Solid-state Proton Research Articles

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.

Experimental study of phase change material (PCM) biochar composite for net-zero built environment applications

This study presents a novel and sustainable method for integrating octadecane phase change material (PCM) into traditional building materials like mortar and gypsum using vacuum-impregnated biochar. Optimising the impregnation conditions resulted in a PCM-biochar composite with 62.21 % PCM loading and a latent heat energy of approximately 116.7 J.g−1, as measured by Differential Scanning Calorimetry (DSC). Thermogravimetric Analysis (TGA) confirmed the composite’s stability at high temperatures, while accelerated DSC validated its phase change capability and stability over 300 cycles. Characterisation via Scanning Electron Microscopy (SEM), Small-Angle X-ray Scattering (SAXS), X-ray Diffraction (XRD), and Solid-State Proton Nuclear Magnetic Resonance (1H NMR) verifies PCM retention within biochar pores and reveals interactions between PCM and biochar. Additionally, the non-pozzolanic nature of biochar is confirmed. Workability tests show reduced consistency with increased PCM-biochar content in mortar. At 40 % sand replacement rate with PCM-biochar, the compressive strength initially decreases by 45.50 % after 28 days, but it improves to 43 MPa after 120 days. Gypsum samples retain adequate strength for retrofitting applications (2 MPa), demonstrating the potential of PCM-biochar composites to enhance thermal energy storage in building materials, thereby supporting Net-zero building objectives.

Oxide Acidity Modulates Structural Transformations in Hydrogen Titanates during Electrochemical Li-Ion Insertion.

Hydrogen titanates (HTOs) form a diverse group of metastable, layered titanium oxides with an interlayer containing both water molecules and structural protons. We investigated how the chemistry of this interlayer environment influenced electrochemical Li+-insertion in a series of HTOs, H2TiyO2y+1·nH2O (y = 3, 4, and 5). We correlated the electrochemical response with the physical and chemical properties of HTOs using operando X-ray diffraction, in situ differential electrochemical mass spectroscopy, solid-state proton nuclear magnetic resonance, and quasi-elastic neutron scattering. We found that the potential for the first reduction reaction trended with the relative acidity of the structural protons. This mechanism was supported with first-principles density functional theory (DFT) calculations. We propose that the electrochemical reaction involves reduction of the structural protons to yield hydrogen gas and formation of a lithiated hydrogen titanate (H2-xLixTiyO2y+1). The hydrogen gas is confined within the HTO lattice until the titanate structure expands upon subsequent oxidation. Our work has implications for the electrochemical behavior of insertion hosts containing hydrogen and structural water molecules, where hydrogen evolution is expected at potentials below the hydrogen reduction potential and in the absence of electrolyte proton donors. This behavior is an example of electrochemical electron transfer to a nonmetal element in a metal oxide host, in analogy to anion redox.

A Solid-State Electrolyte Facilitates Acidic CO2 Electrolysis without Alkali Metal Cations by Regulating Proton Transport.

Electrochemical CO2 reduction (CO2R) in acidic media provides a pathway to curtail CO2 losses by suppressing the formation of (bi)carbonates. In such systems, a high concentration of alkali metal cations is necessary for mitigating the proton-rich environment and suppressing the competing hydrogen evolution reaction. However, a high cation concentration also promotes salt precipitation within the gas diffusion layer, resulting in poor system durability. Here, we resolve this conundrum by replacing the liquid catholyte with a solid-state proton conductor to regulate H+ transport. This is postulated to allow for a locally alkaline environment at the cathode, enabling selective CO2R even without alkali metal cations. We show that this strategy is effective over a broad range of catalyst systems. For instance, we achieve an 87% CO faradaic efficiency (FE) at 300 mA/cm2 using a composite nanoporous Au and single-atom Ni catalyst, with 0.25 M H2SO4 as the anolyte. Stable operation over 110 h and a high single-pass carbon efficiency of 82.8% were also successfully demonstrated. Importantly, we find that this solid-state system is also particularly effective at converting dilute feedstock (5% CO2) with a CO FE of 47.7%, a factor of 16.4 times higher than a conventional system. Our results introduce a simple yet effective design approach for developing efficient acidic CO2R electrolyzers.

Enhanced photocatalytic CO2 conversion into reusable fuels with efficient solid-state proton donors

Lead halide perovskites driven photocatalytic CO2 reduction reaction (CO2RR) is restricted by H2O proton source due to the poor water-resistance of perovskites and difficult dissociation of H2O molecules. In this paper, a novel solid-state proton donor of amino acid modified melamine foam (Ami-MF) is developed, which could improve CO2RR of CsPbBr3/Bi2WO6 S-scheme heterojunction. On the one hand, amino acid molecules possess abundant –COOH and –NH2 groups, which are broken easily by catalyst oxidation compared with H2O, supplying sufficient protons for CO2RR. Product yield of Glu-MF/CsPbBr3/Bi2WO6 reaches 112.81 μmol/g/h, which is 3.8 times higher than that (29.83 μmol/g/h) of H2O-MF/CsPbBr3/Bi2WO6. Moreover, glutamic acid (Glu), cysteine (Cys), arginine (Arg) as typical acidic, neutral and basic amino acids are selected to explore proton supply from different amino acids. Glu-MF/CsPbBr3/Bi2WO6 exhibits the best CO2RR than other two Ami-MF, ascribing to the dicarboxylic structure of Glu. On the other hand, MF is an integral part in solid-state proton donor. Product yield of Glu-MF/CsPbBr3/Bi2WO6 is about 46.2 times higher than that (2.44 μmol/g/h) of powdery Glu/CsPbBr3/Bi2WO6, which ascribes to the efficient gas–solid CO2RR system induced by the three-dimensionality and porosity of MF. This study develops an efficient solid proton donor to enhance perovskites driven CO2RR.

Covalent-Organic Framework with Superior Proton Conduction for Solid-State Proton Battery Application

Covalent-Organic Framework with Superior Proton Conduction for Solid-State Proton Battery Application

Tailored 2D conjugated polymers for pseudocapacitive proton storage

2D conjugated polymers (2D-CPs) are currently attracting substantial attention as host materials in electrochemical energy storage. They show some intriguing properties, such as high conductivity (by elevating the conjugated degree), adjustable redox activity (by controlling the monomers), and stable skeleton structure (low solubility in electrolytes). Herein, two aza-based 2D-CPs with different conjugation degrees are designed and developed for pseudocapacitive proton storage. The detailed electrochemical analysis shows that the highly conjugated 2D-CP (2D-HCP) demonstrates an inferior performance compared to partially conjugated 2D-CP (2D-PCP), especially in terms of the high-rate performance. Though combining various in-situ/ex-situ spectroscopy analyses and theoretical simulation, the reason behind this performance is revealed and is associated with the different solid-state proton diffusion kinetics in these two 2D-CPs. We believe this new understanding can be leveraged to design and develop more suitable 2D-CPs for electrochemical energy storage.

Room-Temperature Superprotonic Conductivity beyond 10-1 S cm-1 in a Co(II) Coordination Polymer.

An efficient design of crystalline solid-state proton conductors (SSPCs) is crucial for the progress of clean energy applications. Developing such materials to make them work at room temperature with a conductivity of ≥10-1 S cm-1 is of significant interest in terms of technical and commercial aspects. Utilizing the recently highlighted "coordinated-water-driven proton conduction" approach, herein, we have rationally synthesized two highly stable and scalable 1D Co(II) coordination polymers (CPs) as SSPCs, PCM-2 {[Co(bpy)(H2O)2(NO3)2]·H2O}n and PCM-3 {[Co2(bpy)2(SO4)2(H2O)6].4H2O}n, with distinct alignments in coordinated water and coordinated oxo-anions (nitrate and sulfate, respectively). The acidity of the metal-bound water molecules in PCM-2 is further enhanced through cooperative long-range continuous H bonds with coordinated Brønsted basic nitrates (proton acceptors), leading to ultrahigh superprotonic conductivities even at 25 °C (1.03 × 10-1 S cm-1 under 95% RH), and reached a maximum of 2.99 × 10-1 S cm-1 at 85 °C (95% RH). The conductivity at 25 °C is even higher than that of commercial Nafion 117 (6.74 × 10-2 S cm-1 at 100% RH). The absence of such an H-bonding interaction in PCM-3 (closed loops) resulted in a lesser conductivity of 5.87 × 10-5 S cm-1 (95% RH, 85 °C). PCM-2 represents the first example of SSPC exhibiting conductivity in the order 10-1 S cm-1 at ambient temperature (25 °C) with excellent recyclability.

Shaping techniques' influence on the electrochemical properties of BaCe0.6Zr0.3Y0.1O3-δ proton conductor

Hydrogen's significance as a clean and high-energy source spans various industries, driving advancements in fuel cell technology, transportation, and renewable energy storage systems. In particular, solid-state proton conductors like perovskite-type materials exhibit promising attributes for applications such as fuel cells and hydrogen sensors. However, conventional shaping techniques like uniaxial pressing impose limitations on device scalability and geometry. To address these challenges, alternative methods are gaining traction, like cold isostatic pressing or additive manufacturing. Each technique offers distinct advantages in shaping materials, impacting their structural and morphological properties. In this study, pellets of BaCe0.6Zr0.3Y0.1O3-δ (BCZY) solid-state electrolyte were fabricated using four different shaping techniques: uniaxial pressing, cold isostatic pressing, 3D extrusion, and lithography. Characterization via X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy provided insights into changes in crystalline structure, sintering quality, and electrochemical properties, respectively.

Self-assembly of water-filled molecular saddles to generate diverse morphologies and high proton conductivity.

The design of single-component organic compounds acting as efficient solid-state proton conduction (SSPC) materials has been gaining significant traction in recent times. Molecular design and controlled self-assembly are critical components in achieving highly efficient SSPC. In this work, we report the design, synthesis, and self-assembly of an organic macrocyclic aza-crown-type compound, P2Mac, which complements synthetic ease with efficient SSPC. P2Mac is derived from the pyridine-2,6-dicarboxamide (PDC) framework and contains polar amide and amine residues in its inner region, while aromatic residues occupy the periphery of the macrocycle. The crystal structure analysis revealed that P2Mac adopts a saddle-shaped geometry. Each P2Mac molecule interacts with one water molecule that is present in its central polar cavity, stabilized by a network of five hydrogen bonds. We could self-assemble P2Mac in a variety of unique, aesthetically pleasing morphologies such as micron-sized octahedra, hexapods, as well as hollow nanoparticles, and microrods. The water-filled polar channels formed through the stacking of P2Mac allow attaining a high proton conductivity value of 21.1 mS cm-1 at 27 °C under a relative humidity (RH) of 95% in the single crystals of P2Mac, while the as-prepared P2Mac pellet sample exhibited about three-orders of magnitude lower conduction under these conditions. The low activation energy of 0.39 eV, calculated from the Arrhenius plot, indicates the presence of the Grotthus proton hopping mechanism in the transport process. This report highlights the pivotal role of molecular design and self-assembly in creating high-performance SSPC organic materials.

Participation of electrochemically inserted protons in the hydrogen evolution reaction on tungsten oxides.

Understanding the mechanisms by which electrodes undergo the hydrogen evolution reaction (HER) is necessary to design better materials for aqueous energy storage and conversion. Here, we investigate the HER mechanism on tungsten oxide electrodes, which are stable in acidic electrolytes and can undergo proton-insertion coupled electron transfer concomitant with the HER. Electrochemical characterization showed that anhydrous and hydrated tungsten oxides undergo changes in HER activity coincident with changes in proton composition, with activity in the order HxWO3·H2O > HxWO3 > HxWO3·2H2O. We used operando X-ray diffraction and density functional theory to understand the structural and electronic changes in the materials at high states of proton insertion, when the oxides are most active towards the HER. H0.69WO3·H2O and H0.65WO3 have similar proton composition, structural symmetry, and electronic properties at the onset of the HER, yet exhibit different activity. We hypothesize that the electrochemically inserted protons can diffuse in hydrogen bronzes and participate in the HER. This would render the oxide volume, and not just the surface, as a proton and electron reservoir at high overpotentials. HER activity is highest in HxWO3·H2O, which optimizes both the degree of proton insertion and solid-state proton transport kinetics. Our results highlight the interplay between the HER and proton insertion-coupled electron transfer on transition metal oxides, many of which are non-blocking electrodes towards protons.

Amino acid modified melamine foam as solid-state proton donor for CsPbBr3-based S-scheme heterojunction driven photocatalytic CO2 reduction

H2O as a proton source affects the stability of lead halide perovskites, restricting the photocatalytic CO2 reduction reaction (CO2RR). In this paper, l-lysine modified melamine foam (L-MF) is designed as an efficient solid-state proton donor to participate in CO2RR of CsPbBr3-based S-scheme heterojunction. On the one hand, abundant –COOH and –NH2 groups of l-lysine would break easily compared with H2O, which provides adequate protons for CO2RR. Moreover, the functionalized –COOH and –NH2 groups of l-lysine as Lewis base could coordinate with unsaturated Pb2+ of CsPbBr3, which could decrease the defect density of perovskite and improve the charge migration of catalyst. On the other hand, three-dimensional and porous melamine foam as a supporter could achieve gas-solid bi-phase CO2RR system, which contributes to mass transfer efficiency between CO2 gas and catalyst, accelerating CO2 conversion into high value-added fuels. Under sunlight irradiation, product yield of CO2RR reaches 73.47 μmol/g/h for L-MF/CsPbBr3/Bi2WO6, which is 2.8- and 72.7-fold of MF/CsPbBr3/Bi2WO6 (25.93 μmol/g/h) and CsPbBr3/Bi2WO6 powder (1.01 μmol/g/h) with H2O as proton source, suggesting the efficient proton supply for CO2RR from solid-state proton donor. This work could open a new avenue to utilize lead halide perovskites-based catalysts for energy conversion.

Acidified Nitrogen Self-Doped Porous Carbon with Superprotonic Conduction for Applications in Solid-State Proton Battery.

Solid proton electrolytes play a crucial role in various electrochemical energy storage and conversion devices. However, the development of fast proton conducting solid proton electrolytes at ambient conditions remains a significant challenge. In this study, a novel acidified nitrogen self-doped porous carbon material is presented that demonstrates exceptional superprotonic conduction for applications in solid-state proton battery. The material, designated as MSA@ZIF-8-C, is synthesized through the acidification of nitrogen-doped porous carbon, specifically by integrating methanesulfonic acid (MSA) into zeolitic imidazolate framework-derived nitrogen self-doped porous carbons (ZIF-8-C). This study reveals that MSA@ZIF-8-C achieves a record-high proton conductivity beyond 10-2 Scm-1 at ambient condition, along with good long-term stability, positioning it as a cutting-edge alternative solid proton electrolyte to the default aqueous H2 SO4 electrolyte in proton batteries.

Efficient Proton Conductor Based on Bismuth Oxide Clusters and Polyoxometalates.

Developing new solid-state electrolyte materials for improving the proton conductivity remains an important challenge. Herein, a novel two-dimensional layered solid-state proton conductor Bi2O2-SiW12 nanocomposite, based on silicotungstic acid (H4SiW12O40) and Bi(NO3)3·5H2O, was synthesized and characterized. The composite consists of a layered cation framework [Bi2O2]2+ and interlayer-embedded counteranionic [SiW12O40]4-, which forms continuous hydrogen bond (O-H···O) networks through the interaction of adjacent oxygen atoms on the surface of the [Bi2O2]2+ and oxygen atoms of the H4SiW12O40. Facile proton transfer along these pathways endows the Bi2O2-SiW12 (30:1) nanocomposite with an excellent proton conductivity of 3.61 mS cm-1 at 90 °C and 95% relative humidity, indicating that the nanocomposite has good prospects as a highly efficient proton conductor.

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.

Synthesis and In Situ Monitoring of Mechanochemical Preparation of Highly Proton Conductive Hydrogen-Bonded Metal Phosphonates.

Crystalline porous materials are recognized as promising proton conductors for the proton exchange membrane (PEM) in fuel cell technology owing to their tunable framework structure. However, it is still a challenging bulk synthesis for real-world applications of these materials. Herein, we report the mechanochemical gram-scale synthesis of two isostructural metal hydrogen-bonded organic frameworks (MHOFs) of Co(II) and Ni(II) based on 1-hydroxyethylidenediphosphonic acid (HEDPH4) with 2,2'-bipyridine (2,2'-bipy): Co(HEDPH3)2(2,2'-bipy)·H2O (1) and Ni(HEDPH3)2(2,2'-bipy)·H2O (2). In situ monitoring of the mechanochemical synthesis using different synchrotron-based techniques revealed a one-step mechanism - the starting materials are directly converted to the product. With the existence of extensive hydrogen bonds with amphiprotic uncoordinated phosphonate hydroxyl and oxygen atoms, both frameworks exhibited proton conduction in the range of 10-4 S cm-1 at room temperature under humid conditions. This study demonstrates the potential of green mechanosynthesis for bulk material preparation of framework-based solid-state proton conductors.

Exploring Proton Pair Motion Away from the Global Proton–Tuple Energy Minimum in Yttrium-Doped Barium Zirconate

Yttrium-doped barium zirconate is one of the fastest solid-state proton conductors. While previous studies suggest that proton–tuples move as pairs in yttrium-doped barium zirconate, a systematic catalog of possible close proton–tuple moves is missing. Such a catalog is essential to simulating dual proton conduction effects. Density functional theory with the Perdew–Burke–Ernzerhof functional is utilized to obtain the total electronic energy for each proton–tuple. The conjugate gradient and nudged elastic band methods are used to find the minima and transition states for proton–tuple motion. In the lowest-energy configuration, protons are in close proximity to each other and the dopant, significantly affecting the backbone structure. The map of moves away from the global minimum proton–tuple shows that the most critical move for long-range proton conduction is a rotation with a barrier range of 0.31–0.41 eV when the two protons are in close proximity.

Anhydrous Superprotonic Conductivity in the Zirconium Acid Triphosphate ZrH5 (PO4 )3.

The development of solid-state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen-based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH5 (PO4 )3 (ZP3), which exhibits record-high proton conductivity of 0.5-3.1×10-2 S cm-1 in the range 25-110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25-110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer.

Bioinspired Design of an Uncharged Ambipolar Helical Scaffold To Achieve Efficient Solid-State Proton Conduction.

This work demonstrates highly efficient solid-state proton conduction in helical organic scaffolds inspired by the biomolecule gramicidin A. The scaffold, 1, derived from a pyridine-2,6-dicarboxamide (PDC) residue adopts a helical conformation that is stabilized by a network of strong bifurcated intramolecular H-bonds between the polar residues that align the inner (concave) face of the molecule, while the aromatic units in 1 are oriented outwards. As a result, the helix attains an ambipolar nature just like gramicidin A. Two different solid forms of 1 could be isolated: a yellow solid from high-polarity solvents and an orange solid from low-polarity solvents. Single-crystal X-ray diffraction (SCXRD) studies showed that in the former, molecules of 1 are stacked in a homochiral fashion, while in the latter heterochiral stacks of 1 were present. The yellow form exhibited an almost ∼300-fold higher conductivity (of up to 0.12 mS cm-1 at 95 °C and 95 % relative humidity) than the orange form as a result of closer intermolecular proximity and lower activation energy of 0.098 eV, thus indicating a Grotthus mechanism of proton transport. This study establishes the key role of bioinspired design and controlled stereo-organization of such discrete uncharged organic molecules in achieving efficient solid-state proton conduction.

Proton-conducting oxides based on LaScO3: structure, properties and electrochemical applications. A focus review

Solid state proton conductors are promising materials for various electrochemical applications. LaScO3 - based oxides are representatives of the proton-conducting oxides with perovskite structure, alternative to conventional cerates and zirconates of alkaline-earth elements. These oxides exhibit a sufficient level of proton conductivity with a combination of good chemical stability in the H2O and CO2 - containing atmospheres. The current review is focused on summarizing and analyzing of the currently available data on LaScO3 - based oxides. The peculiarities of crystal structure and proton defect formation, aspects of synthesis and obtaining dense ceramics, and electrical properties are provided. Additionally, the current state of applications in electrochemical devices of LaScO3 - based oxides is briefly discussed.