Tsun-Kong Sham

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Layer by layer assembly of sandwiched graphene/SnO2 nanorod/carbon nanostructures with ultrahigh lithium ion storage properties

Sandwiched structures consisting of carbon coated SnO2 nanorod grafted on graphene have been synthesized based on a seed assisted hydrothermal growth to form graphene supported SnO2 nanorods, followed by a nanocarbon coating. As a potential anode for high power and energy applications, the hierarchical nanostructures exhibit a greatly enhanced synergic effect with an extremely high lithium storage capability of up to 1419 mA h g−1 benefiting from the advanced structural features.

Microwave-Assisted Synthesis of a Core–Shell MWCNT/GONR Heterostructure for the Electrochemical Detection of Ascorbic Acid, Dopamine, and Uric Acid

In this study, graphene oxide nanoribbons (GONRs) were synthesized from the facile unzipping of multiwalled carbon nanotubes (MWCNTs) with the help of microwave energy. A core-shell MWCNT/GONR-modified glassy carbon (MWCNT/GONR/GC) electrode was used to electrochemically detect ascorbic acid (AA), dopamine (DA), and uric acid (UA). In cyclic voltammograms, the MWCNT/GONR/GC electrode was found to outperform the MWCNT- and graphene-modified GC electrodes in terms of peak current. For the simultaneous sensing of three analytes, well-separated voltammetric peaks were obtained using a MWCNT/GONR/GC electrode in differential pulse voltammetry measurements. The corresponding peak separations were 229.9 mV (AA to DA), 126.7 mV (DA to UA), and 356.6 mV (AA to UA). This excellent electrochemical performance can be attributed to the unique electronic structure of MWCNTs/GONRs: a high density of unoccupied electronic states above the Fermi level and enriched oxygen-based functionality at the edge of the graphene-like structures, as revealed by X-ray absorption near-edge structure spectroscopy, obtained using scanning transmission X-ray microscopy.

Proto-Calcite and Proto-Vaterite in Amorphous Calcium Carbonates

Amorphous order: Amorphous calcium carbonates (ACC) have an intrinsic structure relating to the crystalline polymorphs of calcite and vaterite. The proto-crystalline structures of calcite and vater ...

Comparison of the rate capability of nanostructured amorphous and anatase TiO 2 for lithium insertion using anodic TiO 2 nanotube arrays

Nanostructured amorphous and anatase TiO2 are both considered as high rate Li-insertion/extraction electrode materials. To clarify which phase is more desirable for lithium ion batteries with both high power and high density, we compare the electrochemical properties of anatase and amorphous TiO2 by using anodic TiO2 nanotube arrays (ATNTAs) as electrodes. With the same morphological features, the rate capacity of nanostructured amorphous TiO2 is higher than that of nanostructured anatase TiO2 due to the higher Li-diffusion coefficient of amorphous TiO2 as proved by the electrochemical impedance spectra of an amorphous and an anatase ATNTA electrode. The electrochemical impedance spectra also prove that the electronic conductivity of amorphous TiO2 is lower than that of anatase TiO2. These results are helpful in the structural and componential design of all TiO2 mesoporous structures as anode material in lithium ion batteries. Moreover, all the advantages of the amorphous ATNTA electrode including high rate capacity, desirable cycling performance and the simplicity of its fabrication process indicate that amorphous ATNTA is potentially useful as the anode for lithium ion batteries with both high power and high energy density.

LiFePO4–graphene as a superior cathode material for rechargeable lithium batteries: impact of stacked graphene and unfolded graphene

In this work, we describe the use of unfolded graphene as a three dimensional (3D) conducting network for LiFePO4 nanoparticle growth. Compared with stacked graphene, which has a wrinkled structure, the use of unfolded graphene enables better dispersion of LiFePO4 and restricts the LiFePO4 particle size at the nanoscale. More importantly, it allows each LiFePO4 particle to be attached to the conducting layer, which could greatly enhance the electronic conductivity, thereby realizing the full potential of the active materials. Based on its superior structure, after post-treatment for 12 hours, the LiFePO4–unfolded graphene nanocomposite achieved a discharge capacity of 166.2 mA h g−1 in the 1st cycle, which is 98% of the theoretical capacity (170 mA h g−1). The composite also displayed stable cycling behavior up to 100 cycles, whereas the LiFePO4–stacked graphene composite with a similar carbon content could deliver a discharge capacity of only 77 mA h g−1 in the 1st cycle. X-ray absorption near-edge spectroscopy (XANES) provided spectroscopic understanding of the crystallinity of LiFePO4 and chemical bonding between LiFePO4 and unfolded graphene.

Tuning the electronic behavior of Au nanoparticles with capping molecules

The electronic behavior of gold nanoparticles (NPs) of ∼2 nm capped with dendrimer and thiol molecules was studied with Au L3,2-edge x-ray absorption near-edge structure (XANES). The results reveal the tunability of the d-electron distribution in the Au NPs by selective capping. That is, that the Au atoms in the NPs gain 5d electrons (relative to the bulk) when capped with weakly interacting dendrimers and lose 5d electrons when capped with strongly interacting thiol molecules. A semiquantitative analysis of the d-charge (holes) distribution is presented. This work demonstrates the important role of the capping molecules in the d-charge distribution of Au NPs and the usefulness of XANES in probing the electronic behavior of transition metal NPs.

Rational Design of Atomic-Layer-Deposited LiFePO4 as a High-Performance Cathode for Lithium-Ion Batteries

Atomic layer deposition is successfully applied to synthesize lithium iron phosphate in a layer-by-layer manner by using self-limiting surface reactions. The lithium iron phosphate exhibits high power density, excellent rate capability, and ultra-long lifetime, showing great potential for vehicular lithium batteries and 3D all-solid-state microbatteries.

Hierarchical nanostructured core-shell Sn@C nanoparticles embedded in graphene nanosheets: spectroscopic view and their application in lithium ion batteries.

Hierarchical carbon encapsulated tin (Sn@C) embedded graphene nanosheet (GN) composites (Sn@C-GNs) have been successfully fabricated via a simple and scalable one-step chemical vapor deposition (CVD) procedure. The GN supported Sn@C core-shell structures consist of a crystalline tin core, which is thoroughly covered by a carbon shell and more interestingly, extra voids are present between the carbon shell and the tin core. Synchrotron spectroscopy confirms that the metallic tin core is free of oxidation and the existence of charge redistribution transfer from tin to the carbonaceous materials of the shell, facilitating their intimate contact by chemical bonding and resultant lattice variation. The hybrid electrodes of this material exhibit a highly stable and reversible capacity together with an excellent rate capability, which benefits from the improved electrochemical properties of tin provided by the protective carbon matrix, voids and the flexible GN matrices.

Discharge product morphology and increased charge performance of lithium–oxygen batteries with graphene nanosheet electrodes: the effect of sulphur doping

Sulphur-doped graphene was successfully fabricated and its influence on the discharge product formation in lithium–oxygen batteries was demonstrated. The growth and distribution of the discharge products were studied and a mechanism was proposed. This will have significant implication for cathode catalysts and rechargeable battery performance.