High Proton Concentration Research Articles

A novel merocyanine photoacid for visible light-controlled pH modulation

Merocyanine-based photoacids generate high proton concentrations under visible light irradiation. In the past decade, it has been established that these photoacids offer significant advantages over photoacid generators (PAGs) and hydroxyaryl photoacids, enabling better spatiotemporal control of proton transfer reactions in bulk media. In this study, we modified the core structure of the first generation of meroyanine photoacids. We developed a novel photoacid with color tuning capabilities and high solubility in polar organic solvents. Specifically, by incorporating a cationic benzoindolium moiety as an acceptor, we have altered the photoacid’s light absorption properties. Unlike the first generation of indolium-based merocyanine photoacids, this photoacid can now be activated with green light (λmax = 525 nm) as well as blue (λmax = 450 nm) and ultraviolet (λmax = 365 nm) lights. Furthermore, the novel photoacid exhibits high photo stability, photo-acidity (Π = 3.28 ± 0.08) and moderate reverse reaction rate (k = 1.08 × 10−3 ± 0.00017 s−1) in solution. We envision that with improved color tuning capabilities, this class of photoacids will be a more versatile tool for controlling proton-induced reactions in different systems, including biological reactions.

The effect of lattice incorporation of Cu2+ in BaCe0.6Zr0.2-xY0.15Gd0.05CuxO3-δ proton conductor on its transport properties

In this paper, the introduction of Cu2+ into BaCe0.6Zr0.2-xY0.15Gd0.05CuxO3-δ (x = 0, 0.02, 0.04, 0.06; denoted as BCZYG, BCZYGCu0.02, BCZYGCu0.04 and BCZYGCu0.06, respectively)proton conductor materials. The effects of Cu doping strategy on the crystal structure, morphology and electrical properties of BCZYGCux proton conductor materials were systematically studied. The X-ray diffraction (XRD) results demonstrate that the synthesis of the BCZYGCux proton conductor material were successfully achieved through the solid-state reaction method. The scanning electron microscopy (SEM) analysis and relative density results indicate that an appropriate amount of Cu additions was conducive to lowering the sintering temperature and promoting the density of materials. A comprehensive analysis based on EIS and DRT was conducted to investigate the effects of temperature, testing atmosphere, and doping amount on the influence of conductivity on BCZYGCux proton conductor material. BCZYGCu0.02 has the largest total conductivity of 1.11×10-2 S·cm-1 at 700 ºC in the atmospheres of pO2=0.20 atm and pH2O=0.018 atm. The transference number of the BCZYGCux proton conductor material was calculated using a defect equilibrium model. The proton transference number of BCZYGCu0.02 is 0.97 at 500 °C. The BCZYGCu0.02 proton conductor has higher proton concentration and proton transference number in comparison to BCZYG. In conclusion, the Cu doping strategy has been demonstrated to be an effective method of improving the conductivity and proton transference number of BCZYGCux proton conductor materials. This provides a valuable insight into the optimisation of perovskite proton conductor performance.

Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity.

Solar-driven methanation of carbon dioxide (CO2) with water (H2O) has emerged as an important strategy for achieving both carbon neutrality and fuel production. The selective methanation of CO2 was often hindered by the sluggish kinetics and the multiple competition of other C1 byproducts. To overcome this bottleneck, we utilized a biomass synthesis method to synthesize SiC rods and then constructed a direct Z-scheme heterojunction Co3O4/SiC catalyst. The substantial difference in work functions between SiC and Co3O4 served as a significant source of the charge driving force, facilitating the conversion of CO2 to CH4. The high-valent cobalt Co(IV) in Co3O4 acts as an active species to promote efficient dissociation of water. This favorable condition greatly enhanced the likelihood of a high concentration of electrons and protons around a single site on the catalyst surface for CO2 methanation. DFT calculation showed that the energy barrier of CO2 hydrogenation was significantly reduced at the Co3O4/SiC heterojunction interface, which changed the reaction pathway and completely converted the product from CO to CH4. The optimum CH4 evolution rate of Co3O4/SiC samples was 21.3 μmol g-1 h-1 with 100% selectivity. This study has an important guiding significance for the selective regulation of CO2 to CH4 products in photocatalysis applications.

Electricity generated by upstream proton diffusion in two-dimensional nanochannels.

The movement of ions along the pressure-driven water flow in narrow channels, known as downstream ionic transport, has been observed since 1859 to induce a streaming potential and has enabled the creation of various hydrovoltaic devices. In contrast, here we demonstrate that proton movement opposing the water flow in two-dimensional nanochannels of MXene/poly(vinyl alcohol) films, termed upstream proton diffusion, can also generate electricity. The infiltrated water into the channel causes the dissociation of protons from functional groups on the channel surface, resulting in a high proton concentration inside the channel that drives the upstream proton diffusion. Combined with the particularly sluggish water diffusion in the channels, a small water droplet of 5 µl can generate a voltage of ~400 mV for over 330 min. Benefiting from the ultrathin and flexible nature of the film, a wearable device is built for collecting energy from human skin sweat.

High Proton Conduction in the Octahedral Layers of Fully Hydrated Hexagonal Perovskite-Related Oxides.

Proton conductors have potential applications such as fuel cells, electrolysis cells, and sensors. These applications require new materials with high proton conductivity and high chemical stability at intermediate temperatures. Herein we report a series of new hexagonal perovskite-related oxides, Ba5R2Al2SnO13 (R = Gd, Dy, Ho, Y, Er, Tm, and Yb). Ba5Er2Al2SnO13 exhibited a high proton conductivity without chemical doping (e.g., 0.01 S cm-1 at 303 °C), which is attributed to its high proton concentration and diffusion coefficient. The high diffusion coefficient of Ba5Er2Al2SnO13 can be attributed to the fast proton migration in the octahedral layers. The high proton concentration is attributed to full hydration in hydrated Ba5Er2Al2SnO13 and the large amount of intrinsic oxygen vacancies in the dry sample, as evidenced by both neutron diffraction and thermogravimetric analysis. Ba5Er2Al2SnO13 was found to exhibit high chemical stability under wet atmospheres of O2, air, H2, and CO2. High proton conductivity and high chemical stability indicate that Ba5Er2Al2SnO13 is a superior proton conductor. Ba5R2Al2SnO13 (R = Gd, Dy, Ho, Y, Tm, and Yb) exhibited high electrical conductivity in wet N2, suggesting that these materials also exhibit high proton conductivity. These findings will open new avenues for proton conductors. The high proton conductivity via full hydration and fast proton migration in octahedral layers in highly oxygen-deficient hexagonal perovskite-related materials would be an effective strategy for developing next-generation proton conductors.

Effects of pH-varying thermal modification on sewage sludge: A focus on releasing nitrogen- and phosphorus-containing substances

Sewage sludge is promising for the recovery and utilisation of nutrient components, but its complex nature hinders the release of these components. The combination of pH and thermal modifications shows promise for the release of nutrient components from sludge. However, comprehensive studies on the full spectrum of pH levels and corresponding mechanisms of pH-varying thermal modification are lacking. In this study, the main nutrient components, physicochemical properties, molecular structure, and noncovalent interactions of sludge were comprehensively investigated through pH-varying thermal modification (within a pH range of 2.0 to 12.0 under the same thermal condition). The experimental results showed that the release of main organics, particularly nitrogen (N)-containing organics, was well-fitted, with a tick-like function (R2: 0.74–0.96). The thermal protons exhibited a notable accumulative mutagenic effect on the N-containing organics release, while the thermal hydroxyl ions had a more direct effect, as revealed by the changes in multivalent metals and molecular structures with the protonation–deprotonation of carboxyl groups. The driving force for the release of N-containing organics was identified as the fluctuation of electrostatic interactions at the solid–liquid interface of the sludge. However, the release of phosphorus (P)-containing substances exhibited a contrasting response to that of N-containing substances with varying pH, likely because the reaction sites of thermal protons and thermal hydroxyl ions for P-containing substances were different. Moreover, high concentrations of thermal protons and hydroxyl ions collapsed the Lifshitz–van der Waals interactions of sludge, resulting in a decrease in viscoelasticity and binding strength. These propositions were further confirmed through statistical analyses of the main indicators of the main nutrient components, physicochemical properties, and noncovalent interactions of sludge. These findings can provide a basis for optimising characteristic-specific methods to recovery nutrient components (N/P) from sludge.

Mechanism of local hydrogen entry into Fe sheets induced by atmospheric corrosion: Significance of potential, pH, and rust layer thickness

Local hydrogen entry under a NaCl droplet on Fe sheets was analysed by employing a hydrogenochromic sensor and electrochemical hydrogen permeation tests. Large crystallographic pits barely promoted hydrogen entry, because crystallographic pitting proceeded at potentials higher than the potential of the hydrogen evolution reaction. Hydrogen entry was accelerated because of acidification under an island-like rust layer. The rust layer became thick in its outer regions, mainly owing to severe corrosion and alkalisation around the rust-formed area. Hydrogen entry was prominent under the thick rust layer after disappearance of the droplet, owing to the high concentrations of chloride ions and protons.

Recent Advances in Iridium-based Electrocatalysts for Acidic Electrolyte Oxidation.

Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

High-Temperature Protonic Conduction in La2NiO4+ δ-Based Ruddlesden-Popper Type Oxides: Correlation with Concentration of Interstitial Oxide Ions.

Oxygen-excess La2NiO4+ δ (LNO) conducts oxide ions, electron holes, and hydroxide ions simultaneously on exposing to wet oxygen, exhibiting the potential as a cathode material in protonic ceramic fuel cells. Since the incorporation of protons in oxygen-excess LNO is via the hydration reaction assisted by interstitial oxide ions, in this work, the concentration of interstitial oxide ions is reduced and increased by substituting Ni with Cu and Co, respectively. A higher concentration of interstitial oxide ions leads to a high proton concentration, indicating the predominant role of interstitial oxide ions in the hydration reaction, different from that in the oxygen-deficient oxides, where protons are introduced by dissociative absorption of water molecules by oxygen vacancies. The theoretical calculation indicates that protons in Co-doped LNO prefer to locate between the interstitial oxide ions and unshared apical oxide ions. A trapping effect is found between protons and the oxide ions near Cu, leading to decreased proton mobility. Protonic conductivity at 400-575 °C is then directly measured by a Hebb-Wagner direct current polarization method with La0.99Ca0.01NbO4- δ as the blocking electrode, enabling the observation that Co-doped LNO has the highest protonic conductivity among the samples studied in this work.

Identifying routes for transferring spin polarization from parahydrogen to protic solvents

Repeatable hyperpolarization of high concentrations of mobile protons (> 6 M) using parahydrogen in protic methanol/water is reported here. Different ammoniumbuffers with increasing mobile proton concentrations were added to an...

High proton conduction by full hydration in highly oxygen deficient perovskite

We report high proton conductivity (10 mS cm−1 at 235 °C) of stable BaSc0.8W0.2O2.8, which is attributed to (1) high proton concentration due to full hydration and large amount of oxygen vacancies and (2) high proton mobility due to reduced proton trapping.

Elucidating the Role of Atomically Dilute Copper Centers Impregnating a Phosphamide Polymer for the Preferential Hydrogen Evolution Reaction over CO2 Reduction.

Organic polymers have attracted considerable interest in designing a multifunctional electrocatalyst. However, the inferior electro-conductivity of such metal-free polymers is often regarded as a shortcoming. Herein, a nitrogen- and phosphorus-rich polymer with phosphamide functionality (PAP) in the repeating unit has been synthesized from diaminopyridine (DAP) and phenylphosphonic dichloride (PPDC) precursors. The presence of phosphamide oxygen and pyridine nitrogen in the repeating unit of PAP leads to the coordination of the CuII ion and the incorporation of 3.29 wt % in the polymer matrix (Cu30@PAP) when copper salt is used to impregnate the polymer. Combined with a spectroscopic, microscopic, and DFT study, the coordination and geometry of copper in the PAP matrix has been established to be a distorted square planar CuII in a N2O2 ligand environment where phosphamide oxygen and pyridine nitrogen of the PAP coordinate to the metal center. The copper incorporation in the PAP modulates its electrocatalytic activity. On the glassy carbon electrode, PAP shows inferior activity toward the hydrogen evolution reaction (HER) in 0.5 M H2SO4 while 3 wt % copper incorporation (Cu30@PAP) significantly improves the HER performance with an overpotential of 114 mV at 10 mA cm-2. The notable electrochemical activity with Cu30@PAP occurs due to the impregnation of Cu(II) in PAP, improved electro-kinetics, and better charge transfer resistance (Rct). When changing the electrolyte from H2SO4 to CO2-saturated bicarbonate solution at nearly neutral pH, PAP shows HER as the dominant pathway along with the partial reduction of CO2 to formate. Moreover, the use of Cu30@PAP as an electrolcatalyst could not alter the predominant HER path, and only 20% Faradaic efficiency for the CO2 reduced products has been achieved. Post-chronoamperometric characterization of the recovered catalyst suggests an unaltered valence state of the copper ion and the intact chemical structure of PAP. DFT studies unraveled that the copper sites of Cu30@PAP promote water adsorption while phosphamide-NH of the PAP can weakly hold the CO2 adduct via a hydrogen bonding interaction. A detailed calculation has pointed out that the tetra-coordinated copper centers present in the PAP frame are the reactive sites and that the formation of the [CuI-H] intermediate is the rate-limiting step for both HER and its competitive side reaction, i.e., CO2 reduction to formate or CO formation. The high proton concentration in the electrolyte of pH < 7 leads to HER as the predominant pathway. This combined experimental and theoretical study has highlighted the crucial role of copper sites in electrocatalysis, emphasizing the plausible reason for electrocatalytic selectivity.

Carbon and Energy Efficient Ethanol Electrosynthesis By Acidic CO2 Reduction

The electrochemical CO2 reduction reaction (CO2RR) is one way of mitigating the rising levels of anthropogenic CO2 emissions. Most of the advancements in the CO2RR field have been implemented in basic or neutral electrolytes where a major fraction of the input CO2 converts to carbonate ions through reaction with OH– (Science 360, 783-787 (2018); Nat. Catal. 5, 564-570 (2022)). These approaches result in low carbon efficiency (the percentage of CO2 converted per total CO2 input), typically below 20% toward multicarbon products, resulting in severe energy and cost penalty (Nat. Sustain. 5, 563-573 (2022)).Performing CO2RR in acidic conditions reduces reactant loss to carbonates. In this condition, the (bi)carbonate ion crossover/formation is countered by the high proton concentration in the electrolyte. However, the unshielded cathode surface favors the hydrogen evolution reaction (HER) over CO2RR due to the high availability of protons and the fast kinetics of the HER (Science 372, 1074-1078, (2021); Nat. Catal. 4, 654-662 (2021)).Here, we have developed an interfacial cation matrix (ICM) to modulate the local microenvironment on the cathode surface. The ICM increases the local pH and electric field, promoting multicarbon production. Additionally, we have designed a Copper-Silver catalyst to tune the selectivity towards alcohol production. We improved the ethanol FE to 45% at 200 mA/cm2, which, to our knowledge, represents the highestethanol FE in membrane electrode assembly literature. The system maintains a high carbon efficiency (60%) resulting in a total energy cost of 263 GJ/tonne ethanol, which is the lowest value among current ethanol-producing CO2 electrolysers.

Adsorption of Nickel Ions on the γ-Alumina Surface: Competitive Effect of Protons and Its Impact on Concentration Profiles.

Mesoporous γ-alumina is used as an adsorbent in the decontamination of water from heavy metals (e.g., nickel and cobalt) and as a support for heterogeneous catalysts prepared by impregnation. In these cases, alumina extrudates are in contact with aqueous solutions containing precursors of the active metal phase to be deposited. The proton concentration (or pH) in the metal solution in contact with alumina can impact the adsorption efficiency of decontamination processes and the activities of catalysts. Yet, it is difficult to quantify the effect of the pH inside the pores since protons are not detected by classical imaging techniques. In this article, the effect of protons on nickel adsorption on alumina is evaluated using a novel technique coupling liquid analysis (pH, conductivity, and UV/vis) and laser-induced breakdown spectroscopy (or LIBS) analysis of concentration gradients inside the solid. Both methods are in excellent agreement. The results show a slow diffusion of protons inside alumina pores (diffusion continues even after 940 min), yielding high proton concentration gradients. On the other hand, the nickel species penetrate the extrudates faster but are slowly displaced by protons under certain operating conditions. As a result, different metal concentration profiles are obtained, depending on the initial pH and contact time. These findings are interesting in catalysis since they prove the possibility of controlling the deposition of the active metal on catalysts by regulating the operating conditions of impregnation. For typical industrial impregnation times (a few minutes to 1 to 2 h), protons do not have enough time to deeply penetrate inside extrudates, so the initial pH of the metal solution will have nearly no effect on the metal distribution. Conversely, decontamination processes have much longer contact times; therefore, lower initial pH values should have negative impacts on the adsorption efficiency due to the protons displacing the adsorbed nickel.

High proton conductivity within the ‘Norby gap’ by stabilizing a perovskite with disordered intrinsic oxygen vacancies

Proton conductors are attractive materials with a wide range of potential applications such as proton-conducting fuel cells (PCFCs). The conventional strategy to enhance the proton conductivity is acceptor doping into oxides without oxygen vacancies. However, the acceptor doping results in proton trapping near dopants, leading to the high apparent activation energy and low proton conductivity at intermediate and low temperatures. The hypothetical cubic perovskite BaScO2.5 may have intrinsic oxygen vacancies without the acceptor doping. Herein, we report that the cubic perovskite-type BaSc0.8Mo0.2O2.8 stabilized by Mo donor-doing into BaScO2.5 exhibits high proton conductivity within the ‘Norby gap’ (e.g., 0.01 S cm−1 at 320 °C) and high chemical stability under oxidizing, reducing and CO2 atmospheres. The high proton conductivity of BaSc0.8Mo0.2O2.8 at intermediate and low temperatures is attributable to high proton concentration, high proton mobility due to reduced proton trapping, and three-dimensional proton diffusion in the cubic perovskite stabilized by the Mo-doping into BaScO2.5. The donor doping into the perovskite with disordered intrinsic oxygen vacancies would be a viable strategy towards high proton conductivity at intermediate and low temperatures.

Double-edged effect of frequent freeze-thaw on the stability of zero-valent iron after heavy metal remediation

Freeze-thaw cycles (FTCs) cause dynamic microscale changes in ions and solvents. During freezing, heavy metals adsorbed on zero-valent iron (M-ZVI) and protons are excluded by ice crystals and concentrated in the liquid-like grain boundary region. The high proton concentration in this region leads to the dissolution of the passivation layer of ZVI. To assess the environmental risks of M-ZVI during FTCs, this study evaluated the stability of M-ZVI in this scenario from both microscale and macroscale perspectives. The results showed that the dissolution of the passivation layer had a dual effect on the stability of M-ZVI, which depends on the by-products of M-ZVI. The dissolution of the passivation layer was accompanied by the leaching of heavy metals, such as Ni-ZVI, but it also enhanced the reactivity of ZVI, causing it to re-react with desorbed heavy metals. The stability of Cr-ZVI and Cd-ZVI was improved due to frequent FTCs. Furthermore, changes in the surrounding environment (water dipole moment, ion concentration, etc.) of ZVI affected the crystallization of Fe oxides, increasing the content of amorphous Fe oxide. As low-crystallinity Fe oxides could facilitate ion doping, Ni2+ was doped into Fe3O4 lattice during FTCs, which reduced the mobility of heavy metals. Contrary to traditional views that freezing temperatures slow chemical reactions, this study provides new insights into the application of iron-based materials in cold environments.

Dramatic mitigation of capacity decay and volume variation in vanadium redox flow batteries through modified preparation of electrolytes

Electrolyte imbalance caused by the undesired vanadium-ions cross-over and water transport through the membrane is one of the main critical issues of vanadium redox flow batteries, leading to battery capacity loss and electrolytes volume variation. In this work, the evolution of discharged capacity and electrolyte volume variation were firstly investigated adopting commercial electrolyte for hundreds of charge-discharge cycles in vanadium redox flow batteries employing different membranes, varying thickness and equivalent weight. Subsequently, with the support of a 1D physics-based model, the origin of the main phenomena regulating capacity decay and volume variation has been identified and different modifications in the preparation of electrolytes have been proposed. Electrolytes characterized by an equal proton concentration between the two tanks at the beginning of cycling operation turned out to limit capacity decay, while increasing electrolyte proton concentration was effective also in the mitigation of volume variation. The most promising electrolyte preparation combined the effect of high proton concentration and null osmotic pressure gradient between the two tanks: compared to commercial electrolyte this preparation reduced the capacity decay from 47.7% to 20.9%, increased the coulombic efficiency from 96.2% to 98.9% and the energy one from 79.9% to 83.4%, and also implied a negligible volume variation during cycles. The effectiveness of this electrolyte preparation has been verified with different membranes, increasing the range of validity of the results, that could be thus applied in a real system regardless of the adopted membrane.

The structure and electrical properties of novel BaSn0.15Ce0.35Hf0.25Y0.1Yb0.1Ho0.05O3-δ high-entropy proton-conducting electrolyte

In this article, the structure and electrical properties of BaSn0.15Ce0.35Hf0.25Y0.1Yb0.1Ho0.05O3-δ (referred as BSCHYYbHo in forthcoming discuss) high-entropy ceramic have been investigated. The BCHYYb (short for BaCe0.5Hf0.3Y0.1Yb0.1O3-δ) and BSCHYYbHo pellets were synthesized successfully by the solid-state reaction method. The XRD detection results indicate that there is no secondary phase appeared in BSCHYYbHo and the lattice constant decrease compared to BCHYYb. The surface SEM and EDS images illustrates that BSCHYYbHo is denser than BCHYYb and the elements distribution is more uniform. The DFT calculation proves that BSCHYYbHo has a tend to maintain single phase structure. The electrical properties of BSCHYYbHo is obtained by the DRT analysis and equivalent circuit method based on defect equilibria model. The total conductivity of BSCHYYbHo is about 2.02 × 10-4 ∼1.01 × 10-2 S·cm-1 and standard molar hydration enthalpy of BSCHYYbHo is recorded as − 81.8 kJ/mol. Further, the proton, oxygen vacancies and electron holes conductivity activation energies in BSCHYYbHo is estimated to be 0.45 eV, 1.41 eV and 1.60 eV, respectively. Compared to BCHYYb, BSCHYYbHo electrolyte has higher proton concentration and proton transference number. Overall, BSCHYYbHo ceramic with dense structure and high proton transference number is a potential material for application.

Proton transport through interfaces in nanophase-separation of hydrated aquivion membrane: Molecular dynamics simulation approach

We investigate the effect of temperature and hydration on the nanophase-separated structure and proton conductivity in Aquivion and Nafion membranes using molecular dynamics simulation method. By considering two different temperatures (298 and 353 K) and water contents (10 and 20 wt%), our study reveals that Nafion exhibits better nanophase separation and a more mature internal structure of the water phase compared to Aquivion, leading to facilitated proton dissociation and improved proton conduction through vehicular and hopping mechanisms. This study also identifies the formation of a hydronium-mediated bridge configuration that restricts vehicular mobility at low hydration, resulting in a decrease of the vehicular contribution to proton conduction. From quantitative evaluation of the extent of nanophase-separation using structure factor analysis, we find that Nafion has a shorter correlation length with greater concentration contrast in comparison to Aquivion. At high hydration conditions, the hopping mechanism dominates at low temperature while the vehicular mechanism is dominant at high temperature. At low hydration, the vehicular mechanism is significantly decreased due to hydronium-mediated bridge configurations. It is interesting to note that the proton conductivity in the Aquivion membrane is higher despite the Nafion membrane having a higher proton diffusion. We discover that the greater proton conductivity of Aquivion membrane is caused by its higher proton concentration. In general, our findings offer a fundamental knowledge of the connection between nanophase-separated structure and proton transport characteristics in Nafion and Aquivion systems under a range of temperature and hydration circumstances.

Engineering oxygen vacancy to accelerate proton conduction in Y-doped BaZrO3

Proton conducting oxides have drawn great interest as electrolytes for proton-conducting reversible solid oxide cells (P-RSOCs), but suffered from the inferior ionic conductivity. To accelerate proton conduction, oxygen vacancy engineering via calcium-doping is proposed and validated, which generates more oxygen vacancies to increase proton concentration and importantly tailors the position of oxygen vacancy to accelerate proton diffusion. TG and EIS results show that calcium-doped BaZr0.8Y0.2O3-δ (BZY2), BaZr0.8Ca0.1Y0.2O3-δ (BZCa1Y2), owns higher proton concentration, and demonstrates ionic conductivity of 0.008 S cm−2 at 700 °C, 2.7 times higher than BZY2. The lower activation energy of conductivity in BZCa1Y2 confirms the faster proton conduction behavior. DFT calculation concludes that oxygen vacancies prefer to cluster with Ca site and proton diffusion barrier is decreased most when vacancy is tailored to generate nearing Ca. When considering the concentration of proton and oxygen vacancy, proton diffusion coefficient obtained from Ab-initio Molecular Dynamics simulation is 1.1×10−5 cm2s−1 for BZCa1Y2 in 200 °C, larger than BZY2 (9.0×10−6 cm2s−1) and verifying the accelerated proton diffusion due to the tailored oxygen vacancy. The oxygen vacancy engineering provides a further understanding of proton diffusion in proton conducting oxides and a new promising opportunity to improve conductivity.