Toward Scalable Electrochemical Exfoliation of Molybdenum Disulfide Powder through an Accessible Electrode Design.

Cathodic electrochemical intercalation/exfoliation of transition metal dichalcogenides (TMDs) with bulky tetraalkylammonium-based cations is gaining popularity as it avoids the semiconducting (2H) to metallic (1T) phase transformation in TMDs like molybdenum disulfide (MoS2) and, generally, produces sheets with a larger aspect ratio - important for achieving conformal sheet-to-sheet contact in optoelectronic devices. Large single crystals are typically used as the precursor, but these are expensive, often inaccessible, and result in limited quantities of material. In this paper, a 3D-printable electrochemical cell capable of intercalating gram-scale quantities of commercially available TMD powders is presented. By incorporating a reference electrode in the cell and physically restraining the powder with a spring-loaded mechanism, the system can probe the intercalation electrochemistry, for example, determining the onset of intercalation to be near -2.5 V versus the ferrocene redox couple. While the extent of intercalation depends on precursor quantity and reaction time, a high yield of exfoliated product can be obtained exhibiting average aspect ratios as high as 49 ± 44 similar to values obtained by crystal intercalation. The intercalation and exfoliation of a wide variety of pelletized commercial powders including molybdenum diselenide (MoSe2), tungsten diselenide (WSe2), tungsten disulfide (WS2), and graphitic carbon nitride (gCN) are also demonstrated.

Phosphorene quantum dots: synthesis, properties and catalytic applications.

Phosphorene quantum dots (PQDs) belong to a new class of zero-dimensional functional nanostructures with unique physicochemical and surface properties in comparison with few-layer phosphorene and other 2D analogues. Tunable band gap as a function of number of layers, ease of passivation and high carrier mobility of PQDs have attracted considerable attention in catalysis research due to which spectacular progress has been made in PQD research over the last few years. PQDs are now considered as promising catalytic materials for electrocatalytic water splitting and nitrogen reduction, lithium-sulfur batteries, solar light-driven energy devices and biocatalysis, either in pristine form or as an active component for constructing heterostructures with other 2D materials. In the light of these recent advances, it is worthwhile to review and consolidate PQD research in catalytic applications to understand the challenges ahead and suggest possible solutions. In this review, we systematically summarize various synthetic strategies including ultrasonic and electrochemical exfoliation, solvothermal treatment, blender breaking, milling, crushing and pulsed laser irradiation. Furthermore, the physiochemical properties of PQDs are discussed based on both experimental and theoretical perspectives. The potential applications of PQDs in catalysis with special emphasis on photocatalysis (solar light-driven energy devices) and electrocatalysis (oxygen evolution reactions and hydrogen evolution reactions) -are critically discussed along with the present status, challenges and future perspectives.

Bismuthene nanosheets produced by ionic liquid assisted grinding exfoliation and their use for oxygen reduction reaction.

We report the simple synthesis of bismuthene nanosheets (BiNS) by ionic liquid assisted grinding exfoliation, followed by size selection sequential centrifugation steps for the first time. The exfoliation process results in the formation of self-assembled spherule-like superstructures with abundant edge sites, which are able to catalyze the oxygen reduction reaction (ORR) via a two-electron pathway, with a higher efficiency than the bulk Bismuth. We rationalize the enhanced ORR activity of the BiNS to: (i) the presence of 1 dimensional topological edge states, which provide strong conduction channels for electron hopping between the bismuth layers and (ii) the more active role of edge sites in facilitating O2 adsorption and dissociation of O-O bonds compared to the basal plane. The present study provides a pathway for employing 2D topological insulators as a new class of electrocatalysts for clean energy applications.

Role of Structural Distortion in Stabilizing Electrosynthesized Blue-Emitting Phosphorene Quantum Dots.

Luminescent phosphorene quantum dots (PQDs) have emerged as fascinating nanomaterials for potential applications in optoelectronics, catalysis, and sensing. Herein, we investigate the structural distortion of black phosphorus (BP) under an applied electric field to yield blue luminescent PQDs [average diameter 8 ± 1.5 nm ( N = 60)]. The electrosynthesized PQDs exhibit photoluminescence emission independent of excitation wavelength with 84% quantum efficiency. Structural distortion that occurred during the transformation of BP to PQDs is confirmed by results obtained during transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Further, using first-principles-based density functional theory, calculations on oxygenated and nonoxygenated PQDs augment the experimental observations that an optimum oxygen content maintains the structural integrity of PQDs, above which the structural robustness of PQDs is drastically diminished.

A single-step, electrochemical synthesis of nitrogen doped blue luminescent phosphorene quantum dots.

Herein, we report a one-step strategy for the electrochemical synthesis of nitrogen doped blue luminescent phosphorene quantum dots (NPQDs) from black phosphorus at room temperature. Nitrogen percentage in NPQDs can be varied by the appropriate choice of solvent and supporting electrolyte. NPQDs [average size 6 ± 1.5 nm (N = 50)] obtained in this work exhibit ca. 88.7% quantum efficiency.

Adsorption Kinetics of WS2 Quantum Dots onto a Polycrystalline Gold Surface.

In this work, we report the adsorption kinetics of electrochemically synthesized WS2 quantum dots (QDs) (ca. 3 nm) onto a polycrystalline gold electrode. The Langmuir adsorption isotherm approach was employed to explore the temperature and adsorbate concentration dependence of the experimentally calculated equilibrium constant of adsorption ( Keq) and the free energy for adsorption (Δ Gads). Subsequently, we extract other thermodynamic parameters, such as adsorption rate constant ( Kads), desorption rate constant ( Kd), the enthalpy of adsorption (Δ Hads), and the entropy of adsorption (Δ Sads). Our findings indicate that Δ Gads is temperature-dependent and ca. -7.64 ± 0.6 kJ/mol, Δ Hads = -43.72 ± 1.7 kJ/mol, and Δ Sads = -0.126 ± 0.017 kJ/(mol K). These investigations on the contribution of the enthalpic and entropic forces to the total free energy of this system underscore the role of entropic forces on the stability of the WS2 QDs monolayer and provide new thermodynamic insights into other transition-metal dichalcogenide quantum dot (TMDQD) monolayers as well.