Non-noble metal-transition metal oxide materials for electrochemical energy storage

Interfacial engineering on platinum group metals (PGMs) nanostructures has been intensively explored owing to the intriguing performance enhancement for electrocatalytic reactions. The interfacial electrocatalysts possess remarkable structural advantages including distinctive electronic structure, favorable electron mobility, and improved mechanical stability. In this review, recent research progress in PGMs-based interfacial catalysts for advanced electrocatalysis is summarized. Firstly, we introduce the classification of PGMs-based interfacial catalysts based on typical interface categories including metal/metal, metal/metal compound, and metal/support interfaces. Thereafter, we emphasize the strategies for the fabrication of PGMs-based interfacial catalysts involving thermal annealing strategy, electrochemical treatment, and seed-mediated growth. In addition, an overview of the promotion effect of PGMs-based interfacial catalysts on electrocatalytic performance is elaborated in terms of electronic interaction, strain effect, and synergistic effect. Finally, we propose the existing challenges and further development of interfacial catalysts from the aspects of mechanism exploration for the formation of interface and reaction mechanism investigation. 

Interfacial Engineering of Platinum Group Metals Electrocatalysts for Advanced Electrocatalysis

Co3O4 has been widely investigated as a promising candidate anode material for lithium-ion batteries. We report on the porous Co3O4 column synthesized via a simple liquid phase method for reversible electrochemical lithium storage. The porous column structures are constructed by nanoparticles of 0.5 μm -2 μm in diameter. The porous structure improves the structure stability, shortens the diffusion path of ion/electron, and stabilize the interface of the electrolyte and active material. Impressively, a high discharge capacity of 992 mAh g−1 is obtained at 200 mA g−1 after 100 cycles. This implies the as-synthesized porous Co3O4 column demonstrates remarkable potential as an excellent anode material for lithium-ion batteries.

Porous Co3O4 column as a high-performance Lithium anode material

A well-designed material comprising Co3O4 nanoparticles embedded in one-dimensional porous nitrogen-doped carbon nanofibers (Co3O4@NCNFs) is prepared through electrospinning, immersion in a cobalt-containing zeolitic imidazolate frameworks (ZIF-67/ZIF-8) and follows by calcination and oxidation. The resultant sample displays a high discharge capacity of 332 mAh g−1 after 200 cycles at a current density of 100 mA g−1 and an outstanding long-term performance (181 mAh g−1 at 1 A g−1 over 1000 cycles), which is better than the reported high current density for Co3O4-based materials. The excellent electrochemical performance is attributed to the nanostructure comprising Co3O4 nanoparticles homogeneously embedded in nitrogen-doped carbon nanofibers, which can effectively inhibit the aggregation of Co3O4 nanoparticles, accommodate the volume change during charge and discharge processes and provide high electrical conductivity of the electrode. This work provides a facile method to obtain one-dimensional oxide composites with high electrochemical performance using a new metal-organic framework as the sacrificial template.

Co3O4 nanoparticles embedded in 1D porous N-doped carbon nanofibers derived from ZIFs for high-capacity sodium-ion batteries

Site-selective chiral growth of anisotropic nanoparticles is of great importance to realize the plasmonic nanostructures with delicate geometry and desired optical chirality; however, it remains largely unexplored. This work demonstrates a controlled site-selective chiral growth system based on the seed-mediated growth of anisotropic Au triangular nanoplates. The site-selective chiral growth involves two distinct underlying pathways, faceted growth and island growth, which are interswitchable upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. The pathway switch governs the geometric and chirality evolution of Au triangular nanoplates, giving rise to tailorable circular dichroism spectra. The ability to tune the optical chirality in a controlled manner by manipulating the site-selective chiral growth pathway opens up a promising strategy for exploiting chiral metamaterials with increasing architectural complexity in chiroptical applications.

Site-Selective Chiral Growth of Anisotropic Au Triangular Nanoplates for Tuning the Optical Chirality.

Surface ligands play critical roles in nano-synthesis and thus it is of great importance in expanding the scope of suitable ligands. In this work, we explore phenynyl ligands in modulating the Au-Au interface when growing Au domains on Au seeds. A patchy growth mode is observed where the emerging islands are flat-laying with holes and branches. This growth mode is distinctively different from the conventional facet-controlled growth using weak ligands, and the non-wetting island growth using strong ligands. Through manipulating the molecular structure and the packing of the phenynyl ligands on the Au seeds, the overgrown Au domains are continuously tuned, from patches to islands, extending the plasmon absorption peak into the near-infrared spectral range. We believe that the new ligand with intermediate affinity and the unusual growth mode would expand the control in both synthesis and application. 

/pdf/the-patchy-growth-mode-modulation-of-the-au-au-interface-via-3d468fp1.pdf

The patchy growth mode: Modulation of the Au-Au interface via phenynyl ligands

To develop a long cycle life and good rate capability electrode, tricobalt tetraoxide (Co3O4) nanowires with hierarchical structure composed of ultra-small nanoparticles are directly grown on nickel foam current collector. The size of the nanoparticles is about 10 nm. They are synthesized via a facile hydrothermal route followed by calcination and evaluated as an anode of binder-free lithium-ion batteries. The concentration of reactant and duration of reaction are considered as important synthesis parameters. Co3O4 nanowires electrode exhibits excellent electrochemical performance including outstanding cycling performance, a high reversible discharge capacity and good rate capability, owing to the hierarchical architecture composed of micro-/nanostructures. After rate capacity performance measurements, a capacity of 1060.1 mAh·g−1 is retained. At a rate of 500 mA·g−1, a reversible capacity remains stable as high as 957 mAh·g−1. The enhanced performance is owing to the hierarchical structure of the nanowires and good contact with the substrate which can make electrons efficiently transport from Co3O4 nanowires to the current collectors. The mesoporous structure may facilitate the lithium ion diffusion and mitigate the internal mechanical stress induced by volume variations of the electrode upon cycling, which lead to outstanding electrochemical performance.

Hierarchical Co3O4 Nanowires as Binder Free Electrodes for Reversible Lithium Storage

Continuous tuning the wetting growth of Au on Se nanoparticles.

The invention belongs to the field of preparation and application of inorganic materials and particularly relates to a preparation method and application of porous cobalt oxide. The method comprises the specific steps that 1, cobalt salt and organic acid are dissolved in a mixed solution of N,N-dimethylformamide and absolute ethyl alcohol, and stirring is carried out to form a uniformly-mixed solution; 2, the uniformly-mixed solution obtained in step 1 is put in a hydrothermal reaction kettle to be sealed for a reaction at the temperature of 150-200 DEG C for 6-24 h, the product is naturally cooled to room temperature, washed and dried, and a precursor of cobalt oxide is obtained; 3, the precursor obtained in step 2 is calcined in the air atmosphere and cooled to room temperature, and the porous cobalt oxide is obtained. The preparation method is simple, easy to operate and good in repeatability; porous cobalt oxide particles prepared through the method are uniform, large in specific surface area and high in purity, and the prepared cobalt oxide has good application prospects in the field of lithium ion battery electrode materials.

Preparation method and application of porous cobalt oxide

Hybrid nanostructures have garnered considerable interest because of their fascinating properties owing to the hybridization of materials and their structural varieties. In this study, we report the synthesis of [Au@Rh(OH)3]-Au island heterostructures using a seed-mediated sequential growth method. Through the thiol ligand-mediated interfacial energy, Au@Rh(OH)3 core-shell structures with varying shell thicknesses were successfully obtained. On these Au@Rh(OH)3 core-shell seeds, by modulating the diffusion of HAuCl4 in the porous Rh(OH)3 shell, site-specific growth of Au islands on the inner Au core or on the surface of the outer Rh(OH)3 shell was successfully achieved. Consequently, two types of distinct structures, the Au island-on-[Au@Rh(OH)3] dimer and Au island-Au bridge-[Au@Rh(OH)3] dumbbell structures with thin necks were obtained. Further modulations of the growth kinetics led to the formation of Au plate-Au bridge-[Au@Rh(OH)3] heterostructures with larger structural anisotropy. The flexible structural variations were demonstrated to be an effective means of modulating the plasmonic properties; the Au–Au heterostructures exhibited tunable localized surface plasmon resonance in the visible-near-infrared spectral region and can be used as surface-enhanced Raman scattering (SERS) substrates capable of emitting strong SERS signals. This diffusion-controlled growth of Au bridges in the Rh(OH)3 shells (penetrating growth) is an interesting new approach for structural control, which enriches the tool box for colloidal nanosynthesis. This advancement in structural control is expected to create new approaches for colloidal synthesis of sophisticated nanomaterials, and eventually enable their extensive applications in various fields. Graphical Abstract

/pdf/diffusion-controlled-bridging-of-the-au-island-and-au-core-1j0ideuk.pdf

Diffusion-controlled bridging of the Au Island and Au core in Au@Rh(OH)3 core-shell structure

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