Proton Conduction Mechanism Research Articles

MOF-Based Solid-State Proton Conductors Obtained by Intertwining Protic Ionic Liquid Polymers with MIL-101.

Solid-state proton conductors based on the use of metal-organic framework (MOF) materials as proton exchange membranes are being investigated as alternatives to the current state of the art. This study reports a new family of proton conductors based on MIL-101 and protic ionic liquid polymers (PILPs) containing different anions. By first installing protic ionic liquid (PIL) monomers inside the hierarchical pores of a highly stable MOF, MIL-101, then carrying out polymerization in situ, a series of PILP@MIL-101 composites was synthesized. The resulting PILP@MIL-101 composites not only maintain the nanoporous cavities and water stability of MIL-101, but the intertwined PILPs provide a number of opportunities for much-improved proton transport compared to MIL-101. The PILP@MIL-101 composite with HSO4 - anions shows superprotonic conductivity (6.3×10-2 Scm-1 ) at 85°C and 98% relative humidity. The mechanism of proton conduction is proposed. In addition, the structures of the PIL monomers were determined by single crystal X-ray analysis, which reveals many strong hydrogen bonding interactions with O/NH···O distances below 2.6Å.

Development of Blend Nanofiber Composite Polymer Electrolyte Membranes with Dual Proton Conductive Mechanism and High Stability for Next-Generation Fuel Cells

Blend polymer nanofibers (BNF), consisting of sulfonated polyimide and polybenzimidazole blends doped with phytic acid, were fabricated and composed with Nafion to give BNF composite membranes for polymer electrolyte fuel cells. The BNF composite membrane possessed high mechanical and chemical stabilities and low gas permeability. In addition, the BNF composite membrane showed higher proton conductivity than the commercial Nafion NR211 membrane, not only at low temperatures but also at high temperatures above 100 °C and low relative humidity (ca. 10% RH). The proton conduction mechanism in the BNF composite membranes was examined and revealed that proton hopping conduction occurred besides the vehicle mechanism in the BNF composite membranes. The BNF composite membrane provided improved fuel cell performances compared to the cell using the conventional Nafion NR211 membrane at high humidity, low humidity, and high temperature/low humidity, suggesting the potential of BNF composite membranes for next-generation fuel cells.

Transient water wires mediate selective proton transport in designed channel proteins.

Selective proton transport through proteins is essential for forming and using proton gradients in cells. Protons are conducted along hydrogen-bonded 'wires' of water molecules and polar side chains, which, somewhat surprisingly, are often interrupted by dry apolar stretches in the conduction pathways, inferred from static protein structures. Here we hypothesize that protons are conducted through such dry spots by forming transient water wires, often highly correlated with the presence of the excess protons in the water wire. To test this hypothesis, we performed molecular dynamics simulations to design transmembrane channels with stable water pockets interspersed by apolar segments capable of forming flickering water wires. The minimalist designed channels conduct protons at rates similar to viral proton channels, and they are at least 106-fold more selective for H+ over Na+. These studies inform the mechanisms of biological proton conduction and the principles for engineering proton-conductive materials.

Differences in Water Dynamics between the Hydrated Chitin and Hydrated Chitosan Determined by Quasi-Elastic Neutron Scattering.

Recently, it was reported that chitin and chitosan exhibited high-proton conductivity and function as an electrolyte in fuel cells. In particular, it is noteworthy that proton conductivity in the hydrated chitin becomes 30 times higher than that in the hydrated chitosan. Since higher proton conductivity is necessary for the fuel cell electrolyte, it is significantly important to clarify the key factor for the realization of higher proton conduction from a microscopic viewpoint for the future development of fuel cells. Therefore, we have measured proton dynamics in the hydrated chitin using quasi-elastic neutron scattering (QENS) from the microscopic viewpoint and compared the proton conduction mechanism between hydrated chitin and chitosan. QENS results exhibited that a part of hydrogen atoms and hydration water in chitin are mobile even at 238 K, and the mobile hydrogen atoms and their diffusion increase with increasing temperature. It was found that the diffusion constant of mobile protons is two times larger and that the residence time is two times faster in chitin than that in chitosan. In addition, it is revealed from the experimental results that the transition process of dissociable hydrogen atoms between chitin and chitosan is different. To realize proton conduction in the hydrated chitosan, the hydrogen atoms of the hydronium ions (H3O+) should be transferred to another hydration water. By contrast, in hydrated chitin, the hydrogen atoms can transfer directly to the proton acceptors of neighboring chitin. It is deduced that higher proton conductivity in the hydrated chitin compared with that in the hydrated chitosan is yielded by the difference of diffusion constant and the residence time by hydrogen-atom dynamics and the location and number of proton acceptors.

In Silico Demonstration of Fast Anhydrous Proton Conduction on Graphanol.

Development of new materials capable of conducting protons in the absence of water is crucial for improving the performance, reducing the cost, and extending the operating conditions for proton exchange membrane fuel cells. We present detailed atomistic simulations showing that graphanol (hydroxylated graphane) will conduct protons anhydrously with very low diffusion barriers. We developed a deep learning potential (DP) for graphanol that has near-density functional theory accuracy but requires a very small fraction of the computational cost. We used our DP to calculate proton self-diffusion coefficients as a function of temperature, to estimate the overall barrier to proton diffusion, and to characterize the impact of thermal fluctuations as a function of system size. We propose and test a detailed mechanism for proton conduction on the surface of graphanol. We show that protons can rapidly hop along Grotthuss chains containing several hydroxyl groups aligned such that hydrogen bonds allow for conduction of protons forward and backward along the chain without hydroxyl group rotation. Long-range proton transport only takes place as new Grotthuss chains are formed by rotation of one or more hydroxyl groups in the chain. Thus, the overall diffusion barrier consists of a convolution of the intrinsic proton hopping barrier and the intrinsic hydroxyl rotation barrier. Our results provide a set of design rules for developing new anhydrous proton conducting membranes with even lower diffusion barriers.

Ultrahigh-rate and ultralong-life aqueous batteries enabled by special pair-dancing proton transfer.

The design of Faradaic battery electrodes with high rate capability and long cycle life comparable to those of supercapacitors is a grand challenge. Here, we bridge this performance gap by taking advantage of a unique ultrafast proton conduction mechanism in vanadium oxide electrode, developing an aqueous battery with untrahigh rate capability up to 1000 C (400 A g-1) and extremely long life of 0.2 million cycles. The mechanism is elucidated by comprehensive experimental and theoretical results. Instead of slow individual Zn2+ transfer or Grotthuss chain transfer of confined H+, the ultrafast kinetics and excellent cyclic stability are enabled by rapid 3D proton transfer in vanadium oxide via the special pair dance switching between Eigen and Zundel configurations with little constraint and low energy barriers. This work provides insight into developing high-power and long-life electrochemical energy storage devices with nonmetal ion transfer through special pair dance topochemistry dictated by hydrogen bond.

Construction of biomimetic proton transport channels in metal-organic framework

Construction of proton transport channels in metal-organic frameworks (MOFs) with simple synthesis processes, high proton conductivities and good performance stabilities has been of great interest for proton exchange membrane fuel cell (PEMFC). Herein, we mimic the proton transport behavior of amino acid residues in bacteriorhodopsin, select UiO-66-COOH as the host, glycine and aspartic acid as the functional guest molecules, and then functionalize the MOF framework with amino acids to obtain biomimetic proton transport channels. This strategy endows UiO-66-COOH-Asp a high proton conductivity of 1.19 × 10−2 S/cm at 70 °C and 98% RH, excellent cycle stability of performances and performance durability, which can be comparable to the reported MOFs-based proton conductors. Moreover, the proton conduction mechanism in UiO-66-COOH-Asp is elaborated in detail due to its visual structure, which is also one of the advantages of adopting MOFs as research platform, making it possible to optimize the structure-activity relationship of advanced materials. Notably, this strategy has clear objectives and simple synthesis, which has made certain contributions to both theoretical research and future industrial production of proton conductors.

Investigation of sulfonation degree and temperature on structure, thermal and membrane's properties of sulfonated poly (ether ether ketone)

In this paper, the primary and secondary relationship among factors affecting the sulfonation of poly (ether ether ketone) (PEEK) was investigated in detail by a response surface method in order to solve the problem of performance deterioration caused by excessively high or low sulfonation. Acid-base titration, infrared analysis (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) proved that temperature had the greatest influence on PEEK sulfonation and the sulfonate group was successfully connected to the main chain and the proton conduction mechanism was in accordance with Arrhenius law. Under optimized conditions, 44% sulfonation degree of PEEK was selected to test the dimensional stability, microstructure and proton conductivity, and to explore the influence of temperature on the membrane's structure and performance. The result indicates that the microstructure has become more homogeneous at 60 °C, resulting in continuous proton conduction channels, demonstrating excellent proton conductivity (5.04 × 10−2 S/cm).

Anhydrous proton conductor consisting of protamine-monododecyl phosphate composite with self-assembled structure.

We prepared a protamine-monododecyl phosphate composite by mixing protamine (P) and a monododecyl phosphate (MDP). This P-MDP composite formed an acid-base complex by the electrostatic interaction between cationic protamine and the negatively charged phosphate group. Additionally, according to the X-ray diffraction (XRD) measurements, the composite formed a self-assembled lamellar structure with an interaction between the long alkyl chains of MDP. As a result, the P-MDP composite showed the proton conductivity of 9.5 × 10-4 S cm-1 at 120-130 °C under anhydrous conditions. Furthermore, the activation energy of the proton conduction of the P-MDP composite was approximately 0.18 eV. These results suggested that the proton conduction of the P-MDP composite was based on an anhydrous proton conductive mechanism. In contrast, the anhydrous proton conduction of the P-methanediphosphonic acid (MP) composite, which did not form the self-assembled lamellar structure, was ca. 3 × 10-5 S cm-1 at 120-130 °C and this value was one order of magnitude lower than that of the P-MDP composite. Therefore, the two-dimensional self-assembled proton conductive pathway of the P-MDP composite plays a role in the anhydrous proton conduction.

Proton dynamics in a spark-plasma sintered BaZr0.7Ce0.2Y0.1O3-δ proton conductor investigated by quasi-elastic neutron scattering.

The thermally activated proton dynamics in the perovskite lattice of spark-plasma sintered BaZr0.7Ce0.2Y0.1O3-δ was investigated by quasi-elastic neutron scattering (QENS) and electrochemical impedance spectroscopy (EIS) in the temperature range from 200-600 °C. The quasi-elastic signal could be resolved into two components corresponding to a translational and rotational motion. From a description of the diffusive movements with the Chudley-Elliot jump diffusion model a jump distance of 3.12 Å and residence time of 13.6 ps were found for the translational protonic diffusion at 600 °C. The diffusion coefficients for QENS and EIS follow an Arrhenius law with activation energies of 0.16 eV, 0.58 eV and 0.88 eV for the microscopic proton self-diffusion, the bulk and grain boundaries, respectively. The rotational motion was analyzed using a two-site jump and a spherical rotation model which resulted in O-H distances of 0.89 Å and 0.71 Å, respectively. The data provided by the two-site jump model evidences the Grotthuss-type mechanism behind the translational proton dynamics.

Surface Acidity Dictates Proton Transport in WO3/ZrO2: Proton-Conductive Behavior and Mechanistic Insight

Development of inorganic proton conductors that are applicable in a wide temperature range is crucial for applications such as fuel cells. Most of the reported proton conductors suffer from limited proton conductivity, especially at low temperature. In addition, the mechanism of proton conduction in the conductors is not fully understood, which limits the rational design of advanced proton conductors. In this work, we report the use of metal oxide solid acid as a promising proton conductor. WO3/ZrO2 (WZ) with different surface acidities is synthesized by controlling the content of WO3 on the surface of ZrO2. It is demonstrated that proton conductivity of WZ samples is closely related with their acidity. WZ with the strongest acidity exhibits the highest proton conduction performance at low temperatures, with a proton conductivity of 3.27 × 10-5 S cm-1 at 14 °C. The excellent performance of the WZ-type proton conductor is clarified with theoretical calculations. The results show that the enhanced water adsorption and the lowered activation barrier for breakage of the O-H bond in surface-adsorbed water are the key to the excellent proton-conductive performance of WZ. The experimental results and mechanistic insights gained in this work suggest that WZ is a promising proton conductor, and tailoring the surface acidity of metal oxides is an effective approach to regulate their proton-conductive performance.

Dielectric properties of the non-glycated and in vitro methylglyoxal-glycated cornea of the rabbit eye

The dielectric properties of the non-glycated and in vitro methylglyoxal-glycated cornea of the rabbit eye were tested in the frequency range of 200 Hz to 100 kHz of the electric field and at temperatures of 25 to 140 °C. The denaturation temperature (Td) for the non-glycated cornea and the non-enzymatically glycated cornea are approximately 45 and 55 °C, respectively. The mechanism of proton conduction up to Td in a glycated cornea requires more energy, i.e. more than twice the activation energy (ΔH) than in non-glycated tissue. The dielectric spectra for both examined tissues showed the same characteristic frequency of about 7 kHz assigned to the orientation relaxation time of the polar side groups inside the corneal stroma. These results may be useful in the surgical treatment of the cornea using conductive keratoplasty and in tissue engineering for clinical applications to regenerate this tissue. The medical use of these physico-biological techniques is important because the human cornea protects all eye tissues from various environmental factors.

High Water-Assisted Proton Conductivities of Two Cadmium(II) Complexes Constructed from Zwitterionic Ligands.

Finding more metal complexes with outstanding water stability and high proton conductivity still has important research significance for the energy field. Herein, two highly proton-conductive complexes, one hydrogen-bonded supramolecular framework (HSF) [Cd(CBIA)2(H2O)4]·2H2O (1) and one coordination polymer (CP), {[Cd2(CBIA)2(4,4'-bipy)2(H2O)2]·(CBIA)·(OH)·2H2O}n (2) (4,4'-bipy = 4,4'-bipyridine), were triumphantly assembled using a zwitterionic organic compound, 2-(1-(carboxymethyl)-1H-benzo[d]imidazol-3-ium-3-yl)acetate (HCBIA). In the structure of HSF 1, there are several coordination and lattice H2O units except for the two monodentate CBIA- anions. CP 2 with a one-dimensional (1D) cylindrical structure has free CBIA- units and free H2O units located in the cavity. Thanks to the ability of the uncoordinated carboxyl groups and coordination/lattice water molecules to construct the rich H-bonding networks, both complexes exhibit super-high proton conductivities, reaching 5.09 × 10-3 and 3.41 × 10-3 S cm-1 under 100 °C/98% relative humidity (RH), respectively. Based on the exploration of crystal structure data, combined with the calculated activation energy, and adsorption/desorption plots of nitrogen and water vapor, the causes and differences in proton conductivity of the two complexes, especially the proton-conductive mechanism, are compared and analyzed. This study again confirms that the zwitterionic ligands can exert important effects on forming organo-inorganic hybrid materials with high proton conductivity.

A thermal-stable praseodymium(III) metal-organic framework from a naphthyl acylthiourea-carboxylate ligand: Synthesis, crystal structure and proton conductive properties

Compared with other traditional proton-conducting materials, the structures of metal-organic frameworks (MOFs) are more advantageous in terms of designability and tunability. Considering the strong and flexible coordination ability of carboxylate-based thiourea ligands, we synthesized a [3-(naphthalene-2-carbonyl)-thioureido]-acetic acid (H3L) ligand, and successfully obtained {[Pr(H2L)2(NO3)(H2O)2]·2H2O·MeOH}n (1). 1 is a 1D framework, in which the Pr(III) atoms are bridged by carboxyl oxygen, and then form a three-dimensional solid-state structure under the action of intermolecular hydrogen bonds and π-π stacking interactions. AC impedance measurements uncover that proton conductivity (σ) of 1 has a significant positive temperature and humidity dependence. The σ of MOF 1 can attain 3.41 ​× ​10−4 ​S/cm under 100 ​°C and 98% RH. In addition, the proton-conductive mechanism was discussed based on the structural analysis, H2O vapor adsorption curve and the activation energies evaluated by fitting the Arrhenius equation.

Preparation, crystal structure and proton conductive properties of a water-stable ferrocenyl carboxylate framework

Recently, solid-state materials with high crystallinity characteristics have received considerable attention for applications in the field of proton conductivity, but relevant studies on ferrocene-based carboxylate frameworks are still very rare. Herein, a ferrocene-based hydrogen-bonded organic framework, [FcC(CH3) ​= ​CHCOOH] (namely FHOF 1), (Fc = (η5-C5H5)Fe(η5-C5H4)) bearing both ferrocenyl and carboxylate units has been successfully prepared and structurally characterized. Further experiments have confirmed that introducing ferrocene groups greatly improves the thermal and water stability of 1; in addition, the presence of free carboxyl groups within the framework will enable high proton conductivity to be guaranteed. Proton conductivity was studied for 1 ​at variable relative humidities (68–98% RHs) and temperatures (30–100 ​°C) and was discovered to increase with humidity and temperature. The optimum proton conductivity of 1.58 ​× ​10−3 ​S ​cm−1 was reached at 100 ​°C and 98% RH. Subsequently, activation energy calculations and structural analysis were used to explore the proton conductive mechanism. Finally, we corroborated the structural and electrochemical stability of 1 after completing the AC impedance test by means of PXRD and SEM tests.

Hydrogen Bond Activation by Pyridinic Nitrogen for the High Proton Conductivity of Covalent Triazine Framework Loaded with H3 PO4.

Under high temperature anhydrous conditions, it is still a formidable challenge to improve the performance of proton-conducting materials based on H3 PO4 and elucidate its proton conduction mechanism. Herein, a highly stable covalent triazine frameworks (CTFs) based on H3 PO4 is reported. The more pyridinic nitrogen CTFs contain, the higher proton conductivity is. Compared with H3 PO4 @CTF-L with less pyridinic nitrogen, H3 PO4 @CTF-H has a higher proton conductivity of 1.6×10-1 S cm-1 at 150 °C under anhydrous conditions, which does not decay after about 18 months exposure in air. The high proton conductivity is associated with the formation and breaking of the activated Ntriazine ⋯H+ ⋯H2 PO4 - pairs by pyridinic nitrogen of CTFs. The outstanding long-term stability is mainly attributed to the ultra-strong triazine skeleton structure of CTFs.

Isotropic Anhydrous Superprotonic Conductivity Cooperated with Installed Imidazolium Molecular Motions in a 3D Hydrogen‐Bonded Phosphate Network

AbstractUtilizing molecular motion is essential for the use of anhydrous superprotonic molecular proton conductors (σ beyond 10−4 S cm−1) as electrolytes in hydrogen fuel cells. However, molecular motion contributing to the improvement of intrinsic proton conduction has been limited and little clarified in relation to the proton conduction mechanism, limiting the development of material design guidelines. Here, a salt with a three‐dimensional (3D) hydrogen‐bonded (H‐bonded) phosphate network with imidazolium cations installed inside was studied, whose components are known to exhibit molecular motions that contribute to proton conduction. Despite its anisotropic H‐bonded network, the salt exhibits isotropic anhydrous superprotonic conductivity exceeding 10−3 S cm−1 at ≈351 K, which is the first example for organic molecular crystal. Variable‐temperature X‐ray structural analysis and solid‐state 2H NMR measurements revealed significant 3D molecular motion of imidazolium cations, which accelerate proton conduction via the 3D H‐bonded phosphate network.

Isotropic Anhydrous Superprotonic Conductivity Cooperated with Installed Imidazolium Molecular Motions in a 3D Hydrogen-Bonded Phosphate Network.

Utilizing molecular motion is essential for the use of anhydrous superprotonic molecular proton conductors (σ beyond 10-4 S cm-1 ) as electrolytes in hydrogen fuel cells. However, molecular motion contributing to the improvement of intrinsic proton conduction has been limited and little clarified in relation to the proton conduction mechanism, limiting the development of material design guidelines. Here, a salt with a three-dimensional (3D) hydrogen-bonded (H-bonded) phosphate network with imidazolium cations installed inside was studied, whose components are known to exhibit molecular motions that contribute to proton conduction. Despite its anisotropic H-bonded network, the salt exhibits isotropic anhydrous superprotonic conductivity exceeding 10-3 S cm-1 at ≈351 K, which is the first example for organic molecular crystal. Variable-temperature X-ray structural analysis and solid-state 2 H NMR measurements revealed significant 3D molecular motion of imidazolium cations, which accelerate proton conduction via the 3D H-bonded phosphate network.

Mechanistic Insights into Proton Transport in Pure and Aqueous Phosphoric Acid

The transport of protons plays a key role in a variety of electrochemical processes and technologies. There are two major mechanisms underlying proton transport: the vehicular mechanism where a protonic defect moves with the aid of a molecular entity; and the ‘Grotthuss mechanism’ where a proton diffuses by being transferred between ‘chains’ of host molecules via elementary reactions within the hydrogen bond networks. The latter is regarded as the most efficient proton conductivity mechanism. Although Grotthuss proposed this concept more than 200 years ago, only indirect experimental evidence of the mechanism has thus far been reported. Recently, we observed the first direct experimental observation of proton transfer between the molecules in pure and 85% aqueous phosphoric acid by employing dielectric spectroscopy, and quasi-elastic neutron scattering (QENS). Complementary to these experiments, ab initio molecular dynamics (AIMD) simulations were performed to gain molecular insight into the underlying mechanisms of proton transport allowing for the breaking and forming of covalent bonds since it calculates the forces from electronic structure methods ‘on the fly’.We calculated the self-intermediate scattering function of the protons, indicating three processes at high Q range consisting of two fast Q-independent processes and one slow Q-dependent process, which are in good agreement with QENS results. Also, the self-part of van Hove function of the protons for the fast characteristic time shows surprisingly short proton jumps of only ~0.5 - 0.7 Å confirmed by analysis of an individual proton trajectory. Furthermore, AIMD demonstrates that proton hopping plays an essential role in the long-range proton diffusion through the breaking and forming of hydrogen bonds. Our analysis confirmed the strong proton-proton correlations in these proton jumps. However, this correlated proton transport unexpectedly leads to a decrease of conductivity in these systems. Based on these results, we propose that the expected Grotthuss-like enhancement mechanism of conductivity cannot be realized in bulk liquids where ionic correlations always reduce conductivity, most likely because of the requirement for the momentum conservation. Our findings will propel the design of electrochemical materials with proton transfers involved in charge transport for achieving high proton conductivity in electrochemical applications including fuel cells.

(Invited) A Formalism Relating the Relative Humidity to the Proton Conductivity Mechanism of Membranes

The relationship between relative humidity of gas phase and proton conductivity in proton exchange membranes has been subject of extensive investigations [1],[2]. Herein, a theoretical framework is presented which describes proton transport in relation to stepwise equilibria that reflect the water uptake. In the proposed model, at first, the hydration process is treated as a stepwise equilibrium process, in agreement with experimental observations. Several hierarchical levels of structure evolve with increasing hydration. These levels are easily confirmed by the analysis of the electric response of perfluorinated based membranes by complex dielectric and conductivity spectra. Thus, a wide range of literature data on hydration of Nafion as a function of activity and temperature has been analyzed by means of the proposed model to extract chemical parameters diagnostic of the type of interactions characterizing the hydrophilic domains of membranes.These parameters, which are crucial in order to modulate the ion transport phenomena in ionomers, are then introduced into the model to describe the functional dependence of conductivity on water activity in gas phase. The treatment of proton conductivity is built on the approaches commonly adopted to describe transport in solids [3]. Key proton migration phenomena appropriate to the levels of the structural hierarchy are considered. The conductivity model is used to describe a set of conductivity vs. water uptake data as a function of temperature, with data taken to exceptionally low water contents. The formalism is then used to analyze a set of data for a perfluorosulfonic acid (PFSA) membrane as a function of hydration, temperature and polymer equivalent weight. The main advantage of the proposed framework is the possibility of a straightforward application to multiple membrane types based on the energetics of water uptake. Actually, the focus on chemical interactions allows to better correlate the effects of the morphology and relaxation events of the matrix to the proton migration phenomena of the membrane. Acknowledgements This work has received funding from: (a) the European Union’s Horizon 2020 research and innovation program under grant agreement 881603; (b) the project ‘Advanced Low-Platinum hierarchical Electrocatalysts for low-T fuel cells’ funded by EIT Raw Materials.