Study on the growth mechanism of monolayer and few-layer hexagonal boron nitride films on copper foil.

During the process of synthesizing h-BN on Cu foil via chemical vapor deposition (CVD), low-pressure CVD (LPCVD) typically synthesizes monolayer h-BN films, whereas atmospheric pressure CVD (APCVD) yields few-layer h-BN films. Herein, a growth mechanism for monolayer and few-layer h-BN on Cu foil is proposed using first-principles calculations: Cu(111) passivated h-BN hinders the diffusion of B and N atoms at the subsurface of Cu(111), preventing sufficient transportation of B and N atoms to the existing h-BN layer, thereby leading to the formation of monolayer h-BN in LPCVD. For APCVD, the edges of h-BN are passivated by H, which decreases the barrier energy for the diffusion of B and N atoms on the Cu(111) subsurface, and B and N atoms can easily migrate from the subsurface of Cu(111) to its surface, resulting in the nucleation of h-BN between the existing h-BN and Cu(111), and leading to the formation of few-layer h-BN films. This work provides a theoretical basis at the atomic scale for further understanding the growth of monolayer and few-layer h-BN films on Cu foil.

S-Scheme Boron Phosphide/MoS2 Heterostructure with Excellent Light Conversion Ability for Solar Cells and Water Splitting Photocatalysts.

Monolayer molybdenum disulfide (MoS2) with a suitable direct band gap and strong optical absorption is very attractive for utilization in solar cells and photocatalytic water splitting. Nevertheless, the broader utilization of MoS2 is impeded by its low carrier mobility and limited responsiveness to infrared light. To overcome these challenges, we constructed a variety of stackings for the boron phosphide (BP)/MoS2 van der Waals heterostructure (vdWH), all of which display S-scheme band alignments except for the AC' stacking. The constituent BP monolayer has superior carrier mobility and strong infrared and visible light response, which makes up for the shortcomings of MoS2. The study revealed that the AB stacking exhibits a remarkable power conversion efficiency of 22.27%, indicating its significant application prospect in solar cells. Additionally, the AB stacking also exhibits a promising application prospect in photocatalytic water splitting due to its suitable band structure, S-scheme band alignment, strong optical adsorption characteristic, high solar-to-hydrogen efficiency, and robust built-in electric field. Meanwhile, applying uniaxial tensile strains along the x-axis direction is more beneficial for photocatalytic water splitting. Hence, the AB-stacked BP/MoS2 vdWH shows significant potential for use in both solar cells and photocatalytic water splitting. This work paves the way for exploring the application of S-scheme heterostructures in solar energy conversion systems.

A 2D-0D-2D Sandwich Heterostructure toward High-Performance Room-Temperature Gas Sensing.

The construction of two-dimensional (2D) van der Waals (vdW) heterostructures over black phosphorus (BP) has been attracting significant attention to better utilize its inherent properties. The sandwich of zero-dimensional (0D) noble metals within BP-based vdW heterostructures can provide efficient catalytic channels, modulating their surface redox potentials and therefore inducing versatile functionalities. Herein, we realize a 2D WS2-Au-BP heterostructure, in which Au nanoparticles are connected between BP and WS2 via ionic bonds. The ultralow conduction band minimum position, the reduced adsorption energies of O2, and the increased dissociation barrier energy of O2- into 2O contribute greatly to improving the long-term stability of BP in the air. The formation of heterostructures can reduce the potential barrier energy in target gas molecules, thus enhancing the absorption energy and charge transfer. Taking the paramagnetic NO2 gas molecules as a representative, a stable response magnitude of 2.11 to 100 ppb NO2 is achieved for 80 days, which is far larger than the initial responses of most BP-based materials. A practical gas sensing system is also developed to demonstrate its real-world implementation. This work provides a promising demonstration of 0D noble metal within 2D BP-based vdW heterostructure for simultaneously improving the long-term stability and room-temperature reversible gas sensing.

ZnO-Au@ZIF-8 core-shell nanorod arrays for ppb-level NO2 detection.

ZnO-Au@ZIF-8 core-shell heterostructures were prepared by ZIF-8 encapsulation of sacrificial ZnO-Au nanorods. Because of the catalytic activity of the Au nanoparticles and the sieving effects of the ZIF-8, the ZnO-Au@ZIF-8 heterostructures showed an outstanding response of 1.8 to 5 ppb NO2, and exhibited higher selectivity, stability, anti-humidity and fast response and recovery properties. The combination of the gas-selective catalytic activity of noble metals with the MOF filter used in this work can be easily extended to synthesize other types of MOS@MOF sensors, opening a new avenue for the detection of hazardous gases.

In Situ Construction of Zinc-Mediated Fe, N-Codoped Hollow Carbon Nanocages with Boosted Oxygen Reduction for Zn-Air Batteries.

The rational design of bifunctional oxygen electrocatalysts with unique morphology and luxuriant porous structure is significant but challenging for accelerating the reaction kinetics of rechargeable Zn-air batteries (ZABs). Herein, zinc-mediated Fe, N-codoped carbon nanocages (Zn-FeNCNs) are synthesized by pyrolyzing the polymerized iron-doped polydopamine on the surface of the ZIF-8 crystal polyhedron. The formation of the chelate between polydopamine and Fe serves as the covering layer to prevent the porous carbon nanocages from collapsing and boosts enough exposure and utilization of metal-based active species during carbonization. Furthermore, both the theoretical calculation and experimental results show that the strong interaction between polyhedron and polydopamine facilitates the evolution of high-activity zinc-modulated FeNx sites and electron transportation and then stimulates the excellent bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). As expected, the Zn-air battery with Zn-FeNCNs as an air cathode displays a superior power density (256 mW cm-2) and a high specific capacity (813.3 mA h gZn-1), as well as long-term stability over 1000 h. Besides, when this catalyst is applied to the solid-state battery, the device exhibited outstanding mechanical stability and a high round-trip efficiency under different bending angles.

Waste to treasure: Electrocatalytic upcycling of n-valeraldehyde to octane by Zn-Co bimetallic oxide with atomic level cation defect.

n-Valeraldehyde is widely used in organic synthesis field as an important intermediate and feedstock, which makes it a significant class of environmental pollutants. In view of the high poisonous and harmful of n-valeraldehyde to human health and ecological environment, it is important to develop green and sustainable technology to reduce the pollution of n-valeraldehyde. In this work, electrocatalytic n-valeraldehyde oxidation using Zn-Co bimetallic oxides was applied to control n-valeraldehyde contamination and highly valuable octane production. To further improve the performance of Zn-Co bimetallic oxides, atomic level Zn vacancies were created across the Zn-Co bimetallic oxides (dx-ZnCo2O4) by post-etching and oxygen vacancy filling methods. Electrochemical experiments results showed that dx-ZnCo2O4 owned a much higher octane yield (1193.4 µmol g-1 h-1) and octane selectivity (octane/butene ≈10). Theoretical calculations demonstrated that the introduction of atomic level Zn vacancies in Zn-Co bimetallic oxide changed the electronic distribution around O, Co and Zn atoms, resulted in an alteration in n-valeraldehyde adsorption sites from Co to Zn, reduced the formation barrier of key intermediate *C4H9 and facilitated the transfer of n-valeraldehyde to octane. This study provides a new idea for the development of high-performance electrocatalysts for controlling n-valeraldehyde pollution.

In Situ Atomic-Scale Deciphering of Multiple Dynamic Phase Transformations and Reversible Sodium Storage in Ternary Metal Sulfide Anode.

Ternary metal sulfides (TMSs), endowed with the synergistic effect of their respective binary counterparts, hold great promise as anode candidates for boosting sodium storage performance. Their fundamental sodium storage mechanisms associated with dynamic structural evolution and reaction kinetics, however, have not been fully comprehended. To enhance the electrochemical performance of TMS anodes in sodium-ion batteries (SIBs), it is of critical importance to gain a better mechanistic understanding of their dynamic electrochemical processes during live (de)sodiation cycling. Herein, taking BiSbS3 anode as a representative paradigm, its real-time sodium storage mechanisms down to the atomic scale during the (de)sodiation cycling are systematically elucidated through in situ transmission electron microscopy. Previously unexplored multiple phase transformations involving intercalation, two-step conversion, and two-step alloying reactions are explicitly revealed during sodiation, in which newly formed Na2BiSbS4 and Na2BiSb are respectively identified as intermediate phases of the conversion and alloying reactions. Impressively, the final sodiation products of Na6BiSb and Na2S can recover to the original BiSbS3 phase upon desodiation, and afterward, a reversible phase transformation can be established between BiSbS3 and Na6BiSb, where the BiSb as an individual phase (rather than respective Bi and Sb phases) participates in reactions. These findings are further verified by operando X-ray diffraction, density functional theory calculations, and electrochemical tests. Our work provides valuable insights into the mechanistic understanding of sodium storage mechanisms in TMS anodes and important implications for their performance optimization toward high-performance SIBs.

Molten salt induced formation of chitosan based carbon nanosheets decorated with CoNx for boosting rechargeable Zn-air batteries.

The earth-abundant, low-cost, and efficient oxygen electrode materials offer a potential opportunity to satisfy the large-scale production and application of metal-air batteries. Herein, a molten salt-assisted strategy is developed to anchor transition metal-based active sites via in-situ confining into porous carbon nanosheet. As a result, a chitosan-based porous nitrogen-doped nanosheet decorated with the well-defined CoNx (CoNx/CPCN) was reported. Both structural characterization and electrocatalytic mechanisms demonstrate a prominent synergetic effect between CoNx and porous nitrogen-doped carbon nanosheets forcefully accelerates the sluggish reaction kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Interestingly, the Zn-air batteries (ZABs) equipped with CoNx/CPCN-900 as an air electrode shows outstanding durability for 750 discharge/charge cycles, a high power density of 189.9 mW cm-2, and a high gravimetric energy density of 1018.7 mWh g-1 at 10 mA cm-2. Furthermore, the assembled all-solid cell displays exceptional flexibility and power density (122.2 mW cm-2).

Large gap two-dimensional topological insulators with the coexistence of a significant Rashba effect and piezoelectricity in functionalized PbGe monolayers.

In recent years, two-dimensional (2D) multifunctional materials have become a research hotpot for their wide application range. In this work, PbGe(CN)2 and PbGe(C2H)2 are predicted to realize the piezoelectricity, quantum spin Hall (QSH) insulator, and Rashba effects simultaneously. The topological bandgaps of PbGe(CN)2 and PbGe(C2H)2 are 0.418 and 0.405 eV, respectively, which are much larger than the recently reported value of 0.165 eV for InTeO that can also attain both the piezoelectricity and QSH insulator (PQSHI) effects. The in-plane and out-of-plane piezoelectric effects coexist in both PbGe(CN)2 and PbGe(C2H)2 with the in-plane piezoelectric coefficients d11 of 8.823 and 2.913 pm V-1 and out-of-plane piezoelectric coefficients d31 of 0.638 and 0.608 pm V-1. It is worth noting that there are significant Rashba SOC effects in PbGe(CN)2 and PbGe(C2H)2 and their Rashba splitting parameters are 2.576 and 2.184 eV Å, respectively. The prominent Rashba effects, which don't exist in other PQSHI materials, make PbGe(CN)2 and PbGe(C2H)2 more suitable for application in spintronic devices. Besides, the topological properties can remain robust under the uniaxial strain within the range of -6% to 6%. Our results imply that PbGe(CN)2 and PbGe(C2H)2 qualify as potential candidates for low-power, highly sensitive piezoelectric devices, such as pressure sensors for converting mechanical energy into electrical energy.

Quasi-one-dimensional phosphorene nanoribbons grown on silicon by space-confined chemical vapor transport.

Phosphorene nanoribbons (PNRs) combine the flexibility of one-dimensional (1D) nanomaterials with the large specific surface area and the edge and electron confinement effects of two-dimensional (2D) nanomaterials. In spite of the substantial advances in bulk black phosphorus (BP) manufacturing, achieving PNRs without degradation is still a big challenge. In this work, we present a strategy for the space-confined chemical vapor transport synthesis of quasi-one-dimensional surface-passivated monocrystalline PNRs on a silicon substrate. The growth mechanism of the PNRs is proposed by combining experimental results and DFT calculations, indicating that the P4 molecules can break, restructure, and epitaxially nucleate on the surface of the Au3SnP7 catalyst, and finally prefer to grow along the zigzag (ZZ) direction to form PNRs. The low gas flow rate and an appropriate phosphorus molecule concentration allow the growth of PNRs with structural integrity, which can be regulated by the amount of red phosphorus and the confined space.

Large Gap Two-Dimensional Topological Insulators with the Significant Rashba Effect in Ethynyl and Methyl Functionalized PbSn Monolayers.

Two-dimensional (2D) topological insulators (TIs) have recently attracted a great deal of attention due to their nondissipation electron transmission, stable performance, and easy device integration. However, a primary obstacle to influencing 2D TIs is the small bandgap, which limits their room-temperature applications. Here, we adopted first-principles to predict inversion-asymmetric group IV monolayers, PbSn(C2H)2 and PbSn(CH3)2, to be quantum spin Hall (QSH) insulators with large topological gaps of 0.586 and 0.481 eV, respectively. The nontrivial band topologies, which can survive in a wide range of strain, are characterized by topological invariants Z2, gapless edge states, and the Berry curvature. Another intriguing characteristic is the significant Rashba SOC effect which can also be tuned by feasible compressive and tensile strains. Meanwhile, the hexagonal boron nitride (h-BN) provides a suitable substrate for growth of these films without influencing their topological phases. These novel materials are expected to accelerate the development of advanced quantum devices.

Effect of metal decoration on sulfur-based gas molecules adsorption on phosphorene.

Based on first-principles calculation, the adsorption of sulfur-based gas molecules (H2S, SO2, SO3) on various metal-decorated phosphorenes is researched systematically. Eleven metals (Li, Na, K, Rb, Cs, Ca, Sr, Ba, Ni, La, Tl) which can avoid the formation of clusters on the phosphorene are considered. Noticeably, all metal decorations can enhance the adsorption strength of phosphorene to sulfur-based gas molecules except for H2S on Tl-decorated phosphorene. Meanwhile, the adsorption energy (Eads) shows the trend of Eads(H2S) < Eads(SO2) < Eads(SO3) for the same metal decoration case. In addition, some metal-decorated phosphorene systems exhibit intriguing magnetic and electrical variation after sulfur-based gas molecule adsorptions, indicating that these systems are promising to be candidates for the detection and removal of sulfur-based gas molecules.

Nitrogen-based gas molecule adsorption of monolayer phosphorene under metal functionalization.

Using the first-principles calculation based on density functional theory (DFT), the adsorption properties of nitrogen-based gases molecules (NH3, NO, NO2) on various metal (Li, Na, K, Rb, Cs, Ca, Sr, Ba, Ni, La, Tl) decorated phosphorene systems have been studied systematically. The results show that all metal decorations can improve the adsorption strength of phosphorene to nitrogen-based gases molecules except for Tl decoration. Especially, the adsorption energy of NH3 molecule on Ni decorated phosphorene is 1.305 eV, and the adsorption energies of NO and NO2 on La decorated phosphorene can be up to 2.475 and 3.734 eV, respectively. In addition, after NO and NO2 adsorptions, the electronic and magnetic properties of some metal decorated phosphorenes change, indicating that the metal decorated phosphorenes have great potential in NO and NO2 detection.

Enhancing the ambient stability of few-layer black phosphorus by surface modification.

Based on high-throughput density functional theory calculations, we investigated the adsorption characteristics of various elements across the Periodic Table on few-layer black phosphorus (BP). Using the criterion that the ratio of adsorption energy (E ads) to bulk cohesive energy (E coh) is greater than one (E ads/E coh > 1), we selected fifteen elements. The adsorption of these elements on few-layer BPs could significantly shift their conduction-band minimum (CBM) downward, suggesting the possibility of preventing the few-layer BPs from oxidation if the CBM can be shifted below the O2/O2 - redox potential. Our study offers an efficient approach to overcoming the technical barrier in the practical application of few-layer BPs by enhancing its ambient stability via surface modification.

In situ TEM visualization of superior nanomechanical flexibility of shear-exfoliated phosphorene.

Recently discovered atomically thin black phosphorus (called phosphorene) holds great promise for applications in flexible nanoelectronic devices. Experimentally identifying and characterizing nanomechanical properties of phosphorene are challenging, but also potentially rewarding. This work combines for the first time in situ transmission electron microscopy (TEM) imaging and an in situ micro-manipulation system to directly visualize the nanomechanical behaviour of individual phosphorene nanoflakes. We demonstrate that the phosphorene nanoflakes can be easily bent, scrolled, and stretched, showing remarkable mechanical flexibility rather than fracturing. An out-of-plane plate-like bending mechanism and in-plane tensile strain of up to 34% were observed. Moreover, a facile liquid-phase shear exfoliation route has been developed to produce such mono-layer and few-layer phosphorene nanoflakes in organic solvents using only a household kitchen blender. The effects of surface tensions of the applied solvents on the ratio of average length and thickness (L/T) of the nanoflakes were studied systematically. The results reported here will pave the way for potential industrial-scale applications of flexible phosphorene nanoelectronic devices.

Stacking Fault Enriching the Electronic and Transport Properties of Few-Layer Phosphorenes and Black Phosphorus.

Interface engineering is critical for enriching the electronic and transport properties of two-dimensional materials. Here, we identify a new stacking, named Aδ, in few-layer phosphorenes (FLPs) and black phosphorus (BP) based on first-principles calculation. With its low formation energy, the Aδ stacking could exist in FLPs and BP as a stacking fault. The presence of the Aδ stacking fault induces a direct to indirect transition of the band gap in FLPs. It also affects the carrier mobilities by significantly increasing the carrier effective masses. More importantly, the Aδ stacking enables the fabrication of a whole spectrum of lateral junctions with all the type-I, II, and III alignments simply through the manipulation of the van der Waals stacking without resorting to any chemical modification. This is achieved by the widely tunable electron affinity and ionization potential of FLPs and BP with the Aδ stacking.

Orientation Effects in Ballistic High-Strained P-type Si Nanowire FETs.

In order to design and optimize high-sensitivity silicon nanowire-field-effect transistor (SiNW FET) pressure sensors, this paper investigates the effects of channel orientations and the uniaxial stress on the ballistic hole transport properties of a strongly quantized SiNW FET placed near the high stress regions of the pressure sensors. A discrete stress-dependent six-band k.p method is used for subband structure calculation, coupled to a two-dimensional Poisson solver for electrostatics. A semi-classical ballistic FET model is then used to evaluate the ballistic current-voltage characteristics of SiNW FETs with and without strain. Our results presented here indicate that [110] is the optimum orientation for the p-type SiNW FETs and sensors. For the ultra-scaled 2.2 nm square SiNW, due to the limit of strong quantum confinement, the effect of the uniaxial stress on the magnitude of ballistic drive current is too small to be considered, except for the [100] orientation. However, for larger 5 nm square SiNW transistors with various transport orientations, the uniaxial tensile stress obviously alters the ballistic performance, while the uniaxial compressive stress slightly changes the ballistic hole current. Furthermore, the competition of injection velocity and carrier density related to the effective hole masses is found to play a critical role in determining the performance of the nanotransistors.

Negative index of refraction in metallic metamaterial comprising split-ring resonators.

We numerically investigate the negative index of refraction in a metamaterial composed of metallic split-ring resonators, which exhibits simultaneously negative permittivity and permeability without resorting to additional metallic wires. It is confirmed that, in the left-handed band, negative permittivity is generated in analogy to the cut-wire metamaterial and negative permeability comes from the antisymmetric resonant mode, which occurs at a frequency band about 3 times higher than the fundamental magnetic resonance proposed by Pendry [IEEE Trans. Microwave Theory Tech. 47, 2075 (1999)].