Protonation Of Species Research Articles

The structure and properties of monoprotonated propiolamide and diprotonated cellocidin

Abstract Propiolamide and cellocidin were investigated in superacidic media. In both acetylenic amides, the amide moiety is immediately monoprotonated in anhydrous HF, HF/SbF5 and HF/BF3. An increase of SbF5 does not lead to a more highly protonated species. The salts were characterized by low-temperature Raman, NMR and room temperature IR spectroscopy, as well as by single-crystal X-ray diffraction. The experimental data are discussed together with results of quantum-chemical calculations on the M06-2X/aug-cc-pVTZ level of theory, which are consistent with the observation of pure monoprotonation. The second protonation of the amide moiety or the triple bond is not observed due to the high positive charge caused by the monoprotonation.

Proton Conduction via Water and Ammonia Coordinated Metal Cationic Species in MOF and MHOF Platforms.

Although metal-organic frameworks (MOFs) and metalo hydrogen-bonded organic frameworks (MHOFs) are designed as promising solid-state proton conductors by incorporating various protonic species intrinsically or extrinsically, design and development of such materials by employing the concept of proton conduction through coordinated polar protic solvent is largely unexplored. Herein, we have constructed two proton-conducting materials having different solvent coordinated metal cationic species: In-H2O-MOF, ({[In(H2O)6][In3(Pzdc)6] ⋅ 15H2O}n; H2Pzdc: pyrazine-2,3-dicarboxylic acid) with coordinated water molecules from hexaaquaindium cationic species, and MHOF-4, ([{Co(NH3)6}2(2,6-NDS)2(H2O)2]n; 2,6-H2NDS: 2,6-naphthalenedisulfonic acid) with coordinated ammonia from hexaammoniacobalt cationic species. Interestingly, higher proton conductivity was achieved for In-H2O-MOF (1.5×10-5 S cm-1) than MHOF-4 (6.3×10-6 S cm-1) under the extreme conditions (80 °C and 95 % RH), which could be attributed to enhanced acidity of coordinated water molecules having much lower pKa value than that of coordinated ammonia. Greater charge polarization on hydrogen atoms of In3+-coordinated water molecules than that of Co2+-coordinated ammonia led to the high conductivity of In-H2O-MOF, as evident by quantum chemical studies. Such a comparative study on metal-coordinated protic polar solvents in achieving proton conduction in crystalline solids is yet to be made.

Interaction between the electrochemical properties of powdered activated carbon and the biochemical processes within bacteria in Azo dye biodecolorization: An explanatory mechanism

Drawing on prior reports highlighting the redox mediator properties of powdered activated carbon (PAC), this study was designed to evaluate these properties to enhance the decolorization of azo dye by Klebsiella quasipneumoniae GT7. It was found that the presence of 0.5 % PAC in the medium increased the biodecolorization rate early in incubation. Chemical analysis revealed that dye conversion into aromatic amines occurred in microbial systems both with and without PAC. However, at initial dye concentrations (Cid) of 2 mM or higher, some dye remained on the PAC surface and in the medium. In contrast, the PAC-free system achieved nearly 100 % biodecolorization at all initial dye concentrations. The negative impact of PAC on decolorization efficiency in microbial systems with high initial dye concentrations cannot be solely explained by its redox mediator function. This study used the amphoteric-Donnan model for PAC's electrical double layer (EDL) and Mitchell's chemiosmotic model for bacterial proton motive force (PMF) to explore this. It found that charge storage in PAC's EDL regulates electron transfer fluxes, and proton species enhance the proton motive force across the bacterial membrane. These observations improve the understanding of PAC's role in microbial decolorization and its potential future applications.

Effects of Alpha Particle Fraction on Kinetic Plasma Turbulence

Solar activities have an extraordinary impact on interplanetary space, enriching the plasma dynamics including turbulent heating of various species. The small fraction of alpha particles is believed to play a significant role in the turbulent dynamics of the solar wind. Here we present fully kinetic particle-in-cell simulations to reveal the influences of the alpha particles in decaying plasma turbulence. Multiple run cases with different controlled variations of proton and alpha density are performed to compare and evaluate the energy conversion processes. It is found that the alpha particles can suppress the energy conversion rate with increasing density. Besides, the alpha particles show more heating intermittency than the proton species. Interestingly, on the other hand, the electrons do not show any change in their dynamics, including overall heating. These two positive charge species have more correlation in temperature anisotropy as their densities are comparable. Our results provide valuable insights on the turbulence with different species compositions to a certain extent, especially with abundant heavy particles.

Sewage sludge-derived biocarbons as catalysts of bioanodes in a dual-chamber microbial fuel cell using nejayote as substrate

In this work, nejayote (wastewater from tortilla industry) was evaluated as substrate of a dual-chamber microbial fuel cell (MFC). For this purpose, novel bioanodes were built using Bacillus subtilis (B. subtilis) as the electrochemically active microorganism (EAM), and sewage sludge-derived biocarbon (SSB) and methanol-functionalized SSB (FSSB) as catalysts. The relationship between the physicochemical properties of SSB and FSSB, biocompatibility, electrochemical performance and the percentage of COD removed was analyzed. Up to 70% of chemical oxygen demand (COD) from nejayote was successfully removed using the SSB + B. subtilis bioanode, with the advantage of energy generation by the MFC (Pcell= 1.44 mW m-2 and jcell= 41 mA m-2). An adverse effect was observed when functionalizing SSB to produce FSSB. Despite a fair biocompatibility, the FSSB + B. subtilis bioanode promoted fermentation reactions that increased the COD and charge transfer resistance. The improved performance of SSB + B. subtilis was ascribed to a reasonable biocompatibility, low charge transfer resistance and less limitation to the diffusion of proton species between the biofilm and the substrate. Therefore, the treatment of nejayote in a MFC with the SSB + B. subtilis bioanode was identified as a promising alternative for decreasing COD and generating small amounts of energy, instead of using energy for its remedy.

Inhibiting effect of 2-amino-2-methyl-1-propanol on gelatinous product formation in non-aqueous CO2 absorbents: Experimental study and molecular understanding

Diamines or polyamines with two or more amino groups are suitable for formulating non-aqueous absorbents (NAAs) with high CO2 loading capacity and low regeneration energy consumption. However, these two types of amines in NAAs are prone to produce insoluble gelatinous products after absorbing CO2, resulting in difficult operation of the CO2 capture system. In this study, by using 2-amino-2-methyl-1-propanol (AMP) as an inhibitor, the insoluble gelatinous products of the aminoethylethanolamine (AEEA)-N-methyl-2-pyrrolidone (NMP) (A-A-N) and 3-(methylamino)propylamine (MAPA)-NMP (M-A-N) NAAs were successfully eliminated. The experimental results showed that the AMP-regulated NAAs possessed a high absorption rate, high CO2 loading capacity, excellent desorption efficiency, and stable recyclability. The reaction mechanism of CO2 absorption and the inhibitory mechanism of AMP on the formation of gelatinous products were comprehensively elucidated. Taking the A-A-N system as a representative, AEEA reacted with CO2 to form zwitterionic protonated carbamate species (AEEACO2−(P)H+(S)), which tended to self-aggregate via hydrogen-bond interaction, resulting in the formation of insoluble gelatinous products. With the introduction of AMP, the AMP-derived products could combine easily with AEEACO2−(P)H+(S) via strong electrostatic attraction to form ion pairs, preventing the AEEACO2−(P)H+(S) molecules from self-aggregating to form insoluble gelatinous products. The regeneration heat duty of the A-A-N system was 1.89 GJ∙ton−1 CO2, which was 49.9 % lower than that of the benchmark 30 wt% MEA. Overall, introducing AMP as a gelatinous product inhibitor was beneficial for the development of NNAs with high CO2 absorption capacity and low-energy consumption.

Effect of Cation Nonstoichiometry on Hydration and Charge Transport Processes in Yb-Doped SrZrO3 Perovskite-Type Proton Conductor for Ceramic Electrochemical Cells

The effect of Sr deficiency on the hydration process and ionic and electronic conductivity of Yb-doped SrZrO3 proton conductors with a perovskite-type structure was investigated. Dense SrxZr0.95Yb0.05O3-δ (x = 0.94–1.00) ceramics were prepared using solution combustion synthesis. Thermogravimetry and Raman spectroscopy methods were used to determine the concentration of bulk protonic species. Sr deficiency was found to enhance the hydration ability of the zirconate; however, lowering of Sr content to x = 0.94 deteriorated the proton uptake. The conductivity of the SrxZr0.95Yb0.05O3-δ series depending on the oxygen partial pressure at different humidities was studied by the four-probe direct current technique. Sr-deficient ceramics with x = 0.96 and 0.98 were shown to become purely protonic conductors in humid atmospheres at a temperature close to 500 °C. The ionic conductivity reaches its highest value at a Sr content of x = 0.98 (2 × 10−4 S cm−1 at 500 °C and pH2O = 3.17 kPa). The hydration behavior and transport properties of SrxZr0.95Yb0.05O3-δ are discussed in terms of the defect chemistry model that assumes the distribution of Yb ions over Sr and Zr sites at a large Sr deficiency.

Defect Thermodynamic Modeling of Triple Conducting Perovskites (La,Ba)Fe1-xMxO3-δ for Proton-Conducting Solid-Oxide Cells

Both the experimental and first-principles modeling results revealed the dependence of defect energetics on oxygen non-stoichiometry and magnetic coupling of Fe in the Fe-based perovskite oxides. A generalized defect thermodynamic model of the proton-conducting (La,Ba)Fe1-xMxO3-δ perovskite oxide is developed to allow inclusion of nonlinear δ dependent terms in three key defect reaction energies, namely, the oxygen vacancy formation, hydration, and charge disproportionation reactions. A transition from a large polaron description at lower δ values to a small polaron expression at higher δ is also considered in our analysis. Based on the functional forms of defect energetics on δ as guided by first principles modeling and literature data, the Brouwer diagrams of BaFe0.9Y0.1O3-δ are assessed to provide information on electronic and ionic defect concentration (including the proton species) as a function of O2 and H2O pressure at different temperatures for solid-oxide cell applications.

Vibrational characterization of the various forms of (solvated or unsolvated) mobile proton in the solid state. Advantages, limitations and open questions

A didactic review of (Raman, infrared and neutron) vibrational spectroscopy procedures to study mobile protonic species (H2O, H3O+, H5O2+, “H+”, NH4+, etc.) in solid hydrates, crystals and ceramics is proposed on the basis of paper published since 1970s. Three materials are taken as representative examples: hydrated uranyl phosphate (HUP), oxonium, hydroxonium and ammonium beta- and beta“-aluminas and nominally anhydrous strontium/barium zirconate perovskite. Particular attention is given to the advantages of isotopic substitution and dilution measurements as a function of temperature and partial ion exchange. The vibrational signatures that we consider as being able to serve as references for the different kinds of proton species observed in the proton conductors are presented. We also discuss the signature of protonic species giving no vibrational signature - or whose Raman and infrared signatures are too weak to be clearly detected – that need to be better characterized and understood. The presence of a strong incoherent inelastic neutron scattering background appears characteristic of (mobile) proton conductors.

Tailoring proton transfer species on the membrane surface: An approach to enhance proton conductivity for polymer electrolyte membrane fuel cell

The efficiency of proton conductivity in proton exchange membrane (PEM) depends on how proton species can effectively transfer through the membrane either in hydrous system or anhydrous system. Although the incorporation of proton donors and/or acceptors via chemical modification, blending, including preparing composites in polymer solution state before casting the membrane is a general approach, the proton transfer species may not be effectively functioned as they were randomly existed in PEM. As proton transfer initially occurs at the PEM surface, the decoration of the proton transfer species on the surface can be considered as an alternative choice to develop PEM. The surface modifications can be carried out by attaching the functional molecules and/or polymers to favor the proton transfer. The present review summarizes the approaches to construct the PEM surface with proton conductive species, especially via layer-by-layer, and polymer brushes to enhance the PEM performances.

Understanding the difference in bulk modulus between Y-doped SrCeO3 and Y-doped SrZrO3 by ultrasonic transmission method and density functional theory

Proton-conducting oxides are promising for applications in solid oxide fuel cells and steam electrolysis at intermediate temperatures (400–600 °C). The hydration reaction requires oxide ion vacancies and the protonic conductive species originate from this reaction. Increasing the proton concentration leads to higher proton conductivity but also expands the lattice volume, known as chemical expansion, which may lead to the mechanical failure of the oxide. Thus, it is important to clarify the factors that decrease the chemical expansion. A previous study suggested that chemical expansion could be suppressed by a large bulk modulus. Although this was only a qualitative argument, our study quantitatively clarifies the effect of the bulk modulus experimentally and theoretically. To examine the difference between Ce and Zr, which are typical elements in proton-conducting oxides, 6.25 mol% Y-doped SrZrO3 and SrCeO3 were prepared, and their bulk moduli were quantitatively evaluated. Y-doped SrZrO3 had a larger bulk modulus than Y-doped SrCeO3. Our results support the previous finding that proton-conducting oxides with large bulk modulus suppress chemical expansion. In addition, our theoretical calculations of the force constants showed that the difference in bulk modulus was caused by the Zr-O bonds being more rigid than the Ce-O bonds. Our results should provide useful guidelines for suppressing chemical expansion in proton-conducting oxides.

Defect Thermodynamics and Transport Properties of Proton Conducting Oxide BaZr1−xYxO3−δ (x ≤ 0.1) Guided by Density Functional Theory Modeling

Density functional theory-based thermodynamic modeling was performed to determine the effect of humidity and H2/O2 gas pressure on the defect chemistry and transport properties of proton conducting oxide BaZr1−xYxO3−δ (x ≤ 0.1) in the temperature range of 800–1200 K, relevant for solid oxide fuel/electrolysis cell applications. The first principles charge defect analysis was carried out to obtain the defect energetic ensembles as a function of Fermi level as well as the dependence of the hydration and oxidation reaction energies on complex defect-dopant configurations. It is shown that oxygen vacancies introduced to compensate for the extra Ba vacancies may cause a slight increase in the concentration of hydroxyl and proton species upon hydration of Ba deficient BaZr1−xYxO3−δ, while the overall proton diffusivity is predicted to decrease with increased proton hopping barriers upon trapping near the Ba vacancies. The developed defect model is further demonstrated to be able to describe the bulk defect chemistry and transport properties of BaZr0.9Y0.1O3−δ under the solid oxide cell operating conditions. The theoretical framework developed in this work further allows the inclusion of configurational, energetic and electronic characteristics of the defects that can be used as a complementary tool to experimental measurements for testing various mechanistic pathways or to provide essential mechanistic data.

Stability and Structure of Silver–l-methionine Complexes

Stability and structure of complexes between silver (I) and l-methionine (L) deduced from potentiometric and 1H NMR measurements allow to assume the prevailing of several protonated species. The experimental data are compatible with the formation of the following complexes: AgL, AgL2, AgH2L, AgH1L2, AgH2L2, AgH3L2 and AgH4L2. The coordination sites are obtained by 1H NMR spectra, showing that only the bond between the methylthioether sulfur atom and silver (I) is responsible of the complex stability. The system is studied potentiometrically with silver and glass electrodes at 25 °C and 1.00 mol·dm−3 NaClO4 as ionic medium. Amino acids containing sulfur are few and not extensively studied. In particular, l-methionine, even if it is the most important, enantiomer and their complexes with silver (I) present anticarcinogenic properties, is quite not investigated. In the same experimental conditions, l-methionine protonation constants are determined. The 1H NMR data allow one to assume that, in moderately alkaline solution, silver (I) is bond with six membered chelate rings with sulfur and amino nitrogen, while carboxylic groups are not involved. No polynuclear species are present. The high stability of the complex with ratio 1:2 (silver (I)/l-methionine), involving also two hydrogen ions, predominating in a wide range of hydrogen ion concentration suggests to propose a study for the preparation of an electrode to measure the deprotonated l-methionine concentration.

Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst

Fundamental understanding of the dynamic behaviors at the electrochemical interface is crucial for electrocatalyst design and optimization. Here, we revisit the oxygen reduction reaction mechanism on a series of transition metal (M = Fe, Co, Ni, Cu) single atom sites embedded in N-doped nanocarbon by ab initio molecular dynamics simulations with explicit solvation. We have identified the dissociative pathways and the thereby emerged solvated hydroxide species for all the proton-coupled electron transfer (PCET) steps at the electrochemical interface. Such hydroxide species can be dynamically confined in a “pseudo-adsorption” state at a few water layers away from the active site and respond to the redox event at the catalytic center in a coupled manner within timescale less than 1 ps. In the PCET steps, the proton species (in form of hydronium in neutral/acidic media or water in alkaline medium) can protonate the pseudo-adsorbed hydroxide without needing to travel to the direct catalyst surface. This, therefore, expands the reactive region beyond the direct catalyst surface, boosting the reaction kinetics via alleviating mass transfer limits. Our work implies that in catalysis the reaction species may not necessarily bind to the catalyst surface but be confined in an active region.

Exploiting the Multifunctionality of M2+/Imidazole-Etidronates for Proton Conductivity (Zn2+) and Electrocatalysis (Co2+, Ni2+) toward the HER, OER, and ORR.

This work deals with the synthesis and characterization of one-dimensional (1D) imidazole-containing etidronates, [M2(ETID)(Im)3]·nH2O (M = Co2+ and Ni2+; n = 0, 1, 3) and [Zn2(ETID)2(H2O)2](Im)2, as well as the corresponding Co2+/Ni2+ solid solutions, to evaluate their properties as multipurpose materials for energy conversion processes. Depending on the water content, metal ions in the isostructural Co2+ and Ni2+ derivatives are octahedrally coordinated (n = 3) or consist of octahedral together with dimeric trigonal bipyramidal (n = 1) or square pyramidal (n = 0) environments. The imidazole molecule acts as a ligand (Co2+, Ni2+ derivatives) or charge-compensating protonated species (Zn2+ derivative). For the latter, the proton conductivity is determined to be ∼6 × 10–4 S·cm–1 at 80 °C and 95% relative humidity (RH). By pyrolyzing in 5%H2–Ar at 700–850 °C, core–shell electrocatalysts consisting of Co2+-, Ni2+-phosphides or Co2+/Ni2+-phosphide solid solution particles embedded in a N-doped carbon graphitic matrix are obtained, which exhibit improved catalytic performances compared to the non-N-doped carbon materials. Co2+ phosphides consist of CoP and Co2P in variable proportions according to the used precursor and pyrolytic conditions. However, the Ni2+ phosphide is composed of Ni2P exclusively at high temperatures. Exploration of the electrochemical activity of these metal phosphides toward the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) reveals that the anhydrous Co2(ETID)(Im)3 pyrolyzed at 800 °C (CoP/Co2P = 80/20 wt %) is the most active trifunctional electrocatalyst, with good integrated capabilities as an anode for overall water splitting (cell voltage of 1.61 V) and potential application in Zn–air batteries. This solid also displays a moderate activity for the HER with an overpotential of 156 mV and a Tafel slope of 79.7 mV·dec–1 in 0.5 M H2SO4. Ni2+- and Co2+/Ni2+-phosphide solid solutions show lower electrochemical performances, which are correlated with the formation of less active crystalline phases.

Lithium confinement and dynamics in hexagonal and monoclinic tungsten oxide nanocrystals: a 7Li solid state NMR study.

Mixed-valence tungsten bronzes AxWO3 (A = alkali metal, NH4+, etc.) are a series of compounds with adaptive structural and compositional features that make them a hot research topic in thermoelectrics, electrochromics, catalysis or energy applications in battery electrodes. The mixed hexagonal lithium ammonium bronze Lix(NH4)yWO3 is a new member of this structural family whose properties are compared to those of the pure hexagonal tungsten bronze (NH4)xWO3. Surface and structural (nanoconfined) Li+ cations were characterized by 7Li single pulse excitation and 1H-7Li cross-polarization (CP) NMR experiments. CP build-up curves and two-dimensional heteronuclear correlation solid-state NMR techniques provide information about the spatial connectivity between different proton and Li+ species. At 500 °C the bronze structurally transforms from the hexagonal to a monoclinic phase, and defects are formed that are characterized through the Li+ environment. 7Li exchange spectroscopy (EXSY) NMR experiments provide information about the chemical exchange between the lithium species. The measured 7Li T1 and T2 relaxation time constants and the T1/T2 ratio allow characterizing the local strength of Li+ binding.

Single Molecular Reaction of Water on a ZnO Surface.

The dissociation of a single water molecule on a ZnO(101̅0) surface has been investigated at the atomic level by low temperature STM manipulation combined with DFT calculations. The positive pulses applied from the tip inject electrons into the system and break the bonding between water and the ZnO surface, thus leading to the hopping of water molecules. Negative pulses inject holes wherein the lower energy ones split the free O-H bond pointing out of the surface whereas the higher energy ones split the second O-H bond that is directed to the surface through hydrogen bonding. Moreover, the yielded proton and hydroxyl species present distinctly charged status through different reaction pathways, manifesting their unique impacts on tailoring the surface properties of the metal oxide.

Resolving the Structural Debate for the Hydrated Excess Proton in Water.

It has long been proposed that the hydrated excess proton in water (aka the solvated "hydronium" cation) likely has two limiting forms, that of the Eigen cation (H9O4+) and that of the Zundel cation (H5O2+). There has been debate over which of these two is the more dominant species and/or whether intermediate (or "distorted") structures between these two limits are the more realistic representation. Spectroscopy experiments have recently provided further results regarding the excess proton. These experiments show that the hydrated proton has an anisotropy reorientation time scale on the order of 1-2 ps. This time scale has been suggested to possibly contradict the picture of the more rapid "special pair dance" phenomenon for the hydrated excess proton, which is a signature of a distorted Eigen cation. The special pair dance was predicted from prior computational studies in which the hydrated central core hydronium structure continually switches (O-H···O)* special pair hydrogen-bond partners with the closest three water molecules, yielding on average a distorted Eigen cation with three equivalent and dynamically exchanging distortions. Through state-of-art simulations it is shown here that anisotropy reorientation time scales of the same magnitude are obtained that also include structural reorientations associated with the special pair dance, leading to a reinterpretation of the experimental results. These results and additional analyses point to a distorted and dynamic Eigen cation as the most prevalent hydrated proton species in aqueous acid solutions of dilute to moderate concentration, as opposed to a stabilized or a distorted (but not "dancing") Zundel cation.

Anhydrous Proton Conduction in Crystalline Porous Materials with a Wide Working Temperature Range.

Crystalline porous materials (CPMs), exhibiting high surface areas, versatile structural topologies, and tunable functionality, have attracted much attention in the field of proton exchange membrane fuel cells (PEMFC) for their great potential in solid electrolytes. However, most hydrated CPM proton conductors suffer from the narrow working temperature and the high water/humidity dependence. Considering the practical application in different working environments, CPMs with high anhydrous conductivity from subzero to moderate temperature (>100 °C) are desirable, but it is still a huge challenge. Herein we summarized our recent research work in the anhydrous CPM proton conductors, including to rationally tune the structures of CPMs by using the strategies of pore engineering and protonic species control to achieve wide working temperature conduction, as well as to clarify the conducting mechanism. This spotlight will provide clues to flexibly design and fabricate wide-working-temperature CPM conductors with high protonic conductivity.

Homonuclear J-Coupling Spectroscopy at Low Magnetic Fields using Spin-Lock Induced Crossing*.

Nuclear magnetic resonance (NMR) spectroscopy usually requires high magnetic fields to create spectral resolution among different proton species. Although proton signals can also be detected at low fields the spectrum exhibits a single line if J-coupling is stronger than chemical shift dispersion. In this work, we demonstrate that the spectra can nevertheless be acquired in this strong-coupling regime using a novel pulse sequence called spin-lock induced crossing (SLIC). This techniques probes energy level crossings induced by a weak spin-locking pulse and produces a unique J-coupling spectrum for most organic molecules. Unlike other forms of low-field J-coupling spectroscopy, our technique does not require the presence of heteronuclei and can be used for most compounds in their native state. We performed SLIC spectroscopy on a number of small molecules at 276 kHz and 20.8 MHZ and show that the simulated SLIC spectra agree well with measurements.