Amorphous RuPd bimetallene for hydrogen evolution reaction in acidic and alkaline conditions: a first-principles study.

Metallene materials can provide a large number of active catalytic sites for the efficient use of noble metals as catalysts for hydrogen evolution reaction (HER), whereas the intrinsic activity on the surface is insufficient in crystal phase. The amorphous phase with an inherent long-range disorder can offer a rich coordinate environment and charge polarization on the surface is proposed for promoting the intrinsic catalytic activity on the surface of noble metals. Herein, we designed an amorphous RuPd (am-RuPd) structure by the first principles molecular dynamics method. The performance of the acidic HER on am-RuPd can have a huge enhancement due to the free energy change of hydrogen adsorption close to zero. In alkaline conditions, the H2O dissociation energy barrier on am-RuPd is just 0.49 eV, and it is predicted that the alkaline HER performance of am-RuPd will largely exceed that of Pt nanocrystalline sheets. This work provides a strategy for enhancing the intrinsic catalytic activity on the surface and a way to design an efficient HER catalyst based on metallene materials used in both acidic and alkaline conditions.

First-principles predictions of room-temperature ferromagnetism in orthorhombic MnX2 (X = O, S) monolayers.

Two-dimensional ferromagnets with high spin-polarization at ambient temperature are of considerable interest because they might be useful for making nanoscale spintronic devices. We report that even though bulk phases of MnO2 are generally antiferromagnetic with low ordering temperatures, the corresponding MnO2 and MnS2 monolayers are ferromagnetic, and MnS2 is a high temperature half metallic ferromagnet. Based on first-principles calculations, we find that the MnO2 monolayer is an intrinsic ferromagnetic semiconductor with a Curie temperature TC of ∼300 K, while the half-metallic MnS2 monolayer has a remarkably high TC of ∼1150 K. Both compounds have substantial magnetocrystalline anisotropy, out of plane in the case of MnO2 monolayers, and in plane along the b-axis of orthorhombic MnS2 monolayer. Interestingly, a metal-insulator phase transition occurs in the MnS2 monolayer when the applied biaxial strain is beyond -2%. Tuning near this metal-insulator transition offers additional possibilities for devices. The present work shows that MnX2 (X = O, S) monolayers have the properties required for ultrathin nano-spintronic devices.

In Situ Construction of Built-In Opposite Electric Field Balanced Surface Adsorption for Hydrogen Evolution Reaction.

Achieving a balance between H-atom adsorption and binding with H2 desorption is crucial for catalyzing hydrogen evolution reaction (HER). In this study, the feasibility of designing and implementing built-in opposite electric fields (OEF) is demonstrated to enable optimal H atom adsorption and H2 desorption using the Ni3(BO3)2/Ni5P4 heterostructure as an example. Through density functional theory calculations of planar averaged potentials, it shows that opposite combinations of inward and outward electric fields can be achieved at the interface of Ni3(BO3)2/Ni5P4, leading to the optimization of the H adsorption free energy (ΔGH*) near electric neutrality (0.05 eV). Based on this OEF concept, the study experimentally validated the Ni3(BO3)2/Ni5P4 system electrochemically forming Ni3(BO3)2 through cyclic voltammetry scanning of B-doped Ni5P4. The surface of Ni3(BO3)2 undergoes reconstruction, as characterized by Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS) and in situ Raman spectroscopy. The resulting catalyst exhibits excellent HER activity in alkaline media, with a low overpotential of 33 mV at 10 mA cm-2 and stability maintained for over 360 h. Therefore, the design strategy of build-in opposite electric field enables the development of high-performance HER catalysts and presents a promising approach for electrocatalyst advancement.

Atomic Dispersed Hetero-Pairs for Enhanced Electrocatalytic CO2 Reduction.

Electrochemical carbon dioxide reduction reaction (CO2RR) involves a variety of intermediates with highly correlated reaction and ad-desorption energies, hindering optimization of the catalytic activity. For example, increasing the binding of the *COOH to the active site will generally increase the *CO desorption energy. Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO2RR, but remains an unsolved challenge. Herein, we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier. This system shows an unprecedented CO2RR intrinsic activity with TOF of 3336 h-1, high selectivity toward CO production, Faradaic efficiency of 95.96% at - 0.60 V and excellent stability. Theoretical calculations show that the Mo-Fe diatomic sites increased the *COOH intermediate adsorption energy by bridging adsorption of *COOH intermediates. At the same time, d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of *CO intermediates. Thus, the undesirable correlation between these steps is broken. This work provides a promising approach, specifically the use of di-atoms, for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

Enhancing Photocatalytic Hydrogen Evolution by Synergistic Benefits of MXene Cocatalysis and Homo-Interface Engineering.

Photocatalytic water splitting holds great promise as a sustainable and cost-effectiveness alternative for the production of hydrogen. Nevertheless, the practical implementation of this strategy is hindered by suboptimal visible light utilization and sluggish charge carrier dynamics, leading to low yield. MXene is a promising cocatalyst due to its high conductivity, abundance of active sites, tunable terminal functional groups, and great specific surface area. Homo-interface has perfect lattice matching and uniform composition, which are more conducive to photogenerated carriers' separation and migration. In this study, a novel ternary heterogeneous photocatalyst, a-TiO2 /H-TiO2 /Ti3 C2 MXene (MXTi), is presented using an electrostatic self-assembly method. Compared to commercial P25, pristine anatase, and rutile TiO2 , as-prepared MXTi exhibit exceptional photocatalytic hydrogen evolution performance, achieving a rate of 0.387 mmol h-1 . The significant improvement is attributable to the synergistic effect of homo-interface engineering and Ti3 C2 MXene, which leads to widened light absorption and efficient carrier transportation. The findings highlight the potential of interface engineering and MXene cocatalyst loading as a proactive approach to enhance the performance of photocatalytic water splitting, paving the way for more sustainable and efficient hydrogen production.

Vertical nanoscale strain-induced electronic localization in epitaxial La2/3Sr1/3MnO3 films with ZrO2 nanopillar inclusions.

Unusual electrical transport properties associated with weak or strong localization are sometimes found in disordered electronic materials. Here, we report experimental observation of a crossover of electronic behavior from weak localization to enhanced weak localization due to the spatial influence of disorder induced by ZrO2 nanopillars in (La2/3Sr1/3MnO3)1-x:(ZrO2)x (x = 0, 0.2, and 0.3) nanocomposite films. The spatial strain regions, identified by scanning transmission electron microscopy and high-resolution x-ray diffraction, induce a coexistence of two-dimentional (2D) and three-dimentional (3D) localization and switches to typical 2D localization with increasing density of ZrO2 pillars due to length scale confinement, which interestingly accords with enhancing vertically interfacial strain. Based on the excellent agreement of our experimental results with one-parameter scaling theory of localization, the enhanced weak localization exists in metal range close to the fixed point. These films provide a tunable experimental model for studying localization in particular the transition regime by appropriate choice of the second epitaxial phase.

Spatially Confined PdHx Metallenes by Tensile Strained Atomic Ru Layers for Efficient Hydrogen Evolution.

Hydride metallenes show great potential for hydrogen-related catalytic applications due to favorable electronic structures modulated by interstitial hydrogen atoms and large active surface areas of metallenes. Metallene nanostructures generally have compressive strain relative to bulk, which can affect both the stability and the catalytic behavior of hydride metallenes but in general cannot be controlled. Here, we demonstrate highly stable PdHx metallenes with a tensile strained Ru surface layer and reveal the spatial confinement effect of the Ru skin by multiple spectroscopic characterizations and molecular dynamics simulations. These PdHx@Ru metallenes with a 4.5% expanded Ru outer layer exhibit outstanding alkaline hydrogen evolution reaction activity with a low overpotential of 30 mV at 10 mA cm-2 and robust stability with negligible activity decay after 10,000 cycles, which are superior to commercial Pt/C and most reported Ru-based electrocatalysts. Control experiments and first-principles calculations reveal that the tensile strained Ru outer layer lowers the energy barrier of H2O dissociation and provides a moderate hydrogen adsorption energy.

Functional-Unit-Based Material Design: Ultralow Thermal Conductivity in Thermoelectrics with Linear Triatomic Resonant Bonds.

We demonstrate the use of functional-unit-based material design for thermoelectrics. This is an efficient approach for identifying high-performance thermoelectric materials, based on the use of combinations of functional fragments relevant to desired properties. Here, we reveal that linear triatomic resonant bonds (LTRBs) found in some Zintl compounds provide strong anisotropy both structurally and electronically, along with strong anharmonic phonon scattering. An LTRB is thus introduced as a functional unit, and compounds are then screened as potential thermoelectric materials. We identify 17 semiconducting candidates from the MatHub-3d database that contain LTRBs. Detailed transport calculations demonstrate that the LTRB-containing compounds not only have considerably lower lattice thermal conductivities than other compounds with similar average atomic masses, but also exhibit remarkable band anisotropy near the valence band maximums due to the LTRB. K5CuSb2 is adopted as an example to elucidate the fundamental correlation between the LTRB and thermoelectric properties. The [Sb-Cu-Sb]5- resonant structures demonstrate the delocalized Sb-Sb interaction within each LTRB, resulting in the softening of TA phonons and leading to large anharmonicity. The low lattice thermal conductivity (0.39 W/m·K at 300 K) combined with the band anisotropy results in a high thermoelectric figure of merit (ZT) for K5CuSb2 of 1.3 at 800 K. This work is a case study of the functional-unit-based material design for the development of novel thermoelectric materials.

Origin of giant electric-field-induced strain in faulted alkali niobate films.

A large electromechanical response in ferroelectrics is highly desirable for developing high-performance sensors and actuators. Enhanced electromechanical coupling in ferroelectrics is usually obtained at morphotropic phase boundaries requiring stoichiometric control of complex compositions. Recently it was shown that giant piezoelectricity can be obtained in films with nanopillar structures. Here, we elucidate its origin in terms of atomic structure and demonstrate a different system with a greatly enhanced response. This is in non-stoichiometric potassium sodium niobate epitaxial thin films with a high density of self-assembled planar faults. A giant piezoelectric coefficient of ∼1900 picometer per volt is demonstrated at 1 kHz, which is almost double the highest ever reported effective piezoelectric response in any existing thin films. The large oxygen octahedral distortions and the coupling between the structural distortion and polarization orientation mediated by charge redistribution at the planar faults enable the giant electric-field-induced strain. Our findings demonstrate an important mechanism for realizing the unprecedentedly giant electromechanical coupling and can be extended to many other material functions by engineering lattice faults in non-stoichiometric compositions.

Atomically Dispersed MoOx on Rhodium Metallene Boosts Electrocatalyzed Alkaline Hydrogen Evolution.

Accelerating slow water dissociation kinetics is key to boosting the hydrogen evolution reaction (HER) in alkaline media. We report the synthesis of atomically dispersed MoOx species anchored on Rh metallene using a one-pot solvothermal method. The resulting structures expose the oxide-metal interfaces to the maximum extent. This leads to a MoOx -Rh catalyst with ultrahigh alkaline HER activity. We obtained a mass activity of 2.32 A mgRh -1 at an overpotential of 50 mV, which is 11.8 times higher than that of commercial Pt/C and surpasses the previously reported Rh-based electrocatalysts. First-principles calculations demonstrate that the interface between MoOx and Rh is the active center for alkaline HER. The MoOx sites preferentially adsorb and dissociate water molecules, and adjacent Rh sites adsorb the generated atomic hydrogen for efficient H2 evolution. Our findings illustrate the potential of atomic interface engineering strategies in electrocatalysis.

Dirac Fermion Cloning, Moiré Flat Bands, and Magic Lattice Constants in Epitaxial Monolayer Graphene.

Tuning interactions between Dirac states in graphene has attracted enormous interest because it can modify the electronic spectrum of the 2D material, enhance electron correlations, and give rise to novel condensed-matter phases such as superconductors, Mott insulators, Wigner crystals, and quantum anomalous Hall insulators. Previous works predominantly focus on the flat band dispersion of coupled Dirac states from different twisted graphene layers. In this work, a new route to realizing flat band physics in monolayer graphene under a periodic modulation from substrates is proposed. Graphene/SiC heterostructure is taken as a prototypical example and it is demonstrated experimentally that the substrate modulation leads to Dirac fermion cloning and, consequently, the proximity of the two Dirac cones of monolayer graphene in momentum space. Theoretical modeling captures the cloning mechanism of the Dirac states and indicates that moiré flat bands can emerge at certain magic lattice constants of the substrate, specifically when the period of modulation becomes nearly commensurate with the ( 3 × 3 ) R 30 o \[(\sqrt 3 \; \times \;\sqrt 3 )R{30^o}\] supercell of graphene. The results show that epitaxial single monolayer graphene on suitable substrates is a promising platform for exploring exotic many-body quantum phases arising from interactions between Dirac electrons.

Intrinsic nanostructure induced ultralow thermal conductivity yields enhanced thermoelectric performance in Zintl phase Eu2ZnSb2.

The Zintl thermoelectric phase Eu2ZnSb2 has a remarkable combination of high mobility and low thermal conductivity that leads to good thermoelectric performance. The key feature of this compound is a crystal structure that has a Zn-site with a 50% occupancy. Here we use comparison of experimental thermal conductivity measurements and first principles thermal conductivity calculations to characterize the thermal conductivity reduction. We find that partial ordering, characterized by local order, but Zn-site disorder on longer scales, leads to an intrinsic nanostructuring induced reduction in thermal conductivity, while retaining electron mobility. This provides a direction for identifying Zintl compounds with ultralow lattice thermal conductivity and good electrical conductivity.

Interior Melting of Rapidly Heated Gold Nanoparticles.

Normal melting invariably starts from surfaces or interfaces due to the weaker bonding constraints in these regions. However, we show that melting can be initiated from the interior of gold nanoparticles with high heating rates. We find that melting starts from the surface with the formation of a premelting layer, as usual, but that the premelting layer does not extend to the interior under certain conditions. Instead, liquid nucleation occurs in the core of the nanoparticle. This unexpected interior melting is connected to the slower melting kinetics, which is related to heat transfer near the premelted surface. The required conditions for interior melting are a suitable size of the nanoparticle and a sufficiently fast heating rate. The present results point to a novel melting regime in nanoparticles. We note that the time scales are now accessible using ultrafast tools such as X-ray lasers that can probe dynamical structure changes, suggesting opportunities for experiments.

Adsorption of K Ions on Single-Layer GeC for Potential Anode of K Ion Batteries.

Potassium ion batteries (KIBs) are considered as promising alternatives to lithium ion batteries (LIBs), following the rapid increase of demand for portable devices, and the development of electric vehicles and smart grids. Though there has been a promising breakthrough in KIB tech niques, exploring the promising anode materials for KIBs is still a challenge. Rational design with first-principle methods can help to speed up the discovery of potential anodes for KIBs. With density functional calculations, GeC with graphene-like 2D structure (g-GeC) is shown to be a desired anode material for applications in KIBs. The results show that the 2D g-GeC with a high concentration of K ions is thermodynamically stable, due to the strong interaction between C and Ge in GeC layer with the proper interaction between K and GeC. The storage capacity can be about 320 mAh/g, higher than that (279 mAh/g) in graphite. The low energy barrier (0.13 eV) of K ions diffusion on the honeycomb structure with proper voltage profile indicates the fast charge transfer. These theoretical finds are expected to stimulate the future experimental works in KIBs.

Room-temperature intrinsic ferromagnetism in epitaxial CrTe2 ultrathin films.

While the discovery of two-dimensional (2D) magnets opens the door for fundamental physics and next-generation spintronics, it is technically challenging to achieve the room-temperature ferromagnetic (FM) order in a way compatible with potential device applications. Here, we report the growth and properties of single- and few-layer CrTe2, a van der Waals (vdW) material, on bilayer graphene by molecular beam epitaxy (MBE). Intrinsic ferromagnetism with a Curie temperature (TC) up to 300 K, an atomic magnetic moment of ~0.21 [Formula: see text]/Cr and perpendicular magnetic anisotropy (PMA) constant (Ku) of 4.89 × 105 erg/cm3 at room temperature in these few-monolayer films have been unambiguously evidenced by superconducting quantum interference device and X-ray magnetic circular dichroism. This intrinsic ferromagnetism has also been identified by the splitting of majority and minority band dispersions with ~0.2 eV at Г point using angle-resolved photoemission spectroscopy. The FM order is preserved with the film thickness down to a monolayer (TC ~ 200 K), benefiting from the strong PMA and weak interlayer coupling. The successful MBE growth of 2D FM CrTe2 films with room-temperature ferromagnetism opens a new avenue for developing large-scale 2D magnet-based spintronics devices.

Vacancy ordering induced topological electronic transition in bulk Eu2ZnSb2.

Metal-semiconductor transitions from changes in edge chirality from zigzag to armchair were observed in many nanoribbon materials, especially those based on honeycomb lattices. Here, this is generalized to bulk complex Zintl semiconductors, exemplified by Eu2ZnSb2 where the Zn vacancy ordering plays an essential role. Five Eu2ZnSb2 structural models are proposed to guide transmission electron microscopy imaging. Zigzag vacancy ordering models show clear metallicity, while the armchair models are semiconducting with indirect bandgaps that monotonously increase with the relative distances between neighboring ZnSb2 chains. Topological electronic structure changes based on cation ordering in a Zintl compound point toward tunable and possibly switchable topological behavior, since cations in these are often mobile. Thus, their orderings can often be adjusted by temperature, minor alloying, and other approaches. We explain the electronic structure of an interesting thermoelectric and point the way to previously unidentified types of topological electronic transitions in Zintl compounds.

Binary and Ternary Colloidal Cu-Sn-Te Nanocrystals for Thermoelectric Thin Films.

Recent advances in copper chalcogenide-based nanocrystals (NCs), copper sulfide, and copper selenide derived nanostructures, have drawn considerable attention. However, reports of crystal phase and shape engineering of binary or ternary copper telluride NCs remain rare. Here, a colloidal hot-injection approach for producing binary copper/tin telluride, and ternary copper tin telluride NCs with controllable compositions, crystal structures, and morphologies is reported. The crystal phase and growth behavior of these tellurides are systematically studied from both experimental and theoretical perspectives. The morphology of Cu1.29 Te NCs is modified from 1D nanorods with different aspect ratios to 2D nanosheets and 3D nanocubes, by controlling the preferential growth of specific crystalline facets. A controllable phase transition from Cu1.29 Te to Cu1.43 Te NCs is also demonstrated. The latter can be further converted into Cu2 SnTe3 and SnTe through Sn incorporation. Temperature dependent thermoelectric properties of metal (Cu and Sn) telluride nanostructure thin films are also studied, including Cu1.29 Te, Cu1.43 Te, Cu2 SnTe3 , and SnTe. Cu2 SnTe3 is a low carrier density semimetal with compensating electron and hole Fermi surface pockets. The engineering of crystal phase and morphology control of colloidal copper tin telluride NCs opens a path to explore and design new classes of copper telluride-based nanomaterials for thermoelectrics and other applications.

Second Harmonic Generation Susceptibilities from Symmetry Adapted Wannier Functions.

Elucidating the orbital level origin of second harmonic generation (SHG) in materials and identifying the local contributions is a long-standing challenge. We report a first principles approach for the SHG where the contributions from individual orbitals or atoms can be evaluated via symmetry adapted Wannier functions without semiempirical parameters. We apply this method to the common SHG materials KBe_{2}BO_{3}F_{2}, KCaCO_{3}F, and ß-BaB_{2}O_{4}, and show that the orbitals on noncentrosymmetric sublattices are responsible for SHG effect and the energies of these orbitals control the magnitude.

Copper(I)-Based Flexible Organic-Inorganic Coordination Polymer and Analogues: High-Power Factor Thermoelectrics.

We investigated the transport properties of the single layer and bulk copper(I) 4-hydroxythiophenolate (Cu(SC6H4OH)) coordination polymers and their analogues Cu(SeC6H4OH) and Cu(TeC6H4OH) on the basis of density functional calculations. We found that the bulk phases show superior power factors when compared with single-layer phases. This performance is comparable to the reported best organic thermoelectric candidates p-type poly(3.4-ethylenedioxythiophene) (PEDOT) and n-type poly[Kx(Ni-ett)] (ett = ethylenetetrathiolate). The non-parabolic conduction band minimum of Cu(SeC6H4OH) along the x direction can decouple the transport quantities, Seebeck coefficient, and electrical conductivity to achieve the highest power factor among all the candidates.

Correction: Localization in the SCAN meta-generalized gradient approximation functional leading to broken symmetry ground states for graphene and benzene.

Correction for 'Localization in the SCAN meta-generalized gradient approximation functional leading to broken symmetry ground states for graphene and benzene' by Yubo Zhang et al., Phys. Chem. Chem. Phys., 2020, 22, 19585-19591, DOI: 10.1039/D0CP03567J.