Atomic Stacking Research Articles

Thermoelectric properties of XX- and XY-stacked GeS/GeSe van der Waals heterostructures from DFT and BTP calculations.

This study utilizes density functional theory (DFT) and the Boltzmann transport equation (BTE) to investigate the structural, electronic, and thermoelectric properties of germanium sulfide (GeS) and germanium selenide (GeSe) monolayers, along with their van der Waals (vdW) heterostructures. We analyzed XX-stacked and XY-stacked configurations, where the XX configuration features direct atomic stacking, while the XY configuration exhibits staggered stacking. Our first-principles calculations indicate that the formation of GeS/GeSe heterostructures results in a reduction of bandgaps compared to their bulk and monolayer counterparts, yielding bandgap values of 0.91 eV for the XX configuration and 0.84 eV for the XY configuration. Stability assessments reveal that the XY configuration is more stable, demonstrating a lattice thermal conductivity of 15.21 W/mK compared to 17.95 W/mK for the XX configuration T 300 K. The thermoelectric properties were systematically evaluated across a temperature range of 300-800 K, revealing high Seebeck coefficients of 1.51 mV/K for the XX heterostructure and 1.39 mV/K for the XY heterostructure. reflecting their excellent charge transport capabilities. Notably, the figure of merit (ZT) at 800 K was calculated to be 0.90 for the XX configuration and 1.01 for the XY configuration, underscoring the superior thermoelectric performance of the XY heterostructure. These findings contribute to a comprehensive understanding of 2D GeS/GeSe heterostructures for thermoelectric applications and provide a solid foundation for future research and technological advancements in this domain.

Plastic evolution and phase transition mechanisms in γ-TiAl nano polycrystal by a molecular dynamics simulation

γ-TiAl based alloys are widely regarded as one important high-temperature structural material, however the deformation behaviors are still not clearly clarified. The microscopic plastic deformation and phase transition of γ-TiAl nano polycrystals under compression are investigated by molecular dynamics simulations. The results show that the initial plasticity is dominated by slip of partial dislocations whose continuous formation and secondary slip on the same slip plane result in the generation and disappearance of intrinsic stacking faults (ISFs). At the strain of about 0.2, a continuous structure transformation of “ISF → ESF → TB” is observed, during which the interaction between different ISFs causes the atomic misalignment corresponding to the change in atomic stacking order near ISF. As the compressive strain exceeds 0.2, the FCC-to-BCC phase transition occurs within polycrystals due to the high Mises stress, the high stress level within grains facilitates the expansion of BCC phase from initial FCC phase, and the newly formed BCC phase maintains the atomic-arrangement orderliness of original phase. The interface between FCC and BCC phases obeys the low-energy Kurdjumov-Sachs orientation relationship. This work is helpful for better understanding the atomic-scale deformation behaviors and provides a theoretical guidance for designing high-performance alloy materials.

Solving Ambiguity in EBSD Indexing of Long-Period Stacking Ordered (LPSO) Phase in Mg with Template Matching Approach

Magnesium (Mg) alloys with long-period stacking ordered (LPSO) phases are receiving increasing interest because of their excellent mechanical performance. The close similarity in atomic stacking sequences between different LPSO polytypes and Mg lattice often leads to ambiguous indexing in electron backscatter diffraction (EBSD), a commonly used material characterization technique. Instead of the Hough transformation approach used in commercial software, an alternative indexing approach, which can catch subtle differences by matching experimental patterns with simulated ones, is explored in this study. Our results, showing ~94% of mapping data being correctly indexed as the target phase, 14H LPSO, demonstrate the capability of not only resolving the LPSO phases but also distinguishing different LPSO polytypes. This approach offers a valuable, if not unique, solution for the microscale characterization of LPSO phases, enabling precise microstructure tuning to further promote the mechanical properties of Mg alloys.

Boosting K+‐Ionic Conductivity of Layered Oxides via Regulating P2/P3 Heterogeneity and Reciprocity for Room‐Temperature Quasi‐Solid‐State Potassium Metal Batteries

AbstractSolid‐state potassium metal batteries are promising candidates for grid‐scale energy storage due to their low cost, high energy density and inherent safety. However, solid state K‐ion conductors struggle with poor ionic conductivity due to the large ionic radius of K+‐ions. Herein, we report precise regulation of phase heterogeneity and reciprocity of the P2/P3‐symbiosis K0.62Mg0.54Sb0.46O2 solid electrolyte (SE) for boosting a high ionic conductivity of 1.6×10−4 S cm−1 at 25 °C. The bulk ionic conducting mechanism is explored by elucidating the effect of atomic stacking mode within the layered framework on K+‐ion migration barriers. For ion diffusion at grain boundaries, the P2/P3 biphasic symbiosis property assists in tunning the SE microstructure, which crystallizes in rod‐like particles with lengths of tens of micrometers facilitating long‐distance ion transport and significantly decreasing grain boundary resistance. Potassium metal symmetric cells using the modified SE deliver excellent cycling life over 300 h at 0.1 mA cm−2 and a high critical current density of 0.68 mA cm−2. The quasi‐solid‐state potassium metal batteries (QSSKBs) coupled with two kinds of layered oxide cathodes demonstrate remarkable stability over 300 cycles, outperforming the liquid electrolyte counterparts. The QSSKB system provides a promising strategy for high‐efficiency, safe, and durable large‐scale energy storage.

Boosting K+-Ionic Conductivity of Layered Oxides via Regulating P2/P3 Heterogeneity and Reciprocity for Room-Temperature Quasi-Solid-State Potassium Metal Batteries.

Solid-state potassium metal batteries are promising candidates for grid-scale energy storage due to their low cost, high energy density and inherent safety. However, solid state K-ion conductors struggle with poor ionic conductivity due to the large ionic radius of K+-ions. Herein, we report precise regulation of phase heterogeneity and reciprocity of the P2/P3-symbiosis K0.62Mg0.54Sb0.46O2 solid electrolyte (SE) for boosting a high ionic conductivity of 1.6×10-4 S cm-1 at 25 °C. The bulk ionic conducting mechanism is explored by elucidating the effect of atomic stacking mode within the layered framework on K+-ion migration barriers. For ion diffusion at grain boundaries, the P2/P3 biphasic symbiosis property assists in tunning the SE microstructure, which crystallizes in rod-like particles with lengths of tens of micrometers facilitating long-distance ion transport and significantly decreasing grain boundary resistance. Potassium metal symmetric cells using the modified SE deliver excellent cycling life over 300 h at 0.1 mA cm-2 and a high critical current density of 0.68 mA cm-2. The quasi-solid-state potassium metal batteries (QSSKBs) coupled with two kinds of layered oxide cathodes demonstrate remarkable stability over 300 cycles, outperforming the liquid electrolyte counterparts. The QSSKB system provides a promising strategy for high-efficiency, safe, and durable large-scale energy storage.

Atomic structure of self-buffered BaZr(S, Se)3 epitaxial thin film interfaces

Understanding and controlling the growth of chalcogenide perovskite thin films through interface design is important for tailoring film properties. Here, the film and interface structure of BaZr(S,Se)3 thin films grown on LaAlO3 by molecular beam epitaxy and postgrowth anion exchange is resolved using aberration-corrected scanning transmission electron microscopy. Epitaxial films are achieved from self-assembly of an interface “buffer” layer, which accommodates the large film/substrate lattice mismatch of nearly 40% for the alloy film studied here. The self-assembled buffer layer, occurring for both the as-grown sulfide and post-selenization alloy films, is shown to have rock-salt-like atomic stacking akin to a Ruddlesden–Popper phase. These results provide insights into oxide-chalcogenide heteroepitaxial film growth, illustrating a process that yields relaxed, crystalline, epitaxial chalcogenide perovskite films that support ongoing studies of optoelectronic and device properties.

Mechanical properties of diamane: Orientation dependence of strength and fracture strain

Diamane, the two-dimensional counterpart of diamond, is very promising for novel electronic and nanomechanical devices, which requires additional studies on their physical and mechanical properties. In the present work, the orientation dependence of diamane strength with the detailed analysis of the deformation behavior was carried out by molecular dynamics. Two stacks of diamane layers covered with hydrogen with different chirality θ from 0 to 30° were considered. The atomic stacking of diamane has no effect on its strength. It was found that diamane strength depends non-monotonously on the diamane chirality: the highest strength was found for θ = 10°. The fracture strain decreases with the increase of chiral angle from 0 to 20° and does not change for chirality from 20 to 30°. However, the Young’s modulus does not depend on the diamane chirality. The main deformation mechanisms were revealed: elongation of covalent bonds and rotation of valence angles. For chiral angles from 0 to 20°, the diamane chirality can be controllably changed during tension which results in the increase in fracture strength and strain. The obtained results allow a better understanding of the effect of the diamane morphology on their mechanical properties for future applications.

Polarity control and crystalline quality improvement of AlN thin films grown on Si(111) substrates by molecular beam epitaxy

We attain N-polar and Al-polar AlN thin films on Si(111) substrates by plasma-assisted molecular beam epitaxy. The polarity of AlN epilayers has been validated by wet chemical etching using tetramethylammonium hydroxide and by the direct cross-sectional observation of atomic stacking under high-angle annular dark-field scanning transmission electron microscopy. For the 290 nm-thick as-grown N-polar AlN epilayer, x-ray diffraction (XRD) (002) and (102) ω rocking curve peak full width half maximums (FWHMs) are 475 and 1177 arcsec, and the surface mean square roughness (RMS) is 0.30 nm. We flipped the polarity using the metal-flux-modulation-epitaxy (MME) strategy. The MME strategy promotes anti-phase boundaries (APBs) on the {22¯01} crystalline planes instead of commonly observed lateral planar APBs in AlN epilayers. Merging of the tilted APBs at ∼50 nm leads to a complete Al-polar surface. For the 180 nm-thick Al-polar AlN epilayer, XRD (002) and (102) peak FWHMs are 1505 and 2380 arcsec, and the surface RMS is 1.41 nm. Strain analysis by XRD and Raman spectroscopy indicates a uniform tensile strain of 0.160% across the N-polar AlN epilayer surface and a strain distribution of 0.113%–1.16% through the epilayer. In contrast, the Al-polar AlN epilayer exhibits a much broader tensile strain distribution of 0.482%–2.406% along the growth direction, potentially due to the interaction of polarity inversion and strain relaxation.

Formation Characteristics of Pt-Ni Alloy Nanoparticles Fabricated by Nanolamination of Atomic Layer Deposition in Hydrogen.

Forced-flow atomic layer deposition nanolamination is employed to fabricate Pt-Ni nanoparticles on XC-72, with the compositions ranging from Pt94Ni6 to Pt67Ni33. Hydrogen is used as a co-reactant for depositing Pt and Ni. The growth rate of Pt is slower than that using oxygen reactant, and the growth exhibits preferred orientation along the (111) plane. Ni shows much slower growth rate than Pt, and it is only selectively deposited on Pt, not on the substrate. Higher ratios of Ni would hinder subsequent stacking of Pt atoms, resulting in lower overall growth rate and smaller particles (1.3-2.1nm). Alloying of Pt with Ni causes shifted lattice that leads to larger lattice parameter and d-spacing as Ni fraction increases. From the electronic state analysis, Pt 4f peaks are shifted to lower binding energies with increasing the Ni content, suggesting charge transfer from Ni to Pt. Schematic of the growth behavior is proposed. Most of the alloy nanoparticles exhibit higher electrochemical surface area and oxygen reduction reaction activity than those of commercial Pt. Especially, Pt83Ni17 and Pt87Ni13 show excellent mass activities of 0.76 and 0.59AmgPt -1, respectively, higher than the DOE target of 2025, 0.44AmgPt -1.

Probing the Effect of Alloying Elements on the Interfacial Segregation Behavior and Electronic Properties of Mg/Ti Interface via First-Principles Calculations.

The interface connects the reinforced phase and the matrix of materials, with its microstructure and interfacial configurations directly impacting the overall performance of composites. In this study, utilizing seven atomic layers of Mg(0001) and Ti(0001) surface slab models, four different Mg(0001)/Ti(0001) interfaces with varying atomic stacking configurations were constructed. The calculated interface adhesion energy and electronic bonding information of the Mg(0001)/Ti(0001) interface reveal that the HCP2 interface configuration exhibits the best stability. Moreover, Si, Ca, Sc, V, Cr, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, Sn, La, Ce, Nd, and Gd elements are introduced into the Mg/Ti interface layer or interfacial sublayer of the HCP2 configurations, and their interfacial segregation behavior is investigated systematically. The results indicate that Gd atom doping in the Mg(0001)/Ti(0001) interface exhibits the smallest heat of segregation, with a value of -5.83 eV. However, Ca and La atom doping in the Mg(0001)/Ti(0001) interface show larger heat of segregation, with values of 0.84 and 0.63 eV, respectively. This implies that the Gd atom exhibits a higher propensity to segregate at the interface, whereas the Ca and La atoms are less inclined to segregate. Moreover, the electronic density is thoroughly analyzed to elucidate the interfacial segregation behavior. The research findings presented in this paper offer valuable guidance and insights for designing the composition of magnesium-based composites.

Molecular Dynamics Simulation Study of Aluminum-Copper Alloys' Anisotropy under Different Loading Conditions and Different Crystal Orientations.

The commonly used aluminum-copper alloys in industry are mainly rolled plates and extruded or drawn bars. The aluminum-copper alloys' anisotropy generated in the manufacturing process is unfavorable for subsequent applications. Its underlying mechanism shall be interpreted from a microscopic perspective. This paper conducted the loading simulation on Al-4%Cu alloy crystals at the microscopic scale with molecular dynamics technology. Uniaxial tension and compression loading were carried out along three orientations: X-<1¯12>, Y-<11¯1>, and Z-<110>. It analyzes the micro-mechanisms that affect the performance changes of aluminum-copper alloys through the combination of stress-strain curves and different organizational analysis approaches. As shown by the results, the elastic modulus and yield strength are the highest under tension along the <11¯1> direction. Such is the case for the reasons below: The close-packed plane of atoms ensures large atomic binding forces. In addition, the Stair-rod dislocation forms a Lomer-Cottrell dislocation lock, which has a strengthening effect on the material. The elastic modulus and yield strength are the smallest under tension along the <110> direction, and the periodic arrangement of HCP atom stacking faults serves as the main deformation mechanism. This is because the atomic arrangement on the <110> plane is relatively loose, which tends to cause atomic misalignment. When compressed in different directions, the plastic deformation mechanism is mainly dominated by dislocations and stacking faults. When compressed along the <110> direction, it has a relatively high dislocation density and the maximum yield strength. That should be attributed to the facts below. As the atomic arrangement of the <110> plane itself was not dense originally, compression loading would cause an increasingly tighter arrangement. In such a case, the stress could only be released through dislocations. This research aims to provide a reference for optimizing the processing technology and preparation methods of aluminum-copper alloy materials.

Structural and Hydrogen Evolution Electrocatalysis Properties of Cr–Al–B MAB Phase Thin Films

Thin‐film materials libraries (MLs) in the system Cr–Al–B are synthesized on 100 mm diameter Al2O3 sapphire substrates by combinatorial co‐sputtering from elemental targets at substrate temperatures of 600 and 700 °C to study phase formation of MAB phases (M = transition metal, A = A‐group element, B = boron). The formation of a mixture of two MAB phases Cr2AlB2 and Cr3AlB4 on the larger part of the ML prepared at 700 °C is observed by X‐ray diffraction and cross‐sectional transmission electron microscopy (TEM). Anisotropic growth of large grains of the MAB phases extending throughout the entire film thickness is revealed. Depending on the composition, the microstructure shows different levels of porosity and grain interlinkage. Imaging in the high‐resolution TEM mode identifies regions with Cr2AlB2, Cr3AlB4, and intermixed Cr2AlB2 and Cr3AlB4 atomic stacking sequences. Additional to the structural properties, electrocatalytic activity toward the alkaline hydrogen evolution reaction is measured. Higher activities are linked to crystalline MAB‐phase areas, further enhanced by increased porosity of the film which enlarges the surface area and the exposure of the active (010) planes.

First-principles calculation on the interfacial stability, electronic structure and fracture mechanism of NbN/AlN interface

The interfacial stability of NbN(111)/AlN(0001) including interfacial energy, Wad(work of adhesion) and electronic structure were studied by first-principles calculation. The N1-Nb-cen interface(constructed with N1-terminated AlN(0001) and Nb-terminated NbN(111)) is determined to be the most stable interface which has the smallest interfacial distance(1.11 Å) and largest Wad(15.04 J/m2) among the 28 considered interface models. The electronic structure and ideal tensile stress of the N1-Nb-cen, N2-Nb-top, Al2-N-top and Al1-Nb-cen interfaces were also investigated. The AlN surface has stronger ionic bond than that in NbN surface according to the analysis of Mulliken charges. The bonding feature of N1-Nb-cen interface is ionic with strong covalent, while the other three interfaces have mainly ionic bond. The ideal tensile stress of the N2-Nb-top interface is the largest (22.88 GPa) at the strain of 17 %, which is larger than that of N1-Nb-cen interface. The fracture will occur at the interface for the Al2-N-top and Al1-Nb-cen interfaces, while it occurs at the AlN interior for the N1-Nb-cen and N2-Nb-top interfaces, due to the Wad of the N1-Nb-cen and N2-Nb-top interfaces are larger than the other two interfaces and atomic stacking of AlN surface.

Stereointerface Structure Drives Ferroelectricity in BaZrO3 Films.

Interfacial strain engineering can induce structural transformation and introduce new physical properties into materials, which is an effective method to prepare new multifunctional materials. However, interfacial strain has a limited spatial impact size. For example, in 2D thin films, the critical thickness of biaxial strain is typically less than 20 nm, which is not conducive to the maintenance of a strained structure and properties in thick film materials. The construction of a 3D interface can solve this problem. The large lattice mismatch between the BaZrO3 thin film and the substrate can induce the out-of-phase boundary (OPB) structure, which can extend along the thickness direction with the stacking of atoms. The lattice distortion at the OPB structure can provide a clamping effect for each layer of atoms, thus expanding the spatial influence range of biaxial strain. As a result, the uniform in-plane strain distribution and strain-induced ferroelectricity (Pr = 13 μC/cm2) are maintained along the thickness direction in BaZrO3 films.

Uncovering Nanoindention Behavior of Amorphous/Crystalline High-Entropy-Alloy Composites.

Amorphous/crystalline high-entropy-alloy (HEA) composites show great promise as structural materials due to their exceptional mechanical properties. However, there is still a lack of understanding of the dynamic nanoindentation response of HEA composites at the atomic scale. Here, the mechanical behavior of amorphous/crystalline HEA composites under nanoindentation is investigated through a large-scale molecular dynamics simulation and a dislocation-based strength model, in terms of the indentation force, microstructural evolution, stress distribution, shear strain distribution, and surface topography. The results show that the uneven distribution of elements within the crystal leads to a strong heterogeneity of the surface tension during elastic deformation. The severe mismatch of the amorphous/crystalline interface combined with the rapid accumulation of elastic deformation energy causes a significant number of dislocation-based plastic deformation behaviors. The presence of surrounding dislocations inhibits the free slip of dislocations below the indenter, while the amorphous layer prevents the movement or disappearance of dislocations towards the substrate. A thin amorphous layer leads to great indentation force, and causes inconsistent stacking and movement patterns of surface atoms, resulting in local bulges and depressions at the macroscopic level. The increasing thickness of the amorphous layer hinders the extension of shear bands towards the lower part of the substrate. These findings shed light on the mechanical properties of amorphous/crystalline HEA composites and offer insights for the design of high-performance materials.

Epitaxial Integration of Transferable High-κ Dielectric and 2D Semiconductor.

The synthesis of high-dielectric-constant (high-κ) dielectric materials and their integration with channel materials have been the key challenges in the state-of-the-art transistor architecture, as they can provide strong gate control and low operating voltage. For next-generation electronics, high-mobility two-dimensional (2D) layered semiconductors with dangling-bond-free surfaces and an atomic-thick thickness are being explored as channel materials to achieve shorter channel lengths and less interfacial scattering. Nowadays, the integration of high-κ dielectrics with high-mobility 2D semiconductors mainly relies on atomic layer deposition or transfer stacking, which may cause several undesirable problems, such as channel damage and interface traps. Here, we demonstrate the integration of high-mobility 2D semiconducting Bi2O2Se with transferable high-κ SrTiO3 as a 2D field-effect transistor by direct epitaxial growth. Remarkably, such 2D heterostructures can be efficiently transferred from the water-soluble Sr3Al2O6 sacrificial layer onto arbitrary substrates. The as-fabricated 2D Bi2O2Se/SrTiO3 transistors exhibit an on/off ratio over 104 and a subthreshold swing down to 90 mV/dec. Furthermore, the 2D Bi2O2Se/SrTiO3 heterostructures can be easily transferred onto flexible polyethylene terephthalate (PET) substrates, and the as-fabricated transistors exhibit good potential in flexible electronics. Our study opens up a new avenue for the integration of high-κ dielectrics with high-mobility 2D semiconductors and paves the way for the exploration of multifunctional electronic devices.

Epitaxial growth of c-axis inclined Sr3YCo4O10.5+ δ thin film: Insights into laser-induced voltage signals arising from magnetic anisotropy

We report the laser-induced voltage (LIV) signals in cubic phase Sr3YCo4O10.5+δ (CP-SYCO) thin films with a c-axis tilted and discuss the relationship between the LIV signals and magnetic anisotropy. CP-SYCO thin films were epitaxially deposited on 0°, 5°, 10°, 15°, and 20° miscut LaAlO3 (001) substrates using pulsed laser deposition (laser energy of 200 mJ, post-annealed at 760 °C). The peak voltage of the LIV for the 15° tilted CP-SYCO film is 310 mV (under laser energy of 400 mJ/pulse), with a rising edge of 26 ns. Compared with G-type antiferromagnetic ordered tetragonal phase Sr3YCo4O10.5+δ(OT-SYCO, deposited at a laser energy of 300 mJ, post-annealed at 790 °C) film, the CP-SYCO exhibits much stronger magnetization anisotropy along in-plane and out-plane due to the possible A-type antiferromagnetic moment arrangement. CP-SYCO films also demonstrate significant thermoelectric anisotropy, supporting the transverse thermoelectric effect, which is partially attributed to the contribution of spin entropy. This study provides an understanding of the anisotropic behavior in atomic layer thermoelectric stack materials and explores magnetic anisotropic material systems.

Atomic-scale oxygen-vacancy engineering in Sub-2 nm thin Al2O3/MgO memristors

Ultrathin (sub-2 nm) Al2O3/MgO memristors were recently developed using an in vacuo atomic layer deposition (ALD) process that minimizes unintended defects and prevents undesirable leakage current. These memristors provide a unique platform that allows oxygen vacancies (VO) to be inserted into the memristor with atomic precision and study how this affects the formation and rupture of conductive filaments (CFs) during memristive switching. Herein, we present a systematic study on three sets of ultrathin Al2O3/MgO memristors with VO-doping via modular MgO atomic layer insertion into an otherwise pristine insulating Al2O3 atomic layer stack (ALS) using an in vacuo ALD. At a fixed memristor thickness of 17 Al2O3/MgO atomic layers (∼1.9 nm), the properties of the memristors were found to be affected by the number and stacking pattern of the MgO atomic layers in the Al2O3/MgO ALS. Importantly, the trend of reduced low-state resistance and the increasing appearance of multi-step switches with an increasing number of MgO atomic layers suggests a direct correlation between the dimension and dynamic evolution of the conducting filaments and the VO concentration and distribution. Understanding such a correlation is critical to an atomic-scale control of the switching behavior of ultrathin memristors.

Elucidating the atomic stacking structure of nickel phyllosilicate catalysts and their consequences on efficient hydrogenation of 1,4-butynediol to 1,4-butanediol

The hydrogenation of 1,4-butynediol (BYD) to 1,4-butanediol (BDO) plays a pivotal role in the production of biodegradable plastics, including PBAT and PBS. Herein, we prepared a range of nickel phyllosilicate catalysts with diverse atomic stacking configurations for the direct synthesis of BDO via BYD hydrogenation. In comparison to conventional supported Ni catalysts, the metal sites derived from nickel phyllosilicate demonstrated remarkable hydrogenation activity for the conversion of CC-C-OH alkynol to C-C-C-OH alkanol. Both the physical structures and -importantly- chemical properties of these catalysts were crucial for product selectivity and yield; and a BDO yield of 93.4 % with complete conversion of BYD was achieved at 50 °C and 1 MPa H2 over the Niphy@SiO2-UDP catalyst with a pure 1:1 Ni phyllosilicate structure. Kinetic experiments and theoretical calculations confirmed that the initial hydrogenation of BYD to 1,4-butenediol (BED) was the rate-determining step for the saturated hydrogenation to BDO. The metallic Nisite is responsible for the dissociation of hydrogen, while due to the enhanced synergism derived from the 1:1 atomic stacking phyllosilicate structure, a type of cooperated Ni-Niδ+-acid sites can stabilize the CC electron cloud over the carbon chain of BED intermediate, hence benefiting its further hydrogenation, and suppressing its isomerization to undesired aldol condensation byproduct. Our findings provide valuable insights into the atomic stacking structures of metal phyllosilicate catalysts, revealing the micro-environment of chemical properties and interactions that govern the state/activity of Ni species, which is helpful for the rational design of other hydrogenation catalysts with enhanced performance.

Electronic and thermal properties of Nb2CCl2 MXenes

The molten salt synthesis has recently opened up new opportunities to functionalize two-dimensional MXenes with uniform halogen terminations. In this work, we synthesize Nb2CCl2 MXenes by etching the Al layer from the Nb2AlC precursor in the melt of CuCl2 Lewis acid. In Cl-terminated MXenes, intercalation of water is negligible, so that MXenes get closer to ideal, ordered van der Waals solids. We identify the preferential atomic stacking arrangement, which is of the AB type, as opposed to the AA stack assumed in previous works. We combine X-ray absorption near edge spectroscopy with density functional theory to clarify the local chemical environment of Cl atoms. Using vibrating sample magnetometry and specific heat measurements, we confirm that Nb2CCl2 MXenes are superconducting with a transition temperature of 6.0 K and find a Debye temperature of 320 K. We further show that the transition temperature slightly decreases with applied isostatic pressure.