Search

Atomically thin two-dimensional transition metal dichalcogenides (TMDCs) have been regarded as ideal and promising nanomaterials that bring broad application prospects in extensive fields due to their ultrathin layered structure, unique electronic band structure, and multiple spatial phase configurations. TMDCs with different phase structures exhibit great diversities in physical and chemical properties. By regulating the phase structure, their properties would be modified to broaden the application fields. In this mini review, focusing on the most widely concerned molybdenum dichalcogenides (MoX2: X = S, Se, Te), we summarized their phase structures and corresponding electronic properties. Particularly, the mechanisms of phase transformation are explained, and the common methods of phase regulation or phase stabilization strategies are systematically reviewed and discussed. We hope the review could provide guidance for the phase regulation of molybdenum dichalcogenides nanomaterials, and further promote their real industrial applications.

ABSTRACT: Metal dots-nitrogen-carbon catalysts have become a hot topic in recent years because of special coordination environment. Herein, for the study the W nanodots and nitrogen co-decorated carbon skeleton (W@NC) was prepared for hydrogen evolution reaction (HER). In particular, NaCl templates not only restrict the growth of nanodots, but also improve the purity of phase. By optimizing the feeding ratio of ammonium metatungstate, W nanodots (the size is about 1.2 ± 0.6 nm) dispersed well on N-doped C skeleton, and this special structure could effectively promote electron transfer and ion diffusion during HER process. As a result, the optimized W@NC hybrids exhibited excellent HER performance in alkaline media with a rather low over-potential (228 mV at 10 mA cm–2) and outstanding durability over 10 h.

Metal nanocrystals exhibit unique properties due to their high surface-to-volume ratio and have great potential for applications in the fields of electronics, magnetics, optics and catalysis. However, their high specific surface area leads to easy coarsening in operation, which may greatly degrade their performances, especially when they are exposed to various chemical environments or at high temperatures. Therefore, the direct visualization of nanocrystals' structural evolution when they are coarsening is crucial to gain insight into the mechanism and develop more effective means to improve the size stability of nanocrystals. In this work, we investigated the structural evolution of Pt nanocrystals with sizes of ~ 4 nm on SiNx film in both oxidizing and reducing atmospheres at a moderate temperature (300оС) in the aberration-corrected environmental transmission electron microscopy (ETEM). The sizes of nanocrystals remain almost unchanged when annealed in the oxygen atmosphere with volatile PtOx formation on the surface, hindering nanocrystals sintering and leading to Pt loss. On the other hand, obvious coarsening of nanocrystals resulting from Ostwald-ripening and nanocrystal migration and coalescence was observed in the reducing atmosphere. Our findings reveal the dynamic structural evolution of nanocrystals in different atmospheres and provide possible ways to improve the size stability of nanocrystals.

Morphology engineering has been developed as one of the most widely used strategies for improving the performance of electrocatalysts. However, the harsh reaction conditions and cumbersome reaction steps during the nanomaterials synthesis still limit their industrial applications. Herein, one-dimensional (1D) novel-segmented PtTe porous nanochains (PNCs) were successfully synthesized by the template methods assisted by Pt autocatalytic reduction. The PtTe PNCs consist of consecutive mesoporous architectures that provide a large electrochemical surface area (ECSA) and abundant active sites to enhance methanol oxidation reaction (MOR). Furthermore, 1D nanostructure as a robust sustaining frame can maintain a high mass/charge transfer rate in a long-term durability test. After 2,000 cyclic voltammetry (CV) cycles, the ECSA value of PtTe PNCs remained as high as 44.47 m2·gPt–1, which was much larger than that of commercial Pt/C (3.95 m2·gPt–1). The high catalytic activity and durability of PtTe PNCs are also supported by CO stripping test and density functional theory calculation. This autocatalytic reduction-assisted synthesis provides new insights for designing efficient low-dimensional nanocatalysts.

The long–term stability of proton conductors is one of the most important factors in evaluating materials. Guest molecules can act as “bridges” for proton conduction channels and reside in the channels of covalent organic frameworks, but they are prone to leakage. Therefore, it is important to develop proton conductors with intrinsic proton conductivity. In this paper, we synthesized an intrinsically sulfonated covalent organic framework, TpPa–SO3H, which has a more stable proton conducting performance than that of TpPa@H2SO4 by loading guest molecules. Meanwhile, the proton conductivity of TpPa–SO3H was further improved by coating a superabsorbent polymer through an in situ reaction to obtain PANa@TpPa–SO3H (PANa: sodium polyacrylate). As a result, the modified composite exhibits an ultrahigh proton conductivity of 2.33 × 10−1 S cm−1 at 80 °C under 95% relative humidity (RH). The stability of PANa@TpPa–SO3H makes it an efficient proton transport platform with excellent proton conductivity and long–term durability.

Electrocatalytic water splitting, as a sustainable, pollution-free and convenient method of hydrogen production, has attracted the attention of researchers. However, due to the high reaction barrier and slow four-electron transfer process, it is necessary to develop and design efficient electrocatalysts to promote electron transfer and improve reaction kinetics. Tungsten oxide-based nanomaterials have received extensive attention due to their great potential in energy-related and environmental catalysis. To maximize the catalytic efficiency of catalysts in practical applications, it is essential to further understand the structure–property relationship of tungsten oxide-based nanomaterials by controlling the surface/interface structure. In this review, recent methods to enhance the catalytic activities of tungsten oxide-based nanomaterials are reviewed, which are classified into four strategies: morphology regulation, phase control, defect engineering, and heterostructure construction. The structure–property relationship of tungsten oxide-based nanomaterials affected by various strategies is discussed with examples. Finally, the development prospects and challenges in tungsten oxide-based nanomaterials are discussed in the conclusion. We believe that this review provides guidance for researchers to develop more promising electrocatalysts for water splitting.

Interfacial atomic configuration plays a vital role in the structural stability and functionality of nanocomposites composed of metal nanoparticles (NPs) and two−dimensional semiconductors. In situ transmission electron microscope (TEM) provides a real−time technique to observe the interface structure at atomic resolution. Herein, we loaded bimetallic NiPt truncated octahedral NPs (TONPs) on MoS2 nanosheets and constructed a NiPt TONPs/MoS2 heterostructure. The interfacial structure evolution of NiPt TONPs on MoS2 was in situ investigated using aberration−corrected TEM. It was observed that some NiPt TONPs exhibited lattice matching with MoS2 and displayed remarkable stability under electron beam irradiation. Intriguingly, the rotation of an individual NiPt TONP can be triggered by the electron beam to match the MoS2 lattice underneath. Furthermore, the coalescence kinetics of NiPt TONPs can be quantitatively described by the relationship between neck radius (r) and time (t), expressed as rn = Kt. Our work offers a detailed analysis of the lattice alignment relationship of NiPt TONPs on MoS2, which may enlighten the design and preparation of stable bimetallic metal NPs/MoS2 heterostructures.

Abstract As an important member of the IVA–VIA group compounds, 2D SnSe2 has emerged as a perfect platform for developing diverse applications, especially in high‐performance optoelectronic devices and data storage, etc. However, the bottom‐up synthesis of large‐area uniform, atomically thin SnSe2 crystals with controlled thicknesses has not yet been realized. Herein, we report the large‐area uniform growth of monolayer (1L), bilayer (2L), and few‐layer (FL) 1T‐SnSe2 single‐crystal flakes on mica substrates via a facile chemical vapor deposition (CVD) route. The feeding amount of Sn precursor and flow rate of hydrogen carrier are found to be the key parameters for the thickness‐controlled growth of uniform SnSe2 flakes. More intriguingly, obvious second harmonic generation (SHG) is revealed in the retained inversion symmetry structure of 1T‐SnSe2, with its intensity showing linear dependence with the thickness from monolayer to multilayers. The new findings reported herein should pave the ways for the thickness‐tunable growth of atomically thin SnSe2 crystals, and their unique optical property explorations and applications in nonlinear optics.

This paper is devoted to study the proportional reinsurance/new business and investment problem under the mean-variance criterion in a continuous-time setting. The strategies are constrained in the non-negative cone and all coefficients in the model except the interest rate are stochastic processes adapted the filtration generated by a Markov chain. With the help of a backward stochastic differential equation driven by the Markov chain, we obtain the optimal strategy and optimal cost explicitly under this non-Markovian regime-switching model. The cases with one risky asset and Markov regime-switching model are considered as special cases.

Constructing a heterogeneous interface using different components is one of the effective measures to achieve the bifunctionality of nanocatalysts, while synergistic interactions between multiple interfaces can further optimize the performance of single-interface nanocatalysts. The non-precious metal nanocatalysts MoS2/NiSe2/reduced graphene oxide (rGO) bilayer sandwich-like nanostructure with multiple well-defined interfaces is prepared by a simple hydrothermal method. MoS2 and rGO are layered nanostructures with clear boundaries, and the NiSe2 nanoparticles with uniform size are sandwiched between both layered nanostructures. This multiple-interfaced sandwich-like nanostructure is prominent in catalytic water splitting with low overpotential for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) and almost no degradation in performance after a 20 h long-term reaction. In order to simulate the actual overall water splitting process, the prepared nanostructures are assembled into MoS2/NiSe2/rGO||MoS2/NiSe2/rGO modified two-electrode system, whose overpotential is only 1.52 mV, even exceeded that of noble metal nanocatalyst (Pt/C||RuO2~1.63 mV). This work provides a feasible idea for constructing multi-interface bifunctional electrocatalysts using nanoparticle-doped bilayer-like nanostructures.

As the star material among nonprecious electrocatalysts, molybdenum disulfide (MoS2) has received much attention. However, the catalytic inertness of the basal plane, low conductivity of its steady state (2H phase), and the agglomeration of lamellar structures have seriously hindered its catalytic performance. It is very essential to design and modulate the morphology and phase of MoS2 to improve the above issues by synergistic regulation of electrical structure and defect engineering. Herein, MoS2 was delicately composited on CoP nanoframe derived from a typical metal–organic frame nanostructure (ZIF-67), forming the hollow CoP@MoS2 hetero-nanoframe. This exquisite externally layered and internally hollow CoP@MoS2 electrocatalyst demonstrated excellent catalytic performance for the hydrogen evolution reaction, with a low overpotential of 119 mV at 10 mA cm−2, a small Tafel slope of 49 mV dec−1, a large electric double-layer capacitance of 10.28 mF cm−2, and prominent long-term stability. The remarkable catalytic performance of hollow CoP@MoS2 hetero-nanoframe can be attributed to the unique architecture of the hetero-nanostructures, appropriate component ratios, strong interaction between CoP and MoS2, and large-scale defects and disorder. First-principles density-functional theory calculations can prove the above arguments adequately, the hydrogen adsorption free energy of CoP@MoS2 is close to zero.

Developing efficient and low-cost energy conversion and storage devices and technologies is all-important issue in order to achieve a low-carbon society, whose performance essentially depends on the properties of materials [...]

Aims: To investigate the feasibility of serum extra spindle pole bodies-like 1 (ESPL1) used as a biomarker for patients with hepatitis B virus (HBV)-related hepatocellular carcinoma (HCC). Methods: 131 chronic HBV-infection patients were recruited and divided into HBV S gene integration, non-HBV S gene integration, chronic hepatitis B (CHB), HBV-related liver cirrhosis (LC) and HBV-related HCC group, 24 non-HBV-related HCC patients were selected as HCC control group, 30 people without HBV-infection as healthy control group. Serum ESPL1 were detected and compared. Results: ESPL1 level of integration group was significantly higher than that of non-integration group (346.7 vs 199.6 ng/ml, P = 0.000) and healthy control group (346.7 vs 41.3 ng/ml, P = 0.000). ESPL1 level of non-integration group was significantly higher than that of healthy control group (199.6 vs 41.3 ng/ml, P = 0.000); ESPL1 levels in chronic HBV-infection related groups were increased in turn according to CHB group (95.8 ng/ml), HBV-related LC group (268.2 ng/ml), HBV-related HCC group (279.9 ng/ml) and integration group (346.7 ng/ml). Except that there was no significant difference in ESPL1 levels between HBV-related LC and HCC group ( P = 0.662), pairwise comparisons between other groups showed significant differences ( P < 0.05). ESPL1 level of HBV-related HCC group was significantly higher than that of non-HBV-related HCC group (279.9 vs 46.6 ng/ml, P = 0.000), there was no noticeable difference between non-HBV-related HCC and healthy control group (46.6 vs 41.3 ng/ml, P = 0.848). ESPL1 level of HBV-related HCC group after resection was significantly lower than that of before resection (178.4 vs 260.8 ng/ml, P = 0.000). Conclusions: Chronic HBV-infection patients with high ESPL1 level may indicate HBV S gene integration and is a high-risk population for HBV-related HCC. Serum ESPL1 can be used as a biomarker for screening HBV-related HCC high-risk population and monitoring recurrence.

Efficient and durable catalysts are crucial for the oxygen evolution reaction (OER). The discovery of the high OER catalytic activity in Ni12P5 has attracted a great deal of attention recently. Herein, the microscopic mechanism of OER on the surface of Ni12P5 is studied using density functional theory calculations (DFT) and ab initio molecular dynamics simulation (AIMD). Our results demonstrate that the H2O molecule is preferentially adsorbed on the P atom instead of on the Ni atom, indicating that the nonmetallic P atom is the active site of the OER reaction. AIMD simulations show that the dissociation of H from the H2O molecule takes place in steps; the hydrogen bond changes from Oa-H⋯Ob to Oa⋯H-Ob, then the hydrogen bond breaks and an H+ is dissociated. In the OER reaction on nickel phosphides, the rate-determining step is the formation of the OOH group and the overpotential of Ni12P5 is the lowest, thus showing enhanced catalytic activity over other nickel phosphides. Moreover, we found that the charge of Ni and P sites has a linear relationship with the adsorption energy of OH and O, which can be utilized to optimize the OER catalyst.

As a typical two-dimensional (2D) MXene, Ti3C2O2 has been considered as a potential material for high-performance hydrogen evolution reaction (HER) catalyst, due to its anticorrosion and hydrophilic surface. However, it is still a challenge to improve the Ti3C2O2 surficial HER catalytic activity. In this work, we investigated the HER activity of Ti3C2O2 after the surface was doped with S, Se, and Te by the first principles method. The results indicated that the HER activity of Ti3C2O2 is improved after being doped with S, Se, Te because the Gibbs free energy of hydrogen adsorption (ΔGH) is increased from −2.19 eV to 0.08 eV. Furthermore, we also found that the ΔGH of Ti3C2O2 increased from 0.182 eV to 0.08 eV with the doping concentration varied from 5.5% to 16.7%. The HER catalytic activity improvement of Ti3C2O2 is attributed to the local crystal structure distortion in catalytic active sites and Fermi level shift leads to the p-d orbital hybridization. Our results pave a new avenue for preparing a low-cost and high performance HER catalyst.

Transition metal sulfides have attracted a lot of attention as potential oxygen evolution reaction (OER) catalysts. Bimetallic sulfide possesses superior physicochemical properties due to the synergistic effect between bimetallic cations. By introducing a metal-semiconductor interface, the physicochemical properties of transition metal sulfide can be further improved. Using the solvothermal method, Au@NiCo2S4 core-shell heterostructure nanoparticles (NPs) and bare NiCo2S4 NPs were prepared. The measurement of the OER catalytic performance showed that the catalytic activity of Au@NiCo2S4 core-shell heterostructure was enhanced compared to bare NiCo2S4 NPs. At the current density of 10 mA cm−2, the overpotential of Au@NiCo2S4 (299 mV) is lower than that of bare NiCo2S4 (312 mV). The Tafel slope of Au@NiCo2S4 (44.5 mV dec−1) was reduced compared to that of bare NiCo2S4 (49.1 mV dec−1), indicating its faster reaction kinetics. Detailed analysis of its electronic structure, chemical state, and electrochemical impedance indicates that the enhanced OER catalytic performances of bare Au@NiCo2S4 core-shell NPs were a result of its increased proportion of high-valance Ni/Co cations, and its increased electronic conductivity. This work provides a feasible method to improve OER catalytic performance by constructing a metal-semiconductor core-shell heterostructure.

Low-noble metal electrocatalysts are attracting massive attention for anode and cathode reactions in fuel cells. Pt transition metal alloy nanostructures have demonstrated their advantages in high performance low-noble metal electrocatalysts due to synergy effects. The basic of designing this type of catalysts lies in understanding structure-performance correlation at the atom and electron level. Herein, design threads of highly active and durable Pt transition metal alloy nanocatalysts are summarized, with highlighting their synthetic realization. Microscopic and electron structure characterization methods and their prospects will be introduced. Recent progress will be discussed in high active and durable Pt transition metal alloy nanocatalysts towards oxygen reduction and methanol oxidation, with their structure-performance correlations illustrated. Lastly, an outlook will be given on promises and challenges in future developing of Pt transition metal alloy nanostructures towards fuel cells catalysis uses.

Platinum-based nanomaterials have attracted much interest for their promising potentials in fields of energy-related and environmental catalysis. Designing and controlling the surface/interface structure of platinum-based nanomaterials at the atomic scale and understanding the structure-property relationship have great significance for optimizing the performances in practical catalytic applications. In this review, the strategies to obtain platinum-based catalysts with fantastic activity and great stability by composition regulation, shape control, three-dimension structure construction, and anchoring onto supports, are presented in detail. Moreover, the structure-property relationship of platinum-based nanomaterials are also exhibited, and a brief outlook are given on the challenges and possible solutions in future development of platinum-based nanomaterials towards catalytic reactions.

A series of α-Fe2O3 nanocrystals (NCs) with fascinating morphologies, such as hollow nanoolives, nanotubes, nanospindles, and nanoplates, were prepared through a simple template-free hydrothermal synthesis process. The results showed that the morphologies could be easily controlled by SO42− and H2PO4−. Physical property analysis showed that the α-Fe2O3 NCs exhibited shape- and size-dependent ferromagnetic and optical behaviors. The absorption band peak of the α-Fe2O3 NCs could be tuned from 320 to 610 nm. Furthermore, when applied as electrode material for supercapacitor, the hollow olive-structure exhibited the highest capacitance (285.9 F·g−1) and an excellent long-term cycling stability (93% after 3000 cycles), indicating that it could serve as a candidate electrode material for a supercapacitor.

The Blocking temperature (TB) of Pt/NiFe/IrMn/MgO/Pt multilayers was greatly enhanced from far below room temperature (RT) to above RT by inserting 1 nm thick Mg layer at IrMn/MgO interface. Furthermore, the exchange bias field (Heb) was increased as well by the control of interfacial structures. The evidence for a significant fraction of Mn-O bonding at IrMn/MgO interface without Mg insertion layer was provided by X-ray photoelectron spectroscopy. The bonding between Mn and O can decrease the antiferromagnetism of IrMn film, leading to lower value of TB in Pt/NiFe/IrMn/MgO/Pt multilayers. Ultrathin Mg film inserted at IrMn/MgO interface acting as an oxygen sinking layer can suppress the oxidation reactions between Mn and O and reduce the formation of Mn-O bonding greatly. The oxidation suppression results in the recovery of the antiferromagnetism of IrMn film, which can enhance TB and Heb. Furthermore, the high resolution transmission electron microscopy demonstrates that the Mg insertion layer can efficiently promote a high-quality MgO (200) texture. This study will enhance the understanding of physics in antiferromagnet-based spintronic devices.

By one-pot wet chemical method, Pt-based hollow nanostructures were synthesized at room temperature. Because of the highly damping optical response of the metal, these Pt-based hollow nanostructures exhibited weak thermal effects with a laser focal spot on 4-aminothiophenol (PATP) molecules limiting dimerisation. The isolated surface enhanced Raman scattering (SERS) spectra of PATP, in which the vibrational bands from 4,4′-dimercaptoazobenzene (DMAB) molecules are not observed, were able to be seen, and this was in good agreement with the Raman spectra of PATP powder. In addition, the concentration of PATP molecules was varied, and the illumination time was increased to 2000 s, respectively. It was found that spectra were stable with varied PATP concentrations, and the plasmon-driven chemical conversion of PATP to DMAB was still suppressed, even when the laser illumination time was increased to 2000 s.

Strong nonlinear resistance has been found in the charge ordered ferroelectric iron oxyborate (Fe2OBO3) with a high dielectric constant and giant converse magnetoelectric effect. In low temperature range the I-V nonlinearity increases quickly with decreasing temperature. Transport measurements on polycrystalline and single crystal Fe2OBO3 indicate that the nonlinearity is not induced by grain boundaries. The nonlinear I-V behavior is intrinsically correlated with the charge order phase melting in Fe2OBO3 by detailed in-situ TEM investigations. These results provide an insight into structure-activity relationship of resistance switching effects at atomic and electric scales, which is essential for its potential application as varistors and storage media.

We report on the structural evolution and atomic inter-diffusion characteristics of the bimetallic Ni-Au nanocrystals (NCs) by molecular dynamics simulations studies. Our results reveal that the thermal stability dynamics of Ni-Au NCs strongly depends on the atomic configurations. By engineering the structural construction with Ni:Au = 1:1 atomic composition, compared with core-shell Au@Ni and alloy NCs, the melting point of core-shell Ni@Au NCs is significantly enhanced up to 1215 K. Unexpectedly, with atomic ratio of Au:Ni= 1:9, the melting process initiates from the atoms in the shell of Ni@Au and alloy NCs, while starts from the core of Au@Ni NCs. The corresponding features and evolution process of structural motifs, mixing and segregation are illustrated via a series of dynamic simulations videos. Moreover, our results revealed that the face centered cubic phase Au0.75Ni0.25 favorably stabilizes in NCs form but does not exist in the bulk counterpart, which elucidates the anomalies of previously reported experimental results on such bimetallic NCs.

We report the fabrication and characterizations of oxide heterojunctions composed of TbMnO3 thin films grown on conducting Nb:SrTiO3 substrates. The heterojunctions exhibit rich rectifying characteristics, depending on not only the measurement temperature but also the growth temperature: at 300 K, good rectification appears in both samples; at lower temperatures, the rectification is much smaller in the sample grown at 700 °C, whereas it exhibits a reversed bias dependence and reaches ∼5000 in the sample grown at 780 °C. Regarding to the transport mechanism, the conduction appears to be Schottky-emission-like at high temperatures in both junctions, indicating well-defined band alignment at interface; on the other hand, the space-charge-limited mechanism dictates the low temperature transport. Furthermore, the temperature and frequency dependent capacitance-loss data suggest that the transport dynamics is associated with multiple thermally activated relaxation processes. Finally, transmission electron microscopy studies shed light on the crystalline quality of the junction interfaces, which is believed to dictate the corresponding transport properties.