Size-Dependent Graphene Support for Decorating Gold Nanoparticles as a Catalyst for Hydrogen Evolution Reaction with Machine Learning-Assisted Prediction.

Size-dependent two-dimensional (2D) materials (e.g., graphene) have been recently used to improve their performance in various applications such as membrane filtration, energy storage, and electrocatalysts. It has also been demonstrated that 2D nanosheets can be one of the promising support materials for decorating nanoparticles (NPs). However, the optimum nanosheet size (lateral length and thickness) for supporting NPs has not yet been explored to enhance their catalytic performance. Herein, we elucidate the mechanism behind size-dependent graphene (GP) as a support due to which gold nanoparticles (AuNPs) are used as an active catalyst for the hydrogen evolution reaction (HER). Surprisingly, the decoration of AuNPs increased with the increasing nanosheet size, counter to what is widely reported in the literature (high surface area for smaller nanosheet size). We found that a large graphene nanosheet (lGP; ∼800 nm) used as the AuNP support (lGP/AuNPs) exhibited superior performance for the HER with long-term stability. The lGP/AuNPs with a suitable content of AuNPs provides a low overpotential and a small Tafel slope, being lower than that of other reported carbon-based HER electrocatalysts. This results from highly exposed active sites of well-dispersed AuNPs on lGP giving high conductivity. The laminar structure of the stacked graphene nanosheets and the high wettability of the lGP/AuNPs electrode surface also play crucial roles in enhancing electrolytes for penetration in the electrode, suggesting a highly electrochemical surface area. Moreover, machine learning (Random Forest) was also used to reveal the essential features of the advanced catalytic material design for catalyst-based applications.

Tuning Surface Energy to Enhance MoS2 Nanosheet Production via Liquid-Phase Exfoliation: Understanding the Electrochemical Adsorption of Cesium Chloride.

Environmental pollution caused by radionuclides like Cs-137 and Cs-134 has increased global attention toward public health. Electrochemical adsorption has emerged as a feasible, rapid, and scalable method to treat contaminated water sources. However, graphene and its derivatives have limitations in ion adsorption via physisorption, forming a double layer that restricts the electrode's adsorption capacity. To address this, we propose the use of molybdenum disulfide (MoS2) with its extensive intercalation galleries of MoS2 nanosheets for cesium removal via an electrochemical route. Liquid-phase exfoliation with water and N-methyl-2-pyrrolidone (NMP) was then used to produce MoS2 nanosheets in a scalable quantity (high-yield production). The formation of a mixed solvent possessing relatively equivalent surface energy for exfoliation enabled us to achieve a remarkable exfoliation yield of up to ca. 1.26 mg mL-1, which is one of the highest yields reported to date (without a surfactant being added) and to the best of our knowledge. The 35% v/v of water in NMP displayed a maximum yield while maintaining the structure of the as-exfoliated one. Water exceeding over 66.7% v/v led to the formation of MoO3. Moreover, an insight into the cesium ion removal mechanism through the electrochemical route was demonstrated. It is found that the Cs+ removal follows electrochemical intercalation rather than adsorption. This work aids the understanding of cesium intercalation coupled with a mass-scale production method, which should lead to more efficient and cost-effective removal of radionuclides from contaminated water sources, opening new research avenues in materials and environmental science.

Ultrahigh stable laminar graphene membranes for effective ionic and molecular nanofiltration with a machine learning-assisted study.

Graphene oxide (GO) membranes have gained great attention for water purification due to the formation of stacked nanosheets giving nanocapillary channels. Unlike graphene, the interlayer spacing of GO membranes gets readily expanded in aqueous solution due to their high oxygen content, resulting in poor ion rejection. Herein, we prepared ultralow oxygen-containing graphene (∼1 at%) via facile liquid-phase exfoliation which was formed as membrane laminates. The graphene membranes exhibited ultrahigh stability with no observed swelling or deformation of the laminar structure when kept in water, aqueous salt solutions, and various pH solutions for over one week. The membranes with a high degree of tortuous nanocapillary channels can efficiently reject the ions found in seawater as well as various charged dye molecules. This indicates that the graphene membranes exhibited ionic and molecular sieving properties due to the effect of size exclusion obtained from the narrow nanocapillary channel and electrostatic repulsion from negatively charged graphene nanosheets. Moreover, we also demonstrated machine learning to gain insights into the membrane performance, which allowed us to obtain membrane optimization as a model for water purification technology.

The electrochemistry of size dependent graphene via liquid phase exfoliation: capacitance and ionic transport.

Recently, graphene-based materials have become ubiquitous in electrochemical devices including electrochemical sensors, electrocatalysts, capacitive and membrane desalination and energy storage devices. However, many of the electrochemical properties of graphene (particularly the capacitance and ionic transport) are not yet fully understood. This paper explores the capacitance and ionic transport properties of size dependent graphene (from 100 nm to 1 µm) prepared through the liquid phase exfoliation of graphite in which the size of graphene was finely selected using a multi-step centrifugation technique. Our experiment was then expanded to include basal plane graphene using highly ordered pyrolytic graphite as a model electrode, describing the assumed theoretical graphene capacitance (quoted as 550 F g-1 or 21 µF cm-2) and the electrochemical surface area of the carbon-based materials. This work improves our understanding of graphene electrochemistry (capacitance and ion transport), which should lead to the continuing development of many high-performance electrochemical devices, especially supercapacitors, capacitive desalination and ion-based selective membranes.

Controlling the flake size of bifunctional 2D WSe2 nanosheets as flexible binders and supercapacitor materials.

A new approach using graphene as a conductive binder in electrical supercapacitors has recently been proposed. Graphene shows outstanding properties as a conductive binder, and can be used to replace conductive, additive, and polymer binders. However, graphene follows an EDLC behaviour, which may limit its electrochemical performance. In the process described in this work, we introduced WSe2 nanoflakes as a new approach to using pseudocapacitive materials as binders. The WSe2 nanoflakes were produced through liquid phase exfoliation of bulk WSe2, and the flake size was finely selected using a controlled centrifugation speed. The physical and electrochemical properties of the exfoliated WSe2 flakes were analysed; it was found that the smallest flakes (an average flake size of 106 nm) showed outstanding electrochemical properties, expanding our understanding of transition metal dichalcogenide (TMD) materials, and we were able to demonstrate the applicability of using WSe2 as a binder in supercapacitor electrodes. We also successfully replaced conductive additives and polymer binders with WSe2. The overall performance was improved: capacitance was enhanced by 35%, charge transfer resistance reduced by 73%, and self-discharge potential improved by 9%. This study provides an alternative application of using TMD materials as pseudo capacitive binders, which should lead to the continued development of energy storage technology.

Capacitance of Basal Plane and Edge-Oriented Highly Ordered Pyrolytic Graphite: Specific Ion Effects.

Carbon materials are ubiquitous in energy storage; however, many of the fundamental electrochemical properties of carbons are still not fully understood. In this work, we studied the capacitance of highly ordered pyrolytic graphite (HOPG), with the aim of investigating specific ion effects seen in the capacitance of the basal plane and edge-oriented planes of the material. A series of alkali metal cations, from Li+, Na+, K+, Rb+, and Cs+ with chloride as the counterion, were used at a fixed electrolyte concentration. The basal plane capacitance at a fixed potential relative to the potential of zero charge was found to increase from 4.72 to 9.39 µF cm-2 proceeding down Group 1. In contrast, the edge-orientated samples display capacitance ca. 100 times higher than those of the basal plane, attributed to pseudocapacitance processes associated with the presence of oxygen groups and largely independent of cation identity. This work improves understanding of capacitive properties of carbonaceous materials, leading to their continued development for use in energy storage.

Black phosphorus with near-superhydrophobic properties and long-term stability in aqueous media.

Black phosphorus is a two-dimensional material that has potential applications in energy storage, high frequency electronics and sensing, yet it suffers from instability in oxygenated and/or aqueous systems. Here we present the use of a polymeric stabilizer which prevents the degradation of nearly 68% of the material in aqueous media over the course of ca. 1 month.

Desalination and Nanofiltration through Functionalized Laminar MoS2 Membranes.

Laminar membranes of two-dimensional materials are excellent candidates for applications in water filtration due to the formation of nanocapillaries between individual crystals that can exhibit a molecular and ionic sieving effect, while allowing high water flux. This approach has been exemplified previously with graphene oxide, however these membranes suffer from swelling when exposed to liquid water, leading to low salt rejection and reducing their applicability for desalination applications. Here, we demonstrate that by producing thin (∼5 µm) laminar membranes of exfoliated molybdenum disulfide (MoS2) in a straightforward and scalable process, followed by a simple chemical functionalization step, we can efficiently reject ∼99% of the ions commonly found in seawater, while maintaining water fluxes significantly higher (∼5 times) than those reported for graphene oxide membranes. These functionalized MoS2 membranes exhibit excellent long-term stability with no swelling and consequent decrease in ion rejection, when immersed in water for periods exceeding 6 months. Similar stability is observed when exposed to organic solvents, indicating that they are ideal for a variety of technologically important filtration applications.