Ultralow Thermal Conductivity of a Chalcogenide System Pt3Bi4Q9 (Q = S, Se) Driven by the Hierarchy of Rigid [Pt6Q12]12- Clusters Embedded in Soft Bi-Q Sublattice.

Knowledge of structure-property relationships in solids with intrinsic low thermal conductivity is crucial for fields such as thermoelectrics, thermal barrier coatings, and refractories. Herein, we propose a new "rigidness in softness" structural scheme for intrinsic low lattice thermal conductivity (κL), which embeds rigid clusters into the soft matrix to induce large lattice anharmonicity, and accordingly discover a new series of chalcogenides Pt3Bi4Q9 (Q = S, Se). Pt3Bi4S9-xSex (x = 3, 6) achieved an intrinsic ultralow κL down to 0.39 W/(m K) at 773 K, which is considerably low among the Bi chalcogenide thermoelectric materials. Pt3Bi4Q9 contains the rigid cubic [Pt6Q12]12- clusters embedded in the soft Bi-Q sublattice, involving multiple bonding interactions and vibration hierarchy. The hierarchical structure yields a large lattice anharmonicity with high Grüneisen parameters (γ) 1.97 of Pt3Bi4Q9, as verified by the effective scatter of low-lying optical phonons toward heat-carrying acoustic phonons. Consequently, the rigid-soft coupling significantly inhibits heat propagation, exhibiting low acoustic phonon frequencies (∼25 cm-1) and Debye temperatures (ΘD = 170.4 K) in Pt3Bi4Se9. Owing to the suppressed κL and considerable power factor (PF), the ZT value of Pt3Bi4S6Se3 can reach 0.56 at 773 K without heavy carrier doping, which is competitive among the pristine Bi chalcogenides. Theoretical calculations predicted a large potential for performance improvement via proper doping, indicating the great potential of this structure type for promising thermoelectric materials.

High intrinsic phase stability of ultrathin 2M WS2.

Metallic 2M or 1T'-phase transition metal dichalcogenides (TMDs) attract increasing interests owing to their fascinating physicochemical properties, such as superconductivity, optical nonlinearity, and enhanced electrochemical activity. However, these TMDs are metastable and tend to transform to the thermodynamically stable 2H phase. In this study, through systematic investigation and theoretical simulation of phase change of 2M WS2, we demonstrate that ultrathin 2M WS2 has significantly higher intrinsic thermal stabilities than the bulk counterparts. The 2M-to-2H phase transition temperature increases from 120 °C to 210 °C in the air as thickness of WS2 is reduced from bulk to bilayer. Monolayered 1T' WS2 can withstand temperatures up to 350 °C in the air before being oxidized, and up to 450 °C in argon atmosphere before transforming to 1H phase. The higher stability of thinner 2M WS2 is attributed to stiffened intralayer bonds, enhanced thermal conductivity and higher average barrier per layer during the layer(s)-by-layer(s) phase transition process. The observed high intrinsic phase stability can expand the practical applications of ultrathin 2M TMDs.

1D Insertion Chains Induced Small-Polaron Collapse in MoS2 2D Layers Toward Fast-Charging Sodium-Ion Batteries.

Molybdenum disulfide (MoS2 ) with high theoretical capacity is viewed as a promising anode for sodium-ion batteries but suffers from inferior rate capability owing to the polaron-induced slow charge transfer. Herein, a polaron collapse strategy induced by electron-rich insertions is proposed to effectively solve the above issue. Specifically, 1D [MoS] chains are inserted into MoS2 to break the symmetry states of 2D layers and induce small-polaron collapse to gain fast charge transfer so that the as-obtained thermodynamically stable Mo2 S3 shows metallic behavior with 107 times larger electrical conductivity than that of MoS2 . Theoretical calculations demonstrate that Mo2 S3 owns highly delocalized anions, which substantially reduce the interactions of Na-S to efficiently accelerate Na+ diffusion, endowing Mo2 S3 lower energy barrier (0.38 vs 0.65 eV of MoS2 ). The novel Mo2 S3 anode exhibits a high capacity of 510 mAh g-1 at 0.5 C and a superior high-rate stability of 217 mAh g-1 at 40 C over 15 000 cycles. Further in situ and ex situ characterizations reveal the in-depth reversible redox chemistry in Mo2 S3 . The proposed polaron collapse strategy for intrinsically facilitating charge transfer can be conducive to electrode design for fast-charging batteries.

Cu(II) assisted peroxymonosulfate for antibiotic resistant bacteria inactivation: A potential disinfection technology in swimming pool.

Alternative disinfection technology to chlorination is required to control the risk of antibiotic resistance in swimming pools. In this study, copper ions (Cu(II)), which often exist in swimming pools as algicides, were used to activate peroxymonosulfate (PMS) for the inactivation of ampicillin-resistant E. coli. Cu(II) and PMS showed synergistic effects on E. coli inactivation in weak alkaline conditions, obtaining 3.4 log inactivation in 20 min with 10 µM Cu(II) and 100 µM PMS at pH 8.0. Quenching experiments indicated that radicals (i.e., OH and SO4-) were not the main disinfectors for E. coli inactivation. Based on the structure of Cu(II) and density functional theory calculations, the Cu(II)-PMS complex (Cu(H2O)5SO5) was recommended as the active species for E. coli inactivation. Under the experimental conditions, the PMS concentration had a greater influence on E. coli inactivation than the Cu(II) concentration, possibly because increasing PMS concentration accelerates ligand exchange reaction and facilitates active species generation. By forming hypohalous acids, halogen ions could improve the disinfection efficiency of Cu(II)/PMS. The addition of HCO3- concentration (from 0 to 1.0 mM) and humic acid (0.5 and 1.5 mg/l) did not significantly inhibit the E. coli inactivation. The feasibility of adding PMS to waters containing Cu(II) for the inactivation of antibiotic-resistant bacteria was validated in actual swimming pool waters, where 4.7 log inactivation of E. coli was achieved in 60 min.

A Flexible Humidity Sensor with Wide Range, High Linearity, and Fast Response Based on Ultralong Na2Ti3O7 Nanowires.

A flexible humidity sensor with wide sensing range, superior sensitivity, high linearity, and advanced response/recovery capabilities is extremely desirable for practical applications in human body-related (HBR) monitoring and human-machine interaction (HMI). However, the practical sensor lacks a versatile nanomaterial integrated with sensing capabilities and mechanical flexibility to meet the criteria. Herein, a comprehensive flexible humidity sensor with ultralong Na2Ti3O7 nanowires (>120 µm) is subtly constructed for the first time. Owing to the distinguish nanowires network structure, the sensor exhibits wide sensing range (11-95% RH), high sensitivity (>103), high linearity (R2 > 0.98), and fast response/recovery capability (8.9/2.1 s), as well as excellent respiratory stability (>5000 s). In addition, the Na2Ti3O7-based humidity sensor demonstrates superior flexibility and antibacteria capabilities, and exhibits diverse applications in respiration monitoring, noncontact detection, as well as dynamic interactive display. This work provides a multifunctional humidity sensor with excellent practicability, suggesting the great potential in next-generation human-related flexible/wearable devices.

Ultrathin Mo2S3 Nanowire Network for High-Sensitivity Breathable Piezoresistive Electronic Skins.

Flexible piezosensing electronic skins (e-skins) have attracted considerable interest owing to their applications in real-time human-health monitoring, human-machine interactions, and soft bionic robot perception. However, the fabrication of piezosensing e-skins with high sensitivity, biological affinity, and good permeability at the same time is challenging. Herein, we designed and synthesized Mo2S3 nanowires by inserting ∞1[Mo2+S] chains between MoS2 interlayers. The resulting Mo2S3 nanowires feature high conductivity (4.9 × 104 S m-1) and a high aspect ratio (∼200). An ultrathin (∼500 nm) Mo2S3 nanowire network was fabricated using a simple liquid/liquid interface self-assembly method, showing high piezoresistive sensitivity (5.65 kPa-1), a considerably low pressure detection limit (0.08 Pa), and gratifying air permeability. Moreover, this nanowire network can be directly attached to human skin for real-time human pulse detection, finger movement monitoring, and sign language recognition, exhibiting excellent potential for health monitoring and human-machine interactions.

Improved Polarization in the Sr6 Cd2 Sb6 O7 Se10 Oxyselenide through Design of Lateral Sublattices for Efficient Photoelectric Conversion.

Highly-polarizable materials are favorable for photoelectric conversion due to their efficient charge separation, while precise design of them is still a big challenge. Herein a novel polar oxyselenide, Sr6 Cd2 Sb6 O7 Se10 , is rationally designed. It contains lateral sublattices of polarizable [Sb2 OSe4 ]4- chains and highly-orientated [CdSe3 ]4- chains. The intense polarization was evaluated by significant second-harmonic generation (SHG) signal (maximum: 12.6×AgGaS2 ) in broad spectrum range. The polarization was found to mainly improve the carrier separation with a much longer recombination lifetime (76.5 µs) than that of the nonpolar compound Sr2 Sb2 O2 Se3 (18.0 µs), resulting in better photoelectric performance. The single-crystal photoelectric device exhibited excellent response covering broad spectrum in 500-1000 nm with stable reproducibility. This work provides some new insights into the structure design of highly-polarizable heteroanionic materials for photoelectric conversion.

Caged-Cation-Induced Lattice Distortion in Bronze TiO2 for Cohering Nanoparticulate Hydrogen Evolution Electrocatalysts.

Defect engineering provides a promising approach for optimizing the trade-off between support structures and active nanoparticles in heterojunction nanostructures, manifesting efficient synergy in advanced catalysis. Herein, a high density of distorted lattices and defects are successfully formed in bronze TiO2 through caging alkali-metal Na cations in open voids (Na-TiO2(B)), which could efficiently cohere nanoparticulate electrocatalysts toward alkaline hydrogen evolution reaction (HER). The RuMo bimetallic nanoparticles could directionally anchor on Na-TiO2(B) with a certain angle of ∼22° due to elimination of the lattice mismatch, thus promoting uniform dispersion and small sizing of supported nanoparticles. Moreover, caging Na ions could significantly enhance the hydrophilicity of the substrate in RuMo/Na-TiO2(B), leading to the strengthening synergy of water dissociation and hydrogen desorption. As expected, this Na-caged nanocomposite catalyst rich with structural perturbations manifests a 6.4-fold turnover frequency (TOF) increase compared to Pt/C. The study provides a paradigm for designing stable nano-heterojunction catalysts with lattice-distorted substrates by caging cations toward advanced electrocatalytic transformations.

2D Homologous Series SrFMnBiSn+2 (M = Pb, Ag0.5Bi0.5; n = 0, 1) and Commensurately Modulated Sr2F2Bi2/3S2.

We report three new mixed-anion two-dimensional (2D) compounds: SrFPbBiS3, SrFAg0.5Bi1.5S3, and Sr2F2Bi2/3S2. Their structures as well as the parent compound SrFBiS2 were refined using single-crystal X-ray diffraction data, with the sequence of SrFBiS2, SrFPbBiS3, and SrFAg0.5Bi1.5S3 defining the new homologous series SrFMnBiSn+2 (M = Pb, Ag0.5Bi0.5; n = 0, 1). Sr2F2Bi2/3S2 has a different structure, which is modulated with a q vector of 1/3b* and was refined in superspace group X2/m(0ß0)00 as well as in the 1 × 3 × 1 superstructure with space group C2/m (with similar results). Sr2F2Bi2/3S2 features hexagonal layers of alternating [Sr2F2]2+ and [Bi2/3S2]2-, and the modulated structure arises from the unique ordering pattern of Sr2+ cations. SrFPbBiS3, SrFAg0.5Bi1.5S3, and Sr2F2Bi2/3S2 are semiconductors with band gaps of 1.31, 1.21, and 1.85 eV, respectively. The latter compound exhibits room temperature red photoluminescence at ∼700 nm.

Engineering Metallic Heterostructure Based on Ni3 N and 2M-MoS2 for Alkaline Water Electrolysis with Industry-Compatible Current Density and Stability.

Alkaline water electrolysis is commercially desirable to realize large-scale hydrogen production. Although nonprecious catalysts exhibit high electrocatalytic activity at low current density (10-50 mA cm-2 ), it is still challenging to achieve industrially required current density over 500 mA cm-2  due to inefficient electron transport and competitive adsorption between hydroxyl and water. Herein, the authors design a novel metallic heterostructure based on nickel nitride and monoclinic molybdenum disulfide (Ni3 N@2M-MoS2 ) for extraordinary water electrolysis. The Ni3 N@2M-MoS2  composite with heterointerface provides two kinds of separated reaction sites to overcome the steric hindrance of competitive hydroxyl/water adsorption. The kinetically decoupled hydroxyl/water adsorption/dissociation and metallic conductivity of Ni3 N@2M-MoS2  enable hydrogen production from Ni3 N and oxygen evolution from the heterointerface at large current density. The metallic heterostructure is proved to be imperative for the stabilization and activation of Ni3 N@2M-MoS2 , which can efficiently regulate the active electronic states of Ni/N atoms around the Fermi-level through the charge transfer between the active atoms of Ni3 N and MoMo bonds of 2M-MoS2  to boost overall water splitting. The Ni3 N@2M-MoS2  incorporated water electrolyzer requires ultralow cell voltage of 1.644 V@1000 mA cm-2  with ≈100% retention over 300 h, far exceeding the commercial Pt/C║RuO2 (2.41 V@1000 mA cm-2 , 100 h, 58.2%).

P-type doping in 2M-WS2 for a complete phase diagram.

2M-WS2 as a new phase of transition metal dichalcogenides possesses many novel physical properties, such as superconductivity and topological surface states. The effect of n-type doping on the superconductivity of this material has been studied. However, p-type doping has not been studied, because it is difficult to implement p-type doping in metastable 2M-WS2. In this paper, p-type doping was achieved in 2M-WS2 for the first time by using Mo. With the increase of the Mo content, the carrier concentration rises slightly from 1.42 × 1021 cm-1 to 1.56 × 1021 cm-1. Meanwhile, the superconducting transition temperature decreases monotonously with the increase of Mo doping and reaches a minimum value of 4.37 K at the doping limit of x = 0.6 in W1-xMoxS2. Combining the data of n-type doped 2M-WS2 from our previous research, we summarize the carrier concentration and superconducting transition temperature in a phase diagram, which shows a typical dome-like shape. These results uncover the relationship between the carrier concentration and electronic state of 2M-WS2.