Urea synthesis through the simultaneous electrocatalytic reduction of N2and CO2molecules under ambient conditions holds great promises as a sustainable alternative to its industrial production, in which the development of stable, highly efficient, and highly selective catalysts to boost the chemisorption, activation, and coupling of inert N2and CO2molecules remains rather challenging. Herein, by means of density functional theory computations, we proposed a new class of two‐dimensional nanomaterials, namely, transition‐metal phosphide monolayers (TM2P, TM = Ti, Fe, Zr, Mo, and W), as the potential electrocatalysts for urea production. Our results showed that these TM2P materials exhibit outstanding stability and excellent metallic properties. Interestingly, the Mo2P monolayer was screened out as the best catalyst for urea synthesis due to its small kinetic energy barrier (0.35 eV) for C–N coupling, low limiting potential (−0.39 V), and significant suppressing effects on the competing side reactions. The outstanding catalytic activity of the Mo2P monolayer can be ascribed to its optimal adsorption strength with the key *NCON species due to its moderate positive charges on the Mo active sites. Our findings not only propose a novel catalyst with high‐efficiency and high‐selectivity for urea production but also further widen the potential applications of metal phosphides in electrocatalysis.
more »
« less
Stability of adsorption of Mg and Na on sulfur-functionalized MXenes
Two-dimensional materials composed of transition metal carbides and nitrides (MXenes) are poised to revolutionize energy conversion and storage. In this work, we used density functional theory (DFT) to investigate the adsorption of Mg and Na adatoms on five M 2 CS 2 monolayers (where M = Mo, Nb, Ti, V, and Zr) for battery applications. We assessed the stability of the adatom ( i.e. Na and Mg)-monolayer systems by calculating adsorption and formation energies, as well as voltages as a function of surface coverage. For instance, we found that Mo 2 CS 2 cannot support a full layer of Na nor even a single Mg atom. Na and Mg exhibit the strongest binding on Zr 2 CS 2 , followed by Ti 2 CS 2 , Nb 2 CS 2 and V 2 CS 2 . Using the nudged elastic band method (NEB), we computed promising diffusion barriers for both dilute and nearly full ion surface coverage cases. In the dilute ion adsorption case, a single Mg and Na atom on Ti 2 CS 2 experience ∼0.47 eV and ∼0.10 eV diffusion barriers between the lowest energy sites, respectively. For a nearly full surface coverage, a Na ion moving on Ti 2 CS 2 experiences a ∼0.33 eV energy barrier, implying a concentration-dependent diffusion barrier. Our molecular dynamics results indicate that the three (one) layers (layer) of the Mg (Na) ion on both surfaces of Ti 2 CS 2 remain stable at T = 300 K. While, according to voltage calculations, Zr 2 CS 2 can store Na up to three atomic layers, our MD simulations predict that the outermost layers detach from the Zr 2 CS 2 monolayer due to the weak interaction between Na ions and the monolayer. This suggests that MD simulations are essential to confirm the stability of an ion-electrode system – an insight that is mostly absent in previous studies.
more »
« less
- Award ID(s):
- 1726213
- PAR ID:
- 10336899
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 23
- Issue:
- 44
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 25424 to 25433
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We develop Mg/C/O/H ReaxFF parameter sets for two environments: an aqueous force field for magnesium ions in solution and an interfacial force field for minerals and mineral–water interfaces. Since magnesium is highly ionic, we choose to fix the magnesium charge and model its interaction with C/O/H through Coulomb, Lennard-Jones, and Buckingham potentials. We parameterize the forcefields against several crystal structures, including brucite, magnesite, magnesia, magnesium hydride, and magnesium carbide, as well as Mg 2+ water binding energies for the aqueous forcefield. Then, we test the forcefield for other magnesium-containing crystals, solvent separated and contact ion-pairs and single-molecule/multilayer water adsorption energies on mineral surfaces. We also apply the forcefield to the forsterite–water and brucite–water interface that contains a bicarbonate ion. We observe that a long-range proton transfer mechanism deprotonates the bicarbonate ion to carbonate at the interface. Free energy calculations show that carbonate can attach to the magnesium surface with an energy barrier of about 0.22 eV, consistent with the free energy required for aqueous Mg–CO 3 ion pairing. Also, the diffusion constant of the hydroxide ions in the water layers formed on the forsterite surface are shown to be anisotropic and heterogeneous. These findings can help explain the experimentally observed fast nucleation and growth of magnesite at low temperature at the mineral–water–CO 2 interface in water-poor conditions.more » « less
-
By means of density functional theory computations, we explored the electrochemical performance of an FeSe monolayer as an anode material for lithium and non-lithium ion batteries (LIBs and NLIBs). The electronic structure, adsorption, diffusion, and storage behavior of different metal atoms (M) in FeSe were systematically investigated. Our computations revealed that M adsorbed FeSe (M = Li, Na and K) systems show metallic characteristics that give rise to good electrical conductivity and mobility with low activation energies for diffusion (0.16, 0.13 and 0.11 eV for Li, Na, and K, respectively) of electrons and metal atoms in the materials, indicative of a fast charge/discharge rate. In addition, the theoretical capacities of the FeSe monolayer for Li, Na and K can reach up to 658, 473, and 315 mA h g −1 , respectively, higher than that of commercial graphite (372 mA h g −1 for Li, 284 mA h g −1 for Na, and 273 mA h g −1 for K), and the average open-circuit voltage is moderate (0.38–0.88 V for Li, Na and K). All these characteristics suggest that the FeSe monolayer is a potential anode material for alkali-metal rechargeable batteries.more » « less
-
null (Ed.)Saccharides comprise a significant mass fraction of organic carbon in sea spray aerosol (SSA), but the mechanisms through which saccharides are transferred from seawater to the ocean surface and eventually into SSA are unclear. It is hypothesized that saccharides cooperatively adsorb to other insoluble organic matter at the air/sea interface, known as the sea surface microlayer (SSML). Using a combination of surface-sensitive infrared reflection-absorption spectroscopy and all-atom molecular dynamics simulations, we demonstrate that the marine-relevant, anionic polysaccharide alginate co-adsorbs to an insoluble palmitic acid monolayer via divalent cationic bridging interactions. Ca2+ induces the greatest extent of alginate co-adsorption to the monolayer, evidenced by the ~30% increase in surface coverage, whereas Mg2+ only facilitates one-third the extent of co-adsorption at seawater-relevant cation concentrations due to its strong hydration propensity. Na+ cations alone do not facilitate alginate co-adsorption, and palmitic acid protonation hinders the formation of divalent cationic bridges between the palmitate and alginate carboxylate moieties. Alginate co-adsorption is largely confined to the interfacial region beneath the monolayer headgroups, so surface pressure, and thus monolayer surface coverage, only changes the amount of alginate co-adsorption by less than 5%. Our results provide physical and molecular characterization of a potentially significant polysaccharide enrichment mechanism within the SSML.more » « less
-
As metal/insulator/metal tunnel junctions (MIMTJs), such as magnetic tunnel junctions and Josephson tunnel junctions, push the insulating tunnel barrier (TB) towards the ultrathin regime (<1 nm) defects inherent in current physical vapor deposition methods become a fundamental obstacle to create pinhole-free and defect-free MIMTJs. Atomic layer deposition (ALD) could offer a solution by providing a conformal, leak-free tunnel barrier with low defect density and atomic thickness as demonstrated recently in ALD Al2O3 tunnel barriers. A question arises on the viability of the ALD TBs in practical circuits of multilayer structures on which increased roughness may occur. To answer this question, this work investigates electron tunneling properties of ALD Al2O3 tunnel barriers of 1.1 –1.2 Å in thickness on half-cell MIMTJs of Al/Fe/Nb fabricated on multilayer structures of different surface roughness using in situ scanning tunneling spectroscopy. Remarkably, the tunnel barriers grown on the raised multilayer device analogue only show a moderate decrease in barrier height from 1.63 eV, to 1.51 eV and to 1.27 eV as the surface roughness increases from 0.9 nm to 2.3 nm, and to 15 nm, alongside a slight decrease in ALD coverage from ∼96%, to ∼93% and 84% on these samples. Overall, these results validate the ALD TBs of atomic thickness for future 3D arrays of devices.more » « less