Two Birds with One Stone: Contemporaneously Enhancing OER Catalytic Activity and Stability for Dual-Phase Medium-Entropy Metal Sulfides.

Transition metal-based sulfides exhibit remarkable potential as electrocatalysts for oxygen evolution reaction (OER) due to the unique intrinsic structure and physicochemical characteristics. Nevertheless, currently available sulfide catalysts based on transition metals face a bottleneck in large-scale commercial applications owing to their unsatisfactory stability. Here, the first fabrication of (FeCoNiMn2 )S2 dual-phase medium-entropy metal sulfide (dp-MEMS) is successfully achieved, which demonstrated the expected optimization of stability in the OER process. Benefiting from the "cell wall" -like structure and the synergistic effect in medium-entropy systems, (FeCoNiMn2 )S2 dp-MEMS delivers an exceptionally low overpotential of 169 and 232 mV at current densities of 10 and 100 mA cm-2 , respectively. The enhancement mechanism of catalytic activity and stability is further validated by density functional theory (DFT) calculations. Additionally, the rechargeable Zn-air batteries integrated with FeCoNiMn2 )S2 dp-MEMS exhibit remarkable performance outperforming the commercial catalyst (Pt/C+RuO2 ). This work demonstrates that the dual-phase medium-entropy metal sulfide-based catalysts have the potential to provide a greater application value for OER and related energy conversion systems.

MXene-Bimetallic Hybrids via Mixed Molten Salts Etching for Kinetics-Enhanced and Dendrite-Free Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries with high theoretical energy density (2600 Wh kg-1) are considered to be one of the most promising secondary batteries. However, the practical application of Li-S batteries is limited by the polysulfides shuttling and unstable lithium metal anodes. Herein, an asymmetric separator (CACNM@PP), composed of Co-Ni/MXene (CNM) on the cathode and Cu-Ag/MXene (CAM) on the anode for high-performance Li-S batteries is reported. For the cathode, CNM provides a synergistic effect by integrating Co, Ni, and MXene, resulting in strong chemical interactions and fast conversion kinetics for polysulfides. For the anode, CAM with abundant lithiophilicity active sites can lower the nucleation barrier of Li. Moreover, LiCl/LiF layers are generated in situ as an ion conductor layer during charging and discharging, inducing a uniform deposition of Li. Therefore, the assembled cells with the CACNM@PP separators harvest excellent electrochemical performance. This work provides novel insights into the development of commercially available high-energy density Li-S batteries with asymmetric separators.

SnS/SnS2 Heterostructures Embedded in Hierarchical Porous Carbon as Polysulfides Immobilizer for High-Performance Lithium-Sulfur Batteries.

Driven by the strong adsorptive and catalytic ability of metal sulfides for soluble polysulfides, it is considered as a potential mediator to resolve the problems of shuttle effect and slow reaction kinetics of polysulfides in lithium-sulfur (Li-S) batteries. However, their further development is limited by poor electrical conductivity and bad long-term durability. Herein, one type of new catalyst composed of SnS/SnS2 heterostructures on hierarchical porous carbon (denoted as SnS/SnS2-HPC) by a simple hydrothermal method is reported and used as an interlayer coating on the conventional separator for blocking polysulfides. The SnS/SnS2-HPC integrates the advantages of a porous conductive network for promoting the transport of electrons and an enhanced electrocatalyst for accelerating polysulfides conversion. As a result, such a cell coupled with a SnS/SnS2-HPC interlayer exhibits a long-term lifespan of 1200 cycles. This work provides a new cell configuration by using heterostructures with a built-in electric field formed from a p-n heterojunction to improve the performance of Li-S batteries.

High-Entropy Metal Oxide-Coated Carbon Cloth as Catalysts for Long-Life Li-S Batteries.

Lithium-sulfur (Li-S) batteries with high specific energy density, low cost, and environmental friendliness of sulfur have been regarded as a competitive alternative to replace lithium-ion batteries. However, the shuttle effect and the sluggish conversion rate of lithium polysulfides (LiPSs) have seriously limited the practical application of Li-S batteries. Herein, high-entropy oxides grown on the carbon cloth (CC/HEO) are synthesized by a simple and ultrafast solution combustion method for the sulfur cathode. The as-prepared composites possess abundant HEO active sites for strong interaction with LiPSs, which can significantly promote redox kinetics. Besides, the carbon fiber substrate not only ensures high electrical conductivity but also accommodates large volume change, leading to a stable sulfur electrochemistry. Benefiting from the rational design, the Li-S batteries with CC/HEO as cathode skeleton exhibits good cyclability with a capacity decay rate of 0.057% per cycle after 1000 cycles at 2 C. More importantly, the Li-S batteries with 4.3 mg cm-2 high sulfur loading can still retain a high capacity retention of 78.2% after 100 cycles.

NiO/RuO2 p-n Heterojunction Nanofoam as a High-Performance Electrocatalyst for Desulfurization and Concurrent Hydrogen Evolution.

The development of bifunctional electrocatalysts with excellent performance in both the hydrogen evolution reaction (HER) and sulfide oxidation reaction (SOR) remains a formidable challenge. Herein, we experimentally synthesize a NiO/RuO2 p-n heterojunction nanofoam that exhibits highly desirable electrocatalytic properties for both the HER and the SOR. We further design an electrolytic cell by pairing alkaline HER with SOR utilizing the NiO/RuO2 heterojunction nanofoam as both the anode and the cathode, which demands a low applied voltage of 0.846 V to achieve a current density of 10 mA cm-2. Density functional theory calculations confirm that the formation of the NiO/RuO2 p-n heterojunction nanofoam effectively regulates the electronic structure, thereby boosting the electrocatalytic performances for both HER and SOR. This work not only provides a novel strategy to prepare an efficient and stable nanofoam electrocatalyst for hydrogen production but also highlights the potential application of oxide heterojunction electrocatalysts in treating sulfur-containing waste liquid.

Furnishing Continuous Efficient Bidirectional Polysulfide Conversion for Long-Life and High-Loading Lithium-Sulfur Batteries via the Built-In Electric Field.

Most catalysts cannot accelerate uninterrupted conversion of polysulfides, resulting in poor long-cycle and high-loading performance of lithium-sulfur (Li-S) batteries. Herein, rich p-n junction CoS2 /ZnS heterostructures embedded on N-doped carbon nanosheets are fabricated by ion-etching and vulcanization as a continuous and efficient bidirectional catalyst. The p-n junction built-in electric field in the CoS2 /ZnS heterostructure not only accelerates the transformation of lithium polysulfides (LiPSs), but also promotes the diffusion and decomposition for Li2 S the from CoS2 to ZnS avoiding the aggregation of lithium sulfide (Li2 S). Meanwhile, the heterostructure possesses a strong chemisorption ability to anchor LiPSs and superior affinity to induce homogeneous Li deposition. The assembled cell with a CoS2 /ZnS@PP separator delivers a cycling stability with a capacity decay of 0.058% per cycle at 1.0 C after 1000 cycles, and a decent areal capacity of 8.97 mA h cm-2 at an ultrahigh sulfur mass loading of 6 mg cm-2 . This work reveals that the catalyst continuously and efficiently converts polysulfides via abundant built-in electric fields to promote Li-S chemistry.

First-principles calculations of the BeO monolayer with chemical functionalization.

Recently, extensive experimental and theoretical studies on two-dimensional materials have attracted enormous interest in exploring the properties of these materials by decorating their surfaces. In the present work, we present a detailed investigation of the structures, and electronic and magnetic properties of pristine, hydrogenated, and fluorinated BeO monolayers using the ab initio density functional theory approach. Structurally, the most stable adsorption sites are directly above the host Be atom for half-hydrogenation, above the middle of the Be-O bond for half-fluorination, and directly above the host Be atom and below the host O atom for full-hydrogenation and full-fluorination. Moreover, the electronic and magnetic properties of the BeO monolayer exhibit high sensitivity to chemical functionalization: half-hydrogenation induces nonmagnetic-magnetic transition and the reduction of the band gap reaches about 75%. Full-hydrogenation results in metallization of the BeO monolayer. Half-fluorination makes the BeO monolayer a 100% spin polarized material regardless of the adsorption site. However, depending on different adsorption sites, full-fluorination can produce either magnetically half-metallic or nonmagnetic semiconductor structures. These results demonstrate that the tunability of the electronic and magnetic properties of the BeO monolayer can be realized by chemical functionalization for future nano-electronic and spintronic device applications.

Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors.

Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm(-2) at a scan rate of 5 mV s(-1). This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ~90% after 5000 charge/discharge cycles at 7.5 mA cm(-2). All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

Size-dependent eutectic temperature of Ag-Pb alloy nanoparticles.

In terms of size-dependent cohesive energy model, we have deduced an analytic model to describe the size dependence of the eutectic temperature for Ag-Pb alloy nanoparticles. The eutectic temperature is found to drop with decreasing of the particle diameter. Moreover, a linear relationship exists between the eutectic temperature and the reciprocal of the particle diameter when the diameter is large enough (e.g., 5 nm). The model predictions correspond to the experimental observations.

Amorphous Metal-Organic Framework-Derived Electrocatalyst to Boost Water Oxidation.

Amorphous metal-organic framework (MOF) materials have drawn extensive interest in the design of high-performance electrocatalysts for use in the electrochemical oxygen evolution reaction. However, there are limitations to the utilization of amorphous MOFs due to their low electrical conductivity and unsatisfactory stability. Herein, a novel amorphous-crystalline (AC) heterostructure is successfully constructed by synthesizing a crystalline metal sulfide (MS)-embedded amorphous Ni0.67Fe0.33-MOF, namely an MS/Ni0.67Fe0.33-MOF. It exhibits excellent catalytic performance (a low overpotential of 248 mV at 10 mA cm-2 with a small Tafel slope of 50 mV decade-1), durability, and stability (only 8% degradation of the current density at a constant voltage after 24 h). This work thus sheds light on the engineering of highly efficient catalysts with AC heterointerfaces for optimizing water-splitting systems.

Construction of Co3 O4 /ZnO Heterojunctions in Hollow N-Doped Carbon Nanocages as Microreactors for Lithium-Sulfur Full Batteries.

Lithium-sulfur (Li-S) batteries are promising alternatives of conventional Li-ion batteries attributed to their remarkable energy densities and high sustainability. However, the practical applications of Li-S batteries are hindered by the shuttling effect of lithium polysulfides (LiPSs) on cathode and the Li dendrite formation on anode, which together leads to inferior rate capability and cycling stability. Here, an advanced N-doped carbon microreactors embedded with abundant Co3 O4 /ZnO heterojunctions (CZO/HNC) are designed as dual-functional hosts for synergistic optimization of both S cathode and Li metal anode. Electrochemical characterization and theoretical calculations confirm that CZO/HNC exhibits an optimized band structure that effectively facilitates ion diffusion and promotes bidirectional LiPSs conversion. In addition, the lithiophilic nitrogen dopants and Co3O4/ZnO sites together regulate dendrite-free Li deposition. The S@CZO/HNC cathode exhibits excellent cycling stability at 2 C with only 0.039% capacity fading per cycle over 1400 cycles, and the symmetrical Li@CZO/HNC cell enables stable Li plating/striping behavior for 400 h. Remarkably, Li-S full cell using CZO/HNC as both cathode and anode hosts shows an impressive cycle life of over 1000 cycles. This work provides an exemplification of designing high-performance heterojunctions for simultaneous protection of two electrodes, and will inspire the applications of practical Li-S batteries.

Layered spherical carbon composites with nanoparticles of different metals grown simultaneously inside and outside.

We report a general one-step route to place nanoparticles (NPs) of different noble metals controllably into interior or surface locations of submicron nanoporous carbon spheres (CSs). In particular, Pd and Au NPs can be easily put either inside or outside of the CSs by selecting these metals' differently charged precursor ions. Employing mixed precursor solutions, the method allows different metals to grow simultaneously yet selectively in the separate locations, thus resulting in composites with a complex layered structure, for example Pd or Au outside and Ag inside, Au or Pt outside and Pd inside, and other combinations. The synthesis is fast and needs no additional steps like a functionalization of surfaces. It crucially involves microwave heating, the power setting of which further influences the locations and sizes of the NPs especially in the interior of the amorphous carbon matrix. The three-dimensional composite structures are analyzed by transmission electron microscopy and energy dispersed x-ray spectroscopy combined with quantitative analysis by comparison with simulation. The UV-visible absorption of monometallic and layered composites is compared. The involved mechanisms leading to the selective decoration are discussed; important aspects being the charge of the precursor ions and selective microwave absorption.

Facile and rapid synthesis of spherical porous palladium nanostructures with high catalytic activity for formic acid electro-oxidation.

Highly uniform, spherical porous palladium nanostructures (SPPNs) with rough surfaces were prepared by a facile and rapid ultrasound assisted reduction. The synthesis involves sonicating a solution of K(2)PdCl(4) and ascorbic acid for only 7 min at 40 °C without any additives. The products are isolated structures with a narrow size distribution, and their average diameters are controllable in a range from 40 to 100 nm via the K(2)PdCl(4) concentration. Typical products have a diameter of 52 nm and consist of loosely packed grains of 2-3 nm. They are thus very porous, with a specific surface area of 47 m(2) g(-1). The growth mechanism of SPPNs is discussed on the basis of varying relevant reaction parameters and characterizations from different microscopy techniques, nitrogen absorption analysis, and time-dependent UV-vis spectra. The electrocatalytic performance of the SPPNs was evaluated by electro-oxidation of formic acid. The mass current density per mass of SPPNs (1.88 A mg(-1)) exceeds that of commercial Pd black (1.69 A mg(-1)) and is more than twice that of commercial Pd/C catalyst (0.79 A mg(-1)). Long-term stability of the activity makes this material a promising anode catalyst for direct formic acid fuel cells.

A lotus-inspired 3D biomimetic design toward an advanced solar steam evaporator with ultrahigh efficiency and remarkable stability.

Developing advanced solar-driven interfacial evaporators with both ultrahigh energy efficiency and long-term tolerability is highly desired but still a great challenge. Herein, inspired by the natural lotus, we develop a high-performance solar interfacial evaporator with a novel 3D biomimetic architecture. The lotus-inspired biomimetic evaporator (LBE) combines three key components, including a large "leaf" having strong solar energy absorption ability, hydrophilic "stems" working as water transport channels, and lotus root-like porous "roots" with minimized heat loss for improved respiration. The photothermal part in the LBE, analogous to a lotus leaf, possesses Janus wettability with a hydrophobic side above and a hydrophilic side below, which is achieved by a scalable method of in situ inducing ZIF-67 nanocubes into an electrospun fiber film followed by pyrolysis. In particular, the top side has a unique hierarchical network structure consisting of long porous carbon nanofibers with internally dispersed metal oxide nanocrystals, leading to highly efficient solar absorption of 91.37%. The 3D-LBE exhibits an extremely high evaporation rate of 3.23 kg m-2 h-1 and energy efficiency reaching 153.20% under 1-sun, which exceeds the theoretical limit and is the highest recorded, to the best of our knowledge. Notably, the 3D-LBE also shows impressive pollutant removal capabilities assuring long-term interfacial evaporation stability. The high-performance LBE promises many applications, such as wastewater treatment, sea salt production, and metal recovery.

Abatement of chlorobenzene by plasma catalysis: Parameters optimization through response surface methodology (RSM), degradation mechanism and PCDD/Fs formation.

Dielectric barrier discharge coupled with 10 wt% Co/γ-Al2O3 catalyst was developed to degrade chlorobenzene in this study. The effects of experimental parameters including applied voltage, flow rate, initial chlorobenzene concentration, and their interactions on the chlorobenzene degradation performance were investigated by the response surface methodology integrated with a central composite design. Results indicated that applied voltage was the most significant parameter affecting the mineralization rate and the concentration of ozone generated, while energy yield was mainly determined by initial chlorobenzene concentration. As a key precursor of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorophenols were found during the identification of the intermediates produced during chlorobenzene degradation through GC-MS. Furthermore, HRGC-HRMS was used to detect the remaining byproducts on the catalyst surface after 3 and 10 h discharge time, and three types of PCDD/Fs (2,3,7,8-TCDF, 1,2,3,4,6,7,8-HCDF and OCDD) were detected after 10 h of discharge. The degradation mechanism of chlorobenzene was analyzed based on these detected intermediates, and the possible formation mechanisms of the three PCDD/Fs were proposed for the first time in plasma catalytic degradation of chlorobenzene.

Amorphous FeNiCu-MOFs as highly efficient electrocatalysts for the oxygen evolution reaction in an alkaline medium.

The preparation of low-cost and high-activity oxygen evolution reaction (OER) catalysts is a technical bottleneck in the field of electrolysis of water to produce hydrogen. Amorphous metal-organic frameworks (MOFs) with low-cost transition metals have attracted increasing attention in the catalytic field, yet metal atoms that are the main active sites are still ambiguous. Here, we synthesized a series of amorphous ternary Fex(NiCu)3-x-MOFs via an ultrasonic method. The optimal amorphous FeNiCu-MOF is found to be able to supply a current density of 10 mA cm-2 merely at a low overpotential of 260 mV with a small Tafel slope of 61 mV dec-1 and exhibits high durability over 24 h. Moreover, density functional theory (DFT) calculations show that the Fe atoms are the main active sites for the OER in the FeNiCu-MOF. This work shows that amorphous ternary MOFs have great potential for application in OER electrocatalysts due to the multiple synergistic effects and amorphous MOF structures.

Quantitative analysis of particle distributions by comparison with simulations.

In characterization of metal nanoparticle doped spherical composites, the two-dimensional nature of transmission electron microscopy (TEM) images leads to ambiguities about the true location of the nanoparticles. Walking-in of simulated projections in comparison with actual TEM images leads to quantitative results such as location-dependent particle sizes and particle number density. This method takes advantage of the strength of fuzzy neural network computations via the human hunter-gatherer's visual system's evolved superiority while still allowing quantitative results by use of exact numerical simulations.

Size-dependent nonmagnetic surface layer of ferromagnetic nanoparticles.

Based on the size-dependent melting temperature, we have deduced the analytic models for size-dependent Curie temperature Tc and saturation magnetization at room temperature Ms for ferromagnetic nanocrystals. The Tc(D) and Ms(D) functions decrease with decreasing size D. Agreements between model predictions and the corresponding experimental results enable us to determine the size-dependent thickness of nonmagnetic surface layer phi(D) and lambda(D) in describing Tc(D) and Ms(D), respectively. It is found that the surface layer should be an intrinsic property of ferromagnetic crystals since the nonmagnetic surface layer exists in the whole size range rather than vanishes as D approaches infinite.

Overview of transition metal-based composite materials for supercapacitor electrodes.

Supercapacitors (SCs) can bridge the gap between batteries and conventional capacitors, playing a critical role as an efficient electrochemical storage device in intermittent renewable energy sources. Transition metal-based electrode materials have been investigated extensively as a class of electrode materials for SC application, but they have some limitations due to the sluggish ion/electron diffusion and inferior electronic conductivity, restricting their electrochemical performances towards energy storage. Developing advanced transition metal-based electrode materials is crucial for high energy density along with high specific power and fast charging/discharging rates towards high performance SCs. In this review, we highlight the state-of-the-art of transition metal-based electrode materials (transition metal oxides and their composites, transition metal sulfides and their composites, and transition metal phosphides and their composites), focusing on specific morphologies, components, and power characteristics. We also provide future prospects for transition metal-based electrode materials for SCs and hope this review will shed light on the achievement of higher performance and hold great promise in vast applications for future energy storage and conversion.

Iron oxides nanobelt arrays rooted in nanoporous surface of carbon tube textile as stretchable and robust electrodes for flexible supercapacitors with ultrahigh areal energy density and remarkable cycling-stability.

We report a significant advance toward the rational design and fabrication of stretchable and robust flexible electrodes with favorable hierarchical architectures constructed by homogeneously distributed α-Fe2O3 nanobelt arrays rooted in the surface layer of nanoporous carbon tube textile (NPCTT). New insight into alkali activation assisted surface etching of carbon and in-situ catalytic anisotropic growth is proposed, and is experimentally demonstrated by the synthesis of the Fe2O3 nanobelt arrays/NPCTT. The Fe2O3/NPCTT electrode shows excellent flexibility and great stretchability, especially has a high specific areal capacitance of 1846 mF cm-2 at 1 mA cm-2 and cycling stability with only 4.8% capacitance loss over 10,000 cycles at a high current density of 20 mA cm-2. A symmetric solid-state supercapacitor with the Fe2O3/NPCTT achieves an operating voltage of 1.75 V and a ultrahigh areal energy density of 176 µWh cm-2 (at power density of 748 µW cm-2), remarkable cycling stability, and outstanding reliability with no capacity degradation under repeated large-angle twisting. Such unique architecture improves both mechanical robustness and electrical conductivity, and allows a strong synergistic attribution of Fe2O3 and NPCTT. The synthetic method can be extended to other composites such as MnO nanosheet arrays/NPCTT and Co3O4 nanowire arrays/NPCTT. This work opens up a new pathway to the design of high-performance devices for wearable electronics.