Fabrication of Bipolar Plates from Thermoplastic Elastomer Composites for Vanadium Redox Flow Battery.

A vanadium redox flow battery (VRFB) is a promising large-scale energy storage device, due to its safety, durability, and scalability. The utilization of bipolar plates (BPs), made of thermoplastic vulcanizates (TPVs), synthetic graphite, woven-carbon-fiber fabric (WCFF), and a very thin pyrolytic graphite sheet (GS), is investigated in this study. To boost volumetric electrical conductivity, WCFF was introduced into the TPV composite, and the plate was covered with GS to increase surface electrical conductivity. Created composite BPs acquire the desired electrical conductivity, mechanical strength, and deformation characteristics. Those properties were assessed by a series of characterization experiments, and the morphology was examined using an optical microscope, a scanning electron microscope, and atomic force microscopy. Electrochemical testing was used to confirm the possibility of using the suggested BP in a working VRFB. The laminated BP was utilized in a flow cell to electrolytically convert V(IV) to V(V) and V(II), which achieved comparable results to a commercial graphite bipolar plate. Following these experiments, the laminated bipolar plates' surfaces were examined using X-ray photoelectron spectroscopy, and no evidence of corrosion was found, indicating good durability in the hostile acidic environment.

Kinetic characterization and modeling of sequentially entrapped enzymes in 3D-printed PMMA microfluidic reactors for the synthesis of amorphadiene via the isopentenol utilization pathway.

The development of cascade cell-free systems reduces the requirement for extensive metabolic engineering and optimization to increase in vivo pathway flux. For continuous operation and increased stability, direct enzyme entrapment during reactor fabrication by three-dimensional (3D)-printing allows for simple immobilization procedures without enzyme-specific optimization. In this study, the isopentenol utilization pathway (IUP) was selected for the synthesis of amorphadiene, an antimalaria drug precursor, using a 3D-printed, sequentially immobilized, microfluidic reactor. As an initial proof-of-concept, alkaline phosphatase (ALP) was entrapped in a poly(methyl methacrylate) (PMMA)-based matrix during stereolithographic 3D-printing and was kinetically characterized. No significant shift of the kinetically modeled substrate binding affinity was observed during immobilization and continuous operation of an entrapped ALP microfluidic reactor displayed high stability. The IUP enzymes retained moderate activity during entrapment (6.6%-9.6%) relative to the free enzyme solutions, however the sequentially immobilized IUP microfluidic reactor was severely limited by low pathway flux due to the use of stereolithographic 3D-printing which significantly diluted enzyme concentrations for printing. Although this study demonstrated the use of additive manufacturing for the synthesis of amorphadiene using a complex five-enzyme cascade microfluidic reactor, stereolithographic enzyme entrapment remains limited in scope and dependent on advancements to additive manufacturing technologies.

A Near-Isotropic Proton-Conducting Porous Graphene Oxide Membrane.

A graphene oxide (GO) membrane is an ideal separator for multiple applications due to its morphology, selectivity, controllable oxidation, and high aspect ratio of the 2D nanosheet. However, the anisotropic ion conducting nature caused by its morphology is not favorable toward through-plane conductivity, which is vital for solid-state electrolytes in electrochemical devices. Here, we present a strategy to selectively enhance the through-plane proton conductivity of a GO membrane by reducing its degree of anisotropy with pore formation on the nanosheets through the sonication-assisted Fenton reaction. The obtained porous GO (pGO) membrane is a near-isotropic, proton-conducting GO membrane, showing a degree of anisotropy as low as 2.77 and 47% enhancement of through-plane proton conductivity as opposed to the pristine GO membrane at 25 °C and 100% relative humidity. The anisotropic behavior shows an Arrhenius relationship with temperature, while the water interlayer formation between nanosheets plays a pivotal role in the anisotropic behavior under different values of relative humidity (RH); that is, as low RH increases, water molecules tend to orient in a bimodal distribution clinching the nanosheets and forming a subnanometer, high-aspect-ratio, water interlayer, resulting in its peak anisotropy. Further increase in RH fills the interlayer gap, resulting in behaviors akin to near-isotropic, bulk water. Lastly, implementation of the pGO membrane, as the solid proton-conductive electrolyte, in an alcohol fuel cell sensor has been demonstrated, showcasing the excellent selectivity and response, exceptional linearity, and ethanol detection limits as low as 25 ppm. The amalgamation of excellent performance, high customizability, facile scalability, low cost, and environmental friendliness in the present method holds considerable potential for transforming anisotropic GO membranes into near-isotropic ion conductors to further membrane development and sensing applications.

Ternary Sn-Ti-O Electrocatalyst Boosts the Stability and Energy Efficiency of CO2 Reduction.

Simultaneously improving energy efficiency (EE) and material stability in electrochemical CO2 conversion remains an unsolved challenge. Among a series of ternary Sn-Ti-O electrocatalysts, 3D ordered mesoporous (3DOM) Sn0.3 Ti0.7 O2 achieves a trade-off between active-site exposure and structural stability, demonstrating up to 71.5 % half-cell EE over 200 hours, and a 94.5 % Faradaic efficiency for CO at an overpotential as low as 430 mV. DFT and X-ray absorption fine structure analyses reveal an electron density reconfiguration in the Sn-Ti-O system. A downshift of the orbital band center of Sn and a charge depletion of Ti collectively facilitate the dissociative adsorption of the desired intermediate COOH* for CO formation. It is also beneficial in maintaining a local alkaline environment to suppress H2 and formate formation, and in stabilizing oxygen atoms to prolong durability. These findings provide a new strategy in materials design for efficient CO2 conversion and beyond.

Dispersion modeling in pore networks: A comparison of common pore-scale models and alternative approaches.

Mass transfer in porous media resulting from dispersion occurs in a wide variety of applications such as water treatment, flow batteries, flow in aquifers, enhanced oil recovery, and packed-bed reactors. The underlying mechanisms of dispersion are the molecular diffusion superimposed on the advective transport induced by the fluid flow. Modeling dispersion in pore networks can be performed at a much lower computational cost compared to that in direct numerical simulations (DNS) such as finite element or the lattice Boltzmann methods, so it can be regarded as a suitable alternative provided its accuracy is sufficient. The most common approach to model dispersion in network models is based on the first-order upwind scheme, despite its known limitations in terms of accuracy for certain flow and transport regimes. In this study, three alternative pore-scale models for dispersion, which are more accurate than the existing ones, were derived and tested in pore network simulations. These models were adopted from the CFD literature and are based on a spatial discretization of the advection-diffusion equation using the hybrid and power-law finite difference schemes and the exact solution of the one-dimensional advection-diffusion equation. Finally, considering dispersion problems over arbitrary porous structures, consisting of stick-and-ball geometries, and different flow and mass transfer arrangements, the developed models were validated. Validation was carried-out through comparisons between results obtained with DNS, using a finite element solver, and those from pore network simulations. It is shown that under a wide range of dispersion regimes (up to the onset of the dispersion power-law regime), the relative error (with respect to DNS results) introduced by the power-law and exact solution-based models is consistently below 1%, whereas the use of the upwind scheme leads to >10% of relative error, depending on the dispersion regime. All the dispersion models developed in this study were implemented as part of the open-source network modeling package, OpenPNM.

Highly Photostable and Fluorescent Microporous Solids Prepared via Solid-State Entrapment of Boron Dipyrromethene Dyes in a Nascent Metal-Organic Framework.

We report a strategy to synthesize highly emissive, photostable, microporous materials by solid-state entrapment of boron dipyrromethene (BODIPY) fluorophores in a metal-organic framework. Solvent-free mechanochemistry or accelerated aging enabled quantitative capture and dispersal of the PM605 dye within the ZIF-8 framework starting from inexpensive, commercial materials. While the design of emissive BODIPY solids is normally challenged by quenching in a densely packed environment, herein reported PM605@ZIF-8 materials show excellent emissive properties and to the best of our knowledge an unprecedented ∼10-fold enhancement of BODIPY photostability. Time-resolved and steady-state fluorescence studies of PM605@ZIF-8 show that interchromophore interactions are minimal at low dye loadings, but at higher ones lead to through-pore energy transfer between chromophores and to aggregate species.

Insights into the Effect of Structural Heterogeneity in Carbonized Electrospun Fibrous Mats for Flow Battery Electrodes by X-Ray Tomography.

Electrospun custom made flow battery electrodes are imaged in 3D using X-ray computed tomography. A variety of computational methods and simulations are applied to the images to determine properties including the porosity, fiber size, and pore size distributions as well as the material permeability and flow distributions. The simulations are performed on materials before and after carbonization to determine the effect it has in the internal microstructure and material properties. It is found that the deposited fiber size is constantly changing throughout the electrospinning process. The results also show that the surfaces of the fibrous material are the most severely altered during carbonization and that the rest of the material remained intact. Pressure driven flow is modeled using the lattice Boltzmann method and excellent agreement with experimental results is found. The simulations coupled with the material analysis also demonstrate the highly heterogeneous nature of the flow. Most of the flow is concentrated to regions with high porosity while regions with low porosity shield other pores and starve them of flow. The importance of imaging these materials in 3D is highlighted throughout.

Versatile and efficient pore network extraction method using marker-based watershed segmentation.

Obtaining structural information from tomographic images of porous materials is a critical component of porous media research. Extracting pore networks is particularly valuable since it enables pore network modeling simulations which can be useful for a host of tasks from predicting transport properties to simulating performance of entire devices. This work reports an efficient algorithm for extracting networks using only standard image analysis techniques. The algorithm was applied to several standard porous materials ranging from sandstone to fibrous mats, and in all cases agreed very well with established or known values for pore and throat sizes, capillary pressure curves, and permeability. In the case of sandstone, the present algorithm was compared to the network obtained using the current state-of-the-art algorithm, and very good agreement was achieved. Most importantly, the network extracted from an image of fibrous media correctly predicted the anisotropic permeability tensor, demonstrating the critical ability to detect key structural features. The highly efficient algorithm allows extraction on fairly large images of 500^{3} voxels in just over 200 s. The ability for one algorithm to match materials as varied as sandstone with 20% porosity and fibrous media with 75% porosity is a significant advancement. The source code for this algorithm is provided.

Electrocatalytic Oxygen Reduction Performance of Silver Nanoparticle Decorated Electrochemically Exfoliated Graphene.

We have developed a potentiostatic double-pulse technique for silver nanoparticle (Ag NP) deposition on graphene (GRn) with superior electronic and ionic conductivity. This approach yielded a two-dimensional electrocatalyst with a homogeneous Ag NP spatial distribution having remarkable performance in the oxygen reduction reaction (ORR). GRn sheets were reproducibly prepared by the electrochemical exfoliation of graphite (GRp) at high yield and purity with a low degree of oxidation. Polystyrenesulfonate added during exfoliation enhanced the stability of the GRn solution by preventing the restacking of the graphene sheets and increased its ionic conductivity. The potentiostatic double-pulse technique is generally used to electrodeposit Pt nanoparticles and remains challenging for silver metal that exhibits nucleation and growth potentials relatively close to each other. We judiciously exploited this narrow margin of potential, and for the first time we report Ag NP electrodeposited onto graphene with the subsequent ability to control both the density and the size of metallic nanoparticles. Considering the high activity along with the lower cost of Ag compared to Pt, these findings are highly relevant to the successful commercialization of fuel cells and other electrochemical energy devices.

Effect of water sorption on the electronic conductivity of porous polymer electrolyte membrane fuel cell catalyst layers.

A method is described for measuring the effective electronic conductivity of porous fuel cell catalyst layers (CLs) as a function of relative humidity (RH). Four formulations of CLs with different carbon black (CB) contents and ionomer equivalent weights (EWs) were tested. The van der Pauw method was used to measure the sheet resistance (RS), which increased with RH for all samples. The increase was attributed to ionomer swelling upon water uptake, which affects the connectivity of CB aggregates. Greater increases in RS were observed for samples with lower EW, which uptake more water on a mass basis per mass ionomer. Transient RS measurements were taken during absorption and desorption, and the resistance kinetics were fit using a double exponential decay model. No hysteresis was observed, and the absorption and desorption kinetics were virtually symmetric. Thickness measurements were attempted at different RHs, but no discernible changes were observed. This finding led to the conclusion that the conducting Pt/C volume fraction does not change with RH, which suggests that effective medium theory models that depend on volume fraction alone cannot explain the reduction in conductivity with RH. The merits of percolation-based models were discussed. Optical micrographs revealed an extensive network of "mud cracks" in some samples. The influence of water sorption on CL conductivity is primarily explained by ionomer swelling, and its effects on the quantity and quality of interaggregate contacts were discussed.