Theoretical Study of Heteroatom Doping in Tuning the Catalytic Activity of Graphene for Triiodide Reduction

Graphene with heteroatom doping has found increasing applications in a broad range of catalytic reactions. However, the doping effects accounting for the enhanced catalytic activity still remain elusive. In this work, taking the triiodide electroreduction reaction as an example, we study systematically the intrinsic activity of graphene and explore the origin of doping-induced activity variation using first-principles calculations, in which two typical N and S dopants are tested. The most common graphene structures, basal plane, armchair edge, and zigzag edge, are considered, and it is found that the former two structures show a weak adsorption ability for the iodine atom (the key intermediate in the triiodide electroreduction reaction), corresponding to a low catalytic activity. Doping either N or S can strengthen the adsorption and thus increase the activity, and the codoping of N and S (NS-G) exhibits a synergistic effect. A detailed investigation into the whole process of the triiodide electroreduction reaction at the CH3CN/NS-G interface is also carried out to verify these activity trends. It is found that the zigzag edges which contain spin electrons show a relatively stronger adsorption strength compared with the basal plane and armchair edge, and initial doping would result in the spin disappearance that evidently weakens the adsorption; with the disappearance of spin, however, further doping can increase the adsorption again, suggesting that the spin electrons may play a preliminary role in affecting the intrinsic activity of graphene. We also analyzed extensively the origin of doping-induced adsorption enhancement of graphene in the absence of spin; it can be rationalized from the electronic and geometric factors. Specifically, N doping can result in a more delocalized “electron-donating area” to enhance I adsorption, while S doping provides a localized structural distortion, which activates the nearest sp2-C into coordinatively unsaturated sp3-C. These results explain well the improved activity of the doping and the synergistic effect of the codoping. The understandings are generalized to provide insight into the enhanced activity of the oxygen reduction reaction on heteroatom doped graphene. This work may be of importance toward the design of high-activity graphene based material.

Intrinsically flexible electronic materials for smart device applications

A novel method to fabricate chemically linked conducting polymer–biopolymer composites that are intrinsically flexible and conducting for functional electrode applications is presented. Polypyrrole was synthesised in situ during the cellulose regeneration process using the 1-butyl-3-methylimidazolium chloride ionic liquid as a solvent medium. The obtained polypyrrole–cellulose composite was chemically blended and showed flexible polymer properties while retaining the electronic properties of a conducting polymer. Addition of an ionic liquid such as trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, enhanced the flexibility of the composite. The functional application of these materials in the electrochemically controlled release of a model drug has been demonstrated. This strategy opens up a new design for a wide spectrum of materials for smart electronic device applications wherein the functionality of doping and de-doping of conducting polymers is retained and their processability issue is addressed by exploiting an ionic liquid route.

Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

High-Performance WSe2 CMOS Technology and Integrated Circuits.

Because of their extraordinary structural and electrical properties, two dimensional materials are currently being pursued for applications such as thin-film transistors and integrated circuit. One of the main challenges that still needs to be overcome for these applications is the fabrication of air-stable transistors with industry-compatible complementary metal oxide semiconductor (CMOS) technology. In this work, we experimentally demonstrate a novel high performance air-stable WSe2 CMOS technology with almost ideal voltage transfer characteristic, full logic swing and high noise margin with different supply voltages. More importantly, the inverter shows large voltage gain (~38) and small static power (Pico-Watts), paving the way for low power electronic system in 2D materials.

First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

A boron nitride - graphene - C60 heterostructure

We have fabricated a new van-der-Waals heterostructure composed by BN/graphene/C60. We performed transport measurements on the preliminary BN/graphene device finding a sharp Dirac point at the neutrality point. After the deposition of a C60 thin film by thermal evaporation, we have observed a significant n-doping of the heterostructure. This suggests an unusual electron transfer from C60 into the BN/graphene structure. This BN/graphene/C60 heterostructure can be of interest in photovoltaic applications. It can be used to build devices like p-n junctions, where C60 can be easily deposited in defined regions of a graphene junction by the use of a shadow mask. Our results are contrasted with theoretical calculations.