Exploring Pt-Pd Alloy Nanoparticle Cluster Formation through Conventional Sizing Techniques and Single-Particle Inductively Coupled Plasma-Sector Field Mass Spectrometry.

Accurate characterization of Pt-Pd alloy nanoparticle clusters (NCs) is crucial for understanding their synthesis using Gas-Diffusion Electrocrystallization (GDEx). In this study, we propose a comprehensive approach that integrates conventional sizing techniques-scanning electron microscopy (SEM) and dynamic light scattering (DLS)-with innovative single-particle inductively coupled plasma-sector field mass spectrometry (spICP-SFMS) to investigate Pt-Pd alloy NC formation. SEM and DLS provide insights into morphology and hydrodynamic sizes, while spICP-SFMS elucidates the particle size and distribution of Pt-Pd alloy NCs, offering rapid and orthogonal characterization. The spICP-SFMS approach presented enables detailed characterization of Pt-Pd alloy NCs, which was previously challenging due to the absence of multi-element capabilities in conventional spICP-MS systems. This innovative approach not only enhances our understanding of bimetallic nanoparticle synthesis, but also paves the way for tailoring these materials for specific applications, marking a significant advancement in the field of nanomaterial science.

Coupling the electrocatalytic dechlorination of 2,4-D with electroactive microbial anodes.

This work proves the feasibility of dechlorinating 2,4-D, a customary commercial herbicide, using cathodic electrocatalysis driven by the anodic microbial electrooxidation of sodium acetate. A set of microbial electrochemical systems (MES) were run under two different operating modes, namely microbial fuel cell (MFC) mode, with an external resistance of 120 Ω, or microbial electrolysis cell (MEC) mode, by supplying external voltage (0.6 V) for promoting the (bio)electrochemical reactions taking place. When operating the MES as an MFC, 32% dechlorination was obtained after 72 h of treatment, which was further enhanced by working under MEC mode and achieving a 79% dechlorination. In addition, the biodegradability (expressed as the ratio BOD/COD) of the synthetic polluted wastewater was tested prior and after the MES treatment, which was improved from negative values (corresponding to toxic effluents) up to 0.135 in the MFC and 0.453 in the MEC. Our MES approach proves to be a favourable option from the point of view of energy consumption. Running the system under MFC mode allowed to co-generate energy along the dechlorination process (-0.0120 kWh mol-1 ), even though low removal rates were attained. The energy input under MEC operation was 1.03 kWh mol-1 -a competitive value compared to previous works reported in the literature for (non-biological) electrochemical reactors for 2,4-D electrodechlorination.

Electrified bioreactors: the next power-up for biometallurgical wastewater treatment.

Over the past decades, biological treatment of metallurgical wastewaters has become commonplace. Passive systems require intensive land use due to their slow treatment rates, do not recover embedded resources and are poorly controllable. Active systems however require the addition of chemicals, increasing operational costs and possibly negatively affecting safety and the environment. Electrification of biological systems can reduce the use of chemicals, operational costs, surface footprint and environmental impact when compared to passive and active technologies whilst increasing the recovery of resources and the extraction of products. Electrification of low rate applications has resulted in the development of bioelectrochemical systems (BES), but electrification of high rate systems has been lagging behind due to the limited mass transfer, electron transfer and biomass density in BES. We postulate that for high rate applications, the electrification of bioreactors, for example, through the use of electrolyzers, may herald a new generation of electrified biological systems (EBS). In this review, we evaluate the latest trends in the field of biometallurgical and microbial-electrochemical wastewater treatment and discuss the advantages and challenges of these existing treatment technologies. We advocate for future research to focus on the development of electrified bioreactors, exploring the boundaries and limitations of these systems, and their validity upon treating industrial wastewaters.

Spin transition nanoparticles made electrochemically.

Materials displaying novel magnetic ground states signify the most exciting prospects for nanoscopic devices for nanoelectronics and spintronics. Spin transition materials, e.g., spin liquids and spin glasses, are at the forefront of this pursuit; but the few synthesis routes available do not produce them at the nanoscale. Thus, it remains an open question if and how their spin transition nature persists at such small dimensions. Here we demonstrate a new route to synthesize nanoparticles of spin transition materials, gas-diffusion electrocrystallization (GDEx), wherein the reactive precipitation of soluble metal ions with the products of the oxygen reduction reaction (ORR), i.e., in situ produced H2O2, OH-, drives their formation at the electrochemical interface. Using mixtures of Cu2+ and Zn2+ as the metal precursors, we form spin transition materials of the herbertsmithite family-heralded as the first experimental material known to exhibit the properties of a quantum spin liquid (QSL). Single-crystal nanoparticles of ∼10-16 nm were produced by GDEx, with variable Cu/Zn stoichiometry at the interlayer sites of ZnxCu4-x(OH)6Cl2. For x = 1 (herbertsmithite) the GDEx nanoparticles demonstrated a quasi-QSL behavior, whereas for x = 0.3 (0.3 < x < 1 for paratacamite) and x = 0 (clinoatacamite) a spin-glass behavior was evidenced. Finally, our discovery not only confirms redox reactions as the driving force to produce spin transition nanoparticles, but also proves a simple way to switch between these magnetic ground states within an electrochemical system, paving the way to further explore its reversibility and overarching implications.

pH Transitions and electrochemical behavior during the synthesis of iron oxide nanoparticles with gas-diffusion electrodes.

Gas diffusion electrocrystallization (GDEx) was explored for the synthesis of iron oxide nanoparticles (IONPs). A gas-diffusion cathode was employed to reduce oxygen, producing hydroxyl ions (OH-) and oxidants (H2O2 and HO2 -), which acted as reactive intermediates for the formation of stable IONPs. The IONPs were mainly composed of pure magnetite. However, their composition strongly depended on the presence of a weak acid, i.e., ammonium chloride (NH4Cl), and on the applied electrode potential. Pure magnetite was obtained due to the simultaneous action of H2O2 and the buffer capacity of the added NH4Cl. Magnetite and goethite were identified as products under different operating conditions. The presence of NH4Cl facilitated an acid-base reaction and, in some cases, led to cathodic deprotonation, forming a surplus of hydrogen peroxide, while adding the weak acid promoted gradual changes in the pH by slightly enhancing H2O2 production when increasing the applied potential. This also resulted in smaller average crystallite sizes as follows: 20.3 ± 0.6 at -0.350 V, 14.7 ± 2.1 at -0.550 and 12.0 ± 2.0 at -0.750 V. GDEx is also demonstrated to be a green, effective, and efficient cathodic process to recover soluble iron to IONPs, being capable of removing >99% of the iron initially present in the solution.

Gas Diffusion Electrodes on the Electrosynthesis of Controllable Iron Oxide Nanoparticles.

The electrosynthesis of iron oxide nanoparticles offers a green route, with significant energy and environmental advantages. Yet, this is mostly restricted by the oxygen solubility in the electrolyte. Gas-diffusion electrodes (GDEs) can be used to overcome that limitation, but so far they not been explored for nanoparticle synthesis. Here, we develop a fast, environmentally-friendly, room temperature electrosynthesis route for iron oxide nanocrystals, which we term gas-diffusion electrocrystallization (GDEx). A GDE is used to generate oxidants and hydroxide in-situ, enabling the oxidative synthesis of a single iron salt (e.g., FeCl2) into nanoparticles. Oxygen is reduced to reactive oxygen species, triggering the controlled oxidation of Fe2+ to Fe3+, forming Fe3-xO4-x (0 ≤ x ≤ 1). The stoichiometry and lattice parameter of the resulting oxides can be controlled and predictively modelled, resulting in highly-defective, strain-heavy nanoparticles. The size of the nanocrystals can be tuned from 5 nm to 20 nm, with a large saturation magnetization range (23 to 73 A m2 kg-1), as well as minimal coercivity (~1 kA m-1). Using only air, NaCl, and FeCl2, a biocompatible approach is achieved, besides a remarkable level of control over key parameters, with a view on minimizing the addition of chemicals for enhanced production and applications.

Oxidation-assisted alkaline precipitation: the effect of H2O2 on the size of CuO and FeOOH nanoparticles.

H2O2 was demonstrated to narrow the size distribution and decrease the size of CuO and hydrous FeOOH (2-line ferrihydrite) nanoparticles under conditions of high supersaturation. We introduce oxidation-assisted alkaline precipitation (Ox-AP) and compare it to traditional alkaline precipitation (AP). While for AP, a metal salt solution (e.g., CuCl2) is mixed with an alkali (e.g., NaOH), for Ox-AP, the more reduced form of that metal salt solution (e.g., CuCl) is simultaneously mixed with that alkali and an oxidant (e.g., H2O2). The resulting precipitates were characterized with SEM, XRD, DLS and single particle ICP-MS and shown to be nanoparticles (NPs). Ox-AP CuO NPs were up to 3 times smaller than AP NPs. Ox-AP FeOOH NPs were up to 22.5% smaller than AP NPs. We discuss and propose a possible mechanism of Ox-AP through careful consideration of the known reaction chemistry of iron and copper. We propose that an increased monomer formation rate enhances the nucleation rate, which ultimately results in smaller particles with a more narrow distribution. The more distinct effect of Ox-AP on copper, was attributed to the fast formation of the stable CuO monomer, compared to AP, where the Cu(OH)2 and/or Cu2(OH)3Cl monomers are more likely formed. Although, the exact mechanism of Ox-AP needs experimental confirmation, our results nicely demonstrate the potential of using Ox-AP to produce smaller NPs with a more narrow distribution in comparison to using AP.

Gas Diffusion Electrodes Manufactured by Casting Evaluation as Air Cathodes for Microbial Fuel Cells (MFC).

One of the most intriguing renewable energy production methods being explored currently is electrical power generation by microbial fuel cells (MFCs). However, to make MFC technology economically feasible, cost efficient electrode manufacturing processes need to be proposed and demonstrated. In this context, VITO has developed an innovative electrode manufacturing process based on film casting and phase inversion. The screening and selection process of electrode compositions was done based on physicochemical properties of the active layer, which in turn maintained a close relation with their composition A dual hydrophilic-hydrophobic character in the active layer was achieved with values of εhydrophilic up to 10% while εTOTAL remained in the range 65 wt % to 75 wt %. Eventually, selected electrodes were tested as air cathodes for MFC in half cell and full cell modes. Reduction currents, up to -0.14 mA·cm2- at -100 mV (vs. Ag/AgCl) were reached in long term experiments in the cathode half-cell. In full MFC, a maximum power density of 380 mW·m-2 was observed at 100 Ω external load.

Carbon dioxide reduction by mixed and pure cultures in microbial electrosynthesis using an assembly of graphite felt and stainless steel as a cathode.

Carbon dioxide (CO2) reduction to multi-carbon compounds at the cathode using chemolithoautotrophs is an emerging application of microbial electrosynthesis (MES). In this study, CO2 reduction in MES was investigated at hydrogen evolving potentials, separately by a mixed culture and Clostridium ljungdahlii, using a graphite felt and stainless steel assembly as cathode. The mixed culture reactor produced acetate at the maximum rate of 1.3 mM d(-1), along with methane and hydrogen at -1.1 V/Ag/AgCl. Over 160 days of run-time in four fed-batches, 26% of bicarbonate was converted to acetate between day 28 and 41, whereas in the late batches, methane production prevailed. Out of 45 days of run-time in the C. ljungdahlii reactor, 2.4 mM d(-1) acetate production was achieved at -0.9 V/Ag/AgCl in Batch 1. Simultaneous product degradation occurred when the mixed culture was not selectively enriched. Hydrogen evolution is potentially the rapid way of transferring electrons to the biocatalysts for higher bioproduction rates.

A comprehensive impedance journey to continuous microbial fuel cells.

The aim of the present work was to characterize the impedance response of an air-cathode MFC operating in a continuous mode and to determine intrinsic properties that define its performance which are crucial to be controlled for scalability purposes. The limiting step on electricity generation is the anodic electrochemically-active biofilm, independently of the external resistance, Rext, utilized. However, for Rext below 3 kΩ the internal impedance of the bioanode remained invariable, in good correspondence to the power density profile. The hydraulic retention time (HRT) had an effect on the impedance of both the bioanode and the air-cathode and especially on the overall MFC. The lowest HRT at which the MFC was operable was 3h. Yet, the variation on the HRT did not have a significant impact on power generation. A two constant phase element-model was associated with the EIS response of both bioanode and air-cathode, respectively. Consistency was found between the CPE behaviour and the normal power-law distribution of local resistivity with a uniform dielectric constant, which represented consistent values with the electrical double layer, the Nernst diffusion layer and presumably the biofilm thickness. These results have future implications on MFC monitoring and control, as well as in providing critical parameters for scale-up.

The Role of Nicotine in the Corrosive Behavior of a Ti-6Al-4V Dental Implant.

BACKGROUND: Metals react chemically/electrochemically in electrolytic solutions, such as that present in the oral cavity, which leads to corrosion of metal dental implants. Corrosion can increase the failure rate of dental implants. PURPOSE: This study evaluated the corrosion behavior of nicotine on Ti-6Al-4V under physiological conditions. It was hypothesized that nicotine in artificial saliva would have an adverse effect on the corrosion of Ti-6Al-4V. METHODS: Ti-6Al-4V discs were electrochemically analyzed using a three-electrode electrochemical cell. The disks were immersed in an electrolytic artificial saliva with varying pH (3.0 and 6.5) and nicotine concentration (control, 1 mg/mL, 5 mg/mL, and 20 mg/mL). Open circuit potential, cyclic polarization, and electrochemical impedance spectroscopy (EIS) tests were conducted. RESULTS: Electrochemical parameters indicated that the presence of nicotine significantly reduced (p < .05) the corrosion rate. For example, there was a decrease in corrosion current density from 2.94 × 10(-3) µA/cm(2) to 1.43 × 10(-3) µA/cm(2) in control compared with 20 mg/mL nicotine at pH 6.5. EIS results exhibited an unexpected trend in that the presence of nicotine decreased polarization resistance. This suggested a decrease in passive film growth. CONCLUSIONS: At certain concentrations, nicotine inhibits local corrosion; however, it also prevents the formation of a protective oxide film.

Characterization of anode and anolyte community growth and the impact of impedance in a microbial fuel cell.

BACKGROUND: A laboratory-scale two-chamber microbial fuel cell employing an aerated cathode with no catalyst was inoculated with mixed inoculum and acetate as the carbon source. Electrochemical impedance spectroscopy (EIS) was used to study the behavior of the MFC during initial biofilm (week 1) and maximum power density (week 20). EIS were performed on the anode chamber, biofilm (without anolyte) and anolyte (without biofilm). Nyquist plots of the EIS data were fitted with two equivalent electrical circuits to estimate the contributions of intrinsic resistances to the overall internal MFC impedance at weeks 1 and 20, respectively. RESULTS: The results showed that the system tended to increase power density from 15 ± 3 (week 1) to 100 ± 15 mW/m(2) (week 20) and current density 211 ± 7 (week 1) to 347 ± 29 mA/m(2) (week 20). The Samples were identified by pyrosequencing of the 16S rRNA gene and showed that initial inoculum (week 1) was constituted by Proteobacteria (40%), Bacteroidetes (22%) and Firmicutes (18%). At week 20, Proteobacterial species were predominant (60%) for electricity generation in the anode biofilm, being 51% Rhodopseudomonas palustris. Meanwhile on anolyte, Firmicutes phylum was predominant with Bacillus sp. This study proved that under the experimental conditions used there is an important contribution from the interaction of the biofilm and the anolyte on cell performance. Table 1 presents a summary of the specific influence of each element of the system under study. CONCLUSIONS: The results showed certain members of the bacterial electrode community increased in relative abundance from the initial inoculum. For example, Proteobacterial species are important for electricity generation in the anode biofilms and Firmicutes phylum was predominant on anolyte to transfer electron. R1 is the same in the three systems and no variation is observed over time. The biofilm makes a significant contribution to the charge transfer processes at the electrode (R2 and Cdl) and, consequently, on the performance of the anode chamber. The biofilm can act as a barrier which reduces diffusion of the anolyte towards the electrode, all the while behaving like a porous material. The anolyte and its interaction with the biofilm exert a considerable influence on diffusion processes, given that it presents the highest values for Rd which increased at week 20.

Influence of headspace composition on product diversity by sulphate reducing bacteria biocathode.

Mixed culture of sulphate reducing bacteria named TERI-MS-003 was used for development of biocathode on activated carbon fabric fastened to stainless steel mesh for conversion of volatile fatty acids to reduced organic compounds under chronoamperometric conditions of -0.85V vs. Ag/AgCl (3.5M KCl). A range of chemicals were bioelectrosynthesized, however the gases present in headspace environment of the bioelectrochemical reactor governed the product profile. Succinate, ethanol, hydrogen, glycerol and propionate were observed to be the predominant products when the reactor was hermetically sealed. On the other hand, acetone, propionate, isopropanol, propanol, isobutyrate, isovalerate and heptanoate were the predominant products when the reactor was continuously sparged with nitrogen. This study highlights the importance of head space composition in order to manoeuvre the final product profile desired during a microbial electro-synthesis operation and the need for simultaneously developing effective separation and recovery strategies from an economical and practical standpoint.

Enzymatic electrosynthesis of formate through CO2 sequestration/reduction in a bioelectrochemical system (BES).

Bioelectrochemical system (BES) was operated using the enzyme formate dehydrogenase as catalyst at cathode in its free form for the reduction of CO2 into formic acid. Electrosynthesis of formic acid was higher at an operational voltage of -1V vs. Ag/AgCl (9.37mgL(-1) CO2) compared to operation at -0.8V (4.73mgL(-1) CO2) which was strongly supported by the reduction catalytic current. Voltammograms also depicted a reversible redox peak throughout operation at -1V, indicating NAD(+) recycling for proton transfer from the source to CO2. Saturation of the product was observed after 45min of enzyme addition and then reversibility commenced, depicting a lower and stable formic acid concentration throughout the subsequent time of operation. Stability of the enzyme activity after immobilization on the electrode and product yield will be studied further.

Internal resistance of microfluidic microbial fuel cell: challenges and potential opportunities.

The efficiency of microbial fuel cells (MFCs) is affected by several factors such as activation overpotentials, ohmic losses and concentration polarization. These factors are handled in micro-sized MFCs using special electrodes with physically or chemically modified surfaces constructed with specified materials. Most of the existing µLscale MFCs show great potential in rapid screening of electrochemically-active microbes and electrode performance; although they generate significantly lower volumetric power density compared with their mL counterparts because of their high internal resistance. This review presents the development of microfluidic MFCs, with summarization of their advantages and challenges, and focuses on the efforts done to minimize the adverse effects of internal resistance (ohmic and non-ohmic) on their performance.

The accurate use of impedance analysis for the study of microbial electrochemical systems.

The present critical review aims to portray the principles and theoretical foundations that have been used for the application of electrochemical impedance spectroscopy (EIS) to study electron-transfer mechanisms, mass transfer phenomena and distribution of the heterogeneous properties of microbial electrochemical systems (MXCs). Over the past eight years, the application of this method has allowed major breakthroughs, especially in the field of microbial fuel cells (MFCs); however, it is still most widely extended only to the calculation of internal resistances. The use and interpretation of EIS should greatly improve since the intrinsic knowledge of this field, and efforts and current trends in this field have already allowed its understanding based on rather meaningful physical properties and not only on fitting electrical analogues. From this perspective, the use, analysis and interpretation of EIS applied to the study of MXCs are critically examined. Together with the revision of more than 150 articles directly devoted to this topic, two examples of the correct and improved analysis of EIS data are extensively presented. The first one focuses on the use of graphical methods for improving EIS analysis and the other one concentrates on the elucidation of the constant phase element (CPE) parameters. CPEs have been introduced in equivalent circuit models, sometimes without solid justification or analysis; the effective capacitance has been obtained from CPE parameters, following an unsuitable theory for the case of microbial-electrochemical interfaces. The use of CPE is reviewed in terms of meaningful physical parameters, such as biofilm thickness. The use of a finite-diffusion element is reviewed throughout estimation of accurate values for obtaining the dimensionless numbers, Schmidt and Sherwood, in the context of a dioxygen-reducing-biocathode, under different flow-rate conditions. The use and analysis of EIS in this context are still emerging, but because of the promising potential of MXCs in renewable power generation, wastewater treatment and energy-positive biorefining, among other applications, it becomes necessary to boost our global capacities for the application of EIS-and especially its interpretation-so that we achieve a better understanding and optimization of these systems.