Ion transport of electrolytes determines the performance of many electroactive devices, from fuel cells to batteries to soft mechanical actuators. This dissertation aims to address some fundamental issues regarding ion transport of ion dense electrolytes using electrophoretic NMR and NMR diffusometry. I first describe the design and fabrication of the first instrumentation capable of reliable ENMR on highly ion-dense electrolytes such as ionic liquids and electrolytes for zinc-air batteries. I design a new electrophoretic NMR sample cell using parallel capillaries to investigate the electrophoretic mobilities of pure ionic liquids. It shows the first study of a highly ion-dense electrolyte with electrophoretic NMR. Then I employ NMR diffusometry and electrophoretic NMR to investigate ion association of pure ionic liquids. Then I use electrophoretic NMR technique to investigate the electrophoretic mobilities of electrolytes for zinc-air batteries. For Zn2+ salt added dicyanamide (dca) based ionic liquids, I investigate the effects of Zn2+ salt on chemical shift of dca and ion motion. The combination of mobilities measurements and diffusion measurements provides some new insight of ion aggregation. We explore ion transport of ionic liquids inside the ionic polymer Nafion as a function of hydration level. When ionic liquids diffuse inside ionic polymers, isolated anions diffuse faster (e 4X) than cations at high hydration whereas ion associations result in substantially faster cation diffusion (d 3X) at low hydration inside membranes, revealing prevalent anionic aggregates. Finally, we compare diffusion activation energy measurements in a hydrated perfluorosulfonate ionomer and aqueous solutions of triflic acid, which provides insight into water transport dynamics on sub-nm lengthscales. And we explore the physical meaning of activation energy, characterizing local intermolecular interactions that occur on the pre-diffusional (~ 1 ps) timescale. / Ph. D.

Specific ion effects, identified for more than hundred years, play an important role in a wide range of phenomena and applications. Several mechanisms such as direct ion interaction with molecules have been suggested to explain these effects, but quantitative experimental evidence remains scarce. Electrophoretic NMR (eNMR) has been emerging as a very powerful tool for studying molecular association and ionic transport in a variety of systems. Yet its potential in studying specific ion effect has been unexplored. In this thesis, eNMR was in part developed further as an analytical method and was in part used as one of the main techniques to study ions interacting with macromolecules in aqueous and non-aqueous solutions. The complexation of a large group of cations with poly ethylene oxide (PEO) in methanol was studied with eNMR. The binding of monovalent ions was demonstrated not to follow the Hofmeister order; multivalent cations except barium all showed negligible complexation. As a unifying feature, only cations with surface charge density below a threshold value were able to bind suggesting that ion solvation is critical. The binding mechanism was examined in greater detail for K+ and Ba2+ with oligomeric PEO of different chain lengths. Those two cations exhibited different binding mechanisms. K+ was found to bind to PEO by having at least 6 repeating units wrap around it while retaining the polymer flexibility. On the other hand, Ba2+ (and, to some extent, (BaAnion)+) needs a slightly shorter section to bind, but the molecular dynamics at the binding site slow considerably. The binding of anions with poly (N-isopropylacrylamide) in water was quantified at low salt concentration with eNMR and the binding affinity, though very weak, followed the Hofmeister order. This result indicates the non-electrostatic nature of this specific ion effects. The increase of binding strength with salt concentration is well described by a Langmuir isotherm. The specific ion binding to a protein, bovine serum albumin (BSA), was also studied at pH values where BSA has either net positive and negative charges. Our results show that anions have the same binding affinity irrespective of the surface charge while the binding strength of cations is reversed with the change in net surface charge. This indicates different binding mechanisms for cations and anions. The ionization of cellobiose in alkaline solutions was measured quantitatively by eNMR. The results show a two-step deprotonation process with increasing alkaline strength. Supported by results from 1H-13C HSQC NMR and MD simulation, ionization was proposed to be responsible for the improved solubility of cellulose in alkaline solution. eNMR was also used to characterize the effective charge of tetramethylammonium ions in a variety of solvents. In solvents of high polarity, the results agree well with predictions based on Onsager’s limiting law but for nonpolar solvents deviations were found that were attributed to ion pair formation. / <p>QC 20170216</p>

Even though electrophoretic NMR (eNMR) experiments may provide unique chemical information and have been performed for three decades, the technique is still rarely applied, mainly because several experimental sources of artifacts have to be controlled to achieve accurate results. In this thesis, new experimental setups and protocols for accurate and precise eNMR experiments are presented. These include a novel eNMR sample cell, a radiofrequency filter and methods to suppress bulk flow effects. These developments improved the signal-to-noise ratio by roughly an order of magnitude compared to the U-tube setup previously used for eNMR. Convection-compensated pulse sequences in combination with a phase correction method were found to efficiently suppress bulk flow effects in the experiments and greatly increase experimental accuracy. These experimental setups and protocols were applied to probe association of ions and molecules in solution. It is particularly illustrated that the combination of diffusion and eNMR has great potential to provide quantitative results on ionic and molecular association in a variety of systems. The extent to which ionic surfactants associate with uncharged cyclodextrin probed by eNMR yielded very similar results to those obtained by diffusion NMR experiments. Complexation of a large set of small mono- and polyvalent metal cations to poly(ethylene oxide) was quantified by estimating the effective charge of the polymer through combined diffusion and eNMR information. Significant association was found for cations that have a surface charge density below a critical value. Ion pairing between tetramethylammonium cations and a series of anions in several solvents was also probed by diffusion NMR and eNMR experiments. For the monovalent anions in ethanol and ethanol-water mixture a dependence on ionic size was demonstrated. In water, dimethylsulfoxide, and methanol no such trend and very little pairing was observed. In acetonitrile, a different pattern was seen that did not correlate well with any single ionic parameter. An experimental cell and procedures for electrokinetic studies of solvated proton-conducting polymer materials is also presented. Electro-osmotic flow and diffusion were studied for each molecular component in water-methanol mixtures that swell Nafion membranes. / Elektroforetisk NMR (eNMR) är en experimentell metod som funnits i tre decennier och som kan ge unik kemisk information. Ändå används den sällan då flera experimentella artefakter måste korrigeras för, om man ska få korrekta resultat. I denna avhandling presenteras nya experimentella uppställningar och protokoll ämnade att uppnå korrekta och noggranna resultat. Dessa inkluderar en ny mätcell, ett radiofrekvensfilter och metoder för att minimera effekten av samtidiga bulkflöden i provlösningen. Sammantaget uppnås ungefär en storleksordning högre signal-brus-förhållande jämfört med den U-rörsuppställning som tidigare använts. Konvektions-kompenserande pulssekvenser i kombination med en faskorrektionsteknik minskade också bulkflödeseffekter effektivt, vilket ökade resultatens noggrannhet högst avsevärt. De experimentella uppställningarna och protokollen användes här för att mäta association av joner och molekyler i lösning. Mätningarna visar att kombinationen diffusions- och eNMR har en stor potential att kvantitativt kunna bestämma associationgraden i många olika typer av kemiska system. Associationsgraden mellan joniska tensider och cyklodextriner undersöktes både med eNMR och diffusions-NMR, och resultaten var mycket lika. Komplex-bildningen mellan en serie enkel- och flerladdade metalljoner och poly-(etylenoxid) kvantifierades genom att uppskatta polymerens effektiva laddning från kombinerad diffusions- och eNMR. Betydande komplexbildning hittades för katjoner med ytladdningstäthet under ett kritiskt värde. Jonparbildning mellan tetrametylammoniumjoner och en serie av anjoner i flera olika lösningsmedel undersöktes också med diffusions- och eNMR. För de monovalenta anjonerna i etanol och etanol-vatten-blandning påvisades ett samband med jonstorleken. I vatten, dimetylsulfoxid och metanol var däremot jonparbildningen låg och inget liknande samband hittades. I acetonitril observerades ett annat mönster, som inte korrelerade bra med någon av anjonernas normala joniska karakteristika. Slutligen presenteras en mätcell och procedurer för elektrokinetiska studier i de solvatiserade protonledande polymermaterial som bland annat används i bränsleceller. Elektroosmotiskt flöde och diffusion uppmättes för varje molekylär komponent i Nafion-membran solvatiserade av vatten-metanol-blandningar. / QC20100709

Ionic liquids are continuously finding more and more applications, both in research and in the industry. Many attempts have been made to find parameters that could be used to describe all ionic liquid systems. Five years ago a Japanese group applied the work of Gutmann on ionic liquids to use ionic association to describe solvation effects. The group calculated ionic association from conductivity and diffusion measurements. This report presents a direct approach through electrophoretic NMR to measure ionic association in ionic liquids.  The report contains a brief introduction to ionic liquids and their properties as well as a short explanation of Nuclear Magnetic Resonance (NMR) spectroscopy, diffusion NMR and a more detailed explanation of electrophoretic NMR (eNMR). Experimental setups, taken from previous work by the NMR group at Physical Chemistry KTH, have been modified to allow for measurements in ionic liquid systems. The report discusses the issues that can arise when measuring eNMR in ionic liquids and suggests solutions. The method developed is principally built upon experiments on 1-butyl-3-methyl-imidazolium trifluoroacetate and is directly applicable to other ionic liquid systems. For more viscous systems than the one investigated here, slight changes will need to be made, as explained in the report.  In order to evaluate the method developed during the project the degree of association for 1-butyl-3-methyl-imidazolium trifluoroacetate has been calculated from experimental results and results in similar values as reported by Tokuda et al.. Furthermore, the temperature variation due to Joule heating during a complete eNMR experiment was also investigated by observing change in chemical shift.

PNIPAM (poly(N-Isopropylacrylamide)) is a well-known thermoresponsive polymer. Dissolved in water, it shows a structural change at 32 oC, above which the polymer folds together, and a phase separation occurs. The temperature where the polymer changes structure is known as the LCST (Lower Critical Solution Temperature), and can be modified by adding certain salts to the solution [1]. The mechanism by which the ionic components of the salts affect the LCST is not yet completely understood. The purpose of this master thesis is to study this mechanism. In order to investigate the mechanism, a combination of diffusion NMR and electrophoretic NMR was used, giving the effective charge per molecule which is directly proportional to the grade of association of ions to the polymer. The salts tested were: NaCl, NaClO4, NaSO4, NaI, NaSCN and CaCl2 from which the ClO4-, SCN-, and I- ions, as well as Cl- ions from CaCl2, were found to bind to PNIPAM.

The purpose of this thesis was to investigate how crown ethers behave and interact with different cations and to optimise the setup of the electrophoretic NMR. To get a good electrophoretic NMR measurement the electrophoretic phase shift needs to be big. To increase the phase shift some parameters needed to be adjusted, parameters such as the concentration of crown ether and cation, the duration of magnetic field gradient pulse δ, the magnetic field gradient strength g, the diffusion time Δ and the applied voltage V. The main focus then put on crown ethers 15-crown-5 and 18-crown-6. The cations used were lithium (Li), sodium (Na), potassium (K), caesium (Cs), calcium (Ca) and barium (Ba). The effective charge was obtained by using pulsed gradient NMR to derive the diffusion coefficient and electrophoretic NMR to get the electrophoretic mobility. These data were used to calculate the equilibrium constant of the formed complex. The outcome of the investigation: the affinity for 18-crown-6 was in the following order barium &gt; potassium &gt; caesium &gt; sodium &gt; calcium &gt; lithium and for 15-crown-5 barium &gt; sodium &gt; calcium &gt;  caesium &gt;  potassium &gt; lithium.

<p>The thesis deals partly with methodology including construction</p><p>of hardware and new pulse sequences in the field of electrophoretic</p><p>NMR, and partly with practical use of ENMR and</p><p>diffusion NMR in the investigation of charged colloidal systems.</p><p>Several sources of artefacts are investigated, including gas production</p><p>at the electrodes, electroosmosis and Joule heating</p><p>effects that can cause convection. The electrophoretic double</p><p>stimulated-echo pulse sequence is introduced to suppress these</p><p>artefacts and to increase the feasible measuring range to higher</p><p>electric fields and conductivities.</p><p>The interaction between the non-ionic polymer poly(ethylene</p><p>oxide) PEO and differently charged surfactants is investigated</p><p>using the above mentioned methods. The investigated surfactants</p><p>are the anionic sodium dodecyl sulphate (SDS) and</p><p>potassium laurate (KC12), the cationic dodecyltrimethylammonium</p><p>bromide (CTAB) and the non-ionic octyl β-D-glucoside.</p><p>ENMR is also used to investigate two different mixed micelle</p><p>systems, with SDS as the charged surfactant component and</p><p>dodecyl malono-bis-N-methylglucamide (C12BNMG) respectively</p><p>tetra(ethylene oxide) dodecyl ether (C12EO4) as the nonionic</p><p>surfactant component. A method to calculate the degree</p><p>of counter-ion dissociation, αdissociation, as a function of composition</p><p>is demonstrated.</p><p>Finally diffusion NMR is used to compare transport dynamics</p><p>in gel electrolyte systems based on two differently grafted polymers;</p><p>one amphiphilic system containing polymethacrylate</p><p>grafted partly with polyethylene oxide and partly with fluorocarbons</p><p>and the corresponding nonamphiphilic system grafted</p><p>with only polyethylene oxide. Both systems contain the electrolyte</p><p>lithium bis(trifluoromethylsulfonyl) imide salt dissolved in</p><p>γ-butyrolactone. The results show that the system based on the</p><p>amphiphilic polymer has better transport dynamics and therefore</p><p>is more suited as material for battery</p>

The thesis deals partly with methodology including construction of hardware and new pulse sequences in the field of electrophoretic NMR, and partly with practical use of ENMR and diffusion NMR in the investigation of charged colloidal systems. Several sources of artefacts are investigated, including gas production at the electrodes, electroosmosis and Joule heating effects that can cause convection. The electrophoretic double stimulated-echo pulse sequence is introduced to suppress these artefacts and to increase the feasible measuring range to higher electric fields and conductivities. The interaction between the non-ionic polymer poly(ethylene oxide) PEO and differently charged surfactants is investigated using the above mentioned methods. The investigated surfactants are the anionic sodium dodecyl sulphate (SDS) and potassium laurate (KC12), the cationic dodecyltrimethylammonium bromide (CTAB) and the non-ionic octyl β-D-glucoside. ENMR is also used to investigate two different mixed micelle systems, with SDS as the charged surfactant component and dodecyl malono-bis-N-methylglucamide (C12BNMG) respectively tetra(ethylene oxide) dodecyl ether (C12EO4) as the nonionic surfactant component. A method to calculate the degree of counter-ion dissociation, αdissociation, as a function of composition is demonstrated. Finally diffusion NMR is used to compare transport dynamics in gel electrolyte systems based on two differently grafted polymers; one amphiphilic system containing polymethacrylate grafted partly with polyethylene oxide and partly with fluorocarbons and the corresponding nonamphiphilic system grafted with only polyethylene oxide. Both systems contain the electrolyte lithium bis(trifluoromethylsulfonyl) imide salt dissolved in γ-butyrolactone. The results show that the system based on the amphiphilic polymer has better transport dynamics and therefore is more suited as material for battery

NMR experiments performed under the effect of electric fields, either continuous or pulsed, can provide quantitative parameters related to ion association and ion transport in solution.  Electrophoretic NMR (eNMR) is based on a diffusion pulse-sequence with electric fields applied in the form of pulses. Magnetic field gradients enable the measurement of the electrophoretic mobility of charged species, a parameter that can be related to ionic association. The effective charge of the tetramethylammonium cation ion in water, dimethylsulphoxide (DMSO), acetonitrile, methanol and ethanol was estimated by eNMR and diffusion measurements and compared to the value predicted by the Debye-Hückel-Onsager limiting law. The difference between the predicted and measured effective charge was attributed to ion pairing which was found to be especially significant in ethanol. The association of a large set of cations to polyethylene oxide (PEO) in methanol, through the ion-dipole interaction, was quantified by eNMR. The trends found were in good agreement with the scarce data from other methods. Significant association was found for cations that have a surface charge density below a critical value. For short PEO chains, the charge per monomer was found to be significantly higher than for longer PEO chains when binding to the same cations. This was attributed to the high entropy cost required to rearrange a long chain in order to optimize the ion-dipole interactions with the cations. Moreover, it was suggested that short PEO chains may exhibit distinct binding modes in the presence of different cations, as supported by diffusion measurements, relaxation measurements and chemical shift data. The protonation state of a uranium (VI)-adenosine monophosphate (AMP) complex in aqueous solution was measured by eNMR in the alkaline pH range. The question whether or not specific oxygens in the ligand were protonated was resolved by considering the possible association of other species present in the solution to the complex. The methodology of eNMR was developed through the introduction of a new pulse-sequence which suppresses artifactual flow effects in highly conductive samples. In another experimental setup, using NMR imaging, a constant current was applied to a lithium ion (Li ion) battery model. Here, 7Li spin-echo imaging was used to probe the spin density in the electrolyte and thus visualize the development of Li+ concentration gradients. The Li+ transport number and salt diffusivity were obtained within an electrochemical transport model. The parameters obtained were in good agreement with data for similar electrolytes. The use of an alternative imaging method based on CTI (Constant Time Imaging) was explored and implemented. / <p>QC 20140825</p>