Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocat...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

This perspective covers the use of molybdenum disulfide and related compounds, generally termed MoSx, as electro- or photoelectrocatalysts for the hydrogen evolution reaction (HER). State of the art solutions as well as the most illustrative results from the extensive electro- and photoelectrocatalytic literature are given. The research strategies currently employed in the field are outlined and future challenges pointed out. We suggest that the key to optimising the HER activity of MoS2 is divided into (1) increasing the catalytic activity of the active site, (2) increasing the number of active sites of the catalyst, and (3) improving the electrical contact to these sites. These postulations are substantiated by examples from the existing literature and some new results. To demonstrate the electrocatalytic properties of a highly conductive MoS2 hybrid material, we present the HER activity data for multi-wall MoS2 nanotubes on multi-wall carbon nanotubes (MWMoS2@MWCNTs). This exemplifies the typical data collected for the electrochemical HER. In addition, it demonstrates that the origin of the activity is closely related to the amount of edges in the layered MoS2. The photoelectrocatalytic HER is also discussed, based on examples from literature, with an emphasis on the use of MoSx as either (1) the co-catalyst providing the HER activity for a semiconductor, e.g. Mo3S+4on Si or (2) MoS2 as the semiconductor with an intrinsic HER activity. Finally, suggestions for future catalyst designs are given.

Molybdenum sulfides—efficient and viable materials for electro - and photoelectrocatalytic hydrogen evolution

Graphene and two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant interest due to their unique properties that cannot be obtained in their bulk counterparts. These atomically thin 2D materials have demonstrated strong light–matter interactions, tunable optical bandgap structures and unique structural and electrical properties, rendering possible the high conversion efficiency of solar energy with a minimal amount of active absorber material. The isolated 2D monolayer can be stacked into arbitrary van der Waals (vdWs) heterostructures without the need to consider lattice matching. Several combinations of 2D/3D and 2D/2D materials have been assembled to create vdWs heterojunctions for photovoltaic (PV) and photoelectrochemical (PEC) energy conversion. However, the complex, less-constrained, and more environmentally vulnerable interface in a vdWs heterojunction is different from that of a conventional, epitaxially grown heterojunction, engendering new challenges for surface and interface engineering. In this review, the physics of band alignment, the chemistry of surface modification and the behavior of photoexcited charge transfer at the interface during PV and PEC processes will be discussed. We will present a survey of the recent progress and challenges of 2D/3D and 2D/2D vdWs heterojunctions, with emphasis on their applicability to PV and PEC devices. Finally, we will discuss emerging issues yet to be explored for 2D materials to achieve high solar energy conversion efficiency and possible strategies to improve their performance.

Engineering graphene and TMDs based van der Waals heterostructures for photovoltaic and photoelectrochemical solar energy conversion

Highly ordered mesoporous crystalline MoSe2 is synthesized using mesoporous silica SBA-15 as a hard template via a nanocasting strategy. Selenium powder and phosphomolybdic acid (H3PMo12O40) are used as Se and Mo sources, respectively. The obtained products have a highly ordered hexagonal mesostructure and a rod-like particle morphology, analogous to the mother template SBA-15. The UV-vis-NIR spectrum of the material shows a strong light absorption throughout the entire visible wavelength region. The direct bandgap is estimated to be 1.37 eV. The high surface area MoSe2 mesostructure shows remarkable photocatalytic activity for the degradation of rhodamine B, a model organic dye, in aqueous solution under visible light irradiation. In addition, the synthesized mesoporous MoSe2 possess a reversible lithium storage capacity of 630 mAh g1 for at least 35 cycles without any notable decrease. The rate performance of mesoporous MoSe2 is much better than that of analogously synthesized mesoporous MoS2, making it a promising anode for the lithium ion battery.

Highly Ordered Mesoporous Crystalline MoSe2 Material with Efficient Visible-Light-Driven Photocatalytic Activity and Enhanced Lithium Storage Performance

Sunlight is directly converted to chemical energy in hydrogen-evolving photoelectrochemical cells with semiconductor electrodes. Their Gibbs free energy efficiency of solar-to-hydrogen conversion, 13.3 percent, exceeds the solar-to-fuel conversion efficiency of green plants and approaches the solar-to-electrical conversion efficiency of the best p-n junction cells. In hydrogen-evolving photoelectrodes, electron-hole pairs photogenerated in the semiconductor are separated at electrical microcontacts between the semiconductor and group VIII metal catalyst islands. Conversion is efficient when the island diameters are small relative to the wave-lengths of sunlight exciting the semiconductor; when the island spacings are smaller than the diffusion length of electrons at the semiconductor surface; when the height of the potential energy barriers that separate the photogenerated electrons from holes at the semiconductor surface is raised by hydrogen alloying of the islands; when radiationless recombination of electron-hole pairs at the semiconductor-solution interface between the islands is suppressed by controlling the semiconductor surface chemistry; and when the semiconductor has an appropriate band gap (1.0 to 1.8 electron volts) for efficient solar conversion.

https://science.sciencemag.org/content/sci/223/4641/1141.full.pdf

D. Canfield

Papers

Efficient and stable photoelectrochemical cells constructed with WSe2 and MoSe2 photoanodes