Site Of Na Research Articles

Sodium-Poor, Hydroxyl-Rich, Defective Na2Ti3O7 Prepared by γ-Irradiation and Its Enhanced Proton Conductivity.

The use of γ-irradiation to tailor the physicochemical properties of materials is not widely applied to layered alkali metal oxides. Herein, we show that γ-irradiation (up to 400 kGy) of Na2Ti3O7 leads to a sodium-poor, hydroxyl-rich analogue where the layered structure, plate-like morphology, and textural properties are preserved. The deintercalation of sodium ions modifies the Ti-O bond lengths and expands the unit cell; the latter is supported by density functional theory (DFT) calculations. 23Na solid-state NMR suggests the transport of the symmetric, 7-fold Na2 sites to an intermediate environment, which is closer to the asymmetric, 9-fold Na1 sites. An 8 wt % mass loss (1.4 mol water/mol titanate) is observed, indicating an increased concentration of protons/hydroxyls. These hydroxyl groups (i.e., lattice protons) possess higher thermal stability than solely surface-adsorbed ones in the nonirradiated sample. At 200-400 kGy, the proton conduction (50 °C and ∼70% RH) of ∼10-6 S·cm-1 is 1 order of magnitude larger than that in the nonirradiated sample; the relaxation time decreases from 30 to 2-6 μs with γ-irradiation. The γ-dose dependence of dielectric loss is also present and analyzed using the Jonscher universal power law, indicating the low-frequency dispersion behavior characteristics of high charge densities.

Deep insights into the sodium transport mechanism and phase evolution in Na4VP2O9 cathode/anode material

For the entire intercalation/deintercalation range of Na4VP2O9, quantum mechanics is applied to investigate sodium transport mechanism and a machine learning force field is used instead of ab initio method to offers an applicable method for the full understanding of the complicated Na + movements dynamically. It shows chain of '8′ shaped units horizontally and repeated alternating round aggregate and '8′ shaped long chain vertically. For primitive Na4VP2O9, facile Na+ transportation along a-axis is observed with an energy barrier of 0.16 V. As a cathode material, Na3VP2O9 also shows fast Na + diffusion with a minimal diffusion energy barrier 0.27 eV along a-axis. However, for the fully sodiated state of Na4VP2O9, Na+ diffusion in the lattice is significantly restricted with an energy barrier of 0.92 eV along b-axis. Accordingly, the sodium ion diffusion coefficients at room temperature for Na3VP2O9, Na4VP2O9 and Na5VP2O9 are 1.2 × 10−9 cm2 s−1, 5.9 × 10−9 cm2 s−1 and 8.2 × 10−11 cm2 s−1, respectively. The formation energy convex hull originated from the removal of Na1 sites and the occupation of E8cO8 cavities reveals an intermediate phase, Na3.5VP2O9, for the NaxVP2O9 (3 ≤ x ≤ 4) and three intermediate phases, Na4.5VP2O9, Na4.625VP2O9 and Na4.75VP2O9, for the NaxVP2O9 (4 ≤ x ≤ 5).

Structure of the human dopamine transporter in complex with cocaine.

The dopamine transporter (DAT) is crucial for regulating dopamine signalling and is the prime mediator for the rewarding and addictive effects of cocaine1. As part of the neurotransmitter sodium symporter family, DAT uses the Na+ gradient across cell membranes to transport dopamine against its chemical gradient2. The transport mechanism involves both intra- and extracellular gates that control substrate access to a central site. However, the molecular intricacies of this process and the inhibitory mechanism of cocaine have remained unclear. Here, we present the molecular structure of human DAT in complex with cocaine at a resolution of 2.66 Å. Our findings reveal that DAT adopts the expected LeuT-fold, posing in an outward-open conformation with cocaine bound at the central (S1) site. Notably, while an Na+ occupies the second Na+ site (Na2), the Na1 site seems to be vacant, with the side chain of Asn82 occupying the presumed Na+ space. This structural insight elucidates the mechanism for the cocaine inhibition of human DAT and deepens our understanding of neurotransmitter transport. By shedding light on the molecular underpinnings of how cocaine acts, our study lays a foundation for the development of targeted medications to combat addiction.

Bi3+-activated Na3Ca2TaO6: A novel narrow-band blue-emitting phosphor towards backlight display applications

Developing efficient and stable narrow-band blue phosphors has always been crucial for advancing LED backlighting technology. In this study, a host of Na3Ca2TaO6 with a strong rigid structure and high cationic site symmetry was selected, while Bi3+ was utilized as the activator. A novel narrow-band blue-emitting phosphor Na3Ca2TaO6:Bi3+ was obtained through high temperature solid phase sintering. The excitation peak of Na3Ca2TaO6:0.005Bi3+ is at 370 nm, which can effectively match the near-ultraviolet chip. Under near-ultraviolet light excitation, the Na3Ca2TaO6:0.005Bi3+ sample exhibits narrow-band blue emission, characterized by a dominant peak at 421 nm and a full width at half maximum of 47 nm. Additionally, Na3Ca2TaO6:Bi3+ demonstrates the color purity of 93.7 %, a quantum efficiency of 56.3 % and thermal stability of 80 %@150 °C. Based on crystal structure data, spectral data, and empirical formulas, it can be inferred that Bi3+ occupies the Na2 and Ca site and forms two luminous centers in Na3Ca2TaO6. When Na3Ca2TaO6:Bi3+ is utilized as the blue light component in WLED devices packaging, an impressive NTSC color gamut of 89.4 % can be achieved. The present study is anticipated to serve as a valuable point of reference for the future advancement of phosphors specifically tailored for backlight display applications.

Inducing extra active sites by Lu3+ substitution at Na1 location to achieve enhanced ultra-long lifespan of Na3V2(PO4)3

Currently, the poor intrinsic electronic and ionic conductivity significantly limits the further development of Na3V2(PO4)3 (NVP). In this paper, a feasible improvement strategy is proposed, which uses the sol-gel method to doped Lu3+ into Na3V2(PO4)3. According to the rietveld XRD occupancy refinement, the introduced Lu element occupies the Na1 site, which hardly affects the reversible de-intercalation of the two Na+ at Na2 site, behaving no side effects on the reversible capacity properties of the modified material. Besides, due to the smaller ionic radius of Lu3+ than that of Na+ (86.1 Å vs. 102 Å), Lu3+ substitution can increase the intercellular space within the crystal bulk to accelerate ionic migration and improve the ionic conductivity. Meanwhile, hypervalent and multicharged Lu3+ at Na1 site can cause the slight lattice distortions to induce more active sites for the storage of Na+, favorably increasing the reversible capacity. Furthermore, post-cycling XRD/SEM/XPS measurements demonstrate the significantly improved structural stability of NVP/C@Lu-1 % sample. Before and after cycling XPS spectra verify the stable existence of newly generated LuO band at 199.12 eV, which plays the role of an anchoring column to connect the crystal construction between lattice planes, and reduces the lattice strain to enhance the structure. According to the comparison of V2p XPS spectra before and after cycling, the peak location tends to move lower binding energy after introducing Lu3+ at Na1 site, indicating that NVP/C@Lu-1 % possesses a more stabilized framework. Overall, the optimized NVP/C@Lu-1 % submits an astonishing value of 123.9 mAh g−1 at 0.1C. Even at 7, 30, and 80C, it can release capacities of 97.1, 79.6 and 75.5 mAh g−1, and after 2000, 7500, and 8000 cycles, the capacities still keep 90.5, 73.2 and 68.3 mAh g−1 with retention of 93 %, 92 %, and 90.5 %.

In-situ induction of porous coral structure by phosphomolybdic acid activating V4+/V5+ redox couple of Na3V2(PO4)3

The wide bandgap characteristics of polyanionic group lead to diminished electronic and ionic conductivities of Na3V2(PO4)3 (NVP). Meanwhile, the low capacity and energy also limit its further application. To tackle these obstacles, a triple modification approach is implemented on phosphomolybdic acid (PMA), encompassing the establishment of a porous coral-like structure, Mo4+ incorporation, and MoO3 encapsulation. Significantly, PMA adeptly mitigates the deficiencies in ionic and electronic conductivity through this triple modification strategy, resulting in enhanced electrochemical performance. The strategic induction of V4+/V5+ serves as a catalyst for the creation of a formidable 3.9 V platform, facilitating the liberation of the third Na+ for active involvement in the electrochemical process, thereby augmenting specific capacity to achieve elevated levels. Consequently, the amalgamation of a high plateau and substantial capacity engenders a heightened energy density, effectively remedying the issue of low energy density. Simultaneously, CO(NH2)2, serving as an supplementary nitrogen-doped carbon reservoir, can supplement the imperfections and active sites to efficiently promote the ionic and electronic transfer, thereby enhancing the electronic and ionic conductivity of the materials. Remarkably, the electrochemical storage mechanism and the V4+/V5+ excitation mechanism are elucidated through in-situ electrochemical XRD and ex-situ XPS techniques, which illustrates that the de-intercalation of 2Na+ at Na2 site is accompanied by the phase transition reaction and the migration of the third Na+ at Na1 site occurs along with the solid-solution transformation. Notably, Na3V2(PO4)3/C@15 %PMA@20 %CO(NH2)2 sample reveals a notable 124.2 mAh g−1 at 0.1C and remains 88.27 % after 2000 cycles even at 60C.

Preparation of Nb5+ Doped Na3V2(PO4)3 Cathode Material for Sodium Ion Batteries.

Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs) due to the abundance and low cost of sodium resources. Cathode material plays a crucial role in the performance of sodium ion batteries determining the capacity, cycling stability, and rate capability. Na3V2(PO4)3 (NVP) is a promising cathode material due to its stable three-dimensional NASICON structure, but its discharge capacity is low and its decay is serious with the increase of cycle period. We focused on modifying NVP cathode material by coating carbon and doping Nb5+ ions for synergistic electrochemical properties of carbon-coated NVP@C as a cathode material. X-ray diffraction analysis was performed to confirm the phase purity and crystal structure of the Nb5+ doped NVP material, which exhibited characteristic diffraction peaks that matched well with the NASICON structure. Nb5+-doped NVP@C@Nbx materials were prepared using the sol-gel method and characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Raman and Brunauer -Emmett-Teller (BET) analysis. First-principles calculations were performed based on density functional theory. VASP and PAW methods were chosen for these calculations. GGA in the PBE framework served as the exchange-correlation functional. The results showed the NVP unit cell consisted of six NVP structural motifs, each containing octahedral VO6 and tetrahedral PO4 groups to form a polyanionomer [V2(PO4)3] along with the c-axis direction by PO4 groups, which had Na1(6b) and Na2(18e) sites. And PDOS revealed that after Nb doping, the d orbitals of the Nb atoms also contributed electrons that were concentrated near the Fermi surface. Additionally, the decrease in the effective mass after Nb doping indicated that the electrons could move more freely through the material, implying an enhancement of the electron mobility. The electrochemical properties of the Nb5+ doped NVP@C@Nb cathode material were evaluated through cyclic voltammetry (CV), galvanostatic charge-discharge tests, electrochemical impedance spectroscopy (EIS), and X-ray photoelectric spectroscopy (XPS). The results showed that NVP@C@Nb0.15 achieved an initial discharge capacity as high as 114.27 mAhg-1, with a discharge capacity of 106.38 mAhg-1 maintained after 500 cycles at 0.5C, and the retention rate of the NVP@C@Nb0.15 composite reached an impressive 90.22%. NVP@C@Nb0.15 exhibited low resistance and high capacity, enabling it to create more vacancies and modulate crystal structure, ultimately enhancing the electrochemical properties of NVP. The outstanding performance can be attributed to the Nb5+-doped carbon layer, which not only improves electronic conductivity but also shortens the diffusion length of Na+ ions and electrons, as well as reduces volume changes in electrode materials. These preliminary results suggested that the as-obtained NVP@C@Nb0.15 composite was a promising novel cathode electrode material for efficient sodium energy storage.

Transient kinetics reveal the mechanism of competitive inhibition of the neutral amino acid transporter ASCT2

ASCT2 (alanine serine cysteine transporter 2), a member of the SLC1 (solute carrier 1) family, mediates Na+-dependent exchange of small neutral amino acids across cell membranes. ASCT2 was shown to be highly expressed in tumor cells, making it a promising target for anti-cancer therapies. In this study, we explored the binding mechanism of the high-affinity competitive inhibitor Lc-BPE with ASCT2, using electrophysiological and rapid kinetic methods. Our investigations reveal that Lc-BPE binding requires one or two Na+ ions initially bound to the apo-transporter with high affinity, with Na1 site occupancy being more critical for inhibitor binding. In contrast to the amino acid substrate bound form, the final, third Na+ ion cannot bind, due to distortion of its binding site (Na2), thus preventing the formation of a translocation-competent complex. Based on the rapid kinetic analysis, the application of Lc-BPE generated outward transient currents, indicating that, despite its net neutral nature, the binding of Lc-BPE in ASCT2 is weakly electrogenic, most likely because of asymmetric charge distribution within the amino acid moiety of the inhibitor. The pre-incubation with Lc-BPE also led to a decrease of the turnover rate of substrate exchange and a delay in the activation of substrate-induced anion current, indicating relatively slow Lc-BPE dissociation kinetics. Overall, our results provide new insight into the mechanism of binding of a prototypical competitive inhibitor to the ASCT transporters.

Identification of the potassium-binding site in serotonin transporter

Clearance of serotonin (5-hydroxytryptamine, 5-HT) from the synaptic cleft after neuronal signaling is mediated by serotonin transporter (SERT), which couples this process to the movement of a Na+ ion down its chemical gradient. After release of 5-HT and Na+ into the cytoplasm, the transporter faces a rate-limiting challenge of resetting its conformation to be primed again for 5-HT and Na+ binding. Early studies of vesicles containing native SERT revealed that K+ gradients can provide an additional driving force, via K+ antiport. Moreover, under appropriate conditions, a H+ ion can replace K+. Intracellular K+ accelerates the resetting step. Structural studies of SERT have identified two binding sites for Na+ ions, but the K+ site remains enigmatic. Here, we show that K+ antiport can drive substrate accumulation into vesicles containing SERT extracted from a heterologous expression system, allowing us to study the residues responsible for K+ binding. To identify candidate binding residues, we examine many cation binding configurations using molecular dynamics simulations, predicting that K+ binds to the so-called Na2 site. Site-directed mutagenesis of residues in this site can eliminate the ability of both K+ and H+ to drive 5-HT accumulation into vesicles and, in patch clamp recordings, prevent the acceleration of turnover rates and the formation of a channel-like state by K+ or H+. In conclusion, the Na2 site plays a pivotal role in orchestrating the sequential binding of Na+ and then K+ (or H+) ions to facilitate 5-HT uptake in SERT.

P/s-orbital hybridization induced by Mg-doping to active Na sites in Na2FePO4F cathode for long-life and high-rate sodium-ion batteries

The iron-based fluorophosphate Na2FePO4F (NFPF) is considered as a potential cathode for sodium-ion batteries due to the low-cost, non-toxicity and appropriate working voltage. However, the inferior intrinsic electronic conductivity and the restrained active Na sites bring the limits for full realization of electrochemical properties. Herein, Mg2+ with d0 orbital was introduced in FeO4F2 structure, aimed at activating the Na+ at Na1 site and enhancing the electronic conductivity. Different from the 3d transition metal (TM) elements that form 3d-O2p orbital interactions in the FeO4F2 structure, the Mg with d° contributes p and s orbitals mainly in Mg-O bonds, which corresponds to more stable orbital interaction and lattice structure. The electron distribution of bridge O due to the Mg-doping leads to the wooden barrel effect near the Mg site, thus activating Na+ at Na1 site by lowering the energy barrier of Na+ migration from Na1 to Na2 site. Hence, the obtained NFMPF electrode delivers high specific capacity (121.4 vs. 108.7 mAh g−1 at 0.1 C) and better cycling stability (73.8% vs. 54.2 % after 1000 cycles at 20 C). Overall, regulating the electronic structure and activating Na+ at inactive site is the key to break the bottleneck of low activity, which can be an effective strategy to design cathode materials with excellent electrochemical performance.

Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High-Voltage Barrier to Achieve High Energy Density and Long Life of Sodium-Ion Batteries.

The stable phase transformation during electrochemical progress drives extensive research on vanadium-based polyanions in sodium-ion batteries (SIBs), especially Na3 V2 (PO4 )3 (NVP). And the electron transfer between V3+/4+ redox couple in NVP could be generally achieved, owing to the confined crystal variation during battery service. However, the more favorable V4+/5+ redox couple is still in hard-to-access situation due to the high barrier and further brings about the corresponding inefficiency in energy densities. In this work, the multilevel redox in NVP frame (MLNP) alters reaction pathway to undergo homeostatic solid solution process and breaks the high barrier of V4+/5+ at high voltage, taking by progressive transition metal (V, Fe, Ti, and Cr) redox couple. The diversified reaction paths across diffusion barriers could be realized by distinctive release/uptake of inactive Na1 site, confirmed by the calculations of density functional theory. Thereby its volume change is merely 1.73% during the multielectron-transfer process (≈2.77 electrons). MLNP cathode could achieve an impressive energy density of 440Wh kg-1 , driving the leading development of MLNP among other NASICON structure SIBs. The integration of multiple redox couples with low strain modulates the reaction pathway effectively and will open a new avenue for fabricating high-performance cathodes in SIBs.

A high-entropy carbon-coated Na3V1.9(Mg, Cr, Al, Mo, Nb)0.1(PO4)2F3 cathode for superior performance sodium-ion batteries

A NASICON-type high-entropy carbon-coated Na3V1.9(Mg, Cr, Al, Mo, Nb)0.1(PO4)2F3 (NVPF-HE@C) material was synthesized through the sol-gel route. The incorporation of high entropy elements (Mg, Cr, Al, Mg, Nb) improved the stability of Na2 sites in NVPF without altering its crystal structure, which suppressed the intermediate reactions of Na3V2(PO4)2F3 phase at low potential of 3.4V. This improvement further lifted the specific capacity, capacity retention and Na+ diffusion coefficient of NVPF-HE@C cathode. The fluctuation of Na+ diffusion coefficient at low voltage region decreased 10−14-10−10cm2s−1 to 10−12-10−10cm2s−1. NVPF-HE@C cathode displays the initial specific capacities of 128 mAhg−1 at 1C and 82 mAhg−1 at 5C, while maintaining a low capacity decay of 17% over 800 cycles. The introduction of high-entropy doping provides an effective approach as promoting the electrochemistry properties of NVPF cathode, with potential applicability to other electrode materials in energy storage applications.

Exploring the K+ binding site and its coupling to transport in the neurotransmitter:sodium symporter LeuT.

The neurotransmitter:sodium symporters (NSSs) are secondary active transporters that couple the reuptake of substrate to the symport of one or two sodium ions. One bound Na+ (Na1) contributes to the substrate binding, while the other Na+ (Na2) is thought to be involved in the conformational transition of the NSS. Two NSS members, the serotonin transporter (SERT) and the Drosophila dopamine transporter (dDAT), also couple substrate uptake to the antiport of K+ by a largely undefined mechanism. We have previously shown that the bacterial NSS homologue, LeuT, also binds K+, and could therefore serve as a model protein for the exploration of K+ binding in NSS proteins. Here, we characterize the impact of K+ on substrate affinity and transport as well as on LeuT conformational equilibrium states. Both radioligand binding assays and transition metal ion FRET (tmFRET) yielded similar K+ affinities for LeuT. K+ binding was specific and saturable. LeuT reconstituted into proteoliposomes showed that intra-vesicular K+ dose-dependently increased the transport velocity of [3H]alanine, whereas extra-vesicular K+ had no apparent effect. K+ binding induced a LeuT conformation distinct from the Na+- and substrate-bound conformation. Conservative mutations of the Na1 site residues affected the binding of Na+ and K+ to different degrees. The Na1 site mutation N27Q caused a >10-fold decrease in K+ affinity but at the same time a ~3-fold increase in Na+ affinity. Together, the results suggest that K+ binding to LeuT modulates substrate transport and that the K+ affinity and selectivity for LeuT is sensitive to mutations in the Na1 site, pointing toward the Na1 site as a candidate site for facilitating the interaction with K+ in some NSSs.

Exploring the K+ binding site and its coupling to transport in the neurotransmitter:sodium symporter LeuT

The neurotransmitter:sodium symporters (NSSs) are secondary active transporters that couple the reuptake of substrate to the symport of one or two sodium ions. One bound Na+ (Na1) contributes to the substrate binding, while the other Na+ (Na2) is thought to be involved in the conformational transition of the NSS. Two NSS members, the serotonin transporter (SERT) and the Drosophila dopamine transporter (dDAT), also couple substrate uptake to the antiport of K+ by a largely undefined mechanism. We have previously shown that the bacterial NSS homologue, LeuT, also binds K+, and could therefore serve as a model protein for the exploration of K+ binding in NSS proteins. Here, we characterize the impact of K+ on substrate affinity and transport as well as on LeuT conformational equilibrium states. Both radioligand binding assays and transition metal ion FRET (tmFRET) yielded similar K+ affinities for LeuT. K+ binding was specific and saturable. LeuT reconstituted into proteoliposomes showed that intra-vesicular K+ dose-dependently increased the transport velocity of [3H]alanine, whereas extra-vesicular K+ had no apparent effect. K+ binding induced a LeuT conformation distinct from the Na+- and substrate-bound conformation. Conservative mutations of the Na1 site residues affected the binding of Na+ and K+ to different degrees. The Na1 site mutation N27Q caused a >10-fold decrease in K+ affinity but at the same time a ~3-fold increase in Na+ affinity. Together, the results suggest that K+ binding to LeuT modulates substrate transport and that the K+ affinity and selectivity for LeuT is sensitive to mutations in the Na1 site, pointing toward the Na1 site as a candidate site for facilitating the interaction with K+ in some NSSs.

Structural Evolution of Lithium-Exchanged Na3(VO)2(PO4)2F Cathode under Operation in Sodium Ion Batteries.

Na superionic conductor (NASICON)-type Na3(VO)2(PO4)2F (NVOPF) exhibits excellent cycling stability for high-voltage sodium ion batteries. Various strategies have been developed to form ion-exchanged NVOPF which can enhance the ionic and electronic conductivity. However, the underlying ion transport mechanism and complex structural transitions during battery operation remained uninvestigated. In this work, we prepared lithium-exchanged NVOPF (namely NLVOPF) which shows improved ionic conductivity and increased capacity at high discharging rates. Solid-state nuclear magnetic resonance (SSNMR) revealed the distinctive presence of two kinds of Li-exchanged sites in the NLVOPF, which are attributed to the occupied lithium ions at the Na1 and Na2 sites (namely Li1 and Li2, respectively). The Li1 site was metastably replaced in the first cycle, yet the Li2 site participated in ion insertion/extraction in the subsequent cycles. Our characterizations show that the dynamic doping of lithium in NLVOPF could contribute to the improved cycling stability and capacity retention.

Novel High-Temperature Modification of Belomarinaite KNaSO4: Crystal Structure and Thermal Order–Disorder Phase Transitions

Belomarinaite KNaSO4 (space group P3m1, a = 5.6072(3), c = 7.1781(4) Å and Z = 2) has been studied by high-temperature single crystal X-ray diffraction. The K and Na atoms are disordered, and M1(1c) and M2(1b) sites merge into an M1(2d)(K50%/Na50%) site with increasing temperature, and novel translationsgleiche phase transition of belomarinaite KNaSO4 (P3m1 → P-3m1) was revealed at 123 °C. Then, the temperature increase leads to phase transition of P3¯m1-polymorph of KNaSO4 to α-KNaSO4 (P63/mmc) at 446 °C, and sodium and potassium atoms in K1(1a) and Na1(1b) sites merged into an M4(2a)(K50%/Na50%) site. Crystal structures of KNaSO4 were refined at 300, 500 and 750 °C to R1 = 0.057, 0.056 and 0.048, respectively. The BVS maps and bond-valence energy landscape (BVEL) have been calculated, and the probability of the Na+ migration has been predicted using structural data for belomarinaite at 25 °C. The Na+ ion migration can occur at 2.14 eV in the ab plane and 2.80 eV along the c axis at 25 °C.

Extending the solid solution range of sodium ferric pyrophosphate: Off‐stoichiometric Na3Fe2.5(P2O7)2 as a novel cathode for sodium‐ion batteries

AbstractIron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework, cost‐effectiveness, and high energy density. However, the understanding of the crystal structure is scarce and only a limited candidates have been reported so far. In this work, we found for the first time that a continuous solid solution, Na4−αFe2+α/2(P2O7)2 (0 ≤ α ≤ 1, could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P2O7 unchanged. In particular, a novel off‐stoichiometric Na3Fe2.5(P2O7)2 is thus proposed, and its structure, energy storage mechanism, and electrochemical performance are extensively investigated to unveil the structure–function relationship. The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g−1, a working voltage of 2.9 V (vs. Na+/Na), the retention of 89.2% of the initial capacity after 500 cycles, and enhanced rate capability of 51 mAh g−1 at a current density of 1600 mA g−1. This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na4−αFe2+α/2(P2O7)2, offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.

Perturbation of Na-ion distribution for enhancement of ionic conductivity to a practical level of over 1 mS·cm−1 in Na3ZnGaS4

Na-ion conducting solid-state electrolytes (SSEs) are increasingly garnering attention as potential alternatives to Li-ion conducting SSEs in all-solid-state batteries. In this study, we demonstrate that replacing a small fraction of S2− with I− in Na3ZnGaS4 perturbs Na ion distributions, leading to an increase in vacancy concentration and a decrease in Na-Na distance along the conduction channel. This dual effect of I-substitution results in a remarkable increase in the ionic conductivity (σion) of Na3-xZnGaS4-xIx, from ca. 10−3 mS·cm−1 in pristine Na3ZnGaS4 to 1.12 mS·cm−1 in Na2.9ZnGaS3.9I0.1. Importantly, this enhancement cannot be achieved through simple vacancy incorporation via aliovalent doping. The incorporation of less I− (x = 0.05) or more I− (x = 0.15 and 0.2) also leads to significant improvements in σion, highlighting the effectiveness of disturbing the Na site. Cl- or Br-doped Na3ZnGaS4 similarly enhances σion, but to a more limited extent, underscoring the pivotal role of dopant anion sizes in inducing Na disturbance. We provide evidence for the presence of iodides in a specific sulfur site (S3 site) and the consequential dispersion of Na ions to Na2 and Na3 sites through a combination of theoretical, crystallographic, and spectroscopic studies. Additionally, we demonstrate the electrochemical and moisture stability of Na2.9ZnGaS3.9I0.1. Finally, due to its electrochemical stability and high σion, we exemplify the practicality of Na2.9ZnGaS3.9I0.1 in all-solid-state batteries using Na2Sn ‖ TiS2 full cells.

Unique Substrate Recognition and Sodium–Substrate Binding Stoichiometry in a Bacterial Serotonin Transporter, TuriSERT

All resolved high-resolution structures of the transporters in the neurotransmitter sodium symporter (NSS) family revealed that the NSS members share common structural and mechanistic features for substrate and ion binding and transport. However, a recently reported bacterial orthologue of the human serotonin transporter (hSERT), TuriSERT, possesses a structural characteristic specific for amino acid substrate binding but does transport a biogenic amine. The unique structural feature of TuriSERT requires a novel configuration for coordinating its substrate and ions. In the present study, we characterized TuriSERT expressed in Escherichia coli cells with a fluorescent substrate by biochemical, structural, and pharmacological approaches. Substrate transport by TuriSERT requires Na+ but not Cl−. Replacement of Asp262 by asparagine renders TuriSERT Cl−-dependent. Substitutions of the corresponding Na1 residues did not alter Na+ dependence on substrate transport, whereas the mutation of a Na2 site residue led to a loss of transport activity, suggesting that Na+ binds only to the Na2 site in TuriSERT. In addition, substitutions of several residues essential for recognizing 5-hydroxytryptamine (5-HT) in hSERT had little effect on 5-HT displacement potency in transport assay for TuriSERT. In contrast, mutations of the residues that are proposed to coordinate with 5-HT in our docking model dramatically reduced 5-HT displacement. Furthermore, our results indicated that all tested antidepressants showed a weak inhibitory effect on TuriSERT. The present study demonstrated the existence of a unique substrate binding site and 1:1 stoichiometry of sodium–substrate binding in TuriSERT, a novel structural finding for the NSS transporters.

Ca-substituted Na3ZnGaS4 with enhanced ionic conductivity and its applicability for all-solid-state sodium-ion batteries

Na3ZnGaS4 is a new class of Na + -conducting materials with a sturdy framework consisting of corner-shared super-tetrahedra. The ionic conductivity (σion) of pristine Na3ZnGaS4 is quite low, but it can be improved by introducing defects. Herein, we describe the incorporation of vacancies into Na2 sites of Na3ZnGaS4 via Ca-doping (Na3-xCaxZnGaS4; x = 0–0.2), which leads to a significant increase in σion, reaching 0.28 mS cm−1 (hot-pressed Na2.7Ca0.15ZnGaS4 pellet). The preferential residence of vacancies and Ca2+ in Na + -conducting Na2 sites is theoretically and experimentally verified. Because of simultaneous location of vacancies and Ca2+ in Na2 sites, the increase in σion with 'x' in Na3-xCaxZnGaS4 is not related to a decrease in the migration energy barrier (EA) but rather to an increase in effective hopping frequencies, compensating for the increase in EA. Na2.7Ca0.15ZnGaS4 also exhibits excellent compatibility with Na2Sn anode and TiS2 cathode. A full cell (Na2Sn│Na2.7Ca0.15ZnGaS4│TiS2) delivers a discharge capacity of over 146 mAh g−1TiS2 during 100 charge/discharge cycles at 0.12 mA cm−2 (120 mA g−1TiS2). In comparison to Na3SbS4, Na2.7Ca0.15ZnGaS4 also demonstrates inertness in various organic solvents, which is important for layer-by-layer stacking processes in the fabrication of all-solid-state batteries.