Sc2C, a 2D Semiconducting Electride.

Electrides are exotic materials that typically have electrons present in well-defined lattice sites rather than within atoms. Although all known electrides have an electropositive metal cation adjacent to the electride site, the effect of cation electronegativity on the properties of electrides is not yet known. Here, we examine trivalent metal carbides with varying degrees of electronegativity and experimentally synthesize Sc2C. Our studies identify the material as a two-dimensional (2D) electride, even though Sc is more electronegative than any metal previously found adjacent to an electride site. Further, by exploring Sc2C and Al2C computationally, we find that higher electronegativity of the cation drives greater hybridization between metal and electride orbitals, which opens a band gap in these materials. Sc2C is the first 2D electride semiconductor, and we propose a design rule that cation electronegativity drives the change in its band structure.

Bonding in 2D Donor-Acceptor Heterostructures.

The ability to alter distances between atoms is among the most important tools in materials design. Despite this importance, controlling the interlayer distance in stacks of 2D materials remains a challenge. Here we show from first-principles that stacking electrenes-a new class of electron-donating 2D materials-with other 2D materials provides this control. The resulting donor-acceptor heterostructures have interlayer distances 1 Å less than van der Waals layered materials but 1 Å more than covalent or ionic bonds. This yields a class of quasi-bonds that exhibit characteristics of both ordinary chemical bonds and van der Waals interactions. We show how quasi-bonds have tunable polarities and strengths and that these bonds can be understood by drawing on familiar concepts from molecular orbital theory. We also demonstrate several useful properties of 2D donor-acceptor heterostructures, including superlubricity, ultralow work functions, and greatly improved voltages for lithium-ion batteries.

Band Gap Engineering in a 2D Material for Solar-to-Chemical Energy Conversion.

The electronic structure of 2D semiconductors depends on their thickness, providing new opportunities to engineer semiconductors for energy conversion, electronics, and catalysis. Here we show how a 3D semiconductor, black phosphorus, becomes active for solar-to-chemical energy conversion when it is thinned to a 2D material. The increase in its band gap, from 0.3 eV (3D) to 2.1 eV (2D monolayer), is accompanied by a 40-fold enhancement in the formation of chemical products. Despite this enhancement, smaller flakes also have shorter excited state lifetimes. We deduce a mechanism in which recombination occurs at flake edges, while the "van der Waals" surface of black phosphorus bonds to chemical intermediates and facilitates electron transfer. The unique properties of black phosphorus highlight its potential as a customizable material for solar energy conversion and catalysis, while also allowing us to identify design rules for 2D photocatalysts that will enable further improvements in these materials.

Experimental Demonstration of an Electride as a 2D Material.

Because of their loosely bound electrons, electrides offer physical properties useful in chemical synthesis and electronics. For these applications and others, nanosized electrides offer advantages, but to-date no electride has been synthesized as a nanomaterial. We demonstrate experimentally that Ca2N, a layered electride in which layers of atoms are separated by layers of a 2D electron gas (2DEG), can be exfoliated into two-dimensional (2D) nanosheets using liquid exfoliation. The 2D flakes are stable in a nitrogen atmosphere or in select organic solvents for at least one month. Electron microscopy and elemental analysis reveal that the 2D flakes retain the crystal structure and stoichiometry of the parent 3D Ca2N. In addition, the 2D flakes exhibit metallic character and an optical response that agrees with DFT calculations. Together these findings suggest that the 2DEG is preserved in the 2D material. With this work, we bring electrides into the nanoregime and experimentally demonstrate a 2D electride, Ca2N.

First-Principles Prediction of Electrochemical Electron-Anion Exchange: Ion Insertion without Redox.

It is widely assumed that the gain or loss of electrons in a material must be accompanied by its reduction or oxidation. Here, we report a system in which the insertion/deinsertion of an electron occurs without any reduction or oxidation. Using first-principles methods, we demonstrate this effect in the Y2CF2-[Y2C]2+(e-)2 material system, where (e-) indicates a lattice site containing a bare electron. We present a model in which Y2CF2 is in contact with a fluoride-containing electrolyte and the application of a positive voltage drives fluorination while a negative voltage reverses the process. We show that this chemistry does not change the oxidation states of the host lattice, causes no significant volume expansion, and occurs rapidly at room temperature. Finally, we demonstrate that this mechanism of ion insertion may enable a broad class of anion shuttle battery electrodes, some with gravimetric capacities nearly double those employed in intercalation-type Li-ion batteries.

Control of Surface and Edge Oxidation on Phosphorene.

Phosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differences between oxygen and water oxidants: while pure oxygen produced an oxide layer on the van der Waals surface, water oxidized the material at pre-existing defects such as edges or steps. We propose a mechanism based on the thermodynamics of electron transfer to interpret these observations. This work opens a route to functionalize the basal surface or edges of two-dimensional (2D) black phosphorus through site-selective chemical reactions and presents the opportunity to explore the synthesis of 2D phosphorene oxide by oxidation.