Search Results (30)

The urgency to decarbonize fuels has contributed to a rise in biofuel production, which has culminated in a significant increase in the waste quantity of glycerol produced. Therefore, to convert glycerol waste into high-value products, electrochemical oxidation (EO) is a viable alternative for the co-generation of carboxylic acids, such as formic acid (FA) and green hydrogen (H₂), which are considered energy carriers. The aim of this study is the electroconversion of glycerol into FA by EO using a divided electrochemical cell, driven by a photovoltaic (PV) system, with a dimensionally stable anode (DSA, Ti/TiO₂-RuO₂-IrO₂) electrode as an anode and Ni-Fe stainless steel (SS) mesh as a cathode. To optimize the experimental conditions, studies were carried out evaluating the effects of applied current density (j), electrolyte concentration, electrolysis time, and electrochemical cell configuration (undivided and divided). According to the results, the optimum experimental conditions were achieved at 90 mA cm⁻², 0.1 mol L⁻¹ of Na₂SO₄ as a supporting electrolyte, and 480 min of electrolysis. In this condition, 256.21 and 211.17 mg L⁻¹ of FA were obtained for the undivided and divided cells, respectively, while the co-generation of 6.77 L of dry H₂ was achieved in the divided cell. The electroconversion process under the optimum conditions was also carried out with a real sample, where organic acids like formic and acetic acids were co-produced simultaneously with green H₂. Based on the preliminary economic analysis, the integrated-hybrid process is an economically viable and promising alternative when it is integrated with renewable energy sources such as solar energy. Full article

The modification of catalytic activity through the use of metallic promoters is a key strategy for optimizing performance, as electronic factors play a crucial role in regulating catalytic behavior. This study explores the electronic factors behind the adsorption of glycerol (Gly) on bimetallic nickel-based compounds (${\mathrm{Ni}}_3\mathrm{X}$) using density functional theory (DFT) calculations; incorporating Mn, Fe, Co, Cu, and Zn as promoters effectively tunes the d-band center of these systems, directly influencing their magnetic, adsorption, and catalytic properties. A good correlation between the calculated glycerol adsorption energy and the d-band filling of the studied bimetallic surfaces was identified. Interestingly, this correlation can be rationalized using the celebrated Newns–Anderson model based on the calculated d-band fillings and centers of the systems under study. Additionally, the adsorption energies and relative stability of other electro-oxidation intermediates toward dihydroxyacetone (DHA) were calculated. Notably, the ${\mathrm{Ni}}_3\mathrm{Co}$ and ${\mathrm{Ni}}_3\mathrm{Cu}$ systems exhibit an optimal balance between glycerol adsorption and DHA desorption, making them promising candidates for glycerol electro-oxidation. These theoretical insights address fundamental aspects of developing glycerol valorization processes and advancing alcohol electro-oxidation technologies in fuel cells with noble-metal-free catalysts. Full article

This study explores the development of core–shell electrocatalysts for efficient glycerol oxidation in alkaline media. Carbon-supported M@Pt/C (M = Co, Ni, Sn) catalysts with a 1:1 atomic ratio of metal (M) to platinum (Pt) were synthesized using a facile sodium borohydride reduction method. The analysis confirmed the formation of the desired core–shell structure, with Pt dominating the surface as evidenced by energy-dispersive X-ray spectroscopy (EDS). X-ray diffraction (XRD) revealed the presence of a face-centered cubic (fcc) Pt structure for Co@Pt/C and Ni@Pt/C. Interestingly, Sn@Pt/C displayed a PtSn alloy formation indicated by shifted Pt peaks and the presence of minor Sn oxide peaks. Notably, no diffraction peaks were observed for the core metals, suggesting their amorphous nature. Electrocatalytic evaluation through cyclic voltammetry (CV) revealed superior glycerol oxidation activity for Co@Pt/C compared to all other catalysts. The maximum current density followed the order Co@Pt/C > Ni@Pt/C > Sn@Pt/C > Pt/C. This highlights the effectiveness of the core–shell design in enhancing activity. Furthermore, Sn@Pt/C displayed remarkable poisoning tolerance attributed to a combined effect: a bifunctional mechanism driven by Sn oxides and an electronic effect within the PtSn alloy. These findings demonstrate the significant potential of core–shell M@Pt/C structures for designing highly active and poisoning-resistant electrocatalysts for glycerol oxidation. The presented approach paves the way for further development of optimized catalysts with enhanced performance and stability aiming at future applications in direct glycerol fuel cells. Full article

Extracellular electron transfer (EET) is key to the success of microbial fuel cells (MFCs). Clostridium sp. often occurs in MFC anode communities, but its ability to perform EET remains controversial. We have employed Clostridium pasteurianum DSM 525 as a biocatalyst in a glycerol-fed MFC, designated MFC_DSM. We have also followed the EET of this biocatalyst in the presence of a mediator, namely soluble neutral red (NR), soluble methyl viologen (MV), neutral red film (FNR), or methyl viologen film (FMV). MFC_DSM provided power and current densities (j) of 0.39 μW·cm⁻² and 2.47 μA·cm⁻², respectively, which evidenced that the biocatalyst performs direct electron transfer (DET). Introducing 150.0 µM NR or MV into the MFC_DSM improved the current density by 7.0- and 3.7-fold (17.05 and 8.45 μA·cm⁻²), respectively. After 20 cyclic voltammetry (CV) cycles, the presence of FNR in the MFC_DSM anodic chamber provided an almost twofold higher current density (30.76 µA·cm⁻²) compared to the presence of NR in the MFC_DSM. Introducing MV or FMV into the MFC_DSM anodic chamber gave practically the same current density after 10 CV cycles. The MFC_DSM anodic electrode might interact with FMV weakly than with FNR, so FNR is more promising to enhance C. pasteurianum DSM 525 EET within MFC_DSM. Full article

Mathematical modeling and computer simulation are tools of great importance for the development of fuel cells. Thus, the objective of this work is to carry out the kinetic modeling of glycerol oxidation in a DGFC (direct glycerol fuel cell), considering two different approaches: (1) realistic phenomenological models for the partial oxidation of glycerol in Pt/C, considering its adsorbed intermediates; (2) models of artificial neural networks (ANN—artificial neural networks) for oxidation mainly of PtAg/C and PtAg/MnO_x/C. The models were fitted to experimental data already available for validation and determination of their parameters, both using Matlab software, v. R2018a (MathWorks, Natick, MA, USA). Results for the phenomenological models developed showed excellent fits for the polarization curve, with an RMSE (root mean squared error) value on the order of 0.352 to 0.404 mA/cm², in addition to coverage fractions consistent with the literature for the adsorbed species. The kinetic parameters with the greatest influence on the response of the models were those associated with the consumption of glyceric acid and the formation of tartronic acid and with the dissociative adsorption of water and the formation of Pt-O_ads active sites. Regarding the neural models, excellent prediction fits were obtained for all of them, with RMSE values on the order of 0.008 to 0.014 mA/cm², indicating the possibility of representing the functional interdependence between input variables and the density cell current for cases where it would be too complex to do so via mechanistic modeling (i.e., for PtAg/C and PtAg/MnO_x/C oxidation). Full article

Microbial fuel cells (MFCs) offer sustainable solutions for various biotechnological applications and are a crucial area of research in biotechnology. MFCs can effectively treat various refuse, such as wastewater and biodiesel waste by decomposing organic matter and generating electricity. Certain Pseudomonas species possess extracellular electron transfer (EET) pathways, enabling them to transfer electrons from organic compounds to the MFC’s anode. Moreover, Pseudomonas species can grow under low-oxygen conditions, which is advantageous considering that the electron transfer process in an MFC typically leads to reduced oxygen levels at the anode. This study focuses on evaluating MFCs inoculated with a new Pseudomonas species grown with 1 g.L⁻¹ glycerol, a common byproduct of biodiesel production. Pseudomonas sp. BJa5 exhibited a maximum power density of 39 mW.m⁻². Also, the observed voltammograms and genome analysis indicate the potential production of novel redox mediators by BJa5. Additionally, we investigated the bacterium’s potential as a synthetic biology non-model chassis. Through testing various genetic parts, including constitutive promoters, replication origins and cargos using pSEVA vectors as a scaffold, we assessed the bacterium’s suitability. Overall, our findings offer valuable insights into utilizing Pseudomonas spp. BJa5 as a novel chassis for MFCs. Synthetic biology approaches can further enhance the performance of this bacterium in MFCs, providing avenues for improvement. Full article

The ability of some bacteria to perform Extracellular Electron Transfer (EET) has been explored in bioelectrochemical systems (BES) to obtain energy or chemicals from pure substances or residual substrates. Here, a new pyoverdine-producing Pseudomonas aeruginosa strain was isolated from an MFC biofilm oxidizing glycerol, a by-product of biodiesel production. Strain EL14 was investigated to assess its electrogenic ability and products. In an open circuit system (fermentation system), EL14 was able to consume glycerol and produce 1,3-propanediol, an unusual product from glycerol oxidation in P. aeruginosa. The microbial fuel cell (MFC) EL14 reached a current density of 82.4 mA m⁻² during the first feeding cycle, then dropped sharply as the biofilm fell off. Cyclic voltammetry suggests that electron transfer to the anode occurs indirectly, i.e., through a redox substance, with redox peak at 0.22 V (vs Ag/AgCl), and directly probably by membrane redox proteins, with redox peak at 0.05 V (vs Ag/AgCl). EL14 produced added-value bioproducts, acetic and butyric acids, as well as 1,3 propanediol, in both fermentative and anodic conditions. However, the yield of 1,3-PDO from glycerol was enhanced from 0.57 to 0.89 (mol of 1,3-PDO mol⁻¹ of glycerol) under MFC conditions compared to fermentation. This result was unexpected, since successful 1,3-PDO production is not usually associated with P. aeruginosa glycerol metabolism. By comparing EL14 genomic sequences related to the 1,3-PDO biosynthesis with P. aeruginosa reference strains, we observed that strain EL14 has three copies of the dhaT gene (1,3-propanediol dehydrogenase a different arrangement compared to other Pseudomonas isolates). Thus, this work functionally characterizes a bacterium never before associated with 1,3-PDO biosynthesis, indicating its potential for converting a by-product of the biodiesel industry into an emerging chemical product. Full article

An efficient electrochemical energy conversion system with little to no environmental impact is the fuel cell (FC). FCs have demonstrated encouraging results in various applications and can even run on biofuel, such as bio-glycerol, a by-product of biodiesel. The most effective ways to operate FCs can significantly enhance their effectiveness. Incorporating fuzzy modeling and metaheuristic methods, this work used artificial intelligence to determine the ideal operating parameters for a microfluidic fuel cell (MFC). The concentrations of the following four variables were considered: bio-glycerol concentration, anode electrocatalyst loading, anode electrolyte concentration, and cathode electrolyte concentration. The output power density of the MFC was used to assess its performance. The output power density of the MFC was modeled using fuzzy logic, taking into account the aforementioned operational parameters. A jellyfish search optimizer (JSO) was then used to find the ideal operating conditions. The results were contrasted with response surface methodology (RSM) and experimental datasets to demonstrate the superiority of the proposed integration between fuzzy modeling and the JSO. In comparison with the measured and RSM approaches, the suggested strategy boosted the power density of the MFC by 9.38% and 8.6%, respectively. Full article

Developing a hybrid composite polymer membrane with desired functional and intrinsic properties has gained significant consideration in the fabrication of proton exchange membranes for microbial fuel cell applications. Among the different polymers, a naturally derived cellulose biopolymer has excellent benefits over synthetic polymers derived from petrochemical byproducts. However, the inferior physicochemical, thermal, and mechanical properties of biopolymers limit their benefits. In this study, we developed a new hybrid polymer composite of a semi-synthetic cellulose acetate (CA) polymer derivate incorporated with inorganic silica (SiO₂) nanoparticles, with or without a sulfonation (–SO₃H) functional group (sSiO₂). The excellent composite membrane formation was further improved by adding a plasticizer (glycerol (G)) and optimized by varying the SiO₂ concentration in the polymer membrane matrix. The composite membrane’s effectively improved physicochemical properties (water uptake, swelling ratio, proton conductivity, and ion exchange capacity) were identified because of the intramolecular bonding between the cellulose acetate, SiO₂, and plasticizer. The proton (H⁺) transfer properties were exhibited in the composite membrane by incorporating sSiO₂. The composite CAG–2% sSiO₂ membrane exhibited a higher proton conductivity (6.4 mS/cm) than the pristine CA membrane. The homogeneous incorporation of SiO₂ inorganic additives in the polymer matrix provided excellent mechanical properties. Due to the enhancement of the physicochemical, thermal, and mechanical properties, CAG–sSiO₂ can effectively be considered an eco-friendly, low-cost, and efficient proton exchange membrane for enhancing MFC performance. Full article

The development of MFC using electroactive industrial microorganisms has seen a surge of interest because of the co-generation for bioproduct and electricity production. Vibrio natriegens as a promising next-generation industrial microorganism chassis and its application for microbial fuel cells (MFC) was first studied. Mediated electron transfer was found in V. natriegens MFC (VMFC), but V. natriegens cannot secrete sufficient electron mediators to transfer electrons to the anode. All seven electron mediators supplemented are capable of improving the electronic transfer efficiency of VMFC. The media and carbon sources switching study reveals that VMFCs have excellent bioelectricity generation performance with feedstock flexibility and high salt-tolerance. Among them, 1% glycerol as the sole carbon source produced the highest power density of 111.9 ± 6.7 mW/cm². The insight of the endogenous electronic mediators found that phenazine-1-carboxamide, phenazine-1-carboxylic acid, and 1-hydroxyphenazine are synthesized by V. natriegens via the shikimate pathway and the phenazine synthesis and modification pathways. This work provides the first proof for emerging industrial biotechnology chassis V. natriegens as a novel high salt-tolerant and feedstock flexibility electroactive microorganism for MFC, and giving insight into the endogenous electron mediator biosynthesis of VMFC, paving the way for the application of V. natriegens in MFC and even microbial electrofermentation (EF). Full article

The need for a more sustainable society has prompted the development of bio-based processes to produce fuels, chemicals, and materials in substitution for fossil-based ones. In this context, microorganisms have been employed to convert renewable carbon sources into various products. The methylotrophic yeast Komagataella phaffii has been extensively used in the production of heterologous proteins. More recently, it has been explored as a host organism to produce various chemicals through new metabolic engineering and synthetic biology tools. This review first summarizes Komagataella taxonomy and diversity and then highlights the recent approaches in cell engineering to produce renewable chemicals and proteins. Finally, strategies to optimize and develop new fermentative processes using K. phaffii as a cell factory are presented and discussed. The yeast K. phaffii shows an outstanding performance for renewable chemicals and protein production due to its ability to metabolize different carbon sources and the availability of engineering tools. Indeed, it has been employed in producing alcohols, carboxylic acids, proteins, and other compounds using different carbon sources, including glycerol, glucose, xylose, methanol, and even CO₂. Full article

Ketogenic diets (KDs) are very low-carbohydrate, very high-fat diets which promote nutritional ketosis and impact energetic metabolism. Aquaporins (AQPs) are transmembrane channels that facilitate water and glycerol transport across cell membranes and are critical players in energy homeostasis. Altered AQP expression or function impacts fat accumulation and related comorbidities, such as the metabolic syndrome. Here, we sought to determine whether nutritional ketosis impacts AQPs expression in the context of an atherogenic model. To do this, we fed ApoE^−/− (apolipoprotein E-deficient) mice, a model of human atherosclerosis, a KD (Kcal%: 1/81/18, carbohydrate/fat/protein) or a control diet (Kcal%: 70/11/18, carbohydrate/fat/protein) for 12 weeks. Plasma was collected for biochemical analysis. Upon euthanasia, livers, white adipose tissue (WAT), and brown adipose tissue (BAT) were used for gene expression studies. Mice fed the KD and control diets exhibited similar body weights, despite the profoundly different fat contents in the two diets. Moreover, KD-fed mice developed nutritional ketosis and showed increased expression of thermogenic genes in BAT. Additionally, these mice presented an increase in Aqp9 transcripts in BAT, but not in WAT, which suggests the participation of Aqp9 in the influx of excess plasma glycerol to fuel thermogenesis, while the up-regulation of Aqp7 in the liver suggests the involvement of this aquaporin in glycerol influx into hepatocytes. The relationship between nutritional ketosis, energy homeostasis, and the AQP network demands further investigation. Full article

In this study, Nd_1.6Ca_0.4Ni_1−yCu_yO_4+δ-based electrode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) are investigated. Materials of the series (y = 0–0.4) are obtained by pyrolysis of glycerol-nitrate compositions. The study of crystal structure and high-temperature stability in air and under low oxygen partial pressure atmospheres are performed using high-resolution neutron and in situ X-ray powder diffraction. All the samples under the study assume a structure with Bmab sp.gr. below 350 °C and with I4/mmm sp.gr. above 500 °C. A transition in the volume thermal expansion coefficient values from 7.8–9.3 to 9.1–12.0 × 10⁻⁶, K⁻¹ is observed at approximately 400 °C in air and 500 °C in helium.The oxygen self-diffusion coefficient values, obtained using isotope exchange, monotonically decrease with the Cu content increasing, while concentration dependence of the charge carriers goes through the maximum at x = 0.2. The Nd_1.6Ca_0.4Ni_0.8Cu_0.2O_4+δ electrode materialdemonstrates chemical compatibility and superior electrochemical performance in the symmetrical cells with Ce_0.8Sm_0.2O_1.9, BaCe_0.8Sm_0.2O_3−δ, BaCe_0.8Gd_0.19Cu_0.1O_3−δ and BaCe_0.5Zr_0.3Y_0.1Yb_0.1O_3−δ solid electrolytes, potentially for application in IT-SOFCs. Full article

Antifreeze proteins (AFPs) or thermal hysteresis (TH) proteins are biomolecular gifts of nature to sustain life in extremely cold environments. This family of peptides, glycopeptides and proteins produced by diverse organisms including bacteria, yeast, insects and fish act by non-colligatively depressing the freezing temperature of the water below its melting point in a process termed thermal hysteresis which is then responsible for ice crystal equilibrium and inhibition of ice recrystallisation; the major cause of cell dehydration, membrane rupture and subsequent cryodamage. Scientists on the other hand have been exploring various substances as cryoprotectants. Some of the cryoprotectants in use include trehalose, dimethyl sulfoxide (DMSO), ethylene glycol (EG), sucrose, propylene glycol (PG) and glycerol but their extensive application is limited mostly by toxicity, thus fueling the quest for better cryoprotectants. Hence, extracting or synthesizing antifreeze protein and testing their cryoprotective activity has become a popular topic among researchers. Research concerning AFPs encompasses lots of effort ranging from understanding their sources and mechanism of action, extraction and purification/synthesis to structural elucidation with the aim of achieving better outcomes in cryopreservation. This review explores the potential clinical application of AFPs in the cryopreservation of different cells, tissues and organs. Here, we discuss novel approaches, identify research gaps and propose future research directions in the application of AFPs based on recent studies with the aim of achieving successful clinical and commercial use of AFPs in the future. Full article

There are so many variables affecting the large-scale chemical synthesis of nanoparticles that mass production remains a challenge. Here, using a high-efficiency compact electron beam generator irradiating a low-energy electron beam, we fabricate carbon-supported Pt nanoparticles (Pt/C) in an open chamber to present the applicability of an electron beam to the mass production of metal nanocatalysts for polymer electrolyte membrane fuel cells (PEMFCs). The amount of dispersants (glycerol) and radical scavengers (isopropyl alcohol, IPA), the most important factors in the electron beam-induced fabrication process, is systematically controlled to find the conditions for the synthesis of the particle structure suitable for PEMFC applications. Furthermore, the effects of the structural changes on the electrochemical properties of the catalysts are thoroughly investigated. Through in-depth studies, it is clearly revealed that while dispersants control the nucleation step of monomers affecting the degree of dispersion of nanoparticles, radical scavengers with strong oxidizing power have an effect on the particle growth rate. Therefore, this study is expected to present the applicability of low-energy electron beam to the mass production of metal nanocatalysts for PEMFCs, and to provide insights into the fabrication of nanoparticles using low-energy electron beams. Full article