Exploring the catalytic activity of graphene-based TM-NxC4-x single atom catalysts for the oxygen reduction reaction via density functional theory calculation.

Electrocatalysts for the oxygen reduction reaction (ORR) are extremely crucial for advanced energy conversion technologies, such as fuel cell batteries. A promising ORR catalyst usually should have low overpotentials, rich catalytic sites and low cost. In the past decade, single-atom catalyst (SAC) TM-N4 (TM = Fe, Co, etc.) embedded graphene matrixes have been widely studied for their promising performance and low cost for ORR catalysis, but the effect of coordination on the ORR activity is not fully understood. In this work, we will employ density functional theory (DFT) calculations to systematically investigate the ORR activity of 40 different 3d transition metal single-atom catalysts (SACs) supported on nitrogen-doped graphene supports, ranging from vanadium to zinc. Five different nitrogen coordination configurations (TM-NxC4-x with x = 0, 1, 2, 3, and 4) were studied to reveal how C/N substitution affects the ORR activity. By looking at the stability, free energy diagram, overpotential, and scaling relationship, our calculation showed that partial C substitution can effectively improve the ORR performance of Mn, Co, Ni, and Zn-based SACs. The volcano plot obtained from the scaling relationship indicated that the substitution of N by C could distinctively affect the potential-limiting step in the ORR, which leads to the enhanced or weakened ORR performance. Density of states and d-band center analysis suggested that this coordination-tuned ORR activity can be explained by the shift of the d-band center due to the coordination effect. Finally, four candidates with optimal ORR activity and dynamic stability were proposed from the pool: NiC4, CoNC3, CrN4, and ZnN3C. Our work provides a feasible designing strategy to improve the ORR activity of graphene-based TM-N4 SACs by tuning the coordination environment, which may have potential implication in the high-performance fuel cell development.

Enhanced electrocatalytic hydrogen evolution from nitrogen plasma-tailored MoS2 nanostructures.

Two-dimensional (2D) layered transition metal dichalcogenides such as MoS2 have been viewed as the most favorable candidates for replacing noble metals in catalyzing the hydrogen evolution reaction in water splitting owing to their earth abundance, superb chemical stability, and appropriate Gibbs free energy. However, due to its low number of catalytic sites and basal catalytic inertia, the pristine MoS2 displayed intrinsically unsatisfactory HER catalytic activity. Here, the hydrogen evolution catalytic activities of nanostructured MoS2 powder before and after plasma modification with nitrogen doping were experimentally compared, and the influence of treatment parameters on the hydrogen evolution catalytic performance of MoS2 has been studied. The feasibility of regulating hydrogen evolution catalytic activity by nitrogen doping of MoS2 was verified based on density functional theory calculations. Our work demonstrates a more convenient and faster way to develop cheap and efficient MoS2-based catalysts for electrochemical hydrogen evolution reactions. Additionally, theoretical studies reveal that N-doped MoS2 exhibits strong hybridization between Mo-d and N-p states, causing magnetism to evolve, as confirmed by experiments.

Polymeric heptazine imide by O doping and constructing van der Waals heterostructures for photocatalytic water splitting: a theoretical perspective from transition dipole moment analyses.

Semiconductor-based photocatalysts have received extensive attention for their promising capacity in confronting global energy and environmental issues. In photocatalysis, a large band gap with suitable edge-position is necessary to warrant enough driving force for reaction, whereas a much smaller band gap is needed for visible-light response and high solar energy conversion efficiency. This paradox hinders the development of photocatalysts. Via state-of-the-art first-principles calculations, we find that the transition dipole moments (TDMs) are changed significantly in O-doped partly polymerized g-C3N4, i.e., OH-terminated polymeric heptazine imide (PHI-OH), and concomitantly, an enhancement of visible-light absorption is achieved; meanwhile a large enough band gap can provide a powerful driving force in the photocatalytic watersplitting reaction. Furthermore, by using TDM analysis of the PHI-OH/BC3N heterostructure, direct light excited transition between two building layers can be confirmed, suggesting it as a candidate catalyst for hydrogen evolution. From TDM analysis of the PHI-OH/BCN heterostructure, we also verify a Z-scheme process, which involves simultaneous photoexcitations with strong reducibility and oxidizability. Thus, TDM could be a good referential descriptor for revealing photocatalytic mechanisms in semiconductor photocatalysts and interlayer photoexcitation behavior in layered heterostructures. Hopefully, more strategies via modification of TDMs would be proposed to enhance the visible-light response of a semiconductor without sacrificing its photocatalytic driving force.

Ultra-High-Temperature Ferromagnetism in Intrinsic Tetrahedral Semiconductors.

Ferromagnetic semiconductors exhibit novel spin-dependent optical, electrical, and transport properties, which are promising for next-generation highly functional spintronic devices. However, the possibility of practical applications is hindered by their low Curie temperature. Currently, whether semiconducting ferromagnetism can exist at room temperature is still unclear because of the absence of a solid physical mechanism. Here, on the basis of tight-binding model analysis and first-principles calculations, we report that ferromagnetism in a tetrahedral semiconductor originating from superexchange interactions can be strong enough to survive at room temperature because of the weakening of antiferromagnetic direct-exchange interactions. On the basis of the explored mechanism, a zinc-blende binary transition metal compound, chromium carbide, is predicted to be an intrinsic ferromagnetic tetrahedral semiconductor with a Curie temperature that is as high as ∼1900 K. These findings not only expand the understandings of magnetism in semiconductors but also are of great interest for room-temperature spintronic applications.

Toward Intrinsic Room-Temperature Ferromagnetism in Two-Dimensional Semiconductors.

Two-dimensional (2D) ferromagnetic semiconductors have been recognized as the cornerstone for next-generation electric devices, but the development is highly limited by the weak ferromagnetic coupling and low Curie temperature ( TC). Here, we reported a general mechanism which can significantly enhance the ferromagnetic coupling in 2D semiconductors without introducing carriers. On the basis of a double-orbital model, we revealed that the superexchange-driven ferromagnetism is closely related to the virtual exchange gap, and lowering this gap by isovalent alloying can significantly enhance the ferromagnetic (FM) coupling. On the basis of the experimentally available two-dimensional CrI3 and CrGeTe3, the FM coupling in two semiconducting alloy compounds CrWI6 and CrWGe2Te6 monolayers are calculated to be enhanced by 3∼5 times without introducing any carriers. Furthermore, a room-temperature ferromagnetic semiconductor is achieved under a small in-plane strain (4%). Thus, our findings not only deepen the understanding of FM semiconductors but also open a new door for realistic spintronics.

Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer.

The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr_{3} monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr─Br_{6} units. As an example, we further show that (CrBr_{3})_{2}Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

Confinement boosts CO oxidation on an Ni atom embedded inside boron nitride nanotubes.

To date, most studies of heterogeneous catalysis have focused on metal particles supported on the surface of substrates. However, studies of the catalytic properties of metallic nanoparticles supported on the interior surface of nanotubes are rare. Using first-principles calculations based on density functional theory, we have studied the CO oxidation on a single nickel atom confined in a nitrogen vacancy on the inside surface of boron nitride nanotubes (BNNT). By exploring the Eley-Rideal mechanism, we find that an Ni atom embedded on the interior surface of BNNTs exhibits a much higher catalytic activity for CO oxidation when compared with Ni doped on their outside surface. In addition, the energy barriers of the rate-determining step for CO oxidation on Ni embedded on the inside wall of BNNT(5,5), BNNT(6,6) and BNNT(7,7) are 0.39, 0.29 and 0.33 eV, respectively. The results illustrate the merit of confinement for CO oxidation.

Effect of Coulomb Correlation on the Magnetic Properties of Mn Clusters.

In spite of decades of research, a fundamental understanding of the unusual magnetic behavior of small Mn clusters remains a challenge. Experiments show that Mn2 is antiferromagnetic while small clusters containing up to five Mn atoms are ferromagnetic with magnetic moments of 5 µB/atom and become ferrimagnetic as they grow further. Theoretical studies based on density functional theory (DFT), however, find Mn2 to be ferromagnetic, with ferrimagnetic order setting in at different sizes that depend upon the computational methods used. While quantum chemical techniques correctly account for the antiferromagnetic ground state of Mn2, they are computationally too demanding to treat larger clusters, making it difficult to understand the evolution of magnetism. These studies clearly point to the importance of correlation and the need to find ways to treat it effectively for larger clusters and nanostructures. Here, we show that the DFT+ U method can be used to account for strong correlation. We determine the on-site Coulomb correlation, Hubbard U self-consistently by using the linear response theory and study its effect on the magnetic coupling of Mn clusters containing up to five atoms. With a calculated U value of 4.8 eV, we show that the ground state of Mn2 is antiferromagnetic with a Mn-Mn distance of 3.34 Å, which agrees well with the electron spin resonance experiment. Equally important, we show that on-site Coulomb correlation also plays an important role in the evolution of magnetic coupling in larger clusters, as the results differ significantly from standard DFT calculations. We conclude that for a proper understanding of magnetism of Mn nanostructures (clusters, chains, and layers) one must take into account the effect of strong correlation.

Stabilization of the Metastable Lead Iodide Perovskite Phase via Surface Functionalization.

Metastable structural polymorphs can have superior properties and applications to their thermodynamically stable phases, but the rational synthesis of metastable phases is a challenge. Here, a new strategy for stabilizing metastable phases using surface functionalization is demonstrated using the example of formamidinium lead iodide (FAPbI3) perovskite, which is metastable at room temperature (RT) but holds great promises in solar and light-emitting applications. We show that, through surface ligand functionalization during direct solution growth at RT, pure FAPbI3 in the cubic perovskite phase can be stabilized in nanostructures and thin films at RT without cation or anion alloying. Surface characterizations reveal that long-chain alkyl or aromatic ammonium (LA) cations bind to the surface of perovskite structure. Calculations show that such functionalization reduces the surface energy and plays a dominant role in stabilizing the metastable perovskite phase. Excellent photophysics and optically pumped lasing from the stabilized single-crystal FAPbI3 nanoplates with low thresholds were demonstrated. High-performance solar cells can be fabricated with such directly synthesized stabilized phase-pure FAPbI3 with a lower bandgap. Our results offer new insights on the surface chemistry of perovskite materials and provide a new strategy for stabilizing metastable perovskites and metastable polymorphs of solid materials in general.

Ca-Embedded C2N: an efficient adsorbent for CO2 capture.

Carbon dioxide as a greenhouse gas causes severe impacts on the environment, whereas it is also a necessary chemical feedstock that can be converted into carbon-based fuels via electrochemical reduction. To efficiently and reversibly capture CO2, it is important to find novel materials for a good balance between adsorption and desorption. In this study, we performed first-principles calculations and grand canonical Monte Carlo (GCMC) simulations, to systematically study metal-embedded carbon nitride (C2N) nanosheets for CO2 capture. Our first-principles results indicated that Ca atoms can be uniformly trapped in the cavity center of C2N structure, while the transition metals (Sc, Ti, V, Cr, Mn, Fe, Co) are favorably embedded in the sites off the center of the cavity. The determined maximum number of CO2 molecules with strong physisorption showed that Ca-embedded C2N monolayer is the most promising CO2 adsorbent among all considered metal-embedded materials. Moreover, GCMC simulations revealed that at room temperature the gravimetric density for CO2 adsorbed on Ca-embedded C2N reached 50 wt% at 30 bar and 23 wt% at 1 bar, higher than other layered materials, thus providing a satisfactory system for the CO2 capture and utilization.

New Ferroelectric Phase in Atomic-Thick Phosphorene Nanoribbons: Existence of in-Plane Electric Polarization.

Ferroelectrics have many significant applications in electric devices, such as capacitor or random-access memory, tuning the efficiency of solar cell. Although atomic-thick ferroelectrics are the necessary components for high-density electric devices or nanoscale devices, the development of such materials still faces a big challenge because of the limitation of intrinsic mechanism. Here, we reported that in-plane atomic-thick ferroelectricity can be induced by vertical electric field in phosphorene nanoribbons (PNRs). Through symmetry arguments, we predicted that ferroelectric direction is perpendicular to the direction of external electric field and lies in the plane. Further confirmed by the comprehensive first-principles calculations, we showed that such ferroelectricity is induced by the electron-polarization, which is different from the structural distortion in traditional ferroelectrics and the recent experimental discovery of in-plane atomic-thick ferroelectrics (Science 2016, 353, 274). Moreover, we found that the value of electronic polarization in bilayer is much larger than that in monolayer. Our results show that electron-polarization ferroelectricity maybe the most promising candidate for atomic-thick ferroelectrics.

Realizing half-metallicity in K2CoF4 exfoliated nanosheets via defect engineering.

Two-dimensional (2D) materials with intriguing electronic characteristics open up tremendous opportunities for application in future nanoelectronic devices, and have become one of the hot subjects of today's research. Here, we firstly predict the possibility of realizing a 2D exfoliated ionic bonding nanosheet, namely the K2CoF4 nanosheet, based on first-principles calculations. Through analysis of the cleavage energy, in-plane stiffness and stability, the free-standing K2CoF4 nanosheet can be exfoliated in experiments. It is shown that the K2CoF4 nanosheet with K vacancy can transform into a ferromagnetic half-metal under moderate tensile strain, whereas the pristine K2CoF4 nanosheet is an antiferromagnetic semiconductor. Monte Carlo simulations based on the Heisenberg model predict that the Curie temperature for the K vacancy K2CoF4 nanosheet under 2% tensile strain is higher than room temperature. Therefore, our results suggest that the K2CoF4 nanosheet may be a promising material for spintronic and nanoelectronic applications.

Carrier mobility in double-helix DNA and RNA: A quantum chemistry study with Marcus-Hush theory.

Charge mobilities of six DNAs and RNAs have been computed using quantum chemistry calculation combined with the Marcus-Hush theory. Based on this simulation model, we obtained quite reasonable results when compared with the experiment, and the obtained charge mobility strongly depends on the molecular reorganization and electronic coupling. Besides, we find that hole mobilities are larger than electron mobilities no matter in DNAs or in RNAs, and the hole mobility of 2L8I can reach 1.09 × 10-1 cm2 V-1 s-1 which can be applied in the molecular wire. The findings also show that our theoretical model can be regarded as a promising candidate for screening DNA- and RNA-based molecular electronic devices.

Atomically Thin Transition-Metal Dinitrides: High-Temperature Ferromagnetism and Half-Metallicity.

High-temperature ferromagnetic two-dimensional (2D) materials with flat surfaces have been a long-sought goal due to their potential in spintronics applications. Through comprehensive first-principles calculations, we show that the recently synthesized MoN2 monolayer is such a material; it is ferromagnetic with a Curie temperature of nearly 420 K, which is higher than that of any flat 2D magnetic materials studied to date. This novel property, made possible by the electron-deficient nitrogen ions, render transition-metal dinitrides monolayers with unique electronic properties which can be switched from the ferromagnetic metals in MoN2, ZrN2, and TcN2 to half-metallic ones in YN2. Transition-metal dinitrides monolayers may, therefore, serve as good candidates for spintronics devices.

Two-dimensional silicon monolayers generated on c-BN(111) substrate.

Silicene, a buckled two-dimensional honeycomb structure of silicon, has been experimentally synthesized on very few substrates. Furthermore, synthesizing silicene with a Dirac point is another hot research area. However, only silicene grown on Ag(111) has been reported to have a Dirac point, which has lowered the expectations of researchers. Here, three Si monolayer structures, a Si chain-type structure, a two-dimensional hexagonal close packed compound structure, and a two-dimensional hexagonal close packed structure, are generated on a c-BN(111) substrate using a particle-swarm optimization algorithm implemented in CALYPSO code. Band structure calculations show that all three structures exhibit a metallic nature. In particular, due to the absolutely flat conformation of the latter two structures, a linear dispersion exists near the Fermi energy level, indicating that charge carriers can transport like massless Dirac fermions. Our results open an alternative way of searching for other two-dimensional silicon monolayers with Dirac points.

Improved permeability and selectivity in porous graphene for hydrogen purification.

Porous graphene is a promising material for the realization of low-cost, large-area and lightweight gas separation. However, molecular-sieving membranes based on porous materials reported thus far generally cannot fulfill the requirements of both high permeability and high selectivity. Simultaneously meeting the goals of high permeability and high selectivity remains a great challenge. As we demonstrate here, with the development of an inter-layer-connected porous graphene bilayer, both the permeability and selectivity are significantly improved, and a high criterion of selectivity for H2 over CH4 (10(24) at room temperature) as well as a high flux of H2 (2.4 × 10(5) Gas Permeance Unit) has been reached. Our studies highlight a new approach towards the final goal of high-permeability and high-selectivity molecular-sieving membranes using simple structural engineering.

A B-C-N hybrid porous sheet: an efficient metal-free visible-light absorption material.

The polyphenylene network, known as porous graphene, is one of the most important and widely studied two-dimensional materials. As a potential candidate for photocatalysis and photovoltaic energy generation, its application has been limited by the low photocatalytic activity in the visible-light region. State-of-the-art hybrid density functional theory investigations are presented to show that an analogous B-C-N porous sheet outperforms the pristine polyphenylene network with significantly enhanced visible-light absorption. Compared with porous graphene, the calculated energy gap of the B-C-N hybrid crystal shrinks to 2.7 eV and the optical absorption peak remarkably shifts to the visible light region. The redox potentials of water splitting are well positioned in the middle of the band gap. Hybridizations among B_p, N_p and C_p orbitals are responsible for these findings. Valence and conduction band calculations indicate that the electrons and holes can be effectively separated, reducing charge recombination and improving the photoconversion efficiency. Moreover, the band gap and optical properties of the B-C-N hybrid porous sheet can be further finely engineered by external strain.

Quantum wave packet and quasiclassical trajectory studies of the reaction H(2S) + CH(X2 Π; v = 0, j = 1) → C(1D) + H2 (X1 Σg+): Coriolis coupling effects and stereodynamics.

The quantum mechanics (QM) and quasiclassical trajectory (QCT) calculations have been carried out for the title reaction with the ground minimal allowed rotational state of CH (j = 1) on the 1 (1)A' potential energy surface. For the reaction probability at total angular momentum J = 0, a similar trend of the QM and QCT calculations is observed, and the QM results are larger than the latter almost in the whole considered energy range (0.1-1.5 eV). The QCT integral cross sections are larger than the QM results with centrifugal sudden approximation, while smaller than those from QM method including Coriolis coupling for collision energies bigger than 0.25 eV. The quantum wave-packet computations show that the Coriolis coupling effects get more and more pronounced with increasing of J. In addition to the scalar properties, the stereodynamical properties, such as the average rotational alignment factor , the angular distributions P(θr ), P(ϕr ), P(θr ,ϕr ), and the polarization-dependent generalized differential cross sections have been explored in detail by QCT approach.

The strain effect on colossal oxygen ionic conductivity in nanoscale zirconia electrolytes: a first-principles-based study.

Density functional theory calculations and first-principles molecular dynamics (MD) simulations have been performed to examine the strain effect on the colossal oxygen ionic conductivity in selected sandwich structures of zirconia electrolytes. For the KTaO(3)/YSZ/KTaO(3) sandwich structure with 9.7% lattice mismatch, transition state calculations indicate that the strain effect changes the oxygen migration pathways from straight line into zigzag form and reduces the energy barrier by 0.2 eV. On the basis of our computational results, a possible oxygen ion diffusion highway is suggested. By finite-temperature MD simulations, an activation barrier of 0.33 eV is obtained, corresponding to an oxygen ionic conductivity which is 6.4 × 10(7) times higher than that of the unstrained bulk zirconia at 500 K. A nearly linear relationship is identified between the energy barrier and the lattice mismatch in the sandwich structures.

Tunable band gap and hydrogen adsorption property of a two-dimensional porous polymer by nitrogen substitution.

After substitution of carbon by nitrogen, the electronic structures of the porous graphene have been studied by the density functional theory calculations. The N substitutional site without hydrogen passivation leads to a tunable energy gap of the two-dimensional porous polymer, depending on the number of N atoms in a unit cell. Moreover, the increasing number of N in an aromatic ring enhances the binding energies between hydrogen molecules and pre-adsorbed Li atoms from 1H(2) to 3H(2). Thus, porous polymer materials through controllable synthesis techniques will improve their potential applications in photosplitting of water as well as hydrogen storage.