanode made of hematite (α-Fe2O3) and a hydrous iridium oxide (IrOx) overlayer, which plays a key role in photoelectrochemical water oxidation. Through the use of operando X-ray absorption spectroscopy (XAS), we probe the change in occupancy of the Ir 5d levels during optical band gap excitation of α-Fe2O3. At potentials where no photocurrent is observed, electrons flow from the α-Fe2O3 photoanode to the IrOx overlayer. In contrast, when the composite electrode produces a sustained photocurrent (i.e., 1.4 V vs. RHE), a significant transfer of holes from the illuminated α-Fe2O3 to the IrOx layer is clearly demonstrated. The analysis of the operando XAS spectra further suggests that oxygen evolution actually occurs both at the α-Fe2O3/electrolyte and α-Fe2O3/IrOx interfaces. These findings represent an important outcome for a better understanding of composite photoelectrodes and their use in photoelectrochemical systems, such as hydrogen generation or CO2 reduction from sunlight.

3D-printed photo-spectroelectrochemical devices for in situ and in operando X-ray absorption spectroscopy investigation.

Three-dimensional printed multi-purpose electrochemical devices for X-ray absorption spectroscopy are presented in this paper. The aim of this work is to show how three-dimensional printing can be a strategy for the creation of electrochemical cells for in situ and in operando experiments by means of synchrotron radiation. As a case study, the description of two cells which have been employed in experiments on photoanodes for photoelectrochemical water splitting are presented. The main advantages of these electrochemical devices are associated with their compactness and with the precision of the three-dimensional printing systems which allows details to be obtained that would otherwise be difficult. Thanks to these systems it was possible to combine synchrotron-based methods with complementary techniques in order to study the mechanism of the photoelectrocatalytic process.

The critical role of intragap states in the energy transfer from gold nanoparticles to TiO2.

Cathodoluminescence spectroscopy is profitably exploited to study energy transfer mechanisms in Au and Pt/black TiO2 heterostructures. While Pt nanoparticles absorb light in the UV region, Au nanoparticles absorb light by surface plasmon resonance and interband transitions, both of them occurring in the visible region. The intra-bandgap states (oxygen vacancies) of black TiO2 play a key role in promoting both hot electron transfer and plasmonic resonant energy transfer from Au nanoparticles to the TiO2 semiconductor with a consequent photocatalytic H2 production increase. An innovative criterion is introduced for the design of plasmonic composites with increased efficiency under visible light.

Probing long-lived plasmonic-generated charges in TiO2 /Au by high-resolution X-ray absorption spectroscopy.

Exploiting plasmonic Au nanoparticles to sensitize TiO2 to visible light is a widely employed route to produce efficient photocatalysts. However, a description of the atomic and electronic structure of the semiconductor sites in which charges are injected is still not available. Such a description is of great importance in understanding the underlying physical mechanisms and to improve the design of catalysts with enhanced photoactivity. We investigated changes in the local electronic structure of Ti in pure and N-doped nanostructured TiO2 loaded with Au nanoparticles during continuous selective excitation of the Au localized surface plasmon resonance with X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). Spectral variations strongly support the presence of long-lived charges localized on Ti states at the semiconductor surface, giving rise to new laser-induced low-coordinated Ti sites.

Correction to "Band Gap and Morphology Engineering of Hematite Nanoflakes from an Ex Situ Sn Doping for Enhanced Photoelectrochemical Water Splitting".

[This corrects the article DOI: 10.1021/acsomega.2c04028.].

Charge carrier recombination processes, intragap defect states, and photoluminescence mechanisms in stoichiometric and reduced TiO2 brookite nanorods: an interpretation scheme through in situ photoluminescence excitation spectroscopy in controlled environment.

The study of titanium dioxide (TiO2) in the brookite phase is gaining popularity as evidence has shown the efficient photocatalytic performance of this less investigated polymorph. It has been recently reported that defective anisotropic brookite TiO2 nanorods display remarkable substrate-specific reactivity towards alcohol photoreforming, with rates of hydrogen production significantly (18-fold) higher than those exhibited by anatase TiO2 nanoparticles. To elucidate the basic photo-physical mechanisms and peculiarities leading to such an improvement in the photoactive efficiency, we investigated the recombination processes of photoexcited charge carriers in both stoichiometric and reduced brookite nanorods via photoluminescence excitation spectroscopy in controlled environment. Through an investigation procedure employing both supragap and subgap excitation during successive exposure to oxidizing and reducing gaseous agents, we firstly obtained an interpretation scheme describing the main photoluminescence and charge recombination pathways in stoichiometric and reduced brookite, which includes information about the spatial and energetic position of the intragap states involved in photoluminescence mechanisms, and secondly identified a specific photoluminescence enhancement process occurring in only reduced brookite nanorods, which indicates the injection of a conduction band electron during ethanol photo-oxidation. The latter finding may shed light on the empirical evidence about the exceptional reactivity of reduced brookite nanorods toward the photo-oxidation of alcohols and the concomitant efficiency of photocatalytic hydrogen generation.

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.

Thermoplasmonic In Situ Fabrication of Nanohybrid Electrocatalysts over Gas Diffusion Electrodes for Enhanced H2O2 Electrosynthesis.

Large-scale development of electrochemical cells is currently hindered by the lack of Earth-abundant electrocatalysts with high catalytic activity, product selectivity, and interfacial mass transfer. Herein, we developed an electrocatalyst fabrication approach which responds to these requirements by irradiating plasmonic titanium nitride (TiN) nanocubes self-assembled on a carbon gas diffusion layer in the presence of polymeric binders. The localized heating produced upon illumination creates unique conditions for the formation of TiN/F-doped carbon hybrids that show up to nearly 20 times the activity of the pristine electrodes. In alkaline conditions, they exhibit enhanced stability, a maximum H2O2 selectivity of 90%, and achieve a H2O2 productivity of 207 mmol gTiN-1 h-1 at 0.2 V vs RHE. A detailed electrochemical investigation with different electrode arrangements demonstrated the key role of nanocomposite formation to achieve high currents. In particular, an increased TiOxNy surface content promoted a higher H2O2 selectivity, and fluorinated nanocarbons imparted good stability to the electrodes due to their superhydrophobic properties.

Ultrasound-Driven Defect Engineering in TiO2-x Nanotubes─Toward Highly Efficient Platinum Single Atom-Enhanced Photocatalytic Water Splitting.

Single-atom catalysts (SACs) have demonstrated superior catalytic activity and selectivity compared to nanoparticle catalysts due to their high reactivity and atom efficiency. However, stabilizing SACs within hosting substrates and their controllable loading preventing single atom clustering remain the key challenges in this field. Moreover, the direct comparison of (co-) catalytic effect of single atoms vs nanoparticles is still highly challenging. Here, we present a novel ultrasound-driven strategy for stabilizing Pt single-atomic sites over highly ordered TiO2 nanotubes. This controllable low-temperature defect engineering enables entrapment of platinum single atoms and controlling their content through the reaction time of consequent chemical impregnation. The novel methodology enables achieving nearly 50 times higher normalized hydrogen evolution compared to pristine titania nanotubes. Moreover, the developed procedure allows the decoration of titania also with ultrasmall nanoparticles through a longer impregnation time of the substrate in a very dilute hexachloroplatinic acid solution. The comparison shows a 10 times higher normalized hydrogen production of platinum single atoms compared to nanoparticles. The mechanistic study shows that the novel approach creates homogeneously distributed defects, such as oxygen vacancies and Ti3+ species, which effectively trap and stabilize Pt2+ and Pt4+ single atoms. The optimized platinum single-atom photocatalyst shows excellent performance of photocatalytic water splitting and hydrogen evolution under one sun solar-simulated light, with TOF values being one order of magnitude higher compared to those of traditional thermal reduction-based methods. The single-atom engineering based on the creation of ultrasound-triggered chemical traps provides a pathway for controllable assembling stable and highly active single-atomic site catalysts on metal oxide support layers.

Designing Metasurfaces for Efficient Solar Energy Conversion.

Metasurfaces have recently emerged as a promising technological platform, offering unprecedented control over light by structuring materials at the nanoscale using two-dimensional arrays of subwavelength nanoresonators. These metasurfaces possess exceptional optical properties, enabling a wide variety of applications in imaging, sensing, telecommunication, and energy-related fields. One significant advantage of metasurfaces lies in their ability to manipulate the optical spectrum by precisely engineering the geometry and material composition of the nanoresonators' array. Consequently, they hold tremendous potential for efficient solar light harvesting and conversion. In this Review, we delve into the current state-of-the-art in solar energy conversion devices based on metasurfaces. First, we provide an overview of the fundamental processes involved in solar energy conversion, alongside an introduction to the primary classes of metasurfaces, namely, plasmonic and dielectric metasurfaces. Subsequently, we explore the numerical tools used that guide the design of metasurfaces, focusing particularly on inverse design methods that facilitate an optimized optical response. To showcase the practical applications of metasurfaces, we present selected examples across various domains such as photovoltaics, photoelectrochemistry, photocatalysis, solar-thermal and photothermal routes, and radiative cooling. These examples highlight the ways in which metasurfaces can be leveraged to harness solar energy effectively. By tailoring the optical properties of metasurfaces, significant advancements can be expected in solar energy harvesting technologies, offering new practical solutions to support an emerging sustainable society.

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.