High-performance AEM unitized regenerative fuel cell using Pt-pyrochlore as bifunctional oxygen electrocatalyst.

The performance of fixed-gas unitized regenerative fuel cells (FG-URFCs) are limited by the bifunctional activity of the oxygen electrocatalyst. It is essential to have a good bifunctional oxygen electrocatalyst which can exhibit high activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this regard, Pt-Pb2Ru2O7-x is synthesized by depositing Pt on Pb2Ru2O7-x wherein Pt individually exhibits high ORR while Pb2Ru2O7-x shows high OER and moderate ORR activity. Pt-Pb2Ru2O7-x exhibits higher OER (η@10mAcm-2 = 0.25 ± 0.01 V) and ORR (η@-3mAcm-2 = -0.31 ± 0.02 V) activity in comparison to benchmark OER (IrO2, η@10mAcm-2 = 0.35 ± 0.02 V) and ORR (Pt/C, η@-3mAcm-2 = -0.33 ± 0.02 V) electrocatalysts, respectively. Pt-Pb2Ru2O7-x shows a lower bifunctionality index (η@10mAcm-2, OER- η@-3mAcm-2, ORR) of 0.56 V with more symmetric OER-ORR activity profile than both Pt (>1.0 V) and Pb2Ru2O7-x (0.69 V) making it more useful for the AEM (anion exchange membrane) URFC or metal-air battery applications. FG-URFC tested with Pt-Pb2Ru2O7-x and Pt/C as bifunctional oxygen electrocatalyst and bifunctional hydrogen electrocatalyst, respectively, yields a mass-specific current density of 715 ± 11 A/gcat-1 at 1.8 V and 56 ± 2 A/gcat-1 at 0.9 V under electrolyzer mode and fuel-cell mode, respectively. The FG-URFC shows a round-trip efficiency of 75% at 0.1 A/cm-2, underlying improvement in AEM FG-URFC electrocatalyst design.

Fuel and oxygen harvesting from Martian regolithic brine.

NASA's current mandate is to land humans on Mars by 2033. Here, we demonstrate an approach to produce ultrapure H2 and O2 from liquid-phase Martian regolithic brine at ∼-36 °C. Utilizing a Pb2Ru2O7-δ pyrochlore O2-evolution electrocatalyst and a Pt/C H2-evolution electrocatalyst, we demonstrate a brine electrolyzer with >25× the O2 production rate of the Mars Oxygen In Situ Resource Utilization Experiment (MOXIE) from NASA's Mars 2020 mission for the same input power under Martian terrestrial conditions. Given the Phoenix lander's observation of an active water cycle on Mars and the extensive presence of perchlorate salts that depress water's freezing point to ∼-60 °C, our approach provides a unique pathway to life-support and fuel production for future human missions to Mars.

Co3O4-Impregnated NiO-YSZ: An Efficient Catalyst for Direct Methane Electrooxidation.

Co3O4-impregnated NiO-YSZ (yttria-stabilized zirconia) is a possible electrocatalyst for direct methane electrooxidation with both high catalytic activity and the ability to mitigate coking. The physical and electrochemical properties of Co3O4-impregnated NiO-YSZ anodes are investigated and benchmarked against NiO-YSZ and CeO2-impregnated NiO-YSZ anodes. The following methane electrooxidation activity trend: Co3O4-impregnated NiO-YSZ > CeO2-impregnated NiO-YSZ > NiO-YSZ with io (exchange current density) values of 88, 83, and 2 mA cm-2, respectively, is obtained in the high overpotential region. The high activity of Co3O4-impregnated NiO-YSZ is attributed to the changes in the electronic structure and microstructure with the incorporation of nickel into the lattice of Co3O4 as observed using X-ray photoelectron spectroscopy, temperature-programmed reduction, high-resolution transmission electron microscopy, and field emission scanning electron microscopy. Co3O4-impregnated NiO-YSZ also demonstrated the least coking during operation, confirming its utility as a methane electrooxidation catalyst.

Cobalt-Based Coordination Polymer for Oxygen Reduction Reaction.

Lack of control over the structure and electrically nonconductive properties of coordination polymers (CPs) creates a major hindrance to designing an active electrocatalyst for oxygen reduction reaction (ORR). Here, we report a new semiconductive and low-optical band gap CP structure [{Co3(µ3-OH)(BTB)2(BPE)2}{Co0.5N(C5H5)}], 1, that exhibits high-performance ORR in alkaline medium. The electrical conductivity of compound 1 was measured using impedance spectroscopy and found to be 5 × 10-4 S cm-1. The Ketjenblack EC-600JD carbon used as a support for all the electrochemical methods such as cyclic voltammetry, rotating disk electrode, rotating ring-disk electrode and Koutecký-Levich analysis. The as-synthesized Co-based catalyst has the ability to reduce O2 to H2O by a nearly four-electron process. The crystal structure of 1 shows that the trimeric unit {Co3(µ3-OH)(COO)5N3} and monomeric unit {Co(COO)2(NC5H4)2}2+ are linked with BTB and BPE linkers to form a three-dimensional structure. Theoretical calculations predict that the monomeric center acts as an active catalytic site for ORR. This could be due to the efficient overlap of highest occupied molecular orbital-lowest unoccupied molecular orbital between monomer and O2 molecule. This CP, 1, shows facile 3.6-electron ORR, and it is inexpensive compared with widely used Pt catalysts. Therefore, this CP can be used as a promising cathode material for fuel cells in terms of efficiency and cost effectiveness.

Bifunctional Crosslinking Agents Enhance Anion Exchange Membrane Efficacy for Vanadium Redox Flow Batteries.

A series of cross-linked fluorinated poly (aryl ether oxadiazole) membranes (FPAEOM) derivatized with imidazolium groups were prepared. Poly (N-vinylimidazole) (PVI) was used as the bifunctional cross-linking agent to: a) lower vanadium permeability, b) enhance dimensional stability, and c) concomitantly provide added ion exchange capacity in the resultant anion exchange membranes. At a molar ratio of PVI to FPAEOM of 1.5, the resultant membrane (FPAEOM-1.5 PVI) had an ion exchange capacity of 2.2 meq g-1, a vanadium permeability of 6.8×10-7 cm2 min-1, a water uptake of 68 wt.%, and an ionic conductivity of 22.0 mS cm-1, all at 25°C. Single cells prepared with the FPAEOM-1.5 PVI membrane exhibited a higher coulombic efficiency (> 92%) and energy efficiency (> 86%) after 40 test cycles in vanadium redox flow battery. The imidazolium cation showed high chemical stability in highly acidic and oxidizing vanadium solution as opposed to poor stability in alkaline solutions. Based on our DFT studies, this was attributed to the lower HOMO energy (-7.265 eV) of the HSO4- ion (compared to the OH- ion; -5.496 eV) and the larger HOMO-LUMO energy gap (6.394 eV) of dimethylimidazolium bisulfate ([DMIM] [HSO4]) as compared to [DMIM] [OH] (5.387 eV).