Huijun Zhao

Accurate Control of Multishelled Co3O4 Hollow Microspheres as High-Performance Anode Materials in Lithium-Ion Batteries

More than just an empty shell: Multishelled Co3O4 microspheres were synthesized as anode materials for lithium-ion batteries in high yield and purity. As their porous hollow multishell structure guarantees a shorter Li+ diffusion length and sufficient void space to buffer the volume expansion, their rate capacity, cycling performance, and specific capacity were excellent (1615.8 mA?h?g-1 in the 30th cycle for triple-shelled Co3O4; see graph).

α-Fe2O3 multi-shelled hollow microspheres for lithium ion battery anodes with superior capacity and charge retention

Multi-shelled α-Fe2O3 hollow microspheres were synthesized using carbonaceous microsphere sacrificial templates and utilized for high capacity anode materials in lithium ion batteries (LIBs). Structural aspects including the shell thickness, number of internal multi-shells, and shell porosity were controlled by synthesis parameters to produce hollow microspheres with maximum lithium capacity and stable cycling behavior. Thin, porous, hollow microspheres with three concentric multi-shells showed the best cycling performance, demonstrating excellent stability and a reversible capacity of up to 1702 mA h g−1 at a current density of 50 mA g−1. The electrode performance is attributed to the large specific surface area and enhanced volumetric capacity of the multi-shelled hollow spheres that provide maximum lithium storage, while the porous thin shells facilitate rapid electrochemical kinetics and buffer mechanical stresses that accompany volume changes during de/lithiation.

Growth of Polypyrrole Ultrathin Films on MoS2 Monolayers as High-Performance Supercapacitor Electrodes

A scalable solution-based approach is developed to controllably grow PPy ultrathin films on 2D MoS2 monolayers. When these sandwiched nanocomposites are utilized as supercapacitor electrodes, a record high specific capacitance, remarkable rate capability, and improved cycling stability are achieved, offering a feasible solution to create the next generation of energy-storage device with superior power density and energy density.

Core–Shell Palladium Nanoparticle@Metal–Organic Frameworks as Multifunctional Catalysts for Cascade Reactions

Uniform core-shell Pd@IRMOF-3 nanostructures, where single Pd nanoparticle core is surrounded by amino-functionalized IRMOF-3 shell, are prepared by a facile mixed solvothermal method. When used as multifunctional catalysts, the Pd@IRMOF-3 nanocomposites exhibit high activity, enhanced selectivity, and excellent stability in the cascade reaction. Both experimental evidence and theoretical calculations reveal that the high catalytic performance of Pd@IRMOF-3 nanocomposites originates from their unique core-shell structures.

Three-Dimensional Graphene/Metal Oxide Nanoparticle Hybrids for High-Performance Capacitive Deionization of Saline Water

A novel and general method is proposed to construct three-dimensional graphene/metal oxide nanoparticle hybrids. For the first time, it is demonstrated that this graphene-based composite with open pore structures can be used as the high-performance capacitive deionization (CDI) electrode materials, which outperform currently reported materials. This work will offer a promising way to develop highly effective CDI electrode materials.

Carbonized Nanoscale Metal–Organic Frameworks as High Performance Electrocatalyst for Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is one of the key steps in clean and efficient energy conversion techniques such as in fuel cells and metal-air batteries; however, several disadvantages of current ORRs including the kinetically sluggish process and expensive catalysts hinder mass production of these devices. Herein, we develop carbonized nanoparticles, which are derived from monodisperse nanoscale metal organic frameworks (MIL-88B-NH3), as the high performance ORR catalysts. The onset potential and the half-wave potential for the ORR at these carbonized nanoparticles is up to 1.03 and 0.92 V (vs RHE) in 0.1 M KOH solution, respectively, which represents the best ORR activity of all the non-noble metal catalysts reported so far. Furthermore, when used as the cathode of the alkaline direct fuel cell, the power density obtained with the carbonized nanoparticles reaches 22.7 mW/cm2, 1.7 times higher than the commercial Pt/C catalysts.

Cross-Linked g-C3N4/rGO Nanocomposites with Tunable Band Structure and Enhanced Visible Light Photocatalytic Activity

Cross-linked rather than non-covalently bonded graphitic carbon nitride (g-C3 N4 )/reduced graphene oxide (rGO) nanocomposites with tunable band structures have been successfully fabricated by thermal treatment of a mixture of cyanamide and graphene oxide with different weight ratios. The experimental results indicate that compared to pure g-C3 N4 , the fabricated CN/rGO nanocomposites show narrowed bandgaps with an increased in the rGO ratio. Furthermore, the band structure of the CN/rGO nanocomposites can be readily tuned by simply controlling the weight ratio of the rGO. It is found that an appropriate rGO ratio in nanocomposite leads to a noticeable positively shifted valence band edge potential, meaning an increased oxidation power. The tunable band structure of the CN/rGO nanocomposites can be ascribed to the formation of C-O-C covalent bonding between the rGO and g-C3 N4 layers, which is experimentally confirmed by Fourier transform infrared (FT-IR) and X-ray photoelectron (XPS) data. The resulting nanocomposites are evaluated as photocatalysts by photocatalytic degradation of rhodamine B (RhB) and 4-nitrophenol under visible light irradiation (λ > 400 nm). The results demonstrate that the photocatalytic activities of the CN/rGO nanocomposites are strongly influenced by rGO ratio. With a rGO ratio of 2.5%, the CN/rGO-2.5% nanocomposite exhibits the highest photocatalytic efficiency, which is almost 3.0 and 2.7 times that of pure g-C3 N4 toward photocatalytic degradation of RhB and 4-nitrophenol, respectively. This improved photocatalytic activity could be attributed to the improved visible light utilization, oxidation power, and electron transport property, due to the significantly narrowed bandgap, positively shifted valence band-edge potential, and enhanced electronic conductivity.

Metal–organic frameworks as selectivity regulators for hydrogenation reactions

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon–oxygen group (in preference to the carbon–carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon–carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal–organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon–oxygen rather than the carbon–carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

Rational screening low-cost counter electrodes for dye-sensitized solar cells

Dye-sensitized solar cells have attracted intense research attention owing to their ease of fabrication, cost-effectiveness and high efficiency in converting solar energy. Noble platinum is generally used as catalytic counter electrode for redox mediators in electrolyte solution. Unfortunately, platinum is expensive and non-sustainable for long-term applications. Therefore, researchers are facing with the challenge of developing low-cost and earth-abundant alternatives. So far, rational screening of non-platinum counter electrodes has been hamstrung by the lack of understanding about the electrocatalytic process of redox mediators on various counter electrodes. Here, using first-principle quantum chemical calculations, we studied the electrocatalytic process of redox mediators and predicted electrocatalytic activity of potential semiconductor counter electrodes. On the basis of theoretical predictions, we successfully used rust (α-Fe2O3) as a new counter electrode catalyst, which demonstrates promising electrocatalytic activity towards triiodide reduction at a rate comparable to platinum.

Multishelled TiO2 hollow microspheres as anodes with superior reversible capacity for lithium ion batteries

Herein, uniform multishelled TiO2 hollow microspheres were synthesized, especially 3- and 4-shelled TiO2 hollow microspheres were synthesized for the first time by a simple sacrificial method capable of controlling the shell thickness, intershell spacing, and number of internal multishells, which are achieved by controlling the size, charge, and diffusion rate of the titanium coordination ions as well as the calcination process. Used as anodes for lithium ion batteries, the multishelled TiO2 hollow microspheres show excellent rate capacity, good cycling performance, and high specific capacity. A superior capacity, up to 237 mAh/g with minimal irreversible capacity after 100 cycles is achieved at a current rate of 1 C (167.5 mA/g), and a capacity of 119 mAh/g is achieved at a current rate of 10 C even after 1200 cycles.