The ongoing challenge of water pollution by contaminants of emerging concern calls for more effective wastewater treatment to prevent harmful side effects to the environment and human health. To this end, this study explored for the first time the implementation of single-crystal boron-doped diamond (BDD) anodes in electrochemical wastewater treatment, which stand out from the conventional polycrystalline BDD morphologies widely reported in the literature. The single-crystal BDD presented a pure diamond (sp³) content, whereas the three other investigated polycrystalline BDD electrodes displayed various properties in terms of boron doping, sp³/sp² content, microstructure, and roughness. The effects of other process conditions, such as applied current density and anolyte concentration, were simultaneously investigated using carbamazepine (CBZ) as a representative target pollutant. The Taguchi method was applied to elucidate the optimal operating conditions that maximised either (i) the CBZ degradation rate constant (enhanced through hydroxyl radicals (^•OH)) or (ii) the proportion of sulfate radicals (SO₄^•−) with respect to ^•OH. The results showed that the single-crystal BDD significantly promoted ^•OH formation but also that the interactions between boron doping, current density and anolyte concentration determined the underlying degradation mechanisms. Therefore, this study demonstrated that characterising the BDD material and understanding its interactions with other process operating conditions prior to degradation experiments is a crucial step to attain the optimisation of any wastewater treatment application.

In this work, four different techniques were concurrently applied to study the interplay between local electroactivity and electrode surface characteristics of free-standing, polycrystalline boron-doped diamond (BDD). Scanning electron microscopy, electron back-scatter diffraction, Raman mapping and scanning electrochemical microscopy were used to probe the electrode morphology, grain orientation and boundaries, composition, and local electrochemical activity, respectively. Both nucleation and growth BDD surfaces together with the cross-section area were carefully investigated for the first time in a single study using the combination of all four techniques. This enabled us to obtain significant insights into the highly heterogeneous nature of the polycrystalline BDD material. Notably, boron dopants were confirmed to be non-uniformly distributed over the BDD material, which is characterized by a distinct columnar structure and composition of grains of various orientations. Particularly, the highest electrochemical activity was recorded on the highest doped (111) crystal orientation. In contrast, the averagely boron-doped (100)-oriented facet showed non-conductive nature. This highlights that the local electrochemical activity of the BDD surface is strongly grain-dependent and the most significant factors governing the obtained responses are crystallographic orientation and boron doping. Moreover, increased boron and sp² carbon content in the boundary regions was recognized by Raman mapping. However, such localized enrichment in impurities did not translate into enhanced electrochemical activity, which implies that boron atoms at the inter-grain areas are predominantly inactive. Finally, it is crucial to consider all characteristics of the polycrystalline BDD including crystal orientation, which is particularly relevant if micro- and nanoscale probing is intended.

This study assessed the photoactivity of amorphous and crystalline TiO₂ nanotube arrays (TNA) films in gas phase CO₂ reduction. The TNA photocatalysts were fabricated by titanium anodization and submitted to an annealing treatment for crystallization and/or cathodic reduction to introduce Ti³⁺ and oxygen vacancies into the TiO₂ structure. The cathodic reduction demonstrated a significant effect on the generated photocurrent. The photoactivity of the four TNA catalysts in CO₂ reduction with water vapor was evaluated under UV irradiation for 3 h, where CH₄ and H₂ were detected as products. The annealed sample exhibited the best performance towards methane with a production rate of 78 μmol g_cat⁻¹ h⁻¹, followed by the amorphous film, which also exhibited an impressive formation rate of 64 μmol g_cat⁻¹ h⁻¹. The amorphous and reduced-amorphous films exhibited outstanding photoactivity regarding H₂ production (142 and 144 μmol g_cat⁻¹ h⁻¹, respectively). The annealed catalyst also revealed a good performance for H₂ production (132 μmol g_cat⁻¹ h⁻¹) and high stability up to five reaction cycles. Molecular dynamic simulations demonstrated the changes in the band structure by introducing oxygen vacancies. The topics covered in this study contribute to the Sustainable Development Goals (SDG), involving affordable and clean energy (SDG#7) and industry, innovation, and infrastructure (SDG#9).

Electrochemical wastewater treatment is a promising technique to remove recalcitrant pollutants from wastewater. However, the complexity of elucidating the underlying degradation mechanisms hinders its optimisation not only from a techno-economic perspective, as it is desirable to maximise removal efficiencies at low energy and chemical requirements, but also in environmental terms, as the generation of toxic by-products is an ongoing challenge. In this work, we propose a novel combined experimental and computational approach to (i) estimate the contribution of radical and non-radical mechanisms as well as their synergistic effects during electrochemical oxidation and (ii) identify the optimal conditions that promote specific degradation pathways. As a case study, the distribution of the degradation mechanisms involved in the removal of benzoic acid (BA) via boron-doped diamond (BDD) anodes was elucidated and analysed as a function of several operating parameters, i.e., the initial sulfate and nitrate content of the wastewater and the current applied. Subsequently, a multivariate optimisation study was conducted, where the influence of the electrode nature was investigated for two commercial BDD electrodes and a customised silver-decorated BDD electrode. Optimal conditions were identified for each degradation mechanism as well as for the overall BA degradation rate constant. BDD selection was found to be the most influential factor favouring any mechanism (i.e., 52-85% contribution), given that properties such as its boron doping and the presence of electrodeposited silver could dramatically affect the reactions taking place. In particular, decorating the BDD surface with silver microparticles significantly enhanced BA degradation via sulfate radicals, whereas direct oxidation, reactive oxygen species and radical synergistic effects were promoted when using a commercial BDD material with higher boron content and on a silicon substrate. Consequently, by simplifying the identification and quantification of underlying mechanisms, our approach facilitates the elucidation of the most suitable degradation route for a given electrochemical wastewater treatment together with its optimal operating conditions.

The challenge of doping synthetic diamond with phosphorus stems from the atomic size mismatch between phosphorus and carbon atoms, which previously hindered achieving high phosphorus doping levels. This limitation delayed the exploration of phosphorus-doped diamond (PDD) in electrochemical applications, where it holds potential as a novel and appealing electrode material because PDD uniquely combines diamond's exceptional properties with phosphorus atoms inducing n-type conductivity. In this study, heavily doped PDD electrodes were successfully developed using chemical vapour deposition, followed by comprehensive microstructural and electrochemical characterisations. The influence of phosphorus doping, manipulated via high phosphine gas concentration or time-dependant precursor gas flow control, on the PDD properties was thoroughly examined. PDD layers grown at higher phosphine concentrations demonstrated enhanced phosphorus incorporation, leading to a higher prevalence of fine nano-crystalline diamond grains and non-diamond carbon components, while also slowing the growth rate. Notably, a distinct PDD sample produced under dynamic gas flow with lower phosphine concentration revealed larger grain sizes, increased effective deposition rate, and improved phosphorus levels compared to its counterpart synthesized under static conditions. Cyclic voltammetry in a 1 mol L⁻¹ KCl solution revealed a low double-layer capacitance (<11 µF cm⁻²) in all as-grown PDD electrodes. However, significant differences between the samples emerged during the experiments conducted with redox probes [Ru(NH₃)₆]^3+/2+ and [Fe(CN)₆]^3−/4−. Particularly, higher phosphorus content promoted well-developed voltammograms, significantly reduced peak-to-peak separation values, faster electron transfer rates, and increased peak currents. Furthermore, the possibility of using heavily P-doped diamond electrodes for the detection of two organic analytes, dopamine and ascorbic acid, was successfully manifested. All in all, the as-grown, highly P-doped diamond electrodes proved their ability, first time ever, to record well-defined signals of both inorganic redox probes and complex organic compounds, unravelling their potential in electroanalysis and sensor development and broadening the scope of PDD utilisation.

In this work, non-modified boron-doped diamond (BDD) was employed first time ever as the sensing material for the in-depth voltammetric study of the antiretroviral drug nevirapine (NVP) used to treat HIV infections. Two types of electrode surface pre-treatments, anodic oxidation and alumina-polishing, yielded BDD of different surface chemistry, denoted as O-BDD and p-BDD, respectively. Induced alterations in BDD surface composition reflected in distinct voltammetric responses of NVP, also dependant on the pH of the medium. The electrochemical oxidation of NVP on both electrodes, whose mechanism is proposed herein, has an irreversible character and is controlled by diffusion. The analytical figures of merit were assessed in a pH 2.0 buffer on O-BDD, and in supporting electrolytes of pH 5.0 and 13.0 on p-BDD using differential pulse voltammetry. Overall, NVP provided signals of excellent intra- and inter-day repeatability (RSD ≤ 5.0%) which remained unaffected even in the presence of common interfering compounds (e.g., glucose, ascorbic acid, uric acid, and dopamine). Even though the O-BDD electrode outperformed the p-BDD electrode in terms of sensitivity and the lowest detection limit achieved (0.04 μM), both O-BDD and p-BDD provided highly favourable analytical parameters fulfilling the requirements for clinical application for NVP sensing and monitoring in biofluids. This was also proved by electroanalysis of NVP in synthetic serum samples where recovery values between 96.3 and 103.0% were successfully achieved. Finally, unique properties of BDD allowed to develop a direct, modification-free, and reliable protocol for NVP detection, which paves the way for the full sensor development.

This study presents environmentally friendly and low-cost synthetic routes to produce antimicrobial coatings over 5052 Al alloy based on plasma electrolytic oxidation (PEO) technology. Two methodologies were explored: the decoration with copper and anodic doping with copper ions. The porous oxide layers produced in silicate media presented two porous layers consisting of γ-Al₂O₃ crystalline phase and amorphous phases of aluminosilicate, silica, and Al(OH)₃. Small amounts of copper (<0.3 at.%) were detected in the PEO films. In the Cu-decorated film, copper clusters composed of Cu⁰ and Cu²⁺ species were observed visually as small black dots on the surface. In the Cu-doped film, the Cu²⁺ and Cu⁺ species were homogeneously distributed on the surface. The copper content affected the corrosion performance in aggressive corrosive media. The PEO coatings showed a remarkable antimicrobial activity after 24 h in standard tests. The antimicrobial effectiveness of the Cu-decorated sample was higher against S. aureus, while the Cu-doped sample was more effective against E. coli. The results demonstrated that differences in the PEO coating architecture can affect the material composition and, consequently, the bacterial inactivation mechanism. These findings can serve as a guide to tailor aluminum alloys for specific antimicrobial surfaces.