Dingguo Xia

A metal–organic framework route to in situ encapsulation of Co@Co3O4@C core@bishell nanoparticles into a highly ordered porous carbon matrix for oxygen reduction

Rational design of non-noble metal catalysts with an electrocatalytic activity comparable or even superior to Pt is extremely important for future fuel cell-based renewable energy devices. Herein, we demonstrate a new concept that a metal–organic framework (MOF) can be used as a novel precursor to in situ encapsulate Co@Co3O4@C core@bishell nanoparticles (NPs) into a highly ordered porous carbon matrix (CM) (denoted as Co@Co3O4@C–CM). The central cobalt ions from the MOF are used as a metal source to produce Co metal cores, which are later transformed into a fancy Co@Co3O4 nanostructure via a controlled oxidation. The most notable feature of our Co@Co3O4@C–CM is that the highly ordered CM can provide much better transport pathways than the disordered pure MOF derived nanostructure that can facilitate the mass transport of O2 and an electrolyte. As a result, the well-designed Co@Co3O4@C–CM derived from the MOF shows almost identical activity but superior stability and methanol tolerance for the ORR relative to the commercial Pt/C in alkaline medium. Our work reports a novel Co@Co3O4@C nanostructure from a MOF for the first time and also reveals the important role of the introduction of a highly ordered carbon matrix into the MOF derived catalyst in enhancing the ORR activity and stability. To the best of our knowledge, the Co@Co3O4@C–CM is the most efficient non-noble metal nanocatalyst ever reported for the ORR.

Facile Synthesis of Ultrasmall CoS2 Nanoparticles within Thin N‐Doped Porous Carbon Shell for High Performance Lithium‐Ion Batteries

Cobalt sulfide (CoS2) is considered one of the most promising alternative anode materials for high-performance lithium-ion batteries (LIBs) by virtue of its remarkable electrical conductivity, high theoretical capacity, and low cost. However, it suffers from a poor cycling stability and low rate capability because of its volume expansion and dissolution of the polysulfide intermediates in the organic electrolytes during the battery charge/discharge process. In this study, a novel porous carbon/CoS2 composite is prepared by using nano metal-organic framework (MOF) templates for high-preformance LIBs. The as-made ultrasmall CoS2 (15 nm) nanoparticles in N-rich carbon exhibit promising lithium storage properties with negligible loss of capacity at high charge/discharge rate. At a current density of 100 mA g(-1), a capacity of 560 mA h g(-1) is maintained after 50 cycles. Even at a current density as high as 2500 mA g(-1), a reversible capacity of 410 mA h g(-1) is obtained. The excellent and highly stable battery performance should be attributed to the synergism of the ultrasmall CoS2 particles and the thin N-rich porous carbon shells derieved from nanosized MOF precusors.

Electro- and Photodriven Phase Change Composites Based on Wax-Infiltrated Carbon Nanotube Sponges

Organic phase change materials are usually insulating in nature, and they are unlikely to directly trigger latent heat storage through an electrical way. Here we report a multifunctional phase change composite in which the energy storage can be driven by small voltages (e.g., 1.5 V) or light illumination with high electro-to-heat or photo-to-thermal storage efficiencies (40% to 60%). The composite is composed of paraffin wax infiltrated into a porous, deformable carbon nanotube sponge; the latter not only acts as a flexible encapsulation scaffold for wax but also maintains a highly conductive network during the phase change process (for both solid and liquid states). Uniform interpenetration between the nanotube network and paraffin wax with high affinity results in enhanced phase change enthalpy and thermal conductivity compared to pure paraffin wax. Our phase change composite can store energy in practical ways such as by sunlight absorption or under voltages applied by conventional lithium-ion batteries.

Facile preparation of hierarchically porous carbons from metal-organic gels and their application in energy storage.

Porous carbon materials have numerous applications due to their thermal and chemical stability, high surface area and low densities. However, conventional preparing porous carbon through zeolite or silica templates casting has been criticized by the costly and/or toxic procedure. Creating three-dimensional (3D) carbon products is another challenge. Here, we report a facile way to prepare porous carbons from metal-organic gel (MOG) template, an extended metal-organic framework (MOF) structure. We surprisingly found that the carbon products inherit the highly porous nature of MOF and combine with gels integrated character, which results in hierarchical porous architectures with ultrahigh surface areas and quite large pore volumes. They exhibit considerable hydrogen uptake and excellent electrochemical performance as cathode material for lithium-sulfur battery. This work provides a general method to fast and clean synthesis of porous carbon materials and opens new avenues for the application of metal-organic gel in energy storage.

Fe3O4/Fe/Carbon Composite and Its Application as Anode Material for Lithium-Ion Batteries

A plum pudding-like Fe(3)O(4)/Fe/carbon composite was synthesized by a sol-gel polymerization followed by a heat-treatment process and characterized by X-ray diffraction, Raman spectroscopic analysis, thermogravimetric analysis, scanning electron microscopy with energy-dispersive spectroscopy, transmission electron microscopy, and electrochemical test. In this composite, uniform spherical Fe(3)O(4)/Fe nanoparticles of about 100 nm were embedded into carbon matrix with high monodispersion. As-prepared Fe(3)O(4)/Fe/carbon composite electrode exhibits a stable and reversible capacity of over 600 mA h g(-1) at a current of 50 mA g(-1) between 0.002 V and 3.0 V, as well as excellent rate capability. The plum pudding-like structure, in which trace Fe promotes conductivity and carbon matrix mediates the volume change, can enhance the cycling performance and rate capability of Fe(3)O(4) electrode. This unique structure is valuable for the preparation of other electrode materials.

High-Performance Energy Storage and Conversion Materials Derived from a Single Metal–Organic Framework/Graphene Aerogel Composite

Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities.

Enhanced Cycle Performance of Lithium–Sulfur Batteries Using a Separator Modified with a PVDF-C Layer

High energy density Li-S batteries are highly attractive. However, their use in practical applications has been greatly affected by their poor cycle life and low rate performance, which can be partly attributed to the dissolution of polysulfides from the S cathode and their migration to the Li anode through the separator. While much effort has been devoted to designing the structure of the S cathodes for suppressing the dissolution of polysulfides, relatively little emphasis has been placed on modifying the separator. Herein, we demonstrate a new approach for modifying the separator with a polyvinylidene fluoride-carbon (PVDF-C) layer, where the polysulfides generated in the Li-S cells can be localized on the cathode side. Li-S batteries based on the novel separator and a cathode prepared by the simple mixing of a S powder and super P have delivered discharge capacities of 918.6 mAh g(-1), 827.2 mAh g(-1), and 669.1 mAh g(-1) after 100, 200, and 500 cycles, respectively, at a discharge rate of 0.5 C. Even under current densities of up to 5 C, the cells were able to retain a discharge capacity of 393 mAh g(-1), thereby demonstrating an excellent high rate performance and stability. The exceptional electrochemical performance could be attributed to the intense adsorption capability of the micropores, presence of C-C double bonds, and conductivity of the C network in the PVDF-C layer. This economical and simple strategy to overcome the polysulfide dissolution issues provides a commercially feasible method for the construction of Li-S batteries.

Functional Zeolitic-Imidazolate-Framework-Templated Porous Carbon Materials for CO2 Capture and Enhanced Capacitors

Three types of zeolitic imidazolate frameworks (ZIFs) with different topological structures and functional imidazolate-derived ligands, namely, ZIF-8, ZIF-68, and ZIF69, have been directly carbonized to prepare porous carbon materials at 1000 °C. These as-synthesized porous carbon materials were activated with fused KOH to increase their surface areas and pore volumes for use in gas storage and supercapacitors. The relationship between the local structure of the products and the composition of the precursors has been investigated in detail. The BET surface areas of the resultant activated carbon materials are 2437 (CZIF8a), 1861 (CZIF68a), and 2264 m(2) g(-1) (CZIF69a). CZIF8a exhibits the highest H2 -storage capacities of 2.59 wt.% at 1 atm and 77 K, whereas CZIF69a has the highest CO2 uptake of 4.76 mmol g(-1) at 1 atm and 273 K, owing to its local structure and pore chemical environment. The specific capacities are calculated from the CV curves. CZIF69a exhibits the highest supercapacitor performance of 168 F g(-1) at a scan speed of 5 mV s(-1). These results indicate that the functional chloride group on the benzimidazolate ligand plays a very important role in improving the surface area, pore volume, and, therefore, CO2-capture and supercapacitor properties of the corresponding porous carbon materials.

Controllable synthesis of core–shell Co@CoO nanocomposites with a superior performance as an anode material for lithium-ion batteries

The present study reports a straightforward template-free route for the synthesis of core–shell Co@CoO nanocomposites by the controlled reduction of Co3O4 nanospheres. The target Co@CoO nanoparticles consist of an unsealed hollow porous CoO shell with a metal Co core, in which the outer porous CoO shell as the active anode material can be fully in contact with the electrolyte. The void within the particles provides a remarkable buffer to tolerate volume changes of the electrode materials during the insertion and extraction of lithium. Most importantly, the inner nanosized metal Co core gives a new impetus to the reversible decomposition of Li2O due to its catalytic activity. Furthermore, the exposed metal Co portion outside the nanoshells provides a favorable electrical contact between adjacent particles and greatly improves the efficiency of the electronic connection between the active material and the current collector. The Co@CoO nanocomposite maintains an excellent reversible capacity over 800 mA h g−1 after 50 cycles with an initial coulombic efficiency of 74.2%, which is much higher than that of pure CoO (67.8%). This superior electrochemical performance is closely related to the unique composition and nanostructure of the electrode material. Notably, it is the first case of a hybrid-structured Co@CoO anode material derived from the reduction process from oxide precursors. Such a conclusion may be advantageously used to guide the design of a wide range of nanostructured metal oxides.

Ruthenium-oxide-coated sodium vanadium fluorophosphate nanowires as high-power cathode materials for sodium-ion batteries.

Sodium-ion batteries are a very promising alternative to lithium-ion batteries because of their reliance on an abundant supply of sodium salts, environmental benignity, and low cost. However, the low rate capability and poor long-term stability still hinder their practical application. A cathode material, formed of RuO2 -coated Na3 V2 O2 (PO4 )2 F nanowires, has a 50 nm diameter with the space group of I4/mmm. When used as a cathode material for Na-ion batteries, a reversible capacity of 120 mAh g(-1) at 1 C and 95 mAh g(-1) at 20 C can be achieved after 1000 charge-discharge cycles. The ultrahigh rate capability and enhanced cycling stability are comparable with high performance lithium cathodes. Combining first principles computational investigation with experimental observations, the excellent performance can be attributed to the uniform and highly conductive RuO2 coating and the preferred growth of the (002) plane in the Na3 V2 O2 (PO4 )2 F nanowires.