Highly Occupied Surface States at Deuterium-Grown Boron-Doped Diamond Interfaces for Efficient Photoelectrochemistry.

Polycrystalline boron-doped diamond is a promising material for high-power aqueous electrochemical applications in bioanalytics, catalysis, and energy storage. The chemical vapor deposition (CVD) process of diamond formation and doping is totally diversified by using high kinetic energies of deuterium substituting habitually applied hydrogen. The high concentration of deuterium in plasma induces atomic arrangements and steric hindrance during synthesis reactions, which in consequence leads to a preferential (111) texture and more effective boron incorporation into the lattice, reaching a one order of magnitude higher density of charge carriers. This provides the surface reconstruction impacting surficial populations of CC dimers, CH, CO groups, and COOH termination along with enhanced kinetics of their abstraction, as revealed by high-resolution core-level spectroscopies. A series of local densities of states were computed, showing a rich set of highly occupied and localized surface states for samples deposited in deuterium, negating the connotations of band bending. The introduction of enhanced incorporation of boron into (111) facet of diamond leads to the manifestation of surface electronic states below the Fermi level and above the bulk valence band edge. This unique electronic band structure affects the charge transfer kinetics, electron affinity, and diffusion field geometry critical for efficient electrolysis, electrocatalysis, and photoelectrochemistry.

Electrochemical oxidation of landfill leachate using boron-doped diamond anodes: pollution degradation rate, energy efficiency and toxicity assessment.

Electrochemical oxidation (EO), due to high efficiency and small carbon footprint, is regarded as an attractive option for on-site treatment of highly contaminated wastewater. This work shows the effectiveness of EO using three boron-doped diamond electrodes (BDDs) in sustainable management of landfill leachate (LL). The effect of the applied current density (25-100 mA cm-2) and boron doping concentration (B/C ratio: 500 ppm, 10,000 ppm and 15,000 ppm) on the performance of EO was investigated. It was found that, of the electrodes used, the one most effective at COD, BOD20 and ammonia removal (97.1%, 98.8% and 62%, respectively) was the electrode with the lowest boron doping. Then, to better elucidate the ecological role of LLs, before and after EO, cultivation of faecal bacteria and microscopic analysis of total (prokaryotic) cell number, together with ecotoxicity assay (Daphnia magna, Thamnocephalus platyurus and Artemia salina) were combined for the two better-performing electrodes. The EO process was very effective at bacterial cell inactivation using each of the two anodes, even within 2 h of contact time. In a complex matrix of LLs, this is probably a combined effect of electrogenerated oxidants (hydroxyl radicals, active chlorine and sulphate radicals), which may penetrate into the bacterial cells and/or react with cellular components. The toxicity of EO-treated LLs proved to be lower than that of raw ones. Since toxicity drops with increased boron doping, it is believed that appropriate electrolysis parameters can diminish the toxicity effect without compromising the nutrient-removal and disinfection capability, although salinity of LLs and related multistep-oxidation pathways needs to be further elucidated.

Boron-Doped Diamond/GaN Heterojunction-The Influence of the Low-Temperature Deposition.

We report a method of growing a boron-doped diamond film by plasma-assisted chemical vapour deposition utilizing a pre-treatment of GaN substrate to give a high density of nucleation. CVD diamond was deposited on GaN substrate grown epitaxially via the molecular-beam epitaxy process. To obtain a continuous diamond film with the presence of well-developed grains, the GaN substrates are exposed to hydrogen plasma prior to deposition. The diamond/GaN heterojunction was deposited in methane ratio, chamber pressure, temperature, and microwave power at 1%, 50 Torr, 500 °C, and 1100 W, respectively. Two samples with different doping were prepared 2000 ppm and 7000 [B/C] in the gas phase. SEM and AFM analyses revealed the presence of well-developed grains with an average size of 100 nm. The epitaxial GaN substrate-induced preferential formation of (111)-facetted diamond was revealed by AFM and XRD. After the deposition process, the signal of the GaN substrate is still visible in Raman spectroscopy (showing three main GaN bands located at 565, 640 and 735 cm-1) as well as in typical XRD patterns. Analysis of the current-voltage characteristics as a function of temperature yielded activation energy equal to 93.8 meV.

Kinetics of the Organic Compounds and Ammonium Nitrogen Electrochemical Oxidation in Landfill Leachates at Boron-Doped Diamond Anodes.

Electrochemical oxidation (EO) of organic compounds and ammonium in the complex matrix of landfill leachates (LLs) was investigated using three different boron-doped diamond electrodes produced on silicon substrate (BDD/Si)(levels of boron doping [B]/[C] = 500, 10,000, and 15,000 ppm-0.5 k; 10 k, and 15 k, respectively) during 8-h tests. The LLs were collected from an old landfill in the Pomerania region (Northern Poland) and were characterized by a high concentration of N-NH4+ (2069 ± 103 mg·L-1), chemical oxygen demand (COD) (3608 ± 123 mg·L-1), high salinity (2690 ± 70 mg Cl-·L-1, 1353 ± 70 mg SO42-·L-1), and poor biodegradability. The experiments revealed that electrochemical oxidation of LLs using BDD 0.5 k and current density (j) = 100 mA·cm-2 was the most effective amongst those tested (C8h/C0: COD = 0.09 ± 0.14 mg·L-1, N-NH4+ = 0.39 ± 0.05 mg·L-1). COD removal fits the model of pseudo-first-order reactions and N-NH4+ removal in most cases follows second-order kinetics. The double increase in biodegradability index-to 0.22 ± 0.05 (BDD 0.5 k, j = 50 mA·cm-2) shows the potential application of EO prior biological treatment. Despite EO still being an energy consuming process, optimum conditions (COD removal > 70%) might be achieved after 4 h of treatment with an energy consumption of 200 kW·m-3 (BDD 0.5 k, j = 100 mA·cm-2).

Electrochemical oxidation of PFOA and PFOS in landfill leachates at low and highly boron-doped diamond electrodes.

Polyfluorinated alkyl substances (PFASs) may reach landfill leachates (LLs) due to improper waste management. In this study perfluorooctanoate (PFOA) and perfluorooctane sulphonate (PFOS) were used as representatives of PFASs in the decomposition on boron-doped diamond electrodes (BDDs) with high (10k ppm) and low (0.5k ppm) boron doping concentrations. The result shows that although better COD removal efficacies are obtained on the low-doped BDD (59 % after 8 h), the decomposition rate of PFOA and PFOS was not affected by boron doping. In LLs, at the current density of 75 mA/cm2, averaged removal efficiencies of 80 % and 78 % were achieved for PFOA and PFOS, respectively. But besides concentration of mother compounds, the presence of intermediates during electrolysis should be monitored. After 8 h of LL electrolysis, the presence of long-chain degradates C6F13 and C6F13COO- was still observed only in 10k BDD-PFOA assays, while during 0.5k assays C6F13 and C6F13COO- form more intesively at the beginning of the process. This indirectly confirms the more intensive generation of perfluoroalkoxy and hydroxyl radicals and higher susceptibility to electrolysis of PFOA's long-chain intermediates on 0.5k BDD. This is the first study reporting BDD-electrolysis as promising in PFAS removal from the complex matrix of LLs, despite the oxidation of competing LLs components.

Ligand-Modified Boron-Doped Diamond Surface: DFT Insights into the Electronic Properties of Biofunctionalization.

With the increasing power of computation systems, theoretical calculations provide a means for quick determination of material properties, laying out a research plan, and lowering material development costs. One of the most common is Density Functional Theory (DFT), which allows us to simulate the structure of chemical molecules or crystals and their interaction. In developing a new generation of biosensors, understanding the nature of functional linkers, antibodies, and ligands become essential. In this study, we used DFT to model a bulk boron-doped diamond slab, modified by a functional linker and a surrogate proteins ligand. DTF calculations enable the prediction of electronic transport properties in an electrochemical sensor setup, composed of a boron-doped diamond electrode functionalized by 4-amino benzoic acids and a target surrogated protein-ligand for influenza. Electron conduction pathways and other signatures associated with the detection and measurement of the target analyte are revealed.

Multifrequency nanoscale impedance microscopy (m-NIM): A novel approach towards detection of selective and subtle modifications on the surface of polycrystalline boron-doped diamond electrodes.

In this paper, we describe the modification of Nanoscale Impedance Microscopy (NIM), namely, a combination of contact-mode atomic force microscopy with local impedance measurements. The postulated approach is based on the application of multifrequency voltage perturbation instead of standard frequency-by-frequency analysis, which among others offers more time-efficient and accurate determination of the resultant impedance spectra with high spatial resolution. Based on the impedance spectra analysis with an appropriate electric equivalent circuit, it was possible to map surface resistance and contact capacitance. Polycrystalline heavy boron-doped diamond (BDD) electrodes were the research object. Recent studies have shown that the exposure of such electrodes to oxidizing environment may result in the modification of termination type, and thus it is a key factor in describing the electric and electrochemical properties of BDD. We have successfully applied multifrequency NIM, which allowed us to prove that the modification of termination type is selective and occurs with different propensity on the grains having specific crystallographic orientation. Furthermore, our approach enabled the detection of even subtle submicroscopic surface heterogeneities, created as a result of various oxidation treatments and to distinguish them from the surface heterogeneity related to the local distribution of boron at the grain boundaries.

Optical Detection of Ketoprofen by Its Electropolymerization on an Indium Tin Oxide-Coated Optical Fiber Probe.

In this work an application of optical fiber sensors for real-time optical monitoring of electrochemical deposition of ketoprofen during its anodic oxidation is discussed. The sensors were fabricated by reactive magnetron sputtering of indium tin oxide (ITO) on a 2.5 cm-long core of polymer-clad silica fibers. ITO tuned in optical properties and thickness allows for achieving a lossy-mode resonance (LMR) phenomenon and it can be simultaneously applied as an electrode in an electrochemical setup. The ITO-LMR electrode allows for optical monitoring of changes occurring at the electrode during electrochemical processing. The studies have shown that the ITO-LMR sensor’s spectral response strongly depends on electrochemical modification of its surface by ketoprofen. The effect can be applied for real-time detection of ketoprofen. The obtained sensitivities reached over 1400 nm/M (nm·mg−1·L) and 16,400 a.u./M (a.u.·mg−1·L) for resonance wavelength and transmission shifts, respectively. The proposed method is a valuable alternative for the analysis of ketoprofen within the concentration range of 0.25⁻250 μg mL−1, and allows for its determination at therapeutic and toxic levels. The proposed novel sensing approach provides a promising strategy for both optical and electrochemical detection of electrochemical modifications of ITO or its surface by various compounds.

Nitrogen-Doped Diamond Film for Optical Investigation of Hemoglobin Concentration.

In this work we present the fabrication and characterization of a diamond film which can be utilized in the construction of optical sensors for the investigation of biological samples. We produced a nitrogen-doped diamond (NDD) film using a microwave plasma enhanced chemical vapor deposition (MWPECVD) system. The NDD film was investigated with the use of scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. The NDD film was used in the construction of the fiber optic sensor. This sensor is based on the Fabry-Pérot interferometer working in a reflective mode and the NDD film is utilized as a reflective layer of this interferometer. Application of the NDD film allowed us to obtain the sensor of hemoglobin concentration with linear work characteristics with a correlation coefficient (R²) equal to 0.988.

A rapid-response ultrasensitive biosensor for influenza virus detection using antibody modified boron-doped diamond.

According to the World Health Organization (WHO), almost 2 billion people each year are infected worldwide with flu-like pathogens including influenza. This is a contagious disease caused by viruses belonging to the family Orthomyxoviridae. Employee absenteeism caused by flu infection costs hundreds of millions of dollars every year. To successfully treat influenza virus infections, detection of the virus during the initial development phase of the infection is critical, when tens to hundreds of virus-associated molecules are present in the patient's pharynx. In this study, we describe a novel universal diamond biosensor, which enables the specific detection of the virus at ultralow concentrations, even before any clinical symptoms arise. A diamond electrode is surface-functionalized with polyclonal anti-M1 antibodies, which then serve to identify the universal biomarker for the influenza virus, M1 protein. The absorption of the M1 protein onto anti-M1 sites of the electrode change its electrochemical impedance spectra. We achieved a limit of detection of 1 fg/ml in saliva buffer for the M1 biomarker, which corresponds to 5-10 viruses per sample in 5 minutes. Furthermore, the universality of the assay was confirmed by analyzing different strains of influenza A virus.

Boron-Enhanced Growth of Micron-Scale Carbon-Based Nanowalls: A Route toward High Rates of Electrochemical Biosensing.

In this study, we have demonstrated the fabrication of novel materials called boron-doped carbon nanowalls (B:CNWs), which are characterized by remarkable electrochemical properties such as high standard rate constant (k°), low peak-to-peak separation value (ΔE) for the oxidation and reduction processes of the [Fe(CN)6]3-/4- redox system, and low surface resistivity. The B:CNW samples were deposited by the microwave plasma-assisted chemical vapor deposition (CVD) using a gas mixture of H2/CH4/B2H6 and N2. Growth results in sharp-edged, flat, and long CNWs rich in sp2 as well as sp3 hybridized phases. The achieved high values of k° (1.1 × 10-2 cm s-1) and ΔE (85 mV) are much lower compared to those of the glassy carbon or undoped CNWs. The enhanced electrochemical performance of the B:CNW electrode facilitates the simultaneous detection of DNA purine bases: adenine and guanine. Both separated oxidation peaks for the independent determination of guanine and adenine were observed by means of cyclic voltammetry or differential pulse voltammetry. It is worth noting that the determined sensitivities and the current densities were about 1 order of magnitude higher than those registered by other electrodes.