Construction of unique NiCoP/FeNiCoP hollow heterostructured ellipsoids with modulated electronic structure for enhanced overall water splitting.

Transition metal phosphides have been demonstrated to be promising non-noble catalysts for water splitting, yet their electrocatalytic performance is impeded by unfavorable free energies of adsorbed intermediates. The achievement of nanoscale modulation in morphology and electronic states is imperative for enhancing their intrinsic electrocatalytic activity. Herein, we propose a strategy to expedite the water splitting process over NiCoP/FeNiCoP hollow ellipsoids by modulating the electronic structure and d-band center. These unique phosphorus (P) vacancies-rich ellipsoids are synthesized through an ion-exchange reaction between uniform NiCo-nanoprisms and K3[Fe(CN)6], followed by NaH2PO2-assisted phosphorization under N2 atmosphere. Various characterizations reveals that the titled catalyst possesses high specific surface area, abundant porosity, and accessible inner surfaces, all of which are beneficial for efficient mass transfer and gas diffusion. Moreover, density functional theory (DFT) calculations further confirms that the NiCoP/FeNiCoP heterojunction associated with P vacancies regulate the electronic structures of d-electrons and p-electrons of Co and P atoms, respectively, resulting in a higher desorption efficiency of adsorbed H* intermediates with a lower energy barrier for water splitting. Due to the aforementioned advantages, the resultant NiCoP/FeNiCoP hollow ellipsoids exhibit remarkably low overpotentials of 45 and 266 mV for hydrogen and oxygen evolution reaction to achieve the current densities of 10 and 50 mA cm-2, respectively. This work not only reports the synthesis of a hollow double-shell structure of NiCoP/FeNiCoP but also introduces a novel strategy for constructing a multifunctional electrocatalyst for water splitting.

Power-to-Noise Optimization in the Design of Neural Recording Amplifier Based on Current Scaling, Source Degeneration Resistor, and Current Reuse.

This article presents the design of a low-power, low-noise neural signal amplifier for neural recording. The structure reduces the current consumption of the amplifier through current scaling technology and lowers the input-referred noise of the amplifier by combining a source degeneration resistor and current reuse technologies. The amplifier was fabricated using a 0.18 µm CMOS MS RF G process. The results show the front-end amplifier exhibits a measured mid-band gain of 40 dB/46 dB and a bandwidth ranging from 0.54 Hz to 6.1 kHz; the amplifier's input-referred noise was measured to be 3.1 µVrms, consuming a current of 3.8 µA at a supply voltage of 1.8 V, with a Noise Efficiency Factor (NEF) of 2.97. The single amplifier's active silicon area is 0.082 mm2.

P-doped Co3S4/NiS2 heterostructures embedded in N-doped carbon nanoboxes: Synergistical electronic structure regulation for overall water splitting.

Water splitting using transition metal sulfides as electrocatalysts has gained considerable attention in the field of renewable energy. However, their electrocatalytic activity is often hindered by unfavorable free energies of adsorbed hydrogen and oxygen-containing intermediates. Herein, phosphorus (P)-doped Co3S4/NiS2 heterostructures embedded in N-doped carbon nanoboxes were rationally synthesized via a pyrolysis-sulfidation-phosphorization strategy. The hollow structure of the carbon matrix and the nanoparticles contained within it not only result in a high specific surface area, but also protects them from corrosion and acts as a conductive pathway for efficient electron transfer. Density functional theory (DFT) calculations indicate that the introduction of P dopants improves the conductivity of NiS2 and Co3S4, promotes the charge transfer process, and creates new electrocatalytic sites. Additionally, the NiS2-Co3S4 heterojunctions can enhance the adsorption efficiency of hydrogen intermediates (H*) and lower the energy barrier of water splitting via a synergistic effect with P-doping. These characteristics collectively enable the titled catalyst to exhibit excellent electrocatalytic activity for water splitting in alkaline medium, requiring only small overpotentials of 150 and 257 mV to achieve a current density of 10 mA cm-2 for hydrogen and oxygen evolution reactions, respectively. This work sheds light on the design and optimization of efficient electrocatalysts for water splitting, with potential implications for renewable energy production.

Amorphous and defective Co-P-O@NC ball-in-ball hollow structure for highly efficient electrocatalytic overall water splitting.

Electrochemical water splitting using hollow and defect-rich catalysts has emerged as a promising strategy for efficient hydrogen production. However, the rational design and controllable synthesis of such catalysts with intricate morphology and composition present significant challenges. Herein, we propose a template-engaged approach to fabricate a novel ball-in-ball hollow structure of Co-P-O@N-doped carbon with abundant oxygen vacancies. The synthesis process involves the preparation of uniform cobalt-glycerate (Co-gly) polymer microspheres as precursors, followed by surface coating with ZIF-67 layer, adjustable chemical etching by phytic acid, and controllable pyrolysis at high temperature. The resulting ball-in-ball structure offers a large number of accessible active sites and high redox reaction centers, facilitating efficient charge transport, mass transfer, and gas evolution, which are beneficial for the acceleration of electrocatalytic reaction. Additionally, density functional theory (DFT) calculations indicate that the incorporation of oxygen and the presence of Co-P dangling bonds in CoP significantly enhance the adsorption of oxygenated species, leading to improved intrinsic electroactivity at the single-site level. As a sequence, the titled catalyst exhibits remarkable electrocatalytic activity and stability for water splitting in alkaline media. Notably, it only requires a low overpotential of 283 mV to achieve a current density of 10 mA cm-2 for the oxygen evolution reaction. This work may provide some new insights into the design of complex hollow structures of phosphides with abundant defects for energy conversion.

Optimized Solid Electrolyte Interphase and Solvation Structure of Potassium Ions in Carbonate Electrolytes for High-Performance Potassium Metal Batteries.

The introduction of electrolyte additives is one of the most potential strategies to improve the performance of potassium metal batteries (PMBs). However, designing an additive that can alter the K+ solvation shell and essentially inhibit K dendrite remains a challenge. Herein, the amyl-triphenyl-phosphonium bromide was introduced as an additive to build a stable solid electrolyte interphase layer. The amyl-TPP cations can form a cation shielding layer on the metal surface during the nucleation stage, preventing K+ from gathering at the tip to form K dendrites. Besides, the cations can be preferentially reduced to form Kx Py with fast K+ transport kinetics. The Br- anions, as Lewis bases with strong electronegativity, can not only coordinate the Lewis acid pentafluoride to inhibit the formation of HF, but also change the K+ solvation structure to reduce solvent molecules in the first solvation structure. Therefore, the symmetrical battery exhibits a low deposition overpotential of 123 mV at 0.1 mA cm-2 over 4200 h cycle life. The full battery, paried with a perylene-tetracarboxylic dianhydride (PTCDA) cathode, possesses a cycle life of 250 cycles at 2 C and 81.9% capacity retention. This work offers a reasonable electrolyte design to obtain PMBs with long-term stablity and safety.

Facile and High-Efficiency Chemical Presodiation Strategy on the SnS2/rGO Composite Anode for Stable Sodium-Ion Batteries.

SnS2/reduced graphite oxide (rGO) composite materials show great potential as high-performance anode candidates in sodium-ion batteries (SIBs) owing to their high specific capacities and power densities. However, the repeated formation/decomposition of the solid electrolyte interface (SEI) layer around composite anodes usually consumes additional sodium cations, resulting in poor Coulombic efficiency and decreasing specific capacity upon cycling. Therefore, in order to compensate for the large irreversible sodium loss of the SnS2/rGO anode, this study has proposed a facile strategy by implementing organic solutions of sodium-biphenyl/tetrahydrofuran (Na-Bp/THF) and sodium-naphthylamine/dimethoxyethane (Na-Naph/DME) as chemical presodiation reagents. Particularly, the storage stability of Na-Bp/THF and Na-Naph/DME in ambient air accompanied by their presodiation behavior on the SnS2/rGO anode has been investigated, and both reagents exhibited desirable ambient air-tolerant storage stability with favorable sodium supplement effects even after 20 days of storage. More importantly, the initial Coulombic efficiency (ICE) of SnS2/rGO electrodes could be controllably increased by immersing in a presodiation reagent for different durations. Consequently, with a facile chemical presodiation strategy of immersion in Na-Bp/THF solution for only 3 min in ambient air, the presodiated SnS2/rGO anode has exhibited an outstanding electrochemical performance with a high ICE of 95.6% as well as an ultrahigh specific capacity of 879.2 mAh g-1 after 300 cycles (83.5% of its initial capacity), highly superior to the pristine SnS2/rGO anode. This efficient and scalable presodiation strategy provides a new avenue for the prevailing application of other anode candidates in high-energy SIBs.

Construction of Fe-doped NiS-NiS2 Heterostructured Microspheres Via Etching Prussian Blue Analogues for Efficient Water-Urea Splitting.

Developing efficient and robust non-precious-metal-based catalysts to accelerate electrocatalytic reaction kinetics is crucial for electrochemical water-urea splitting. Herein, Fe-doped NiS-NiS2 heterostructured microspheres, an electrocatalyst, are synthesized via etching Prussian blue analogues following a controlled annealing treatment. The resulting microspheres are constructed by mesoporous nanoplates, granting the virtues of large surface areas, high structural void porosity, and accessible inner surface. These advantages not only provide more redox reaction centers but also strengthen structural robustness and effectively facilitate the mass diffusion and charge transport. Density functional theory simulations validate that the Fe-doping improves the conductivity of nickel sulfides, whereas the NiS-NiS2 heterojunctions induce interface charge rearrangement for optimizing the adsorption free energy of intermediates, resulting in a low overpotential and high electrocatalytic activity. Specifically, an ultralow overpotential of 270 mV at 50 mA cm-2 for the oxygen evolution reaction (OER) is achieved. After adding 0.33 M urea into 1 M KOH, Fe-doped NiS-NiS2 obtains a strikingly reduced urea oxidation reaction potential of 1.36 V to reach 50 mA cm-2 , around 140 mV less than OER. This work provides insights into the synergistic modulation of electrocatalytic activity of non-noble catalysts for applications in energy conversion systems.

Encapsulating Fe2 O3 Nanotubes into Carbon-Coated Co9 S8 Nanocages Derived from a MOFs-Directed Strategy for Efficient Oxygen Evolution Reactions and Li-Ions Storage.

The development of high-efficiency, robust, and available electrode materials for oxygen evolution reaction (OER) and lithium-ion batteries (LIBs) is critical for clean and sustainable energy system but remains challenging. Herein, a unique yolk-shell structure of Fe2 O3 nanotube@hollow Co9 S8 nanocage@C is rationally prepared. In a prearranged sequence, the fabrication of Fe2 O3 nanotubes is followed by coating of zeolitic imidazolate framework (ZIF-67) layer, chemical etching of ZIF-67 by thioacetamide, and eventual annealing treatment. Benefiting from the hollow structures of Fe2 O3 nanotubes and Co9 S8 nanocages, the conductivity of carbon coating and the synergy effects between different components, the titled sample possesses abundant accessible active sites, favorable electron transfer rate, and exceptional reaction kinetics in the electrocatalysis. As a result, excellent electrocatalytic activity for alkaline OER is achieved, which delivers a low overpotential of 205 mV at the current density of 10 mA cm-2 along with the Tafel slope of 55 mV dec-1 . Moreover, this material exhibits excellent high-rate capability and excellent cycle life when employed as anode material of LIBs. This work provides a novel approach for the design and the construction of multifunctional electrode materials for energy conversion and storage.

Hierarchical CoFe LDH/MOF nanorods array with strong coupling effect grown on carbon cloth enables efficient oxidation of water and urea.

Oxygen evolution reaction (OER) and urea oxidation reaction (UOR) play important roles in the fields of hydrogen energy production and pollution treatment. Herein, a facile one-step chemical etching strategy is provided for fabricating one-dimensional hierarchical nanorods array composed of CoFe layered double hydroxide (LDH)/metal-organic frameworks (MOFs) supported on carbon cloth as efficient and stable OER and UOR catalysts. By precisely controlling the etching rate, the ligands from Co-MOFs are partially removed, the corresponding metal centers then coordinate with hydroxyl ions to generate ultrathin amorphous CoFe LDH nanosheets. The resultant CoFe LDH/MOFs catalyst possesses large active surface area, enhanced conductivity and extended electron/mass transfer channels, which are beneficial for catalytic reactions. Additionally, the intimate contact between CoFe LDH and MOFs modulates the local electronic structure of the catalytic active site, leading to enhanced adsorption of oxygen-containing intermediates to facilitate fast electrocatalytic reaction. As a result, the optimized CoFe LDH/MOF-0.06 exhibits superior OER activity with a low overpotential of 276 at a current density of 10 mA cm-2with long-term durability. Additionally, it merely requires a voltage of 1.45 V to obtain 10 mA cm-2in 1 M KOH solution with 0.33 urea and is 56 mV lower than the one in pure KOH. The work presented here may hew out a brand-new route to construct multi-functional electrocatalysts for water splitting, CO2reduction, nitrogen reduction reactions and so on.

Integrated Design of Hierarchical CoSnO3@NC@MnO@NC Nanobox as Anode Material for Enhanced Lithium Storage Performance.

Transition-metal oxides (TMOs) are potential candidates for anode materials of lithium-ion batteries (LIBs) due to their high theoretical capacity (∼1000 mA h/g) and enhanced safety from suppressing the formation of lithium dendrites. However, the poor electron conductivity and the large volume expansion during lithiation/delithiation processes are still the main hurdles for the practical usage of TMOs as anode materials. In this work, the CoSnO3@NC@MnO@NC hierarchical nanobox (CNMN) is then proposed and fabricated to solve those issues. The as-prepared nanobox contains hollow cubic CoSnO3 as a core and dual N-doped carbon-"sandwiched" MnO particles as a shell. As anode materials of LIBs, the hollow and carbon interlayer structures effectively accommodate the volume expansion while dual active TMOs of CoSnO3 and MnO efficiently increase the specific capacity. Notably, the dual-layer structure of N-doped carbons plays a critical functional role in the incorporated composites, where the inner layer serves as a reaction substrate and a spatial barrier and the outer layer offers electron conductivity, enabling more effective involvement of active anode materials in lithium storage, as well as maintaining their high activity during lithium cycling. Subsequently, the as-prepared CNMN exhibits a high specific capacity of 1195 mA h/g after the 200th cycle at 0.1C and an excellent stable reversible capacity of about 876 mA h/g after the 300th cycle at 0.5C with only 0.07 mA h/g fade per cycle after 300 cycles. Even after a 250 times fast charging/discharging cycle both at 5C, it still retains a reversible capacity of 422.6 mA h/g. We ascribe the enhanced lithium storage performances to the novel hierarchical architectures achieved from the rational design.

Structural phase transformation from SnS2/reduced graphene oxide to SnS/sulfur-doped graphene and its lithium storage properties.

In this work, we demonstrate an interesting structural phase transition from SnS2/reduced graphene oxide to SnS/sulfur-doped graphene at a moderate calcination temperature of 500 °C under an inert atmosphere. It is discovered that SnS2 chemically bound to rGO with a weakened C-S bond is easier to break and decompose into SnS, whereas it is difficult for pure-phase crystalline SnS2 to experience phase transformation at this temperature. Moreover, the thin-layered structure of SnS2 and rGO is an important factor for the effective doping of the dissociated Sx into graphene. Density functional theory calculations also reveal the feasibility of the structural phase transition process. Morphology characterization shows that partial SnS maintains the original nanosheet structure (∼100 nm) and the others are decomposed into tiny nanoparticles (10-20 nm). A high S-doping amount reduces the irreversible lithium storage sites on graphene, and the first coulombic efficiency is as high as 81.7%. In addition, thin-layered and small-sized SnS can alleviate the structural damage caused by volume expansion and shrinkage; therefore, a high specific capacity of 893.9 mA h g-1 is retained after 100 cycles.

Well-defined CoSe2@MoSe2 hollow heterostructured nanocubes with enhanced dissociation kinetics for overall water splitting.

Hollow heterostructures have tremendous advantages in electrochemical energy storage and conversion areas due to their unique structure and composition characteristics. Here, we report the controlled synthesis of hollow CoSe2 nanocubes decorated with ultrathin MoSe2 nanosheets (CoSe2@MoSe2) as an efficient and robust bifunctional electrocatalyst for overall water splitting in a wide pH range. It is found that integrating ultrathin MoS2 nanosheets with hollow CoSe2 nanocubes can provide abundant active sites, promote electron/mass transfer and bubble release and facilitate the migration of charge carriers. Additionally, the surface electron coupling in the heterostructures enables it to serve as a source of sites for H+ and/or OH- adsorption, thus reducing the activation barrier for water molecules adsorption and dissociation. As a result, the title compound, CoSe2@MoSe2 hollow heterostructures, exhibits an overpotential of 183 mV and 309 mV at a current density of 10 mA cm-2 toward hydrogen evolution reactions and oxygen evolution reactions in 1.0 M KOH, respectively. When applied as both cathode and anode for overall water splitting, a low battery voltage of 1.524 V is achieved along with excellent stability for at least 12 h. This work provides a new idea for the design and synthesis of high-performance catalysts for electrochemical energy storage and conversion.

Sandwich-like SnS2/Graphene/SnS2 with Expanded Interlayer Distance as High-Rate Lithium/Sodium-Ion Battery Anode Materials.

SnS2 materials have attracted broad attention in the field of electrochemical energy storage due to their layered structure with high specific capacity. However, the easy restacking property during charge/discharge cycling leads to electrode structure instability and a severe capacity decrease. In this paper, we report a simple one-step hydrothermal synthesis of SnS2/graphene/SnS2 (SnS2/rGO/SnS2) composite with ultrathin SnS2 nanosheets covalently decorated on both sides of reduced graphene oxide sheets via C-S bonds. Owing to the graphene sandwiched between two SnS2 sheets, the composite presents an enlarged interlayer spacing of ∼8.03 Šfor SnS2, which could facilitate the insertion/extraction of Li+/Na+ ions with rapid transport kinetics as well as inhibit the restacking of SnS2 nanosheets during the charge/discharge cycling. The density functional theory calculation reveals the most stable state of the moderate interlayer spacing for the sandwich-like composite. The diffusion coefficients of Li/Na ions from both molecular simulation and experimental observation also demonstrate that this state is the most suitable for fast ion transport. In addition, numerous ultratiny SnS2 nanoparticles anchored on the graphene sheets can generate dominant pseudocapacitive contribution to the composite especially at large current density, guaranteeing its excellent high-rate performance with 844 and 765 mAh g-1 for Li/Na-ion batteries even at 10 A g-1. No distinct morphology changes occur after 200 cycles, and the SnS2 nanoparticles still recover to a pristine phase without distinct agglomeration, demonstrating that this composite with high-rate capabilities and excellent cycle stability are promising candidates for lithium/sodium storage.

Porous ZnO/Co3O4/N-doped carbon nanocages synthesized via pyrolysis of complex metal-organic framework (MOF) hybrids as an advanced lithium-ion battery anode.

Metal oxides have a large storage capacity when employed as anode materials for lithium-ion batteries (LIBs). However, they often suffer from poor capacity retention due to their low electrical conductivity and huge volume variation during the charge-discharge process. To overcome these limitations, fabrication of metal oxides/carbon hybrids with hollow structures can be expected to further improve their electrochemical properties. Herein, ZnO-Co3O4 nanocomposites embedded in N-doped carbon (ZnO-Co3O4@N-C) nanocages with hollow dodecahedral shapes have been prepared successfully by the simple carbonizing and oxidizing of metal-organic frameworks (MOFs). Benefiting from the advantages of the structural features, i.e. the conductive N-doped carbon coating, the porous structure of the nanocages and the synergistic effects of different components, the as-prepared ZnO-Co3O4@N-C not only avoids particle aggregation and nanostructure cracking but also facilitates the transport of ions and electrons. As a result, the resultant ZnO-Co3O4@N-C shows a discharge capacity of 2373 mAh g-1 at the first cycle and exhibits a retention capacity of 1305 mAh g-1 even after 300 cycles at 0.1 A g-1. In addition, a reversible capacity of 948 mAh g-1 is obtained at a current density of 2 A g-1, which delivers an excellent high-rate cycle ability.

Construction of SnS2-SnO2 heterojunctions decorated on graphene nanosheets with enhanced visible-light photocatalytic performance.

Heterostructures formed by the growth of one kind of nanomaterial in/on another have attracted increasing attention due to their microstructural characteristics and potential applications. In this work, SnS2-SnO2 heterostructures were successfully prepared by a facile hydrothermal method. Due to the enhanced visible-light absorption and efficient separation of photo-generated holes and electrons, the SnS2-SnO2 heterostructures display excellent photocatalytic performance for the degradation of rhodamine (RhB) under visible-light irradiation. Additionally, it is found that the introduction of graphene into the heterostructures further improved photocatalytic activity and stability. In particular, the optimized SnS2-SnO2/graphene photocatalyst can degrade 97.1% of RhB within 60 min, which is about 1.38 times greater than that of SnS2-SnO2 heterostructures. This enhanced photocatalytic activity could be attributed to the high surface area and the excellent electron accepting and transporting properties of graphene, which served as an acceptor of the generated electrons to suppress charge recombination. These results provide a new insight for the design and development of hybrid photocatalysts.

Environmentally benign synthesis of Co3O4-SnO2 heteronanorods with efficient photocatalytic performance activated by visible light.

One-dimensional (1D) heterostructured photocatalysts with controllable texture properties and compositions have attracted increasing interest owing to their unique optical, structural, and electronic advantages. Herein, 1D Co3O4-SnO2 heteronanorods were rationally designed and synthesized through a facile solution-based approach. Benefiting from both of their heterostructural and compositional characteristics, the resulting Co3O4-SnO2 heteronanorods exhibit high photocatalytic performance for the degradation of Rhodamine B (RhB) under visible-light irridation. In particular, the photocatalyst with a Co3O4/SnO2 mass ratio of 1:1 provides the best photocatalytic performance, which can degrade 90% RhB within 120 min. Besides, several reaction parameters affecting RhB degradation, such as churning time, calcination temperature and pH value, are investigated in detail. The enhanced photocatalytic activity can be attributed to the broadening of absorption spectrum to visible-light regions and the efficient charge separation of photogenerated electron-hole pairs due to the formed p-n heterojunctions. The strategy reported here can be able to expand to fabricate other heterostructured photocatalysts for practical applications in the fields of photocatalysis, water splitting, and solar cells.

Construction of Ni-doped SnO2-SnS2 heterojunctions with synergistic effect for enhanced photodegradation activity.

Construction of heterostructures with proper band alignment and effective transport and separation of photogenerated charges is highly expected for photocatalysis. In this work, Ni-doped SnO2-SnS2 heterostructures (NiSnSO) are simply prepared by thermal oxidation of Ni-doped hierarchical SnS2 microspheres in the air. When applied for the photodegradation of organic contaminants, these NiSnSO exhibit excellent catalytic performance and stability due to the following advantages: (1) Ni doping leads to the enhancement of light harvesting of SnS2 in the visible light regions; (2) the formed heterojunctions promote the transport and separation of photogenerated electrons from SnS2 to SnO2; (3) Ni-SnO2 quantum dots facilitate the enrichment of reactants, provide more reactive centers and accelerate product diffusion in the reactive centers; (4) the SnS2 hierarchical microspheres constituted by nanoplates provide abundant active sites, high structural void porosity and accessible inner surface to faciliate the catalytic reactions. As a result, the optimized NiSnSO can photodegrade 92.7% methyl orange within 80 min under the irradiation of simulated sunlight, greatly higher than those of pure SnS2 (29.8%) and Ni-doped SnS2 (52.1%). These results reveal that the combination of heteroatom doping and heterostructure fabrication is a very promising strategy to deliver nanomaterials for effectively photocatalytic applications.

Sandwiched spherical tin dioxide/graphene with a three-dimensional interconnected closed pore structure for lithium storage.

Low reversion of lithium oxide (Li2O) and the tin (Sn) coarsening causing irreversible capacity loss is the main reason for the poor cycle performance in tin dioxide (SnO2) based composites. In this research, a novel sandwiched spherical tin dioxide/graphene with a three-dimensional interconnected closed pore structure is synthesized. The microstructural characterization shows that the spherical graphene with submicron sized diameters interconnects with each other forming an interconnected flexible conductive network, whereas a large number of SnO2 nanoparticles (approximately 5 nm) are limited homogeneously in between the interlayers of the sphere-like graphene shell. The sandwich structure of the SnO2/graphene and the closed graphene sphere can provide double protection for the SnO2. When it is used as an anode material for energy storage, the generated Li2O can remain in close contact with Sn to make the conversion reaction (SnO2 + 4Li+ + 2e- ↔ Sn + Li2O) highly reversible in situ and the reversibility even does not diminish markedly after 100 cycles. A high reversible specific capacity of 914.8 mA h g-1 is expressed in the sandwiched spherical SnO2/graphene composite at 100 mA g-1 after 100 cycles, which is significantly higher than that of a SnO2/graphene aerogel with an open pore structure.

Encapsulating CoS2-CoSe2 heterostructured nanocrystals in N-doped carbon nanocubes as highly efficient counter electrodes for dye-sensitized solar cells.

Designing low-cost electrocatalysts combining the features of outstanding catalytic activity, excellent electrical conductivity, and high chemical stability remains a critical challenge for the large-scale fabrication of dye-sensitized solar cells (DSSCs). Here we report the controlled synthesis of CoS2-CoSe2 heterostructured nanocrystals encapsulated in N-doped carbon hollow nanocubes (CoS2-CoSe2@NC) through simultaneous sulfurization and selenization of polydopamine coated Prussian blue analogs. Benefiting from both structural and compositional characteristics, namely, the synergistic effect of CoS2-CoSe2 heterojunctions, the conductive N-doped carbon coating and the porous structure of the nanocubes, the resultant CoS2-CoSe2@NC nanocubes exhibit excellent electrocatalytic activity and cycling stability toward the generation of I3- ions in DSSCs. A typical device achieves a high power conversion efficiency (PCE) of 8.45% under AM1.5G illumination (100 mW cm-2), superior to that of a standard Pt-based device (8.07%). These results demonstrate that the as-synthesized CoS2-CoSe2@NC nanocubes are promising alternatives to Pt in DSSCs. The work represented here not only provides a promising strategy to design efficient and robust CE catalysts, but also can be extended for synthesizing other novel metal sulfide/selenide hybrid materials for applications in the fields of energy conversion and storage.

Prussian blue-derived synthesis of uniform nanoflakes-assembled NiS2 hierarchical microspheres as highly efficient electrocatalysts in dye-sensitized solar cells.

It's urgent and challenging to explore cost-effective and robust electrocatalyst in the development of large-scaled dye-sensitized solar cells (DSSCs). In this work, we develop a novel strategy to prepare 3D hierarchical NiS2 microspheres constructed by nanoflakes through a facile chemical etching/anion exchange reaction. Nickel-cobalt Prussian blue analogous (PBA) nanocubes and (NH4)2S are employed to initially produce uniform γ-NiOOH/NiS x hierarchical microspheres, which were then converted to uniform 3D hierarchical NiS2 microspheres by a controlled annealing treatment. Due to their favorable structural features, the as-obtained NiS2 hierarchical microspheres possess large surface areas, high structural void porosity and accessible inner surface. All of these advantages facilitate the mass diffusion and charge transport between electrolyte and counter electrode material. As a result, the titled NiS2 hierarchical microspheres exhibit excellent electrocatalytic activity toward the reduction of I3 - ions in DSSCs. A typical DSSC with NiS2 achieves an impressive power conversion efficiency of 8.46% under AM1.5G illumination (100 mW cm-2), higher than that of pyrolysis Pt electrodes (8.04%). Moreover, the fast activity onset and relatively long stability further demonstrate that the NiS2 hierarchical microspheres are promising alternatives to Pt in DSSCs.