Patric Jannasch

Lund University | LU · Department of Chemistry

The development of recyclable crosslinked thermosetting fibres is a challenging research topic. In the present work, we have designed and synthesized polyurethane fibres from fructose‐derived 5‐chloromethylfurfural (CMF) and lignin‐derived monomeric phenols. The greenhouse gas emissions associated with the production of CMF showed comparable result...

There is currently a great need for rigid, high‐performance and processable bio‐based polymers and plastics as alternatives to the fossil‐based materials used today. Here, we report on the straightforward synthesis and polymerization of lignin‐derived methacrylate monomers based on the methyl esters of 4‐hydroxybenzoic, vanillic, and syringic acid,...

Ionomers based on poly(arylene piperidinium)s with varying ion exchange capacities are evaluated in different combinations of anode and cathode electrodes in anion exchange membrane fuel cells. The operational conditions are chosen with an asymmetrical regime including a dry anode with 50% relative humidity at the inlet, and full humidification at...

Poly(arylene piperidinium)s are attractive anion exchange membranes (AEMs) for alkaline membrane fuel cells and water electrolyzers because of their high chemical stability and hydroxide conductivity. Here, ether‐ and fluorine‐free hydroxide conducting poly(quaterphenyl piperidinium) membranes with very similar ion exchange capacity (IEC), but diff...

Alkaline ion‐solvating membranes derived from a tetrazole functionalized poly(arylene alkylene) are prepared, characterized and evaluated as electrode separators in alkaline water electrolysis. The base polymer, poly[[1,1′‐biphenyl]‐4,4′‐diyl(1,1,1‐trifluoropropan‐2‐yl)], is synthesized by superacid catalyzed polyhydroxyalkylation and subsequently...

This review provides a depth of knowledge on the synthesis, properties and performance of aryl ether-free anion exchange polymer electrolytes for electrochemical and energy devices.

Traditionally, alkaline water electrolysis (AWE) uses diaphragms to separate anode and cathode and is operated with 5–7 M KOH feed solutions. The ban of asbestos diaphragms led to the development of polymeric diaphragms, which are now the state of the art material. A promising alternative is the ion solvating membrane. Recent developments show that...

Incorporating hydrolytically sensitive functional groups into polymer backbones provides a feasible strategy to trigger their degradation to the starting monomers, thus enabling chemical recycling of the material. Here, we present...

Anion exchange membrane water electrolysis (AEMWE) has a great potential to be established as a high-performance and low-capital cost technology for hydrogen production. Higher current densities can be achieved with...

Over recent years, non-fluorinated ion exchange membranes based on poly(terphenylene) backbones carrying different functional groups have shown potential application for vanadium redox flow batteries (VRFBs). Generally, the ion exchange membrane in VRFBs is a critical component in terms of the output power, longterm stability and cost. Yet, the sho...

Well-designed block copolymers with a controlled co-continuous microphase morphology can be applied as efficient anion exchange membranes (AEMs) for fuel cells and water electrolyzers. In the present work, we have prepared and studied a series of BAB triblock copolymers consisting of a central cationic polyfluorene A block with flanking hydrophobic...

Reversible crosslinking offers an attractive strategy to modify and improve the properties of polymer materials while concurrently enabling a pathway for chemical recycling. This can, for example, be achieved by incorporating a ketone functionality into the polymer structure to enable post-polymerization crosslinking with dihydrazides. The resultin...

Ag nanoparticles (Ag NPs) are among the most promising candidates to replace Pt as the catalyst for the oxygen reduction reaction (ORR) in anion exchange membrane fuel cells (AEMFCs). However, synthesizing size- controlled Ag NPs with efficient catalytic performance is still challenging. Herein, uniform Ag NPs are produced through a γ-radiation ind...

Multi-gigawatt-scale hydrogen production by water electrolysis is central in the green transition when it comes to storage of energy and forming the basis for sustainable fuels and materials. Alkaline water electrolysis plays a key role in this context, as the scale of implementation is not limited by the availability of scarce and expensive raw ma...

Isosorbide is a well-investigated and accessible biomass-derived compound that has found wide use in medicine, cosmetics, and material sciences. The efforts to employ this rigid bicyclic diol as a sustainable...

Polybenzimidazole (PBI) is currently considered as a membrane material for alkaline water electrolyzers (AWEs), and has to be fed with highly concentrated aqueous KOH electrolytes in order to ensure sufficient...

Poly(xanthene)s (PXs) carrying trimethylammonium, methylpiperidinium, and quinuclidinium cations were synthesized and studied as a new class of anion exchange membranes (AEMs). The polymers were prepared in a superacid-mediated polyhydroxyalkylation involving 4,4′-biphenol and 1-bromo-3-(trifluoroacetylphenyl)-propane, followed by quaternization re...

Polymeric anion-exchange membranes (AEMs) with alkali-stable quaternary ammonium (QA) cations are essential components for the development of alkaline membrane fuel cells and water electrolyzers. Ionic loss by β-elimination reactions typically accelerates at low water contents, i.e., high alkali concentrations, which makes QA cations attached to po...

Incorporating rigid cyclic acetal and ketal units into polymer structures is an important strategy toward recyclable high-performance materials from renewable resources. In the present work, citric acid, a widely used platform chemical derived from biomass, has been efficiently converted into di- and tricyclic diketones. Ketalization with glycerol...

Alkaline membrane fuel cells can operate using nonprecious metals as catalysts, but rely on polymeric membranes with high hydroxide conductivity and alkali-resistance, which are hard to find. A new membrane is now reported comprising ferrocenium cations in magnetically aligned domains with an excellent combination of these properties.

Molecularly well-designed proton exchange membranes (PEMs) with a high local concentration of strongly acidic groups have the potential to fulfill the strict requirements for fuel cell operation under high temperature and low humidity. Here, we have prepared a series of well-defined and tunable PEMs based on poly(p-phenylene alkylene) backbones fun...

Anion exchange membrane water electrolysis (AEMWE) is a potentially low-cost and sustainable technology for hydrogen production that combines the advantages of proton exchange membrane water electrolysis and traditional alkaline water...

Energy conversion devices such as alkaline membrane fuel cells and water electrolyzers rely critically on durable anion exchange membranes (AEMs) with high hydroxide conductivity. In this context, poly(arylene piperidinium)s have emerged as one of the top candidate materials. Here, we report on the preparation and properties of poly(arylene alkylen...

Anion exchange membranes (AEMs) functionalized with certain alicyclic quaternary ammonium cations show high alkaline stability, which is necessary for use in fuel cells and water electrolyzers. Here, we have prepared and studied a series of poly(fluorene alkylene)s incorporating N,N-dimethylpiperidinium (DMP) and 6-azoniaspiro[5.5]undecane (ASU) ca...

We here report on the synthesis and polymerization of nitrile-containing methacrylate monomers, prepared via straightforward nitrilation of the corresponding lignin-inspired aldehyde. The polymethacrylates reached exceptionally high glass transition temperatures (Tg values), i.e., 150, 164, and 238 °C for the 4-hydroxybenzonitrile, vanillonitrile,...

To develop anion exchange membranes (AEMs) that combine high chemical stability and hydroxide conductivity, we have designed and prepared poly(arylene piperidine)s carrying tunable mono- or dicationic side chains. Poly(biphenyl piperidine) and poly(biphenyl N-methylpiperidine), respectively, were first synthesized by superacid-catalyzed polyhydroxy...

A rigid diol with a cyclic acetal structure was synthesized by facile acetalation of fructose-based 5-hydroxymethyl furfural (HMF) and partly bio-based di-trimethylolpropane (di-TMP). This diol (Monomer T) was copolymerized with potentially bio-based flexible polytetrahydrofuran and diisocyanates to prepare thermoplastic poly(cycloacetal-urethane)s...

Awakening interest in anion exchange membrane fuel cells (AEMFC) for low temperature applications has led to an increased demand for high-performing polymers stable under alkaline conditions. In this study a poly(p-terphenylene piperidinium)-based membrane and ionomer was synthesized and applied in membrane electrode assemblies (MEAs), with porous...

We present here a series of thermoresponsive glycopolymers in the form of poly(N-isopropylacrylamide)-co-(2-[β-manno[oligo]syloxy] ethyl methacrylate)s. These copolymers were prepared from oligo-β-mannosyl ethyl methacrylates that were synthesized through enzymatic catalysis, and were subsequently investigated with respect to their aggregation and...

Rechargeable batteries that use redox-active organic compounds are currently considered an energy storage technology for the future. Functionalizing redox-active groups onto conducting polymers to make conducting redox polymers (CRPs) can effectively solve the low conductivity and dissolution problems of redox-active compounds. Here, we employ a so...

In the pursuit of anion exchange membranes (AEMs) with high alkaline stability and hydroxide conductivity, we have prepared and characterized a series of poly(fluorene alkylene)s in which each fluorene unit was functionalized with dual pairs of quaternary piperidinium cations on flexible alkyl spacer chains. First, ether-free precursor polymers wer...

Solid single-ion conducting electrolytes based on well-defined block copolymers show great potential for use in lithium batteries. Here, we report on triblock copolymers with an ion-conductive poly(ethylene oxide) (PEO) center block and two flanking blocks of poly(lithium 2,3,5,6-tetrafluorostyrene-4-trifluoromethanesulfonamide). The copolymers wer...

Phosphonated aromatic polymers show several important advantages as proton exchange membranes (PEMs), including high thermal and chemical stability. However, the conductivity needs to be significantly enhanced for most electrochemical applications. Here, we have prepared a series poly(p-terphenyl perfluoroalkylene)s functionalized with highly acidi...

Levulinic acid derived from lignocellulose is an important biobased building block chemical. Here, we report on the synthesis and polymerization of a rigid spirocyclic diester monomer to produce polyesters and...

A series of regioisomeric isosorbide mono-epoxides, as well as diastereomerically pure mono-epoxy derivatives, have been prepared and studied. Anionic ring-opening polymerization of methoxy-capped monomers produced linear polyethers tethered with isosorbide...

p>Rechargeable batteries that use redox-active organic compounds are currently considered as an energy storage technology for the future. Conducting redox polymers (CRPs) are organic materials being both electronically conducting and resilient to dissolution. While insolubility is an advantageous property for active battery materials, it complicate...

We have prepared a series of 12 d-isosorbide-2-alkanoate-5-methacrylate monomers as single regioisomers with different pendant linear C2–C20 alkanoyl chains using biocatalytic and chemical acylations. By conventional radical polymerization, these monomers provided high-molecular-weight biobased poly(alkanoyl isosorbide methacrylate)s (PAIMAs). Samp...

High alkaline stability is critical for polymeric anion exchange membranes (AEMs) and ionomers for use in alkaline electrochemical energy conversion and storage devices such as fuel cells, electrolyzer cells and advanced batteries. Here, we have prepared and studied ether-free polyfluorenes tethered with N,N-dimethylpiperidinium (DMP) and 6-azonia-...

The potential application of a 50 μm thick anion exchange membrane prepared based on poly(terphenyl piperidinium-co-trifluoroacetophenone) (PTPT) is investigated for vanadium redox flow batteries (VRFBs). The PTPT exhibits a considerably lower vanadium permeation than Nafion 212. Therefore, the self-discharge duration of the VRFB based on PTPT is m...

Rigid-rod polymers tethered with delocalized anions and flexible ion conductive side chains present a synthetic pathway towards thin, single-ion conducting electrolyte membranes with low bulk resistance and high mechanical stability. In the present work we have synthesized poly(p-phenylene) (PpP) copolymers carrying lithium trifluoromethanesulfonim...

Hypothesis Colloidal particles that interact via a long-ranged repulsive barrier in combination with a very short-ranged attractive minimum can “polymerize” to form highly anisotropic structures. Motivated by previous experimental achievements in non-aqueous solvents, and recent theoretical predictions, we hypothesize that it is possible to constru...

Different anion-exchange membranes (AEMs) based on polystyrene (PS)-carrying benzyltrimethyl ammonium cations are currently being developed for use in alkaline fuel cells and water electrolyzers. However, the stability in relation to these state-of-the-art cations needs to be further improved. Here, we introduce highly alkali-stable mono- and spiro...

Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bic...

Salt-containing supramolecular assemblies of rigid-rod polymers tethered with flexible ion-solvating side chains represent a synthetic pathway towards thin ion-conducting solid electrolyte membranes with high dimensional stability. In the present work we have synthesized poly(p-phenylene)s (PpPs) carrying di-, tri- and tetra(ethylene oxide) side ch...

Four novel poly(phenylene oxide)-based anion exchange membranes were investigated for electrochemical performance, ionic conductivity and water transport properties in an operating anion exchange membrane fuel cell (AEMFC) , using Pt/C gas diffusion electrodes with Tokuyama ionomer. The poly(phenylene oxide)-membranes have a 1- or 5-carbon alkyl sp...

Vapor phase polymerization (VPP) is used to fabricate a series of tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes on carbon paper. The series of VPP PEDOT/tosylate coatings has varying levels of crystallinity and electrical conductivity because of the use (or not) of nonionic triblock copolymers in the oxidant solution during syn...

There is currently an intensive development of sugar-based building blocks toward the production of renewable high-performance plastics. In this context, we report on the synthesis of a rigid diol with a spirocyclic structure via a one-step acid-catalyzed acetalation of fructose-sourced 5-hydroxymethylfurfural and pentaerythritol. Preliminary life...

We report on aryl ether-free 2,7-diphenylfluorene-based copolymers tethered with quinuclidinium (Qui) cations via hexyl spacers prepared through superacid catalyzed Friedel-Crafts polycondensation and quaternization reactions. The 2,7-diphenylfluorene monomers were prepared by Suzuki coupling and employed to increase polymer backbone stiffness. Cor...

Bio-based rigid diols are key building blocks in the development and preparation of high performance bioplastics with improved thermal and dimensional stability. Here, we report on the straightforward two-step synthesis of a diol with a spirocyclic acetal structure, starting from bio-based vanillin and pentaerythritol. According to a preliminary li...

We report on the straightforward metal-free synthesis of poly(p-terphenyl perfluorophenylsulfonic acid)s by efficient superacid-catalyzed Friedel-Crafts polycondensations of commercially available perfluoroacetophenone and p-terphenyl, followed by sulfonation of the pendant pentafluorophenyl groups via a selective and quantitative thiolation-oxidat...

Pyridinium triflate protic ionic liquids have been demonstrated to be highly dissociated, and nonstoichiometric compositions have been used in protic energy devices such as the all-organic proton battery. Herein, we use a combination of pulsed field gradient NMR spectroscopy and electrochemical impedance spectroscopy to investigate the charge trans...

Nonstoichiometric protic ionic liquids have recently gained interest because proton acceptors are crucial in the electrolyte of many electrochemical applications such as fuel cells, proton batteries and supercapacitors. In the present work we have prepared and studied several protic poly(ionic liquid)s doped with acid in nonstoichiometric amounts....

Solid single-Li⁺-ion conducting polymer electrolytes are currently explored for safe high-temperature lithium batteries. In the present work we have prepared and studied materials based on alternating mesogen-like naphthalene sulfonate units interconnected by flexible poly(ethylene oxide) (PEO) segments in order to induce microphase separation and...

Ion exchange membranes with high ionic contents typically suffer from excessive water uptake and dilution effects which compromise both mechanical properties and ion conductivity. In the present work we develop and compare partial quaternization, copolymerization and crosslinking as three different synthetic strategies to balance the ion exchange c...

We show that glycoside hydrolases can catalyse the synthesis of glycosyl acrylate monomers using renewable hemicellulose as glycosyl donor, and we also demonstrate the preparation of novel glycopolymers by radical polymerisation of these monomers. For this, two family 5 β-mannanases (TrMan5A from Trichoderma reesei and AnMan5B from Aspergillus nige...

Hemicellulose is a promising renewable raw material for the production of hydrogels. This polysaccharide exists in large amounts in various waste streams, in which they are usually impure and heavily diluted. Several downstream processing methods can be combined to concentrate and purify the hemicellulose. However, such an approach can be costly; h...

Isosorbide is a stiff bicyclic diol derived from glycose-based polysaccharides, and is thus an attractive building block for novel rigid bioplastics. In the present work a highly regioselective biocatalytic approach for the synthesis of isosorbide 5-methacrylate was developed. The Lipozyme RM IM (Rhizomucor miehei lipase) catalyzed process is strai...

Non stoichiometric protic ionic liquids (NSPILs) are efficient electrolytes for protic electrochemical devices such as the all-organic proton battery, which has been suggested as a sustainable approach to energy storage. NSPILs contain a mixture of proton donors and acceptors and are ideal for this purpose due to their high proton conductivity, hig...

Aromatic polymers functionalised with cycloaliphatic quaternary ammonium (QA) cations are currently emerging as base-stable anion exchange membranes (AEMs) for use in alkaline fuel cells and water electrolyzers. In the present work we have first prepared poly(biphenyl piperidine)s in superacid-mediated polycondensations, and then introduced differe...

The objective of the present work is to, in a single material, combine a number of molecular design strategies that have proven successful in the preparation of high-performance anion-exchange membranes (AEMs) for alkaline fuel cells. Hence, we here report on highly conductive and alkali-stable poly(phenylene oxide)s carrying flexible side chains a...

Anion exchange membrane fuel cells (AEMFC) or hydroxide exchange membrane fuel cells (HEMFC) are emerging as possible alternatives to proton exchange membrane fuels cells [1]. The alkaline environment in these fuel cells make possible the use of platinum free catalysts since the oxygen reduction is more easily catalysed. In addition, the higher pH...