Search

Optimal electron transfer with the catalyst through modulation of a graphene support with non-covalent adsorbents for achieving maximized activity and stability.

Tungsten trioxide (WO3) is an abundant, versatile oxide that is widely explored for catalysis, sensing, electrochromic devices, and numerous other applications. The exploitation of WO3 in nanosheet form provides potential advantages in many of these fields because the 2D structures have high surface area and preferentially exposed facets. Relative to bulk WO3, nanosheets expose more active sites for surface-sensitive sensing/catalytic reactions, and improve reaction kinetics in cases where ionic diffusion is a limiting factor (e.g. electrochromic or charge storage). Synthesis of high aspect ratio WO3 nanosheets, however, is more challenging than other 2D materials because bulk WO3 is not an intrinsically layered material, making the widely-studied sonication-based exfoliation methods used for other 2D materials not well-suited to WO3. WO3 is also highly complex in terms of how the synthesis method affects the properties of the final material. Depending on the route used and subsequent post-synthesis treatments, a wide variety of different morphologies, phases, exposed facets, and defect structures are created, all of which must be carefully considered for the chosen application. In this review, the recent developments in WO3 nanosheet synthesis and their impact on performance in various applications are summarized and critically analyzed.

MoO3 has potential advantages in price and weight over more widely studied WO3 for electrochromic devices, but it typically suffers from inferior electrochromic performance. Here, it is demonstrate...

It is challenging to achieve highly efficient thermoelectric materials due to the conflicts between thermopower (Seebeck coefficient) and electrical conductivity. These parameters are the core factors defining the thermoelectric property of any material. Here, we report the use of isovalent substitution as a tool to decouple the interdependency of the Seebeck coefficient and the electrical properties of cerium-doped bismuth selenide thermoelectric material. With this strategy, we can achieve a simultaneous increase in both the electrical conductivity and the Seebeck coefficient of the material by tuning the concentration of cerium doping, due to formation of neutral impurities and consequently the improvement of carrier mobility. Our theoretical calculation reveals a downward shift of the valence band with cerium concentration, which influences the thermoelectric enhancement of the synthesized materials. Finally, an order of magnitude enhancement of the figure of merit is obtained due to isovalent substitution, thus providing a new avenue for enhancing the thermoelectric performance of materials.

To date, researchers have revealed that the electrocatalytic activity of 2-dimensional (2D) layered transition metal dichalcogenides (TMDCs) such as MoS2 can be improved by making free standing vertical structures to expose edge sites for efficient water splitting. However, poor electrical conductivity and structural instability restrict the practical application of vertical structures for efficient electrocatalytic activities. Here, a homogeneously attached MoS2 structure on well-ordered 3-dimensional nickel (3D-Ni) is reported for efficient hydrogen evolution reaction (HER). This homogeneously attached structure of MoS2 leads to abundant active sites and well-ordered 3D-Ni structures, solving the conductivity issue of MoS2 and ensuring the structural stability during electrocatalytic processes. By controlling the amount of MoS2 on the 3D-Ni, it is found that the electrochemical active area (ECSA) is increased by 5 times (50 cm2 of active sites) compared to normal MoS2 grown on 2D-Ni (9 cm2 of active sites). It is also found that the charge transfer resistance (Rct) of attached MoS2 structures on 3D-Ni (1 Ω) is 16 times lower than MoS2 grown on 2D-Ni (16 Ω). In addition, the proposed attached structure of MoS2 is stable in acidic electrolytes for continuous electrocatalytic activity and can be mass producible for practical applications.

To date, nanostructures of 3d-group transition metal (i.e., Fe, Co, Ni, etc.) derivatives show the highest electrocatalytic performance among non-noble-metal electrocatalysts for water splitting in acidic electrolyte. However, the poor electrochemical conductivity (∼10–4 S/cm) of nanostructures restricts practical application for overall electrocatalytic activity. Herein, continuously networked nanostructures of phase-tuned nickel sulfide foams for efficient water splitting electrocatalysts in both acidic and alkaline electrolytes are reported. Because continuously networked nanostructures of nickel sulfide foams possess an integral structure, they exhibit high electrochemical conductivity (∼1 S/cm), which eases adsorption/desorption of H+ and OH– ions for efficient overall water splitting. By tuning the stoichiometry of sulfur, four different phases of continuously networked nanostructures of nickel sulfides (αNiS, βNiS, Ni3S2, and Ni7S6) foams are formed by facile phase transformation of nickel. Among t...

Oxide aerogels are pore–solid networks notable for their low density, large pore volume, and high surface area. This three-dimensional arrangement of pore and solid provides critical properties: the high surface area required to maximize the number of active sites and a through-connected porosity that plumbs reactants to the active interior. In decontamination applications where reactivity beyond adsorption is desired to degrade deleterious molecules, oxide aerogels offer multiple avenues to add oxidative power to this unique arrangement of pore and solid. For protection against chemical warfare agents or toxic industrial chemicals, metal-oxide aerogels with their oxide/hydroxide surfaces afford stability under ambient conditions against competing sorbents such as water and oxygen. In this review, strategies to maximize sorptive capacity and degradation rate by modifying surface functionality, compositing with dissimilar oxides, or adding metallic nanoparticles and the subsequent impact on decontamination performance will be summarized and expected directions for future research will be discussed based on the observed trends.

Tungsten trioxide (WO

Two-dimensional (2D) transitional metal oxides (TMOs) are an attractive class of materials due to the combined advantages of high active surface area, enhanced electrochemical properties, and stability. Among the 2D TMOs, 2D tungsten oxide (WO3) nanosheets possess great potential in electrochemical applications, particularly in electrochromic (EC) devices. However, feasible production of 2D WO3 nanosheets is challenging due to the innate 3D crystallographic structure of WO3. Here we report a novel solution-phase synthesis of 2D WO3 nanosheets through simple oxidation from 2D tungsten disulfide (WS2) nanosheets exfoliated from bulk WS2 powder. The complete conversion from WS2 into WO3 was confirmed through crystallographic and elemental analyses, followed by validation of the 2D WO3 nanosheets applied in the EC device. The EC device showed color modulation of 62.57% at 700 nm wavelength, which is 3.43 times higher than the value of the conventional device using bulk WO3 powder, while also showing enhanceme...

In recent years, two-dimensional black phosphorus (BP) has seen a surge of research because of its unique optical, electronic, and chemical properties. BP has also received interest as a potential thermoelectric material because of its high Seebeck coefficient and excellent charge mobility, but further development is limited by the high cost and poor scalability of traditional BP synthesis techniques. In this work, high-quality BP is synthesized using a low-cost method and utilized in a PEDOT:PSS film to create the first ever BP composite thermoelectric material. The thermoelectric properties are found to be greatly enhanced after the BP addition, with the power factor of the film, with 2 wt % BP (36.2 μW m–1 K–2) representing a 109% improvement over the pure PEDOT:PSS film (17.3 μW m–1 K–2). A simultaneous increase of mobility and decrease of the carrier concentration is found to occur with the increasing BP wt %, which allows for both Seebeck coefficient and electrical conductivity to be increased. Thes...

Researchers have revealed that the electrocatalytic activity can be improved by creation of defects in the crystal lattice of 2D layered transition metal dichalcogenides (TMDCs) or ternary metal chalcogenides (TMCs) such as MoS2 or Cu2MoS4, respectively. However, the role of anion substitution in the enhancement of overall electrocatalytic activity in TMCs remains unproven. Here, we show the substitution of anion atom sulfur (S) with selenium (Se) in a new electrocatalyst Cu2WS4 for efficient hydrogen evolution reaction (HER) activity. The higher electrocatalytic activity of Cu2WS4 after anion atom substitution can be attributed to the creation of chemical strain in the lattice, which causes an increase of active sites for hydrogen adsorption and desorption. Experimentally, the anion substituted Cu2W(SySe1 − y)4 samples show superior electrocatalytic activities with a low onset potential of −0.320 V at 10 mA cm−2 for the HER, which is two-fold lower than that of the pristine Cu2WS4 (−0.650 V at 10 mA cm−2) sample. In addition, after 1000 cycles with continuous electrolysis in an acid electrolyte for 12 h, the anion substituted samples Cu2W(SySe1 − y)4 preserve their structure and robust catalytic activity perfectly. As a result, our work demonstrates a new approach for developments of real applications of TMCs in energy conversion.

Graphene quantum dots (GQDs) are promising luminescent materials for various light-emitting, biological, and energy applications due to their low toxicity compared to cadmium-based semiconductor quantum dots. The practical application and use of GQDs is driven by their luminescent characteristics. As such, a critical need exists to control and tailor the emission properties of these materials to suit the targeted optoelectronic applications. In this review, the fundamental properties, synthesis methods, and strategies for incorporating GQDs into optoelectronic devices are discussed. We present the fundamentals on luminescence mechanism of GQDs, including reflections on the defect-related properties (i.e., oxygen functional groups and odd-numbered carbon rings in the basal plane). We then offer new guidelines for the fabrication of GQDs aimed at increasing the luminescence efficiency. Finally, we introduce strategies for integrating GQDs into optoelectronic devices based on architectural design of the fundamental properties.

In this work, we present the experimental investigation on the contact resistance of graphene/single-walled carbon nanotube (SWCNT) junction using transfer length method with the simple equivalent circuit model. We find that p–n like junctions are formed in graphene/SWCNT transistors, and the contact resistance in the junction is observed to be ~ 494 and ~ 617 kΩ in case of metallic SWCNT (m-SWCNT) and semiconducting SWCNT (s-SWCNT), respectively. In addition, the contact resistance increases from 617 to 2316 kΩ as Vg increases from − 30 to − 10 V. Through our study, high carrier density induced from doping in both graphene and SWCNT leads to low contact resistance. This development of contact engineering, namely modulation of carrier density in the junction and contact length (Lcon) scaling shows the potential for all-carbon based electronics. Electronic supplementary material The online version of this article (10.1186/s40580-017-0130-1) contains supplementary material, which is available to authorized users.

Transition metal phosphides are among the most promising materials for achieving efficient electrocatalytic performance without the use of rare or expensive noble metals. However, previous research into phosphides for the hydrogen evolution reaction (HER) or oxygen evolution reaction (OER) has focused on high-temperature vapor-phase processes, which are not practical for large-scale applications. Here, we introduce a simple, one-step solution-phase method of phosphide synthesis by modifying Cu2WS4 using triphenylphosphine (TPP), which serves to substitute S with P and transform the normally inactive basal plane of Cu2WS4 into a defect-rich, activated basal plane. The OER activity was significantly enhanced by phosphorus substitution, with the resulting Tafel slope of the sample with approximate to 8 at% phosphorus reaching 194 mV dec(-1), a result close to that of the best OER catalyst (RuO2, 151 mV dec(-1)). The sample possessed stable OER performance, showing no degradation in current density over approximate to 24 hours (500 cycles), proving the robust and stable nature of the phosphorus substitution. These results open the possibility for further phosphide catalyst development using this low-cost, solution-phase method.

Transition metal phosphides are among the most promising materials for achieving efficient electrocatalytic performance without the use of rare or expensive noble metals. However, previous research into phosphides for the hydrogen evolution reaction (HER) or oxygen evolution reaction (OER) has focused on high-temperature vapor-phase processes, which are not practical for large-scale applications. Here, we introduce a simple, one-step solution-phase method of phosphide synthesis by modifying Cu

Two-dimensional (2D) transitional metal oxides (TMOs) are an attractive class of materials due to the combined advantages of high active surface area, enhanced electrochemical properties, and stability. Among the 2D TMOs, 2D tungsten oxide (WO

H.Y. and K.L. contributed equally to this work. This study was supported by the Center for Advanced Soft Electronics as Global Frontier Project (CASE-2013M3A6A5073173) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT, and Future Planning. This study was also supported by Multi-Ministry Collaborative R&D Program (Development of Techniques for Identification and Analysis of Gas Molecules to Protect Against Toxic Substances) through the National Research Foundation of Korea (NRF) funded by KNPA, MSIT, MOTIE, ME, NFA (Grant No. 2017M3D9A1073501).

Water splitting plays an important role in electrochemical and photoelectrochemical conversion of energy devices. Electrochemical water splitting by the hydrogen evolution reaction (HER) is a straightforward route to produce hydrogen (H2), which requires an efficient electrocatalysts to minimize energy consumption. Recent advances have created a rapid rise in new electrocatalysts, particularly those based on non-precious metals. In this review, we present a comprehensive overview of the recent developments of ternary and quaternary 6d-group transition metal chalcogenides (TMCs) based electrocatalysts for water splitting, especially for HER. Detailed discussion is organized from binary to quaternary TMCs including, surface engineering, heterostructures, chalcogen substitutions, and hierarchically structural design in TMCs. Moreover, emphasis is placed on future research scope and important challenges facing these electrocatalysts for further development in their performance towards water splitting.&nbsp

PEG-functionalized graphene quantum dots (GQDs) are shown to promote fast exciton dissociation in organic solar cells. Short-chain PEG promotes the most favorable interaction with other organic layers, and the overall efficiency is improved by 36% when compared to the reference devices. The mechanism of enhancement is shown to be increased absorption due to fewer charges remain-ing in the bound state.