Theoretically designed two-dimensional γ-C4O as an effective gas separation membrane for hydrogen purification.

A high-performance gas separation membrane for hydrogen (H2) purification is still highly desirable for the sustainable development of our society. Based on the structure of γ-graphyne, we theoretically designed the two-dimensional nanomaterials γ-C4X (X = O, S or Se) with intrinsic pores that may be suitable for gas separation. By first-principles calculations, we obtained the geometric structures of γ-C4X, and confirmed that γ-C4O and γ-C4S are stable at room temperature. Due to the moderate size of the intrinsic pores, γ-C4O exhibits a lower diffusion barrier and higher permeance for H2 than those of γ-C4S. It is worth noting that at room temperature, the high selectivity (1019) for separating H2 from a H2/CH4 mixture by γ-C4O shows great potential for H2 purification. Moreover, the classic molecular dynamics simulations at 300 K demonstrate that H2 can easily permeate through the intrinsic pores of γ-C4O membranes with high permeability and selectivity, which supports our first-principles calculations.

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.

A remarkable two-dimensional membrane for multifunctional gas separation: halogenated metal-free fused-ring polyphthalocyanine.

We theoretically explore the structural and mechanical properties of metal-free fused-ring polyphthalocyanine (H2PPc) and halogenated H2PPc (F-H2PPc and Cl-H2PPc) membranes, and the energy profiles for gaseous H2, CO, CH4, CO2 and N2 molecules adsorbing on and passing through these monolayers. Importantly, we reconsider in depth the values of the parameters in the definition of permeance, and corroborate the validity of the model from first-principles theory with the results of H2 diffusion from classic molecular dynamics simulations. With well-defined nanosized pores, halogenated H2PPc monolayers turn out to be multifunctional gas separation membranes, i.e. F-H2PPc for H2/CO, H2/CH4, CO2/N2, CO2/CH4, CO/CH4 and N2/CH4 separation as well as Cl-H2PPc for H2/CO, H2/CH4 and H2/CO2 separation, which should be of great potential in energy and environmental fields.

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.

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.

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.

Boron-substituted graphyne as a versatile material with high storage capacities of Li and H2: a multiscale theoretical study.

Based on density functional theory (DFT), first-principles molecular dynamics (MD), and the grand canonical ensemble Monte Carlo (GCMC) method, we investigated the boron substitution in aromatic rings of graphyne in terms of geometric and electronic structures as well as its bifunctional application including Li and H2 storage. The calculated binding energies of B-doped graphyne (BG) are significantly enhanced at two adsorptive sites compared to pristine graphyne, leading to high lithiation potentials of 2.7 V in 6Li@1BG, and even higher with 3.0 V in 6Li@3BG. Thus, 6Li@1BG with a capacity of 1125 mA h g(-1), which is much larger than other carbon materials, is proposed to be a good anode material in lithium-ion batteries. For further hydrogen storage in 6Li@nBG, the results show that it can steadily adsorb at least 8H2 in DFT, MD and GCMC computations, and the excess gravimetric H2 uptake is 7.4 wt% at ambient conditions, exceeding the 2017 DOE target. Our multiscale simulations demonstrate that chemical modifications in two-dimensional carbon structures are very promising for high lithium storage and hydrogen uptake.

Two-Dimensional BAs/InTe: A Promising Tandem Solar Cell with High Power Conversion Efficiency.

Tandem solar cells (SCs) connecting two subcells with different absorption bands have the potential to reach the commercialized photovoltaic standard. However, the performance improvement of tandem architectures is still a challenge, primarily owing to the mismatch of band gaps in two subcells. Here, we demonstrate a two-dimensional (2D) BAs/InTe-based tandem SC, which could achieve solar-to-electric conversion efficiency higher than 30%. First, the narrow band gap of hexagonal single-layer BX (X = P and As) and wide band gap of single-layer YZ (Y = Ga and In, Z = S, Se, and Te) are found to have high thermodynamic stability based on density functional theory calculations. Next, considering narrow and wide band gaps at the HSE06 functional, single-layer BX/YZ-based tandem SCs are built to effectively capture a broad-band solar spectrum by combining such two subcells. Since the band gap of single-layer BAs matches well with that of the InTe monolayer, the power conversion efficiency of BAs/InTe-based tandem SC can reach as high as 30.2%. Moreover, it is important to note that the used materials, including few-layer GaZ and InSe, have been experimentally prepared, which strongly supports the high feasibility of the designed 2D tandem SCs in this work. Our constructed 2D-material-based devices can be competitive in realizing commercialized high-performance tandem SCs.

Tunable Topological State, High Hole-Carrier Mobility, and Prominent Sunlight Absorbance in Monolayered Calcium Triarsenide.

Designing novel two-dimensional (2D) materials is highly desirable for material innovation. Here, we propose monolayered calcium triarsenide (1L CaAs3) as a new 2D semiconductor with a series of encouraging functionalities. In contrast to the ∼33 meV small band gap in bulk CaAs3, 1L CaAs3 possesses a large direct band gap of 0.92 eV with a high hole mobility of ∼104 cm2 V-1 s-1. The electronic properties of 2D CaAs3 can be manipulated significantly by the layer thickness and external strains. Remarkably, 2D CaAs3 suggests a topologically nontrivial-trivial state transition under thickness reduction and strain engineering, which is attributed to the drastic surface relaxation and pinch effect under compression. A semiconductor-semimetal transition is also revealed when the layer thickness is greater than 3L. Furthermore, 1L CaAs3 exhibits prominent visible-light absorption compared with the crystalline silicon. All these desired properties render 2D CaAs3 a promising candidate for use in electronic and photovoltaic devices.

Nanoporous MoS2 monolayer as a promising membrane for purifying hydrogen and enriching methane.

We present a theoretical prediction of a highly efficient membrane for hydrogen purification and natural gas upgrading, i.e. laminar MoS2 material with triangular sulfur-edged nanopores. We calculated from first principles the diffusion barriers of H2 and CO2 across monolayer MoS2 to be, respectively, 0.07 eV and 0.17 eV, which are low enough to warrant their great permeability. The permeance values for H2 and CO2 far exceed the industrially accepted standard. Meanwhile, such a porous MoS2 membrane shows excellent selectivity in terms of H2/CO, H2/N2, H2/CH4, and CO2/CH4 separation (>103, > 103, > 106, and > 104, respectively) at room temperature. We expect that the findings in this work will expedite theoretical or experimental exploration on gas separation membranes based on transition metal dichalcogenides.

Graphdiyne as a High-Efficiency Membrane for Separating Oxygen from Harmful Gases: A First-Principles Study.

We theoretically explored the adsorption and diffusion properties of oxygen and several harmful gases penetrating the graphdiyne monolayer. According to our first-principles calculations, the oxidation of the acetylenic bond in graphdiyne needs to surmount an energy barrier of ca. 1.97 eV, implying that graphdiyne remains unaffected under oxygen-rich conditions. In a broad temperature range, graphdiyne with well-defined nanosized pores exhibits a perfect performance for oxygen separation from typical noxious gases, which should be of great potential in medical treatment and industry.

A promising monolayer membrane for oxygen separation from harmful gases: nitrogen-substituted polyphenylene.

We theoretically demonstrate that N-substitutional doping dramatically reduces the diffusion barrier for oxygen passing through the pores of polyphenylene, leading to a massive enhancement in O2 selectivity over various harmful gases with excellent permeance at appropriate temperatures for O2 across an N-doped polyphenylene in a unit cell.