Surfaces — Open Access Journal

The challenges of diazonium salts stabilization have been overcome by their isolation as metal salts such as tetrachloroaurate(III). The cleavage of molecular nitrogen from diazonium salts even at very low potential or on reducing surfaces by fine tuning the substituents on the phenyl ring expanded their applications as surface modifiers in forensic science, nanomedicine engineering, catalysis and energy. The robustness of the metal–carbon bonding produced from diazonium salts reduction has already opened an era for further applications. The integration of experimental and calculations in this field catalyzed its speedy progress. This review provides a narrative of the progress in this chemistry with stress on our recent contribution, identifies potential applications, and highlights the needs in this emerging field. For these reasons, we hope that this review paper serves as motivation for others to enter this developing field of surface modification originating from diazonium salts. Full article

Porous crystalline Ni-doped TiO₂ films were produced using DC plasma electrolytic oxidation in refrigerated H₂SO₄ aqueous solutions containing NiSO₄. The crystalline phase structure consisted of a mixture of anatase and rutile, ranging from ~30 to ~80 wt % rutile. The oxide films obtained at low NiSO₄ concentration showed the highest photocurrent values under monochromatic irradiation in the UV-vis range, outperforming pure TiO₂. By increasing NiSO₄ concentration above a threshold value, the photoelectrochemical activity of the films decreased below that of undoped TiO₂. Similar results were obtained using cyclic voltammetry upon polychromatic UV-vis irradiation. Glow discharge optical emission spectrometry (GD-OES) analysis evidenced a sulfur signal peaking at the TiO₂/Ti interface. XPS spectra revealed that oxidized Ni²⁺, S⁴⁺ and S⁶⁺ ions were included in the oxide films. In agreement with photocurrent measurements, photoluminescence (PL) spectra confirmed that less intense PL emission, i.e., a lower electron-hole recombination rate, was observed for Ni-doped samples, though overdoping was detrimental. Full article

Among the novel class of mono-elemental two-dimensional (2D) materials, termed Xenes, phosphorene is emerging as a great promise for its peculiar chemical and physical properties. This review collects a selection of the recent breakthroughs that are related to the application of phosphorene in catalysis and electrocatalysis. Noteworthy, thanks to its intrinsic Lewis basic character, pristine phosphorene turned out to be more efficient and more selective than other non-metal catalysts, in chemical processes as the electroreduction of nitrogen to ammonia or the alkylation of nucleophiles with esters. Once functionalized with transition metals nanoparticles (Co, Ni, Pd, Pt, Ag, Au), its catalytic activity has been evaluated in several processes, mainly hydrogen and oxygen evolution reactions. Under visible light irradiation, it has shown a great improvement of the activity, demonstrating high potential as a photocatalyst. Full article

Here we describe a simple and straightforward synthesis of different multifunctional magnetic nanoparticles by using surface bound thiol-groups as transfer agents in a free radical polymerization process. The modification includes a first step of surface silanization with (3-mercaptopropyl)trimethoxysilane to obtain thiol-modified nanoparticles, which are further used as a platform for modification with a broad variety of polymers. The silanization was optimized in terms of shell thickness and particle size distribution, and the obtained materials were investigated by dynamic light scattering (DLS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). Subsequently, the free radical polymerization of different monomers (tert-butyl acrylate (tBA), methyl methacrylate (MMA), styrene, 2-vinyl pyridine (2VP), and N-isopropylacrylamide (NIPAAm)) was examined in the presence of the thiol-modified nanoparticles. During the process, a covalently anchored polymeric shell was formed and the resulting core–shell hybrid materials were analyzed in terms of size (DLS, TEM), shell thickness (TGA, TEM), and the presence of functional groups (attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FT-IR)). Hereby, the shell leads to a different solution behavior of the particles and in some cases an increased stability towards acids. Moreover, we examined the influence of the nanoparticle concentration during polymerization and we found a significant influence on dispersity of the resulting polymers. Finally, we compared the characteristics of the surface bound polymer and polymer formed in solution for the case of polystyrene. The herein presented approach provides straightforward access to a wide range of core–shell nanocomposites. Full article

A series of WO₃, BiVO₄ and WO₃/BiVO₄ heterojunction coatings were deposited on fluorine-doped tin oxide (FTO), by means of reactive radio frequency (RF) plasma (co)sputtering, and tested as photoanodes for water splitting under simulated AM 1.5 G solar light in a three-electrode photoelectrochemical (PEC) cell in a 0.5 M NaSO₄ electrolyte solution. The PEC performance and time stability of the heterojunction increases with an increase of the WO₃ innermost layer up to 1000 nm. A two-step calcination treatment (600 °C after WO₃ deposition followed by 400 °C after BiVO₄ deposition) led to a most performing photoanode under back-side irradiation, generating a photocurrent density of 1.7 mA cm⁻² at 1.4 V vs. SCE (i.e., two-fold and five-fold higher than that generated by individual WO₃ and BiVO₄ photoanodes, respectively). The incident photon to current efficiency (IPCE) measurements reveal the presence of two activity regions over the heterojunction with respect to WO₃ alone: The PEC efficiency increases due to improved charge carrier separation above 450 nm (i.e., below the WO₃ excitation energy), while it decreases below 450 nm (i.e., when both semiconductors are excited) due to electron–hole recombination at the interface of the two semiconductors. Full article

The effects induced by post-synthesis hydrogenation on ZnFe₂O₄ flat films in terms of photoelectrochemical (PEC) performance of photoanodes for water oxidation have been deeply investigated as a function of the pre-annealing temperature of the materials. The structure and morphology of the films greatly affect the efficacy of the post synthesis treatment. In fact, highly compact films are obtained upon pre-annealing at high temperatures, and this limits the exposure of the material bulk to the reductive H₂ atmosphere, making the treatment largely ineffective. On the other hand, a mild hydrogen treatment greatly enhances the separation of photoproduced charges in films pre-annealed at lower temperatures, as a result of the introduction of oxygen vacancies with n-type character. A comparison between present results and those obtained with ZnFe₂O₄ nanorods clearly demonstrates that specific structural and/or surface properties, together with the initial film morphology, differently affect the overall contribution of post-synthesis hydrogenation on the efficiency of zinc ferrite-based photoanodes. Full article

Surface chemistry plays a major role in photocatalytic and photoelectrochemical processes taking place with the participation of TiO₂. The synthesis methods, surface characterizations, theoretical research methods, and hardware over the last decade generated opportunities for progress in the surface science of this photocatalyst. Very recently, attention was paid to the design of photocatalysts at the nanoscale level by adjusting the types of exposed surfaces and their ratio, the composition and the surface structure of nanoparticles, and that of individual surfaces. The current theoretical methods provide highly detailed designs that can be embodied experimentally. The present review article describes the progress in the surface science of TiO₂ and TiO₂-based photocatalysts obtained over the last three years. Such aspects including the properties of macro- and nano-scale surfaces, noble-metal-loaded surfaces, doping with Mg and S, intrinsic defects (oxygen vacancies), adsorption, and photoreactions are considered. The main focus of the article is on the anatase phase of TiO₂. Full article

Concerning diamond-based electronic devices, the H-terminated diamond surface is one of the most used terminations as it can be obtained directly by using H₂ plasma, which also is a key step for diamond growth by chemical vapour deposition (CVD). The resultant surfaces present a p-type surface conductive layer with interest in power electronic applications. However, the mechanism for this behavior is still under discussion. Upward band bending due to surface transfer doping is the most accepted model, but has not been experimentally probed as of yet. Recently, a downward band bending very near the surface due to shallow acceptors has been proposed to coexist with surface transfer doping, explaining most of the observed phenomena. In this work, a new approach to the measurement of band bending by angle-resolved X-ray photoelectron spectroscopy (ARXPS) is proposed. Based on this new interpretation, a downward band bending of 0.67 eV extended over 0.5 nm was evidenced on a (100) H-terminated diamond surface. Full article

Macroporous TiO₂ monolith was prepared by a microphase separation method. After citric acid was added to the synthesis procedure, the yield of the titanium precursor has been significantly increased, and the stability of macroporous structure can be obviously enhanced. Anatase and rutile phase of TiO₂ were obtained after a 550 °C and 800 °C calcination, respectively. Full article

A quantum nutcracker, a recently proposed catalytic system for hydrogen dissociation, consists of two inert components: an organic molecule such as a transition metal phthalocyanine and an inert surface such as Cu or Au. The reaction takes place at the interface between the two components, which are weakly bonded by Van der Waals (VdW) forces. Here, we explore a method used to tune the reaction barrier in a quantum nutcracker system for hydrogen dissociation. By employing density-functional-theory calculations, we find that the H₂ entry barrier, which is the rate-limiting barrier, is reduced by replacing the phthalocyanine by porphyrin derivatives such as octaethylporphyrin (OEP) and tetraphenylporphyrin (TPP). The system remains active if a dissociated H atom is adsorbed on the transition metal ion. Metallic two-dimensional materials such as NbS₂ and CoS₂ are good candidates for the quantum nutcracker. The present design of a quantum nutcracker for hydrogen dissociation provides new opportunities with which to induce catalytic activity in VdW-bonded systems. Full article

Two-dimensional (2D) materials attracted widespread interest as unique and novel properties different from their bulk crystals, providing great potential for semiconductor devices and applications. Recently, the family of 2D materials has been expanded including but not limited to graphene, hexagonal boron nitride (h-BN), transition metal carbides (TMCs), and transition metal dichalcogenides (TMDCs). Metal-catalyzed chemical vapor deposition (CVD) is an effective method to achieve precise synthesis of these 2D materials. In this review, we focus on designing various binary alloys to realize controllable synthesis of multiple CVD-grown 2D materials and their heterostructures for both fundamental research and practical applications. Further investigations indicated that the design of the catalytic substrate is an important issue, which determines the morphology, domain size, thickness and quality of 2D materials and their heterostructures. Full article

In the present study, we use commercial digitally printed ceramic tiles, functionnalized by AgNPs doped micro–TiO₂, to investigate the mechanism of Ag in the continouos photocatalytic antibacterial activity. The novelty of the research lies in the attempt to understand the mechanism of Ag, supported on TiO₂, able to exhibit the same antibacterial activity of a standard system containing Ag species, but here, totally embedded on the tile surface, and thus not free to move and damage the bacteria cell. UV/vis diffuse reflectance spectroscopy (DRS) of AgNPs–TiO₂ tiles indicated an enhanced visible light response, wherein a new absorption band was produced around 18,000–20,000 cm⁻¹ (i.e., in the 400–600 nm range) owing to the surface plasmon resonance (SPR) of AgNPs. The antibacterial photocatalytic experiments were conducted towards the inactivation of E. coli under solar light and indoor light. It was found that the degradation speed of E. coli in the presence of AgNPs–TiO₂ tiles is solar light-intensity depending. This justifies the semiconductor behavior of the material. Furthermore, the AgNPs–TiO₂ tiles exhibit a high ability for the inactivation of E. coli at a high load (10⁴–10⁷ colony-forming unit (CFU)/mL). Additionally, AgNPs–TiO₂ tiles showed a remarkable antibacterial activity under indoor light, which confirms the good photocatalytic ability of such tiles. On the basis of the reactive oxygen species (ROS) quenching experiments, O₂^•− species and h⁺ were more reactive for the inactivation of E. coli rather than ^•OH species. This is because of the different lifetime (bacteria are more likely oxidized by ROS with longer lifetime); in fact, O₂^•− and h⁺ exhibit a longer lifetime compared with ^•OH species. The generation of H₂O₂ as the most stable ROS molecule was also suggested. Full article

K-ion batteries (KIBs) have emerged as an auspicious alternative to Li-ion batteries (LIBs) owing to their uniform distribution, plentiful reserves, the low cost of K resources, and their similar physicochemical properties to Li resources. The development of KIBs is seriously limited by cathode materials. Here, a hybrid of K₃V₂(PO₄)₃ (KVP) particles triple-coated by amorphous carbon, carbon nanotubes (CNTs), and reduced graphene oxide (rGO) nanosheets (KVP/C/CNT/rGO) was fabricated by a facile ball milling process followed by heat treatment. Consequently, a stable capacity of 57 mAh g⁻¹ can be achieved at 0.2C, and a slow capacity decaying rate (0.06% per cycle) is displayed during 500 cycles under a high current density of 5C. The remarkable reversible capacity and excellent long-term cycling life are mainly due to the enhanced interwoven C/CNT/rGO networks and superior KVP crystal structure stability, which can provide multi-channel for fast electron transport and effective K⁺ diffusion. Full article

Heterogeneous photocatalysis in the gas phase has been applied as a promising technique for organic syntheses in mild conditions. Modified zeolites have been used under UV irradiation as novel photocatalysts. In this study, we preliminarily investigated the photoxidation of cyclohexane on ferrierite and MoO_x-functionalized ferrierite in a gas–solid continuous flow reactor. In the presence of UV light, MoO_x-functionalized ferrierite showed the formation of benzene and cyclohexene as reaction products, indicating the occurrence of photocatalysed cyclohexane oxydehydrogenation. By contrast, unmodified ammonium ferrierite exhibited relevant activity for total oxidation of cyclohexane to carbon dioxide and water. The influence of Mo loading on cyclohexane conversion and products selectivity was evaluated. Full article

We have investigated three-dimensional (3D) MoS₂ nanoarchitectures doped with different amount of Ni to boost the hydrogen evolution reaction (HER) in alkaline environment, where this reaction is normally hindered. As a comparison, the activity in acidic media was also investigated to determine and compare the role of the Ni sites in both media. The doping of MoS₂, especially at high loadings, can modify its structural and/or electronic properties, which can also affect the HER activity. The structural and electronic properties of the Ni doped 3D-MoS₂ nanoarchitecture were studied by X-ray diffraction (XRD), Raman spectroscopy, scanning and transmission electronic microscopy (SEM; TEM), and X-ray photoemission Spectroscopy (XPS). XPS also allowed us to determine the Ni-based species formed as a function of the dopant loading. The HER activity of the materials was investigated by linear sweep voltammetry (LSV) in 0.5 M H₂SO₄ and 1.0 M KOH. By combining the physicochemical and electrochemical results, we concluded that the Ni sites have a different role in the HER mechanism and kinetics in acidic and in alkaline media. Thus, NiS_x species are essential to promote HER in alkaline medium, whereas the Ni-Mo-S ones enhance the HER in acid medium. Full article

Over the last few years, Nitinol (NiTi) has become one of the most attractive alloy materials for industrial applications. However, its implementation is still problematic due to its surface nickel content, making it sensitive to pitting corrosion. In applications, it is often necessary to modify NiTi surfaces by using organic coatings, which provides new physico-chemical properties as well as functionalities and often contributes to a reinforcement of the alloy corrosion resistance. In this work, we assess the differences between the molecular layers made out of methylphosphonic acid (C₁P) and the bi-phosphonic acid derivatives: (methylimino)dimethylene-bisphophonic acid (MIP₂) and 1-hydroxyethylidene-1,1-diphosphonic acid (HEP₂) using conventional (CG) and electro-assisted (EG) graftings. The surface modifications with the bi-phosphonic derivatives (MIP₂) and (HEP₂) carried out with the EG process lead to denser layers and a reinforced NiTi corrosion resistance. Full article

The coating of highly stressed components with chemical vapor deposition (CVD) diamond can extend their lifetime. In particular, the combination of steel substrates with diamond layers would find many applications in industrial production. However, there are some challenges, for example, the high mismatch in the thermal expansion between steel and diamond, which commonly leads to the delamination of the coating. Thus, a pre-treatment of the substrate surface is needed. Particle blasting has been established in some studies as a suitable process. However, apart from particle residues in the surface of the substrate, these surfaces have a stochastic character, which limits their reproducibility and modification options. This paper presents some instructions for the recording and derivation of defined properties of those surfaces. The conversion of characteristic surface features into quantitative process parameters could serve as the foundation for the manufacturing of deterministic microstructures, especially those produced by ultrasonic vibration superimposed machining. This should increase the reproducibility and the possibilities of the modification with regard to the structural shaping of the functional surface. The design was developed using both a kinematic surface simulation tool as well as a finite elements analysis for the cooling process of the coating–substrate–composite. A high accordance with real finished surfaces was achieved. Full article

Corrosion resistance of steel has attracted substantial interest for manufacturing applications to reduce costs corresponding to part failures, unexpected maintenance, and shortening lifespan. Meanwhile, millions of tonnes of slag, non-recyclable glass, and automotive shredder residue (ASR) are discarded into landfills every year, polluting the environment. Combining these two major issues, we delivered an alternative solution to enhance corrosion resistance of high-C steel. In this research, utilisation of these wastes (which were chemically bonded into steel substrate) as sources for production of multi-hybrid layering—including the multi-phase ceramic layer, the carbide layer, and the selective diffusion layer—was successfully achieved by single step surface modification technology. High-resolution topographical imaging by SEM and chemical composition analysis in micron-volume by electron probe micro analyser (EPMA) were performed. Nano-characterisation by atomic force microscopy (AFM) using the PeakForce quantitative nanomechanical mapping (PF-QNM) method was conducted to define Young’s modulus value of each phase in detail. Results revealed improvement of corrosion resistance by 39% and a significantly increased hardness of 13.58 GPa. This integrated approach is prominent for economic and environmental sustainability, consolidating industry demands for more profits, producing durable, steel components in a cost effective way to reduce dependency on new resources, and minimising negative impacts to the environment from disposal of wastes to the landfills. Full article