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Despite acknowledgment of structural reconstruction of materials following oxygen evolution reaction (OER) reaction, the role of support during the reconstruction process has been ignored. Given this, we directly in situ transform the residual iron present in raw single-walled carbon nanotubes (SWCNT) into Fe2O3 and thus build Fe2O3-CNT as the model system. Intriguingly, an anomalous self-optimization occurred on SWCNT and the derived components show satisfactory electrochemical performance. Soft X-ray absorption spectroscopy (sXAS) analysis and theory calculation correspondingly indicate that self-optimization yields stronger interaction between SWCNT and Fe2O3 nanoparticles, where the electrons migrate from Fe2O3 to optimized SWCNT. Such polarization will generate a positive charge center and thus boost the OER activity. This finding directly observes the self-optimization of support effect, providing a new perspective for OER and related electrochemical reactions.

Lithium-sulfur (Li-S) batteries have attracted widespread attention due to their high theoretical energy density. However, their practical application is still hindered by the shuttle effect and the sluggish conversion of lithium polysulfides (LiPSs). Herein, monodisperse molybdenum (Mo) nanoparticles embedded onto nitrogen-doped graphene (Mo@N-G) were developed and used as a highly efficient electrocatalyst to enhance LiPS conversion. The weight ratio of the electrocatalyst in the catalyst/sulfur cathode is only 9%. The unfilled d orbitals of oxidized Mo can attract the electrons of LiPS anions and form Mo–S bonds during the electrochemical process, thus facilitating fast conversion of LiPSs. Li-S batteries based on the Mo@N-G/S cathode can exhibit excellent rate performance, large capacity, and superior cycling stability. Moreover, Mo@N-G also plays an important role in room-temperature quasi-solid-state Li-S batteries. These interesting findings suggest the great potential of Mo nanoparticles in building high-performance Li-S batteries.

Rationally designing cheap and efficient electrocatalysts at the atomic level is highly desirable for the hydrogen evolution reaction (HER). Here, we demonstrate a metallic MoS2 electrocatalyst decorated with platinum single atoms. When combined with electron microscopy observations, our synchrotron X-ray characterizations and theoretical calculations clearly reveal that the doped Pt atoms bond to S atoms on the surface of MoS2. Notably, these Pt single atoms serve as critical active centers for the HER through capturing H+ from the solution. The optimized Pt-MoS2 catalysts achieve significantly enhanced HER performance due to the single-atom coordination effect. This finding is expected to facilitate further realization of hybridized catalysts through the monatomic riveting strategy.

Layered transition metal dichalcogenides (TMDs) belong to a versatile family of two-dimensional materials, having exceptional optical, electronic, physical, and chemical properties. In fact, the in...

Dispersing catalytically active metals as single atoms on supports represents the ultimate in metal utilization efficiency and is increasingly being used as a strategy to design hydrogen evolution reaction (HER) electrocatalysts. Although platinum (Pt) is highly active for HER, given its high cost it is desirable to find ways to improve performance further while minimizing the Pt loading. Here, we use onion-like nanospheres of carbon (OLC) to anchor stable atomically dispersed Pt to act as a catalyst (Pt1/OLC) for the HER. In acidic media, the performance of the Pt1/OLC catalyst (0.27 wt% Pt) in terms of a low overpotential (38 mV at 10 mA cm−2) and high turnover frequencies (40.78 H2 s−1 at 100 mV) is better than that of a graphene-supported single-atom catalyst with a similar Pt loading, and comparable to a commercial Pt/C catalyst with 20 wt% Pt. First-principle calculations suggest that a tip-enhanced local electric field at the Pt site on the curved support promotes the reaction kinetics for hydrogen evolution. Isolating metal atoms on supports is becoming an increasingly studied approach to design water splitting electrocatalysts. Here, the authors prepare a hydrogen evolution catalyst comprising atomically dispersed Pt atoms on curved carbon supports, which outperform similar catalysts where the support is flat.

Numerous experiments have demonstrated that the metal atom is the active center of monoatomic catalysts for hydrogen evolution reaction (HER), while the active sites of nonmetal doped atoms are often neglected. By combining theoretical prediction and experimental verification, we designed a unique ternary Ru-N 4 -P coordination structure constructed by monodispersed Ru atoms supported on N,P dual-doped graphene for highly efficient hydrogen evolution in acid solution. The density functional theory calculations indicate that the charge polarization will lead to the most charge accumulation at P atoms, which results in a distinct nonmetallic P active sites with the moderate H ∗ adsorption energy. Notably, these P atoms mainly supply highly efficient catalytic sites with ultrasmall absorption energy of 0.007 eV. Correspondingly, the Ru-N 4 -P demonstrated outstanding HER performance not only in an acidic condition but also in alkaline environment. Notably, the performance of Ru-NPC catalyst at high current is even superior to the commercial Pt/C catalysts, whether in acidic or alkaline medium. Our in situ synchrotron radiation infrared spectra demonstrate that a P-H ads intermediate is continually emerging on the Ru-NPC catalyst, actively proving the nonmetallic P catalytically active site in HER that is very different with previously reported metallic sites.

Because the reconstruction of catalysts is generally observed during oxidation reactions, understanding the intrinsic structure-related reconstruction ability of electrocatalysts is highly desirable but challenging. Herein, a controllable hydrolysis strategy is developed to obtain nickel hydroxide electrocatalysts with controllable nickel vacancy (VNi) concentrations, as confirmed by advanced spectroscopic characterization. Electrochemical measurements show that the reconstruction can be promoted with the increase of VNi concentration to generate true active components, thereby boosting activities for both oxygen evolution reaction (OER) and urea oxidation reaction (UOR). Density functional theory calculations confirm that the increased VNi concentration yields decreased formation energies of the true active components during reactions. This work provides fundamental understanding of the reconstruction ability of electrocatalysts in anodic oxidation reactions from the view of intrinsic defects.

Atomic intercalation in two-dimensional (2D) layered materials can be used to engineer the electronic structure at the atomic scale and generate tuneable physical and chemical properties which are quite distinct in comparison with the pristine material. Among them, electron-doped engineering induced by intercalation is an efficient route to modulate electronic states in 2D layers. Herein, we demonstrate a semiconducting to metallic phase transition in zirconium diselenide (ZrSe2) single crystals via controllable incorporation of copper (Cu) atoms. Our angle resolved photoemission spectroscopy (ARPES) measurements and first-principles density functional theory (DFT) calculations clearly revealed the emergence of conduction band dispersion at the M/L point of the Brillouin zone due to Cu-induced electron doping in ZrSe2 interlayers. Moreover, electrical measurements in ZrSe2 revealed semiconducting behavior, while the Cu-intercalated ZrSe2 exhibited a linear current–voltage curve with metallic character. The atomic intercalation approach may have high potential for realizing transparent electron-doping systems for many specific 2D-based nanoelectronic applications.

Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, they have limitations owing to the extremely low metal-loading content on supports, difficulty in the precise control of the metal location and amount as well as low stability at high temperatures. We prepared a highly doped single metal atom hybrid via a single-step thermal pyrolysis of glucose, dicyandiamide, and inorganic metal salts. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that nitrogen atoms doped into the graphene matrix were pivotal for metal atom stabilization by generating a metal-Nx coordination structure. Due to the strong anchoring effect of the graphene matrix, the metal loading content was over 4 wt.% in the isolated atomic hybrid (the Pt content was as high as 9.26 wt.% in the Pt-doped hybrid). Furthermore, the single iron-doped hybrid (Fe@N-doped graphene) showed a remarkable electrocatalytic performance for the oxygen reduction reaction. The peak power density was ∼199 mW·cm−2 at a current density of 310 mA·cm−2 and superior to that of a commercial Pt/C catalyst when it was used as a cathode catalyst in assembled zinc-air batteries. This work offered a feasible approach to design and fabricate highly doped single metal atoms (SMAs) catalysts for potential energy applications.

Hierarchical microstructures assembled with nanostructures can effectively enhance the electrochemical performances of electrode materials for rechargeable Li/Na-ion batteries. Due to the large ionic radius of sodium, this kind of design and synthesis is more important for Na-battery cathodes, which represent a cost-effective alternative for energy storage applications. Here ball-in-ball hierarchical microspheres assembled with micron shaped flakes of the P2-type Na0.7Ni0.18Mn0.64Co0.18O2 have been designed and synthesized via hydrothermal reaction followed by stepwise calcination process. As a cathode material of the Na-ion battery, this novel and uniform hierarchical structure exhibits very high specific capacity and superior rate performance with discharge capacities of 208 mAh g−1 at 0.05 C and 46 mAh g−1 at 10 C, and an excellent cycling stability with about 78% capacity retention at 1 C after 50 cycles. These performances are better than any layered oxide cathode material for reversible Na-ion batteries reported in the literature, prepared via the conventional solid-state method. Combining ex-situ x-ray absorption spectroscopy characterization, x-ray diffraction, field emission scanning electron microscopy, scanning transmission electron microscopy and electrochemical characterization, we demonstrate that the superior performances can be attributed to the unique ball-in-ball hierarchical structure assembled with micron shaped flakes. This configuration could effectively reduce the path of Na ion diffusion, increases the contact area between electrodes and electrolyte and buffers the volume changes during the Na ion insertion/extraction processes.

The integration of active components and conductive supports forming free-standing electrodes is highly desirable for a series of energy storage and conversion devices. Herein, a facile hydrothermal method is developed to achieve the coupling of NiFe layered double hydroxide (LDH) and single-walled carbon nanotubes (SWNT) film, forming an integrated flexible electrode for oxygen evolution reaction (OER). The electrode requires a low overpotential of 250 mV to reach a current density of 10 mA cm–2 in 1 M KOH, and shows rapid reaction kinetics with a Tafel slope of 35 mV dec–1. Advanced soft X-ray absorption near-edge structure measurements efficiently indicate strong interfacial electron coupling between the LDH and SWNT, which authentically contributes to superior OER performance. This work provides a new strategy to design binder-free and flexile electrodes for practical application.

In most cases, layered transition metal dichalcogenides (LTMDs), containing metallic phases, show electrochemical behavior different from their semiconductor counterparts. Typically, two-dimensional layered metallic 1T-MoS2 demonstrates better electrocatalytic performance for water splitting compared to its 2H counterpart. However, the characteristics of low metallic phase concentration and poor stability limit its applications in some cases. Herein, we demonstrate a simple and efficient bottom-up wet-chemistry strategy for the large-scale synthesis of nanoscopic ultrathin Mo1–xWxS2 nanosheets with enlarged interlayer spacing and high metallic phase concentration. Our characterizations, including X-ray absorption fine structure spectroscopy (XAFS), high-angle annular dark-fieldscanning transmission electron microscopy (HAADF-STEM), and X-ray photoelectron spectroscopy (XPS) revealed that the metallic ultrathin ternary Mo1–xWxS2 nanosheets exhibited distorted metal–metal bonds and a tunable metallic phase concentration. As a proof of concept, this optimized catalyst, with the highest metallic phase concentration (greater than 90%), achieved a low overpotential of about–155 mV at a current density of –10 mA/cm2, a small Tafel slope of 67 mV/dec, and an increased turnover frequency (TOF) of 1.3 H2 per second at an overpotential of –300 mV (vs. reversible hydrogen electrode (RHE)), highlighting the importance of the metallic phase. More importantly, this study can lead to a facile solvothermal route to prepare stable and high-metallicphase-concentration transition-metal-based two-dimensional materials for future applications.

Rational design of bifunctional oxygen electrocatalysts with high activity and low cost is crucial but still challenging for the development of rechargeable energy storage devices. In this work, a novel bimetallic phosphide confined within P, N co-doped carbon layers is achieved through a space-confinement phosphorization strategy. Electrochemical measurements demonstrate that the obtained bimetallic phosphide nanoparticle-containing hybrid can serve as a highly efficient bifunctional oxygen reduction and evolution reaction (ORR/OER) catalyst. It delivers a small potential difference of 0.75 V in 0.1 M KOH solution along with long-term catalytic durability, superior to most of the non-precious metal catalysts reported to date. The detailed synchrotron-based spectra results combined with structural characterizations reveal that the constructed hierarchical structure endows the confined bimetallic phosphide catalyst with abundant catalytic sites and stable spatial structure, thereby achieving remarkable electrocatalytic performance. This work opens up a facile way to design effective and durable bifunctional oxygen electrocatalysts for practical applications in renewable energy production, especially in rechargeable metal–air batteries and regenerative fuel cells.

The oxygen evolution reaction (OER) involving multi-step electron transfer is a challenging approach for water-splitting due to its sluggish kinetics. It is desirable to explore more efficient electro-catalysts with earth-abundant elements. Herein, we employed a high-temperature polymerization method to develop a structure consisting of graphitic carbon nitride (g-C3N4) nanopatch enveloped carbon nanotubes (CNTs), where isolated Ni and Fe atoms were embedded into the tri-s-triazine units of g-C3N4 by forming a metal–Nx structure. The designed dual-metal catalyst exhibited remarkable OER performance with an extremely low overpotential (∼326 mV at 10 mA cm−2) and a small Tafel slope (67 mV per decade), which is superior to those of state-of-the-art electrocatalysts with metal–Nx coordination and the benchmark IrO2/C catalyst. In combination with atomic microscopy observations, our synchrotron-based X-ray absorption spectroscopy results revealed that, as compared to single-metal (Fe or Ni) doped hybrids, the electronic structures of both Ni and Fe atoms were reconfigured in the obtained dual-metal samples. Notably, increase of the oxidative state in Ni sites after multi-metal doping directly contributed to more active sites and favored the OER process, assisted by the porous structure and good electrical contacts between CNTs and g-C3N4. This investigation clearly demonstrated a unique synergistic effect in atomically dual-metal doped catalysts, thus it may provide a versatile route to regulate the electronic structures of single atomic catalysts through engineering of neighboring elements and coordination number.

Few-layer ternary FePS3 nanosheets, prepared via chemical vapor transport synthesis and ball-milling exfoliation, exhibit excellent electrocatalytic performance for the oxygen evolution reaction in an alkaline medium. Combined with first principles calculations, our X-ray spectroscopy and HRTEM results clearly reveal that the introduction of in-plane defects in FePS3 layers after exfoliation and formation of a FePS3-FeOOH heterostructure during the OER process largely contribute to the catalytic activity enhancement.

We present high quality WX2 (X = S, Se) single crystals synthesized via an improved chemical vapor transport technique. Morphological and structural characteristics of the as-grown layered single crystals were analyzed using SEM, TEM, XPS, Raman spectroscopy, XRD and UV visible spectroscopy characterization techniques. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and charge-discharge analysis reveal the insights for WX2 single crystals to be used an as excellent material for electrochemical supercapacitors. Notably the obtained supercapacitor electrodes show excellent cycle stability and high capacitance retention of 80 and 99% for WS2 and WSe2 respectively after 20,000 cycles, suggesting their high potential in electrochemical energy storage applications.

Developing flexible electrode is essential for new generation wearable electronics and energy devices. Combining with membrane-assisted vacuum filtration, highly flexible and stable hybridized electrodes, containing of S-doped graphene, carbon nano-onion (OLC) and Ni3S2 composite (GCNi3S2) are obtained. X-ray absorption characterizations reveal the transfer of electrons from C to Ni atoms due to the tight interface between Ni3S2 and GO/OLC, indicating the synergistic effect on fast redox reaction and ultrashort ion diffusion pathway among the hybrid electrodes. The assembled flexible symmetrical all-solid-state supercapacitor exhibits high volumetric capacitance of 55.3 F cm−3, along with an outstanding energy density of 3.63 Wh cm−3 and excellent stability of 5000 cycles with 97.2% capacitance remaining. The bending tests further confirm outstanding flexible performance in the capacitor device. Moreover, the assembled micro supercapacitor with GCNi3S2 electrode indicates the advantage of this membrane-assisted assembled strategy for easily realizing various flexible films as multitype supercapacitor's electrode which is otherwise difficult for powder-like materials.

LiMn2O4 (LMO) spinel cathode materials are modified with MoO3 coating synthesized using a simple wet chemical method. The surface modified samples show much better capacity retention than pristine LMO. In specially, 3 wt% MoO3 coated sample (LMO/M3) exhibit superior rate specific capacity with 110, 90 and 75 mAhg−1 at 5, 7 and 10 C, respectively. In addition, after 900 cycles at a current of 2 C, a capacity retention of 69.1% was achieved for LMO/M3, which is higher than the 39.6% for the pristine LMO. The enhancements of the electrochemical performance can be largely attributed to the stabilization of the cathode structure by suppressing the manganese dissolution in the electrolyte and in favor for Li+ ion diffusion after MoO3 coating.

Rational design and facet-engineering of nanocrystal is an effective strategy to optimize the catalytic performance of abundant and economic semiconductor-based photocatalysts. In this study, we demonstrate a novel ternary Cu2MoS4 nanotube with the {010} facet exposed, synthesized via a hydrothermal method. Compared with two-dimensional Cu2MoS4 nanosheet with the {001} facet exposed, this one-dimensional nanotube exhibits highly enhanced performance of photodegradation and water splitting. Both theoretical calculations and experimental results suggest that the conduction band minimum (CBM) of the {010} facet crystal shows lower potential than that of the {001} facet. In particular, the up-shifted CBM in Cu2MoS4 nanotube is significantly beneficial for the absorption of dye molecules and reduction of H+ to H2. These results may open a new route for realizing high-efficiency photocatalysts based on Cu2MX4 by facet engineering.

Two-dimensional stable metallic 1T-MoSe2 with expanded interlayer spacing of 10.0 A in situ grown on SWCNTs film is fabricated via a one-step solvothermal method. Combined with X-ray absorption near-edge structures, our characterization reveals that such 1T-MoSe2 and single-walled carbon nanotubes (abbreviated as 1T-MoSe2/SWCNTs) hybridized structure can provide strong electrical and chemical coupling between 1T-MoSe2 nanosheets and SWCNT film in a form of C–O–Mo bonding, which significantly benefits a high-efficiency electron/ion transport pathway and structural stability, thus directly enabling high-performance lithium storage properties. In particular, as a flexible and binder-free Li-ion anode, the 1T-MoSe2/SWCNTs electrode exhibits excellent rate capacity, which delivers a capacity of 630 mAh/g at 3000 mA/g. Meanwhile, the strong C–O–Mo bonding of 1T-MoSe2/SWCNTs accommodates volume alteration during the repeated charge/discharge process, which gives rise to 89% capacity retention and a capacity of 9...

Spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is one of the most promising high voltage cathode materials for future application. Herein, we report a simple method to prepare nanoscale TiO 2 -coated LNMO composites (LNMO-T). The thin TiO 2 coating layer was pasted on the surface of host material, which favors Li + ions diffusions. Compared to the bare LNMO, the surface modified composites LNMO-T shows outstanding rate capability and excellent cycling ability. In particularly, a discharge capacity of 74.5 mAh/g can be still delivered at 15 C and about 88.5% capacity retention at 2 C after 500 cycles. These results suggest that the TiO 2 coating can not only suppress the dissolution of manganese in the electrolyte but also enhance the conductivity of cathode. This study demonstrates that the potential of developing high energy density cathode materials by surface modification with TiO 2 membrane at nanoscale for future applications.

Layered Cu2MoS4, consisting of earth-abundant elements, is regarded as a potential catalyst for the hydrogen evolution reaction (HER). Herein, we demonstrate a Cu2O-based template strategy to synthesise hierarchical hollow nanostructures of Cu2MoS4. The characterizations reveal that the electrochemically active surface of the hollow Cu2MoS4 is largely enhanced, in contrast to the nanosheet or nanoparticle structures. As the direct outcome, the designed hierarchical hollow structures display excellent HER activities with a low overvoltage and small Tafel slope. This study may provide new inspiration for the research of other ternary sulphide materials as well as subsequently accelerating their applications in the field of catalysis.

Layered transition metal disulfides are currently being widely studied for advanced energy generation and storage applications. Here we report a facile template-assisted solvothermal strategy to obtain a hierarchical nanotubular structure consisting of ultrathin MoS2 nanosheets with a metallic 1T phase. Synchrotron radiation based X-ray absorption fine structure (XAFS) and X-ray photoelectron spectroscopy (XPS) are used to investigate the structure and electronic properties of the 1T-MoS2, which are largely different from annealed samples. Its hierarchical structure makes the obtained nanotubular 1T-MoS2 an excellent electrode material for supercapacitors, with a high specific capacitance of 328.547 F g−1 at a current density of 1 A g−1 and 243.66 F g−1 at a current density of 15 A g−1. Moreover, the material displays excellent capacitance retention, retaining 98.4% capacity after 5000 cycles at a current density of 3 A g−1. Notably, a high specific capacitance of 250 F g−1 at 1 A g−1 is also achieved in a two-electrode symmetrical cell, suggesting its great potential for new-generation supercapacitors.

Thin, planar nanojunctions between layered 2H/1T-MoS2 and graphitic C3N4 (g-C3N4) were fabricated and 1T phase nanojunctions allowed faster photogenerated electrons across the junction interfaces to facilitate hydrogen evolution. This research represents a proof of concept for the rational fabrication of thin 1T phase interfacial junctions and the importance of the 1T phase for further improving the HER perfomance.

Vertical 1T-MoS2 nanosheets with an expanded interlayer spacing of 9.8 A were successfully grown on a graphene surface via a one-step solvothermal method. Such unique hybridized structures provided strong electrical and chemical coupling between the vertical nanosheets and graphene layers by means of C–O–Mo bonding. The merits are very beneficial for a high-efficiency electron/ion transport pathway and structural stability. As a proof of concept, the lithium ion battery with the as-obtained hybrid's electrode exhibited excellent rate performance with a 666 mA h g−1 capacity at a high current density of 3500 mA g−1. We can extend this method to produce various metallic 1T-MX2 (M = transition metal; X = chalcogen) vertically edged on a graphene frame as one of the promising hetero-structures for several specific applications in the fields of electronics, optics and catalysis.

Ultrafine noble metal nanoparticles decorated on onion-like carbon (OLC) were successfully prepared without any reductant or surfactant. Particularly, the as-prepared Pt–OLC nanocomposite not only exhibited superior electrocatalytic activity and stability for the hydrogen evolution reaction as compared with the commercial 20% Pt/C, but also showed enhanced supercapacitor performance with a specific capacitance almost four times larger than that of OLC. Notably, the C–O functional groups on the surface of OLC will increase after the reaction because of the oxidation by O2 and chloroplatinic acid, which is very useful for the reuse of OLC and helpful for the decoration of noble metal nanoparticles on OLC. This work provides a simple and straightforward method for the facile preparation of metal composite nanocatalysts with high catalytic activity.

Ultrafast and high capacity all-carbon supercapacitors with 3D porous aerogel electrode are realized by combining carbon nanostructures of various dimensionalities, including 0D carbon onions, 1D carbon nanotubes, and 2D graphene oxide. The synergistic effects from the different forms of nanocarbons render this hybrid outstanding capacitance with excellent stability, even at ultrafast charge-discharge rates.

Layered tungsten disulfide (WS2) is a potential electrode material for electric double layer capacitance (EDLC) and hydrogen evolution reaction (HER). However, the electrochemical performance of WS2 has been hindered by the semiconducting nature and poor active sites. Herein, we have demonstrated a bottom-up hydrothermal approach to fabricate metallic 1T-WS2 nanoislands in situ grown on flexible single-walled carbon nanotube nonwovens (1T-WS2@SWCNT). The robust hybrids with a tight interface possess nanoscopic few-layered WS2 pieces with an abundance of exposed sites, along with a unique woven-architecture originating from the high conductive carbon nanotube network. The in situ-growing enhanced interface between metallic WS2 nanoislands and SWCNTs provides a relatively strong electrical coupling integrity, which facilitates charge transfer during electrochemical reactions. The merits of rich active sites, excellent conductivity and well bonding-interactions are significantly beneficial to improve the electrochemical performance. Particularly, in contrast to the pure material, the as-obtained hybrids are found to exhibit higher EDLC capacity (226 mF cm−2), almost 646-fold higher than pure 1T-WS2, smaller Tafel slope (57 mV per decade) and lower HER overpotential (∼25 mV) than any WS2-based materials reported so far.

Thanks to its larger surface and free volume, hollow nanostructure and nanomaterials are one kind of highly desirable electrodes for efficiently enhancing sodium-ion battery performance, especially at high rate. Herein, we demonstrate a design of hierarchical semi-open hollow structure, assembling with molybdenum selenide (MoSe2) nanosheets embedded on the nitrogen doped carbon matrix. The unique hollow structure can not only enable sufficient electrode/electrolyte interaction and fast electron transportation, but also suppress volume expansion during the insertion/extraction of sodium ion. As a direct outcome, the MoSe2/carbon anode exhibits excellent cycling and rate performance with a specific capacity of 431 mAh g−1 at 200 ​mA ​g−1, maintaining 87.7% capacity after 120 cycles. Notably, a discharge capacity of 199.1 mAh g−1 can be achieved even at an ultra-high current density of 20 ​A ​g−1, indicating quick Na+ storage ability. The results may open a new way to realize high-rate anode for ion battery applications.

Despite the fact that two-dimensional layered magnetic materials hold immense potential applications in the field of spintronic devices, tunable magnetism is still a challenge due to the lack of controllable synthesis. Herein, high-quality single crystals MPS3 (M= Mn, Fe) of millimeter size were synthesized through the chemical vapor transport method. After systemic structural characterizations, magnetic properties were studied on the bulk MPS3 layers through experiments, along with first principle theoretical calculations. The susceptibilities as well as the EPR results evidently revealed unique isotropic and anisotropic behavior in MnPS3 and FePS3 crystals, respectively. It is worth noting that both of these materials show antiferromagnetic states at measured temperatures. The estimated antiferromagnetic transition temperature is 78 K for bulk MnPS3 and 123 K for FePS3 crystals. The spin polarized density functional theory calculations confirmed that the band gap of the antiferromagnetic states could be generated owing to asymmetric response all over the energy range. The ferromagnetic state in MnPS3 and FePS3 is less stable as compared to the antiferromagnetic state, resulting in antiferromagnetic behavior. Additionally, frequency-dependent dielectric functions for parallel and perpendicular electric field component vectors, along with the absorption properties of MPS3, are thoroughly investigated.

Atomic intercalation of different agents into two-dimensional layered materials can engineer the intrinsic structure at the atomic scale and thus tune the physical and chemical properties for specific applications. Here we successfully introduce tin (Sn) atoms into the interlayer of α-MoO3 nanobelts forming a new MoO3-Sn intercalation with ultra-stable structure. Combining with theoretical calculations, our synchrotron radiation-based characterizations and electron microscope observations clearly reveal that the intercalated Sn atoms could bond with five O atoms, forming a pentahedral structure. Subsequently, the Sn-O bonds induce a less distorted [MoO6] octahedral structure, resulting in a unique structure that is distinct with pristine α-MoO3 or any other Molybdenum oxides. Employing as anode for lithium-ion battery, the as-prepared MoO3-Sn nanobelts display a much higher capacity of 520 mAh/g at 500 mA/g than α-MoO3 nanobelts (291 mAh/g), with a Coulombic efficiency of 99.5%. Moreover, owing to the str...

Developing highly efficient catalysts for oxygen evolution reaction (OER) in neutral media is extremely crucial for microbial electrolysis cells and electrochemical CO2 reduction. Herein, a facile one-step approach is developed to synthesize a new type of well-dispersed iridium (Ir) incorporated cobalt-based hydroxide nanosheets (nominated as CoIr) for OER. The Ir species as clusters and single atoms are incorporated into the defect-rich hydroxide nanosheets through the formation of rich Co-Ir species, as revealed by systematic synchrotron radiation based X-ray spectroscopic characterizations combining with high-angle annular dark-field scanning transmission electron microscopy measurement. The optimized CoIr with 9.7 wt% Ir content displays highly efficient OER catalytic performance with an overpotential of 373 mV to achieve the current density of 10 mA cm-2 in 1.0 m phosphate buffer solution, significantly outperforming the commercial IrO2 catalysts. Further characterizations toward the catalyst after undergoing OER process indicate that unique Co oxyhydroxide and high valence Ir species with low-coordination structure are formed due to the high oxidation potentials, which authentically contributes to superior OER performance. This work not only provides a state-of-the-art OER catalyst in neutral media but also unravels the root of the excellent performance based on efficient structural identifications.

Admittedly, the surface atomic structure of heterogenous catalysts toward the electrochemical oxygen reduction reaction (ORR) are accepted as the important features that can tune catalytic activity and even catalytic pathway. Herein, a surface engineering strategy to controllably synthesize a carbon-layer-wrapped cobalt-catalyst from 2D cobalt-based metal-organic frameworks is elaborately demonstrated. Combined with synchrotron radiation X-ray photoelectron spectroscopy, the soft X-ray absorption near-edge structure results confirmed that rich covalent interfacial CoNC bonds are efficiently formed between cobalt nanoparticles and wrapped carbon-layers during the polydopamine-assisted pyrolysis process. The X-ray absorption fine structure and corresponding extended X-ray absorption fine structure spectra further reveal that the wrapped cobalt with Co-N coordinations shows distinct surface distortion and atomic environmental change of Co-based active sites. In contrast to the control sample without coating layers, the 800 °C-annealed cobalt catalyst with N-doped carbon layers enwrapping achieves significantly enhanced ORR activity with onset and half-wave potentials of 0.923 and 0.816 V (vs reversible hydrogen electrode), highlighting the important correlation between surface atomic structure and catalytic property.

Here we demonstrate a ternary Cu2NiZn alloy substrate for controllably synthesizing monolayer graphene using a liquid carbon precursor cyclohexane via a facile CVD route. In contrast with elemental metal or bimetal substrates, the alloy-induced synergistic effects that provide an ideal metallic platform for much easier dehydrogenation of hydrocarbon molecules, more reasonable strength of adsorption energy of carbon monomer on surface and lower formation energies of carbon chains, largely renders the success growth of monolayer graphene with higher electrical mobility and lower defects. The growth mechanism is systemically investigated by our DFT calculations. This study provides a selective route for realizing high-quality graphene monolayer via a scalable synthetic method by using economic liquid carbon supplies and multialloy metal substrates.

Transition metal dichalogenides (TMDCs) with unique layered structures hold promising potential as transducers for photothermal therapy. However, the low photothermal conversion efficiency and poor stability in some cases limit their practical applications. Herein, we demonstrate the fabrication of ultrathin homogeneous hybridized TMDC nanosheets and their use for highly efficient photothermal tumor ablation. In particular, the nanosheets were composed of metallic WSe2 intercalated with polyvinylpyrrolidone (PVP), which was facilely prepared through a solvothermal process from the mixture of selenourea crystals, WCl6 powder along with PVP polymeric nanogel. Our characterizations revealed that the obtained nanosheets exhibited excellent photothermal conversion efficiency, therapeutic demonstration with improved biocompatibility and physiological stability attributing to the combined merits of metallic phase of WSe2 and hydrophilic PVP insertion. Both the histological analysis of vital organs and in vitro/in vivo tests confirmed the nanosheets as actively effective and biologically safe in this phototherapeutic technique. Findings from this non-invasive experiment clearly emphasize the explorable therapeutic efficacy of the layered-based hybrid agents in future cancer treatment planning procedures.

With the unique-layered structure, MXenes show potential as electrodes in energy-storage devices including lithium-ion (Li+ ) capacitors and batteries. However, the low Li+ -storage capacity hinders the application of MXenes in place of commercial carbon materials. Here, the vanadium carbide (V2 C) MXene with engineered interlayer spacing for desirable storage capacity is demonstrated. The interlayer distance of pristine V2 C MXene is controllably tuned to 0.735 nm resulting in improved Li-ion capacity of 686.7 mA h g-1 at 0.1 A g-1 , the best MXene-based Li+ -storage capacity reported so far. Further, cobalt ions are stably intercalated into the interlayer of V2 C MXene to form a new interlayer-expanded structure via strong V-O-Co bonding. The intercalated V2 C MXene electrodes not only exhibit superior capacity up to 1117.3 mA h g-1 at 0.1 A g-1 , but also deliver a significantly ultralong cycling stability over 15 000 cycles. These results clearly suggest that MXene materials with an engineered interlayer distance will be a rational route for realizing them as superstable and high-performance Li+ capacitor electrodes.

Developing efficient and low-cost defective carbon-based catalysts for the oxygen reduction reaction (ORR) is essential to metal-air batteries and fuel cells. Active sites engineering toward these catalysts is highly desirable but challenging to realize boosted catalytic performance. Herein, a sandwich-like confinement route to achieve the controllable regulation of active sites for carbon-based catalysts is reported. In particular, three distinct catalysts including metal-free N-doped carbon (NC), single Co atoms dispersed NC (Co-N-C), and Co nanoparticles-contained Co-N-C (Co/Co-N-C) are controllably realized and clearly identified by synchrotron radiation-based X-ray spectroscopy. Electrochemical measurements suggest that the Co/Co-N-C catalyst delivers optimized ORR performance due to the rich Co-Nx active sites and their synergistic effect with metallic Co nanoparticles. This work provides deep insight for rationally designing efficient ORR catalyst based on active sites engineering.

Two dimensional (2D) single crystal layered transition materials have had extensive consideration owing to their interesting magnetic properties, originating from their lattices and strong spin-orbit coupling, which make them of vital importance for spintronic applications. Herein, we present synthesis of a highly crystalline tungsten diselenide layered single crystal grown by chemical vapor transport technique and doped with nickel (Ni) to tailor its magnetic properties. The pristine WSe2 single crystal and Ni-doped crystal were characterized and analyzed for magnetic properties using both experimental and computational aspects. It was found that the magnetic behavior of the 2D layered WSe2 crystal changed from diamagnetic to ferromagnetic after Ni-doping at all tested temperatures. Moreover, first principle density functional theory (DFT) calculations further confirmed the origin of room temperature ferromagnetism of Ni-doped WSe2, where the d-orbitals of the doped Ni atom promoted the spin moment and thus largely contributed to the magnetism change in the 2D layered material.

In this work we directly synthesized molybdenum disulfide (MoS2) nanosheets on carbon nanotube film (MoS2@CNT) via a two-step chemical vapor deposition method (CVD). By etching the obtained MoS2@CNT into 10% wt HNO3, the morphology of MoS2 decorated on CNT bundles was modulated, resulting in more catalytic active MoS2 edges being exposed for significantly enhanced electrochemical performance. Our results revealed that an 8 h acid etching sample exhibited the best performance for the oxygen evolution reaction, i.e., the current density reached 10 mA/cm2 under 375 mV over-potential, and the tafel slope was as low as 94 mV/dec. The enhanced behavior was mainly originated from the more catalytic sites in MoS2 induced by the acid etching treatment and the higher conductivity from the supporting CNT films. Our study provides a new route to produce two-dimensional layers on CNT films with tunable morphology, and thus may open a window for exploring its promising applications in the fields of catalytic-, electronic-, and electrochemical-related fields.