Unveiling Atomic-Scaled Local Chemical Order of High-Entropy Intermetallic Catalyst for Alkyl-Substitution-Dependent Alkyne Semihydrogenation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 20193 - 20204

Опубликована: Июль 15, 2024

High-entropy intermetallic (HEI) nanocrystals, composed of multiple elements with an ordered structure, are immense interest in heterogeneous catalysis due to their unique geometric and electronic structures the cocktail effect. Despite tremendous efforts dedicated regulating metal composition advanced synthetic methodologies improve performance, surface local chemical order HEI correlation activity at atomic level remain obscure yet challenging. Herein, by determining three-dimensional (3D) structure quinary PdFeCoNiCu (PdM) using atomic-resolution electron tomography, we reveal that regulates structures, which further mediates alkyl-substitution-dependent alkyne semihydrogenation. The 3D PdM nanocrystals feature (intermetallic) core enclosed a disordered (solid-solution) shell rather than surface. lattice mismatch between results apparent near-surface distortion. increases annealing temperature, driving redistribution Pd M surface, but geometrical (chemically disordered) configurations compositions essentially unchanged. We investigate catalytic performance different orders toward semihydrogenation across broad range alkynes, finding density hindrance effect alkyl substitutions on alkynes two key factors selective anticipate these findings will clarify controversy regarding and/or effects catalysts inspire future studies tuning engineering enhanced catalysts.

Язык: Английский

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Weak electron-phonon coupling in layered electrides

Physical review. B./Physical review. B, Год журнала: 2025, Номер 111(4)

Опубликована: Янв. 7, 2025

In layered electrides, the conducting electrons fill two-dimensional interstitial voids between atomic planes, which is expected to result in weakened electron-phonon coupling and give rise high mobility conductivity. this paper, using density functional theory, we explore room-temperature scattering transport properties of seven electrides belonging alkaline earth subpnictogenide family (Ca2N, Sr2N, Sr2P, Ba2N, Ba2P, Ba2As, Ba2Sb) compare them three traditional high-conductivity metals (Cu, Au, Al). Several are found have low rates compared with metals, resulting from weak interaction, 3 13× lower than shown originate spatial separation lattice. Sr2N Ca2N predicted be best conductors among anisotropy, due reduced leading long average mean-free paths for backscattering reaching 48 nm. However, display highest conductivities owing their larger distribution modes, originating higher electronic velocities. These findings may help guide discovery exceptionally record locked icon Physics Subject Headings (PhySH)Electrical conductivityElectronic structureTransport phenomenaLayered crystalsBoltzmann theoryDensity theoryLandauer formula

Язык: Английский

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Magnetic electrides: Recent advances in materials realization and application prospects

Applied Physics Reviews, Год журнала: 2025, Номер 12(1)

Опубликована: Фев. 19, 2025

The coupling of magnetism in multidimensional inorganic electrides has attracted significant attention the fields spintronics, materials science, and chemistry. Inorganic exhibit a wide range promising applications due to their remarkable properties, such as unique magnetic behavior, low work function, nontrivial topological states, high electron mobility. Despite rapid advancements this emerging field, comprehensive reviews on remain scarce. This review aims provide thorough analysis research progress electrides. We examine development preparation methods, classifications, regulatory mechanisms magnetism, along with various properties potential applications. Finally, we discuss challenges future prospects for electrides, highlighting breakthroughs exciting field.

Язык: Английский

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Electride transition in liquid aluminum under high pressure and high temperature

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(1)

Опубликована: Янв. 3, 2025

Despite the conventional view of liquid aluminum (l-Al) as a simple metal governed by free-electron model, it exhibits unique bonding characteristics. This study uncovers gradual transition from free electron to electride behavior in l-Al at high pressure and temperature, forming type two-component where atomic states coexist. The proportion increases with temperature until reaching saturation, leading notable changes pair-correlation function coordination number saturation pressure. Furthermore, this was found profoundly impact thermodynamic dynamic properties, evidenced anomalous crossovers isothermal bulk modulus, thermal expansivity, heat capacity, sound speed, self-diffusion coefficient correlated varying temperature. finding described work will deepen our understanding electronic structure also lay ground for interpreting predicting new physical chemical under extreme conditions.

Язык: Английский

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Assessing Dimensionality in Electrides

The Journal of Physical Chemistry C, Год журнала: 2025, Номер 129(6), С. 3211 - 3217

Опубликована: Янв. 31, 2025

Electrides are fascinating materials that so electron-rich excess electrons localized in interstitial, atom-sized voids. In extreme cases, electride present at such high concentrations their wave functions overlap, creating continuous pathways of electrons. Although the topology these can profoundly influence properties and uses materials, quantifying dimensionality remains an outstanding challenge. Indeed, some most well-studied electrides have been assigned to several different dimensionalities. We introduce a strategy for dimensionality, which we then apply classify many previously reported electrides. demonstrate how is closely related emerging application electrides─their use as mixed conductors both anions resembles hydride diffusion materials. total, describing electronic structure while also showing relevance this descriptor understanding chemical physical characteristics.

Язык: Английский

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Ambient pressure superconductivity mediated by vanadium d electrons in electride 2H−VN2

Physical review. B./Physical review. B, Год журнала: 2025, Номер 111(6)

Опубликована: Фев. 28, 2025

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2D Multifunctional Spin‐Orbit Coupled Dirac Nodal Line Materials

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 27, 2025

Abstract 2D spin‐orbit coupled Dirac nodal line (SOC‐DNL) materials integrated with multifunctional properties are the cornerstone for constructing an abundant application pool, but remain largely limited. Here, a combination of symmetry analysis, high‐throughput screening, and first‐principles calculations employed to identify comprehensive set 473 nonmagnetic antiferromagnetic (AFM) SOC‐DNL materials, spanning 5 layer groups 12 magnetic space groups. Building on potential these it further integrates their topological electride, multiferroic, characteristics, revealing unique systems expanded functionalities promising applications. Specifically, three representative cases highlighted illustrate distinctive features: i) The electride material so‐MoS₂, which exhibits floating surface states highly anisotropic Fermi surfaces; ii) ferroelastic β‐PbO, demonstrates multiferroic behavior driven by hole‐doping‐induced magnetism polarization‐switch‐enabled phase transitions; iii) AFM system Ti 2 O, features lower work function, significantly enhancing its catalytic performance NH 3 synthesis. These findings not only establish database exploration also enhance multifunctionality, paving way diverse applications in quantum science, spintronics, energy‐related technologies.

Язык: Английский

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Leading role of satellite interstitial electrons in superconductivity in ternary superlithide Li14CP

Matter and Radiation at Extremes, Год журнала: 2025, Номер 10(2)

Опубликована: Март 1, 2025

The discovery of pressure-induced superconducting electrides has sparked a intense wave interest in novel superconductors. However, opinions vary regarding the relationship between non-nuclear attractors (NNAs) and superconductivity, with two opposing views currently represented by materials Li6P Li6C. Here, we choose ternary Li–C–P as model system reveal underlying mechanism which NNAs contribute to superconductivity. loosely bound superlithide Li14CP covalently bond Li form unique satellite interstitial electrons (SIEs) around near Fermi level, dominating First-principles calculations show that SIEs progressively increase number couple strongly phonons at high pressure. Moreover, surface nesting associated induces phonon softening, further enhancing electron–phonon coupling giving Tc 10.6 K 300 GPa. leading role superconductivity is general one also relevant recently predicted Our work presented here reshapes understanding NNA-dominated holds promise for guiding future discoveries designs high-temperature

Язык: Английский

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Selective Hydrodeoxygenation of Lignin via Aryl Ether C–O Bond Cleavage: Cs-Mediated Cu Surface Engineering

ACS Catalysis, Год журнала: 2024, Номер 14(24), С. 18774 - 18785

Опубликована: Дек. 10, 2024

Lignin is a pivotal building block of lignocellulose biomass and the most abundant aromatic polymer in nature. Selective hydrodeoxygenation (HDO) via target cleavage aryl ether C–O bonds great importance for lignin biorefinery. However, preserving aromaticity during HDO efficient production arenes remains challenge. Herein, low electronegativity Cs was utilized to customize chemical environment geometric construction highly dispersed Cu sites on mesoporous SiO2 nanospheres. The electron density around evidently increased while coordination precisely tailored. hydrogenation deoxygenation activities were effectively balanced. Owing synergy between electron-rich Cuδ− center, saturated rings efficiently inhibited, preferential selectivity toward bond obtained. from anisole reached 83% 2Cs/Cu@NS-SiO2, intrinsic activity based active significantly 0.34 mmol·mCu–2·h–1, more than doubled that Cu@NS-SiO2 without modification. Besides, remarkable arene 76.3% achieved among depolymerized monomers organic solvent-extracted lignin. This study offers promising approach valorizing into high-value arenes.

Язык: Английский

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Electrides: emerging electronic materials for catalysis

Fundamental Research, Год журнала: 2024, Номер unknown

Опубликована: Дек. 1, 2024

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