Catalyst Development for High-Temperature Polymer Electrolyte Membrane Fuel Cell (HT-PEMFC) Applications.

A constant increase in global emission standard is causing fuel cell (FC) technology to gain importance. Over the last two decades, a great deal of research has been focused on developing more active catalysts to boost the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC), as well as their durability. Due to material degradation at high-temperature conditions, catalyst design becomes challenging. Two main approaches are suggested: (i) alloying platinum (Pt) with low-cost transition metals to reduce Pt usage, and (ii) developing novel catalyst support that anchor metal particles more efficiently while inhibiting corrosion phenomena. In this comprehensive review, the most recent platinum group metal (PGM) and platinum group metal free (PGM-free) catalyst development is detailed, as well as the development of alternative carbon (C) supports for HT-PEMFCs.

Performance degradation and mitigation of high temperature polybenzimidazole-based polymer electrolyte membrane fuel cells.

To meet challenges associated with climate changes due to the continuous increase in global energy demand, implementation of hydrogen and fuel cell technologies, especially the polymer electrolyte membrane type, are recognized as potential solutions. The high temperature polymer electrolyte membrane fuel cell based on acid doped polybenzimidazoles has attracted enormous R&D attention due to the simplified construction and operation of the power system. In order to improve the reliability and lifetime of the technology, studies on material degradation and mitigation are essential. The present work is a comprehensive review of the current knowledge on degradation mechanisms of the fuel cell components including the acid loss, polymer oxidation and catalyst instability due to the metal dissolution and carbon support corrosion. The durability results are updated according to the categories of steady state and dynamic operations. Durability protocols, diagnostic techniques and mitigation strategies are also discussed.

Membrane Assemblies with Soft Protective Layers: Dense and Gel-Type Polybenzimidazole Membranes and Their Use in Vanadium Redox Flow Batteries.

Polybenzimidazole (PBI) membranes show excellent chemical stability and low vanadium crossover in vanadium redox flow batteries (VRFBs), but their high resistance is challenging. This work introduces a concept, membrane assemblies of a highly selective 2 µm thin PBI membrane between two 60 µm thick highly conductive PBI gel membranes, which act as soft protective layers against external mechanical forces and astray carbon fibers from the electrode. The soft layers are produced by casting phosphoric acid solutions of commercial PBI powder into membranes and exchanging the absorbed acid into sulfuric acid. A conductivity of 565 mS cm-1 is achieved. A stability test indicates that gel mPBI and dense PBI-OO have higher stability than dense mPBI and dense py-PBI, and gel/PBI-OO/gel is successfully tested for 1070 cycles (ca. 1000 h) at 100 mA cm-2 in the VRFB. The initial energy efficiency (EE) for the first 50 cycles is 90.5 ± 0.2%, and after a power outage stabilized at 86.3 ± 0.5% for the following 500 cycles. The initial EE is one of the highest published so far, and the materials cost for a membrane assembly is 12.35 U.S. dollars at a production volume of 5000 m2 , which makes these membranes very attractive for commercialization.

Correction: Duburg et al. Composite Polybenzimidazole Membrane with High Capacity Retention for Vanadium Redox Flow Batteries. Molecules 2021, 26, 1679.

The authors wish to make the following changes to their paper [...].

Composite Polybenzimidazole Membrane with High Capacity Retention for Vanadium Redox Flow Batteries.

Currently, energy storage technologies are becoming essential in the transition of replacing fossil fuels with more renewable electricity production means. Among storage technologies, redox flow batteries (RFBs) can represent a valid option due to their unique characteristic of decoupling energy storage from power output. To push RFBs further into the market, it is essential to include low-cost materials such as new generation membranes with low ohmic resistance, high transport selectivity, and long durability. This work proposes a composite membrane for vanadium RFBs and a method of preparation. The membrane was prepared starting from two polymers, meta-polybenzimidazole (6 µm) and porous polypropylene (30 µm), through a gluing approach by hot-pressing. In a vanadium RFB, the composite membrane exhibited a high energy efficiency (~84%) and discharge capacity (~90%) with a 99% capacity retention over 90 cycles at 120 mA·cm-2, exceeding commercial Nafion® NR212 (~82% efficiency, capacity drop from 90% to 40%) and Fumasep® FAP-450 (~76% efficiency, capacity drop from 80 to 65%).

Self-assembled Zn phthalocyanine as a robust p-type selective contact in perovskite solar cells.

The use of self-assembled monolayers (SAMs) as selective charge extracting layers in perovskite solar cells is a great approach to replace the commonly used charge selective contacts, as they can easily modify the interface to enhance the final solar cell performance. Here, we report a novel synthetic approach of the commonly known zinc phtalocyanine (ZnPc) molecule TT1, widely employed in dye-sensitized solar cells and previously used in perovskite solar cells. TT1 is used as a p-type selective contact, and it demonstrates its ability to form SAM on top of the indium tin oxide (ITO) transparent electrode, obtaining higher efficiencies compared to Pedot:PSS based perovskite solar cells. The differences observed, with an enhanced open-circuit voltage and overall efficiency in TT1 devices are correlated with differences in energetics rather than recombination kinetics.

Push-Pull Zinc Phthalocyanine Bearing Hexa-Tertiary Substituted Carbazolyl Donor Groups for Dye-Sensitized Solar Cells.

An asymmetrical, push-pull phthalocyanine bearing bulky tert-butylcarbazolyl moieties as electron donor and carboxylic acid as anchoring group was synthetized and tested as a photosensitizer in dye-sensitized solar cells (DSSC). The new photosensitizer was characterized by 1H and 13C NMR, UV-Vis and mass spectrometry. The bulky tert-butylcarbazolyl moieties avoid the aggregation of the phthalocyanine dye. DFT studies indicate that the HOMO is delocalized throughout the -electron system of the substituted phthalocyanine and the LUMO is located on the core of the molecule with a sizable electron density distribution on carboxyl groups. The new dye has been used as a photosensitizer in transparent and opaque dye-sensitized solar cells, which exhibit poor efficiencies related to a low Jsc.

Radical condensation between benzylic alcohols and acetamides to form 3-arylpropanamides.

A new radical condensation reaction is developed where benzylic alcohols and acetamides are coupled to generate 3-arylpropanamides with water as the only byproduct. The transformation is performed with potassium tert-butoxide as the only additive and gives rise to a variety of 3-arylpropanamides in good yields. The mechanism has been investigated experimentally with labelled substrates, trapping experiments and spectroscopic measurements. The findings indicate a radical pathway where potassium tert-butoxide is believed to serve a dual role as both base and radical initiator. The radical anion of the benzylic alcohol is proposed as the key intermediate, which undergoes coupling with the enolate of the amide to form the new C-C bond. Subsequent elimination to the corresponding cinnamamide and olefin reduction then affords the 3-arylpropanamides.

Manganese(III) Porphyrin-Catalyzed Dehydrogenation of Alcohols to form Imines, Tertiary Amines and Quinolines.

Manganese(III) porphyrin chloride complexes have been developed for the first time as catalysts for the acceptorless dehydrogenative coupling of alcohols and amines. The reaction has been applied to the direct synthesis of imines, tertiary amines and quinolines where only hydrogen gas and/or water are formed as the by-product(s). The mechanism is believed to involve the formation of a manganese(III) alkoxide complex which degrades into the aldehyde and a manganese(III) hydride species. The latter reacts with the alcohol to form hydrogen gas and thereby regenerates the alkoxide complex.