Graphdiyne Enabled Nitrogen Vacancy Formation in Copper Nitride for Efficient Ammonia Synthesis.

The electrocatalytic reduction of nitrate is promising for sustainable ammonia synthesis but suffers from slow reduction kinetics and multiple competing reactions. Here, we report a catalyst featuring copper nitride (Cu3N) anchored on a novel graphdiyne support (termed Cu3N/GDY), which is used for electrocatalytic reduction of nitrate to produce ammonia. The GDY absorbed hydrogen and enabled nitrogen (N) vacancy formation in Cu3N for the fast nitrate reduction reaction (NO3RR). Further, the distinct absorption sites formed by GDY and N vacancy enabled the excellent selectivity and stability of NO3RR. Notably, the Cu3N/GDY catalyst achieved a high ammonia yield (YNH3) up to 35280 µg h-1 mgcat.-1 and a high Faradaic efficiency (FE) of 98.1% using 0.1 M NO3- at -0.9 V versus a reversible hydrogen electrode (RHE). Using electron paramagnetic resonance (EPR) technology and in situ X-ray absorption fine structure (XAFS) spectroscopy measurement, we visualized the N vacancy formation in Cu3N and electrocatalytic NO3RR enabled by GDY. These findings show the promise of GDY in sustainable ammonia synthesis and highlight the efficacy of Cu3N/GDY as a catalyst.

Chiral Stacking Identification of Two-Dimensional Triclinic Crystals Enabled by Machine Learning.

Chiral materials possess broken inversion and mirror symmetry and show great potential in the application of next-generation optic, electronic, and spintronic devices. Two-dimensional (2D) chiral crystals have planar chirality, which is nonsuperimposable on their 2D enantiomers by any rotation about the axis perpendicular to the substrate. The degree of freedom to construct vertical stacking of 2D monolayer enantiomers offers the possibility of chiral manipulation for designed properties by creating multilayers with either a racemic or enantiomerically pure stacking order. However, the rapid recognition of the relative proportion of two enantiomers becomes demanding due to the complexity of stacking orders of 2D chiral crystals. Here, we report the unambiguous identification of racemic and enantiomerically pure stackings for layered ReSe2 and ReS2 using circular polarized Raman spectroscopy. The chiral Raman response is successfully manipulated by the enantiomer proportion, and the stacking orders of multilayer ReSe2 and ReS2 can be completely clarified with the help of second harmonic generation and scanning transmission electron microscopy measurements. Finally, we trained an artificial intelligent Spectra Classification Assistant to predict the chirality and the complete crystallographic structures of multilayer ReSe2 from a single circular polarized Raman spectrum with the accuracy reaching 0.9417 ± 0.0059.

Deep-Ultraviolet and Helicity-Dependent Raman Spectroscopy for Carbon Nanotubes and 2D Materials.

Recent progress of Raman spectroscopy on carbon nanotubes and 2D materials is reviewed as a topical review. The Raman tensor with complex values is related to the chiral 1D/2D materials without mirror symmetry for the mirror in the propagating direction of light, such as chiral carbon nanotube and black phosphorus. The phenomenon of complex Raman tensor is observed by the asymmetric polar plot of helicity-dependent Raman spectroscopy using incident circularly-polarized lights. First-principles calculations of resonant Raman spectra directly give the complex Raman tensor that explains helicity-dependent Raman spectra and laser-energy-dependent relative intensities of Raman spectra. In deep-ultraviolet (DUV) Raman spectroscopy with 266 nm laser, since the energy of the photon is large compared with the energy gap, the first-order and double resonant Raman processes occur in general k points in the Brillouin zone. First-principles calculation is necessary to understand the DUV Raman spectra and the origin of double-resonance Raman spectra. Asymmetric line shapes appear for the G band of graphene for 266 nm laser and in-plane Raman mode of WS2 for 532 nm laser, while these spectra show symmetric line shapes for other laser excitation. The interference effect on the asymmetric line shape is discussed by fitting the spectra to the Breit-Wigner-Fano line shapes.

Observing Axial Chirality of Chiral Single-Wall Carbon Nanotubes by Helicity-Dependent Raman Spectra.

Helicity-dependent Raman spectra of an isolated, chiral, single-wall carbon nanotube (SWNT) are reported using circularly polarized light. A polar plot of polarized Raman intensity for the radial breathing mode (RBM), which is excited by left-handed or right-handed circularly polarized light, shows asymmetric angle dependence relative to the nanotube axis direction, which reflects the axial chirality of a SWNT. The asymmetry in the polar plot of the RBM can be analyzed by a complex Raman tensor. The complex phase of each component of the Raman tensor has a maximum at chiral angle θ = 15° of a SWNT which is between two achiral SWNTs, that is, zigzag (θ = 0°) and armchair (θ = 30°) SWNTs. Considering the interaction between the chiral SWNT and the circularly polarized light, we discuss the origin of the complex phases excited by the opposite helicity of the circularly polarized light.

Enhanced Layer-Breathing Modes in van der Waals Heterostructures Based on Twisted Bilayer Graphene.

The characterization of interlayer coupling in two-dimensional van der Waals heterostructures (vdWHs) is essential to understand their quantum behaviors and structural functionalities. Interlayer shear and layer-breathing (LB) phonons carry rich information on interlayer interaction, but they are usually too weak to be detected via standard Raman spectroscopy due to the weak electron-phonon coupling (EPC). Here, we report a universal strategy to enhance LB modes of vdWHs based on twisted bilayer graphene (tBLG). In both tBLG/hBN and tBLG/MoS2 vdWHs, the resonantly excited electrons in tBLG can strongly couple to LB phonons extended over the entire layers in the vdWHs, whose resonance condition is tunable by the twist angle of tBLG. In vdWHs containing twisted graphene layers with multiple twisted interfaces, the EPC of LB phonons coming from the collective LB vibrations of entire heterostructure layers can be tuned by resonant excitation of programmable van Hove singularities according to each twisted interface. The universality and tunability of enhanced LB phonons by tBLG make it a promising method to investigate EPC and interlayer interaction in related vdWHs.

Giant electrically tunable magnon transport anisotropy in a van der Waals antiferromagnetic insulator.

Anisotropy is a manifestation of lowered symmetry in material systems that have profound fundamental and technological implications. For van der Waals magnets, the two-dimensional (2D) nature greatly enhances the effect of in-plane anisotropy. However, electrical manipulation of such anisotropy as well as demonstration of possible applications remains elusive. In particular, in-situ electrical modulation of anisotropy in spin transport, vital for spintronics applications, has yet to be achieved. Here, we realized giant electrically tunable anisotropy in the transport of second harmonic thermal magnons (SHM) in van der Waals anti-ferromagnetic insulator CrPS4 with the application of modest gate current. Theoretical modeling found that 2D anisotropic spin Seebeck effect is the key to the electrical tunability. Making use of such large and tunable anisotropy, we demonstrated multi-bit read-only memories (ROMs) where information is inscribed by the anisotropy of magnon transport in CrPS4. Our result unveils the potential of anisotropic van der Waals magnons for information storage and processing.

Spectroscopic visualization and phase manipulation of chiral charge density waves in 1T-TaS2.

The chiral charge density wave is a many-body collective phenomenon in condensed matter that may play a role in unconventional superconductivity and topological physics. Two-dimensional chiral charge density waves provide the building blocks for the fabrication of various stacking structures and chiral homostructures, in which physical properties such as chiral currents and the anomalous Hall effect may emerge. Here, we demonstrate the phase manipulation of two-dimensional chiral charge density waves and the design of in-plane chiral homostructures in 1T-TaS2. We use chiral Raman spectroscopy to directly monitor the chirality switching of the charge density wave-revealing a temperature-mediated reversible chirality switching. We find that interlayer stacking favours homochirality configurations, which is confirmed by first-principles calculations. By exploiting the interlayer chirality-locking effect, we realise in-plane chiral homostructures in 1T-TaS2. Our results provide a versatile way to manipulate chiral collective phases by interlayer coupling in layered van der Waals semiconductors.

Hydrogen Radical-Induced Electrocatalytic N2 Reduction at a Low Potential.

Realizing efficient hydrogenation of N2 molecules in the electrocatalytic nitrogen reduction reaction (NRR) is crucial in achieving high activity at a low potential because it theoretically requires a higher equilibrium potential than other steps. Analogous to metal hydride complexes for N2 reduction, achieving this step by chemical hydrogenation can weaken the potential dependence of the initial hydrogenation process. However, this strategy is rarely reported in the electrocatalytic NRR, and the catalytic mechanism remains ambiguous and lacks experimental evidence. Here, we show a highly efficient electrocatalyst (ruthenium single atoms anchored on graphdiyne/graphene sandwich structures) with a hydrogen radical-transferring mechanism, in which graphdiyne (GDY) generates hydrogen radicals (H•), which can effectively activate N2 to generate NNH radicals (•NNH). A dual-active site is constructed to suppress competing hydrogen evolution, where hydrogen preferentially adsorbs on GDY and Ru single atoms serve as the adsorption site of •NNH to promote further hydrogenation of NH3 synthesis. As a result, high activity and selectivity are obtained simultaneously at -0.1 V versus a reversible hydrogen electrode. Our findings illustrate a novel hydrogen transfer mechanism that can greatly reduce the potential and maintain the high activity and selectivity in NRR and provide powerful guidelines for the design concept of electrocatalysts.

Columnar Lithium Deposition Guided by Graphdiyne Nanowalls toward a Stable Lithium Metal Anode.

Lithium metal is the most promising anode for lithium batteries, but the growth of lithium dendrites leads to rapid attenuation of battery capacity and a series of safety problems during the plating/stripping process. Utilization of carbon materials for improving the Li metal anode stability represents a feasible strategy; particularly, the high affinity for lithium endows graphdiyne (GDY) with a promising capability for stabilizing Li metal anodes. Herein, vertically aligned GDY nanowalls (NWs) were uniformly grown on a copper foil, which allowed for dendrite-free, columnar deposition of lithium, desired for a stable Li metal anode. The highly lithiophilic GDY NWs afforded plentiful and evenly distributed active sites for Li nucleation as well as uniform distribution of Li-ion flux for Li growth, resulting in smooth, columnar Li deposition. The resultant Li metal electrode based on the Cu-GDY NWs was able to cycle stably for 500 cycles at 1 mA cm-2 and 2 mA h cm-2 with a high Coulombic efficiency of 99.2% maintained. A symmetric battery assembled by lithium-loaded Cu-GDY NWs (Cu-GDY NWs@Li) showed a long lifespan over 1000 h at 1 mA cm-2 and 1 mA h cm-2. Furthermore, a full cell assembled by Cu-GDY NWs@Li and LiFePO4 was able to cycle stably for 200 cycles at a high current of 5 C, indicating the potential applications in practical Li metal batteries at high rates. This work demonstrated great potential of GDY-based materials toward applications in Li metal batteries of high safety and high energy density.

Rapid Synthesis of Graphdiyne Films on Hydrogel at the Superspreading Interface for Antibacteria.

Graphdiyne (GDY), a two-dimensional (2D) carbon material with diacetylenic linkages (-C≡C-C≡C-) structures, has attracted enormous attention in various fields. However, the controlled synthesis of GDY films is still challenging because of the low alkyne coupling efficiency and out-of-plane growth. Here, we employed a highly efficient Cu(II)-N,N,N',N'-tetramethylethylenediamine (Cu(II)-TMEDA) catalyst and constructed a superspreading liquid/liquid interface on a hydrogel for rapid and controllable synthesis of GDY thin films. GDY films with controllable thickness from 4 to 50 nm and large-scale uniform morphology can be prepared within 2 h at room temperature. The mechanism of growth was revealed to be a nucleation and in-plane extension process. Meanwhile, the as-grown GDY films showed excellent photothermal conversion efficiency, which induces the release of Cu(II) ions from the hydrogel and exhibits high efficiency in synergistic antibacteria.

Quantum interference directed chiral raman scattering in two-dimensional enantiomers.

Raman scattering spectroscopy has been a necessary and accurate tool not only for characterizing lattice structure, but also for probing electron-photon and electron-phonon interactions. In the quantum picture, electrons at ground states can be excited to intermediate energy levels by photons at different k-points in the Brillouin zone, then couple to phonons and emit photons with changed energies. The elementary Raman processes via all possible pathways can interfere with each other, giving rise to intriguing scattering effects. Here we report that quantum interference can lead to significant chiral Raman response in monolayer transitional metal dichalcogenide with triclinic symmetry. Large circular intensity difference observed for monolayer rhenium dichalcogenide originates from inter-k interference of Raman scattering excited by circularly polarized light with opposite helicities. Our results reveal chiral Raman spectra as a new manifestation of quantum interference in Raman scattering process, and may inspire induction of chiral optical response in other materials.

Graphdiyne/Graphene/Graphdiyne Sandwiched Carbonaceous Anode for Potassium-Ion Batteries.

Graphdiyne (GDY) has been considered as an appealing anode candidate for K-ion storage since its triangular pore channel, alkyne-rich structure, and large interlayer spacing would endow it with abundant active sites and ideal diffusion paths for K-ions. Nevertheless, the low surface area and disordered structure of bulk GDY typically lead to unsatisfied K storage performance. Herein, we have designed a GDY/graphene/GDY (GDY/Gr/GDY) sandwiched architecture affording a high surface area and fine quality throughout a van der Waals epitaxy strategy. As tested in a half-cell configuration, the GDY/Gr/GDY electrode exhibits better capacity output, rate capability, and cyclic stability as compared to the bare GDY counterpart. In situ electrochemical impedance spectroscopy/Raman spectroscopy/transmission electron microscopy are further applied to probe the K-ion storage feature and disclose the favorable reversibility of GDY/Gr/GDY electrode during repeated potassiation/depotassiation. A full-cell device comprising a GDY/Gr/GDY anode and a potassium Prussian blue cathode enables a high cycling stability, demonstrative of the promising potential of the GDY/Gr/GDY anode for K-ion batteries.

Complex Raman Tensor in Helicity-Changing Raman Spectra of Black Phosphorus under Circularly Polarized Light.

In anisotropic two-dimensional materials, complex values of Raman tensors are necessary to explain the abnormal linearly polarized Raman spectra. In this work, we measured the helicity-changing Raman spectra of few-layer black phosphorus (BP) excited by circularly polarized light. We observed that the polarized Raman intensities of the Ag modes show a deflection angle that depends on the sample orientation, thickness, and laser excitation energy. To understand the deflection, we calculated the resonant Raman spectra by first-principles calculations, which give complex Raman tensors as a function of laser excitation energy. In particular, the phase difference between the elements of the complex Raman tensor is relevant to the deflection angle. The calculated results of monolayer BP reproduce the experimental helicity-resolved Raman spectra of few-layer BP satisfactorily.

Highly Efficient Photothermal Conversion and Water Transport during Solar Evaporation Enabled by Amorphous Hollow Multishelled Nanocomposites.

Solar evaporation, which enables water purification without consuming fossil fuels, has been considered the most promising strategy to address global scarcity of drinkable water. However, the suboptimal structure and composition designs still result in a trade-off between photothermal conversion, water transport, and tolerance to harsh environments. Here, an ultrastable amorphous Ta2 O5 /C nanocomposite is designed with a hollow multishelled structure (HoMS) for solar evaporation. This HoMS results in highly efficient photoabsorption and photothermal conversion, as well as a decrease of the actual water evaporation enthalpy. A superfast evaporation speed of 4.02 kg m-2 h-1 is achieved. More importantly, a World Health Organization standard drinkable water can be achieved from seawater, heavy-metal- and bacteria-containing water, and even from extremely acidic/alkaline or radioactive water sources. Notably, the concentration of pseudovirus SC2-P can be decreased by 6 orders of magnitude after evaporation.

Monitoring Strain-Controlled Exciton-Phonon Coupling in Layered MoS2 by Circularly Polarized Light.

The modulation of exciton-phonon coupling by strain greatly affects the optical and optoelectronic properties of two-dimensional (2D) materials. Although photoluminescence and optical absorption spectra have been used to characterize the overall change of exciton-phonon coupling under strain, there has been no effective method to distinguish the evolution of the major contributions of exciton-phonon coupling, that is, deformation potential (DP) and Fröhlich interaction (FI). Here we report the direct monitoring of the evolution of DP and FI under strain in layered MoS2 using circularly polarized Raman spectroscopy. We found that the relative proportions of DP and FI can be well evaluated by the circular polarization ratio of the E2g1 mode for strained MoS2. Further, we demonstrated that the strain control of DP and FI in MoS2 is dominated by the excitonic effect. Our method can be extended to other 2D semiconductors and would be helpful for manipulating exciton-phonon couplings by strain.

Polarized Raman Spectroscopy for Determining Crystallographic Orientation of Low-Dimensional Materials.

Raman spectroscopy is a fast and nondestructive characterization technique, which has been widely used for the characterization of the composition and structure information of various materials. The symmetry-dependent Raman tensor allows the detection of crystallographic orientation of materials by using polarization information. In this Perspective, we discuss polarized Raman spectroscopy as a powerful tool for determination of the crystallographic orientation of various materials. First, we introduce the basic principles of polarized Raman spectroscopy and the corresponding experimental setups; the determination of crystallographic orientation of two-dimensional (2D) materials with in-plane isotropy and in-plane anisotropy using linearly polarized Raman scattering are then discussed. Furthermore, we discuss that using circularly polarized Raman spectroscopy, the azimuthal angle of materials in three dimensions (3D) can be characterized. In the final section, we show that the orientation distribution of nanomaterial assemblies can be measured using polarized Raman spectroscopy by introducing the orientation distribution function.

Hetero-site nucleation for growing twisted bilayer graphene with a wide range of twist angles.

Twisted bilayer graphene (tBLG) has recently attracted growing interest due to its unique twist-angle-dependent electronic properties. The preparation of high-quality large-area bilayer graphene with rich rotation angles would be important for the investigation of angle-dependent physics and applications, which, however, is still challenging. Here, we demonstrate a chemical vapor deposition (CVD) approach for growing high-quality tBLG using a hetero-site nucleation strategy, which enables the nucleation of the second layer at a different site from that of the first layer. The fraction of tBLGs in bilayer graphene domains with twist angles ranging from 0° to 30° was found to be improved to 88%, which is significantly higher than those reported previously. The hetero-site nucleation behavior was carefully investigated using an isotope-labeling technique. Furthermore, the clear Moiré patterns and ultrahigh room-temperature carrier mobility of 68,000 cm2 V-1 s-1 confirmed the high crystalline quality of our tBLG. Our study opens an avenue for the controllable growth of tBLGs for both fundamental research and practical applications.

Nonlinear Amplification of Chirality in Self-Assembled Plasmonic Nanostructures.

Molecular chirality transfer and amplification is at the heart of the fundamental understanding of chiral origin and fabrication of artificial chiral materials. We investigate here the nonlinear amplification effect in the chiral transfer from small molecules to assembled plasmonic nanoparticles. Our results show clearly a recognizable nonlinear behavior of the electronic and plasmonic circular dichroism activities, demonstrating the validity of the "majority-rules" principle operating in both the three-dimensional interface-confined molecularly chiral environment and the assembled plasmonic nanoparticles. Such twin "majority-rules" effects from the self-assembled organic-inorganic nanocomposite system have not been reported previously. By establishing a direct correlation between the dynamic template of the molecularly chiral environment and the nonlinear chiral amplification in the nanoparticle assemblies, this study may provide an insightful understanding of the hierarchical and cooperative chiral information transfer from molecular levels to nanoscales.

Characterization of Excitonic Nature in Raman Spectra Using Circularly Polarized Light.

We propose a technique of Raman spectroscopy to characterize the excitonic nature and to evaluate the relative contribution of the two kinds of electron/exciton-phonon interactions that are observed in two-dimensional transition-metal dichalcogenides (TMDCs). In the TMDCs, the electron/exciton-phonon interactions mainly originate from the deformation potential (DP) or the Fröhlich interaction (FI) which give the mutually different Raman tensors. Using a circularly polarized light, the relative proportion of the DP and the FI can be defined by the ratio of helicity-polarized intensity that is observed by MoS2. By this analysis, we show that the excitonic FI interaction gradually increases with decreasing temperature, contributes equally to DP at ∼230 K, and dominates at lower temperatures. The excitonic effect in the Raman spectra is confirmed by modulating the dielectric environment for the exciton and by changing the laser power.

Anisotropic Raman spectrum and transport properties of AuTe2Br flakes.

Topological semimetal (TSM) AuTe2Br thin flakes have been studied by Raman spectroscopy and magneto-transport measurement. The angle-resolved polarized Raman spectrum of AuTe2Br (bulk and thin flake) shows strong anisotropy. Together with high resolution transmission electron microscopy (TEM), we establish a non-destructive method to determine the crystallographic orientation of AuTe2Br flakes. At high temperature (T > 50 K), the magneto-resistance (MR) of AuTe2Br thin flakes shows typical parabolic-like behavior, which can be well fitted by the two-fluid model. However, at low temperature (T ⩽ 30 K), the MR of thin flakes (<17 nm) clearly deviates from the two-fluid model as well as from the Kohler's rule, suggesting a new type of scattering emerging below 30 K. Several possible scattering mechanisms are discussed and the respective corrections to MR are compared with our experimental data. In addition, the conductivity of these metallic crystals is also found to be highly anisotropic, with the hole mobility along the a axis about five times higher than that along the c axis.