Surface Electronic Properties Research Articles

First‐Principles Active‐Site Model Design for High‐Entropy‐Alloy Catalyst Screening: The Impact of Host Element Selection on Catalytic Properties

AbstractActive‐site models comprise miniature active sites on the host element, providing one of effective descriptors for screening high‐entropy‐alloy (HEA) catalysts using machine learning. This study investigates the impact of host elements on the electronic properties of active sites via density functional theory (DFT), where the active‐site model is used in the HEA electrocatalysts. Also, the appropriate host element selection significantly affects the system's surface structures, electronic, and catalytic properties that adsorbate adsorption energy, d‐band center, Bader charge, Zero‐point energy, and entropy are used as accuracy verification parameters compared to the original surface. Ultimately, the novel guideline for active‐site model construction is proposed using the simple example of PtPdFeCoNi high‐entropy alloys. This investigation demonstrates that the host element selection is a crucial parameter to the active‐site models, influencing the electronic structure and electrocatalytic properties.

Molecular modeling study on the water-electrode surface interaction in hydrovoltaic energy

The global energy problem caused by the decrease in fossil fuel sources, which have negative effects on human health and the environment, has made it necessary to research alternative energy sources. Renewable energy sources are more advantageous than fossil fuels because they are unlimited in quantity, do not cause great harm to the environment, are safe, and create economic value by reducing foreign dependency because they are obtained from natural resources. With nanotechnology, which enables the development of different technologies to meet energy needs, low-cost and environmentally friendly systems with high energy conversion efficiency are developed. Renewable energy production studies have focused on the development of hydrovoltaic technologies, in which electrical energy is produced by making use of the evaporation of natural water, which is the most abundant in the world. By using nanomaterials such as graphene, carbon nanoparticles, carbon nanotubes, and conductive polymers, hydrovoltaic technology provides systems with high energy conversion performance and low cost, which can directly convert the thermal energy resulting from the evaporation of water into electrical energy. The effect of the presence of water on the generation of energy via the interactions between the ion(s) and the liquid–solid surface can be enlightened by the mechanism of the hydovoltaic effect. Here, we simply try to get some tricky information underlying the hydrovoltaic effect by using DFT/B3LYP/6-311G(d, p) computations. Namely, the physicochemical and electronic properties of the graphene surface with a water molecule were investigated, and how/how much these quantities (or parameters) changed in case of the water molecule contained an equal number of charges were analyzed. In these computations, an excess of both positive charge and negative charge, and also a neutral environment was considered by using the Na+, Cl−, and NaCl salt, respectively.

Enhancement of Sulfur Source-Dependent Zn Vacancies in Different Photocatalytic Performances of ZnIn2S4 Nanoparticles.

This study focuses on the synthesis and investigation of ZnIn2S4 nanoparticle (NP) photocatalysts treated with different sulfur sources, thioacetamide (TAA), or thiourea (TU), to explore their wavelength-dependent photocatalytic activity. The research aims to understand the impact of Zn vacancies present on the surface of ZnIn2S4 NPs. The investigation involves electron spin resonance and in situ X-ray photoelectron spectroscopy to study the photocatalytic activity of ZnIn2S4-TU and ZnIn2S4-TAA NPs, following the characterization of surface morphology and electronic properties using high-resolution transmission electron microscopy and X-ray diffraction. Additionally, the study delves into the wavelength-dependent photocatalytic degradation (PCD) activity of the ZnIn2S4 NPs using 2,5-hydroxymethylfurfural (HMF) across a wide range. Notably, the selective oxidation of HMF using ZnIn2S4-TU NPs resulted in the formation of 2,5-furandicarboxylic acid (FDCA) via 2,5-diformylfuran, with an efficiency exceeding 40% over the broad wavelength range. The research demonstrates that the irradiation wavelength for PCD is influenced by the number of defect structures introduced into the ZnIn2S4 NPs through the sulfur source.

Highly Efficient Solar-driven Dry Reforming of Methane on a Rh/LaNiO3 Catalyst through a Light-induced Metal-to-metal Charge Transfer Process.

As an energy-saving and green method, solar-driven dry reforming of methane (DRM) is expected to introduce new activation processes and prevent sintering and coking of the catalysts. However, it still lacks an efficient way to the coordinate regulation of activation of reactants and lattice oxygen migration. In this work, Rh/LaNiO3 is designed as a highly efficient photothermal catalyst for solar-driven DRM, which performs production rates of 452.3mmol h-1 gRh -1 for H2 and 527.6mmol h-1 gRh -1 for CO2 under a light intensity of 1.5W cm-2 , with an excellent stability. Moreover, a remarkable light-to-chemical energy efficiency (LTCEE) of 10.72% is achieved under a light intensity of 3.5W cm-2 . The characterizations of surface electronic and chemical properties and theoretical analysis demonstrate that strong adsorption for CH4 and CO2 , light-induced metal-to-metal charge transfer (MMCT) process and high oxygen mobility together bring Rh/LaNiO3 excellent performance for solar-driven DRM. This article is protected by copyright. All rights reserved.

Methodology and implementation of a tunable deep-ultraviolet laser source for photoemission electron microscopy

Photoemission electron microscopy (PEEM) is a unique and powerful tool for studying the electronic properties of materials and surfaces. However, it requires intense and well-controlled light sources with photon energies ranging from the UV to soft X-rays for achieving high spatial resolution and image contrast. Traditionally, many PEEMs were installed at synchrotron light sources to access intense and tunable soft X-rays. More recently, the maturation of solid-state lasers has opened a new avenue for laboratory-based PEEMs using laser-based UV light at lower photon energies. Here, we report on the characteristics of a laser-based UV light source that was recently integrated with a PEEM instrument. The system consists of a high repetition rate, tunable wavelength laser coupled to a harmonics generation module, which generates deep-UV radiation from 192 nm to 210 nm. We comment on the spectral characteristics and overall laser system stability, as well as on the effects of space charge within the PEEM microscope at high UV laser fluxes. Further, we show an example of imaging on gallium nitride, where the higher UV photon energy and flux of the laser provides considerably improved image quality, compared to a conventional light source. These results demonstrate the capabilities of laser-based UV light sources for advancing laboratory-based PEEMs.

Selective adsorption of carbonyl compounds from bio-oil by seaweed-derived carbon: A theoretical study

Bio-oil is a renewable fuel widely used in the chemical industry, but its high oxygen content results in thermal instability and a low heating value. In order to address this issue, the current study aims to use seaweed-derived biochar as a substrate to selectively adsorb carbonyl compounds from the volatile matter during the bio-oil condensation process. The interaction between acetone and different nitrogen-rich seaweed-derived carbon models were analysed using acetone as a model compound and density functional theory. The adsorption structure, energy, and surface electronic properties between acetone and each seaweed-derived carbon model were analysed. Since nitrogen electronegativity is higher than carbon’s, electron-rich nitrogen, and electron-deficient carbon are formed, thereby increasing the adsorption capacity of nitrogen-doped carbon. The results of this study will provide insight into the adsorption mechanism of seaweed biochar and offer a new approach to reducing the oxygen content of bio-oil and improving its quality.

Electronic Structure and Surface Chemistry of Hexagonal Boron Nitride on HOPG and Nickel Substrates.

The effect of point defects and interactions with the substrate are shown by density functional theory calculations to be of significant importance for the structure and functional properties of hexagonal boron nitride (h-BN) films on highly ordered pyrolytic graphite (HOPG) and Ni(111) substrates. The structure, surface chemistry, and electronic properties are calculated for h-BN systems with selected intrinsic, oxygen, and carbon defects and with graphene hybrid structures. The electronic structure of a pristine monolayer of h-BN is dependent on the type of substrate, as h-BN is decoupled electronically from the HOPG surface and acts as bulk-like h-BN, whereas on a Ni(111) substrate, metallic-like behavior is predicted. These different film/substrate systems therefore show different reactivities and defect chemistries. The formation energies for substitutional defects are significantly lower than for intrinsic defects regardless of the substrate, and vacancies formed during film deposition are expected to be filled by either ambient oxygen or carbon from impurities. Significantly lower formation energies for intrinsic and oxygen and carbon substitutional defects were predicted for h-BN on Ni(111). In-plane h-BCN hybrid structures were predicted to be terminated by N-C bonding. Substitutional carbon on the boron site imposes n-type semiconductivity in h-BN, and the n-type character increases significantly for h-BN on HOPG. The h-BN film surface becomes electronically decoupled from the substrate when exceeding monolayer thickness, showing that the surface electronic properties and point defect chemistry for multilayer h-BN films should be comparable to those of a freestanding h-BN layer.

In-doped Sn3O4 flower-like nanosheets for efficient visible-light photocatalytic hydrogen production

Improving photocatalytic activity is crucial for promoting photocatalytic hydrogen production. Element doping is a feasible strategy to accelerate carrier separation and migration rate. Herein, a simple one-pot hydrothermal process was used to create In doped Sn3O4 composite photocatalyst. It was demonstrated that the addition of In considerably raises the concentration of oxygen vacancy, which provides more unsaturated active sites, thus regulating the photocatalyst's electronic structure and surface properties, and promoting the carrier migration efficiency. Meanwhile, the light absorption range of samples after doping is redshifted, and the light absorption capacity is enhanced, which effectively improves the photocatalytic activity. Due to this, the optimal sample's average hydrogen production under visible light reached 22.83 μmol g−1 h−1, 4.5 folds more than that of Sn3O4, and shown good stability. This research presents a novel approach for the development of metal oxide photocatalyst with excellent activity and durability.

Coexistence of surface oxygen vacancy and interface conducting states in LaAlO3/SrTiO3 revealed by grazing-angle resonant soft x-ray scattering

Oxide heterostructures have shown rich physics phenomena, particularly in the conjunction of exotic insulator–metal transition (IMT) at the interface between polar insulator LaAlO3 and non-polar insulator SrTiO3 (LaAlO3/SrTiO3). The polarization catastrophe model has suggested an electronic reconstruction, yielding to metallicity at both the interface and surface. Another scenario is the occurrence of surface oxygen vacancy at LaAlO3 (surface-Ov), which has predicted surface-to-interface charge transfer, yielding metallic interface but insulating surface. To clarify the origin of IMT, one should probe surface-Ov and the associated electronic structures at both the surface and the buried interface simultaneously. Here, using grazing-angle resonant soft x-ray scattering (GA-RSXS) supported with first-principles calculations, we reveal the co-existence of the surface-Ov state and the interface conducting state only in conducting LaAlO3/SrTiO3 (001) films. Interestingly, both the surface-Ov state and the interface conducting state are absent for the insulating film. As a function of Ov density, while the surface-Ov state is responsible for the IMT, the spatial charge distribution is found responsible for a transition from two-dimensional-like to three-dimensional-like conductivity accompanied by spectral weight transfer, revealing the importance of electronic correlation. Our results show the importance of surface-Ov in determining interface properties and provide a new strategy in utilizing GA-RSXS to directly probe the surface and buried interface electronic properties in complex oxide heterostructures.

Dual-Doping Strategy for Enhancing Hydrogen Evolution on Molybdenum Carbide Catalysts

Hydrogen evolution reaction (HER) is a topic of great interest due to its efficient hydrogen production properties, which can address the increasing demand for clean and sustainable energy sources. On the other hand, molybdenum carbide (MoC) has been widely studied due to its noble metal-like surface electronic properties. In the HER process, it is crucial to regulate the Mo−H bonding energy effectively and increase the electron transfer rate on the MoC catalyst surface in a rational manner. In this study, we introduce highly electronegative nitrogen and non-noble transition metal atoms (Cu or Co) into the molybdenum carbide crystal lattice (N−M−MoC, M: Cu, or Co), which leads to a dual—doping effect. This effect results in the rearrangement of the electronic configuration on the catalyst surface and the enrichment of electrons around Mo atom, leading to an optimization in the Mo−H bonding energy. Moreover, the unique two-dimensional nano-sheet structure of the N−M−MoC materials further promotes the electron transfer and exposure of active sites. Benefiting from the above, the HER performance of the N−M−MoC is significantly improved. Among them, N−Cu−MoC exhibits the lowest overpotential (η10 = 158 mV) and highest stability (about 30 h) in alkaline solutions.

Structural and electronic properties of Tl films on Ag(111): From (3×3) surface alloy to moiré superstructure

Surface alloys between the heavy metals Bi, Pb, or Sb and noble metals, such as Ag(111), are known for their giant Rashba splitting. Although thallium (Tl) should result in isostructural surface alloys, its structural and electronic properties remained elusive. The authors present here a detailed work on the structural and electronic properties of Tl films epitaxially grown on Ag(111) surfaces. By combining experimental LEED, AES, STM/STS, and IPE with $a\phantom{\rule{0}{0ex}}b$ $i\phantom{\rule{0}{0ex}}n\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}o$ band structure and charge distribution calculations, the $s$,${p}_{z}$-derived surface state of the TlAg${}_{2}$ surface alloy is identified, with a weak, but finite, Rashba splitting.

Size-modulated photo-thermal catalytic CO2 hydrogenation performances over Pd nanoparticles

Size of metal nanoparticles significantly influences their catalytic behaviors. However, it is still challenging to obtain monodispersed metal nanoparticles with successively tuned sizes to unveil their size-dependent catalytic performances, especially for photo-thermal catalytic reverse water–gas shift (RWGS) reaction. Herein, a library of Pd nanoparticles of 2.8, 3.4, 4.7, 5.3, 6.3 and 8.1 nm were synthesized and supported on TiO2 for photo-thermal catalytic RWGS reaction. The catalytic activity presented volcano-like dependence on sizes of Pd nanoparticles with 6.3 Pd/TiO2 exhibiting the highest catalytic efficiency. Based on the results of X-ray photoelectron spectroscopic analysis, photo-to-thermal conversion efficiency evaluation and density functional theory (DFT) calculations following the formate (*HCOO) pathway revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) measurements, the volcano-type tendency in catalytic activity could be attributed to the superposition of size-governed surface electronic properties over Pd nanoparticles.

Experimental Evidence for Alloying Effects in Au–Pt-Catalyzed Low-Temperature CH4Activation with NO

The activation of methane with nitric oxide at low temperatures (300–400 °C) and atmospheric pressure was studied on Au–Pt nanoparticles with different Au/Pt ratios supported on alumina. The reaction forms HCN, a valuable chemical intermediate, via concurrent or successive C–H bond cleavage, NO dissociation, and C–N coupling reactions. The catalysts with different Au/Pt ratios had similar particle morphology and bulk properties, as evidenced by scanning transmission electron microscopy imaging and X-ray absorption near-edge structure spectroscopy, respectively. However, they exhibited different electronic and geometric surface properties, according to in situ diffuse reflectance infrared Fourier transform spectra of preadsorbed CO, a likely consequence of Au surface enrichment. These differences had catalytic implications, where the relative proportion of electron-deficient Pt sites on the surface of the catalysts was found to track with activity, expressed as turnover frequency for the total CH4 conversion and HCN formation. Based on the activity trend, kinetic comparison of reaction orders, temperature-programmed desorption experiments, and comparisons to the literature, it is proposed that the CH4–NO catalysis occurred mainly on contiguous Pt sites, that the higher C–H activation activity of electron-deficient Pt species may be related to weaker adsorption of CH4, and that the higher NO dissociation activity of metallic Pt species may have contributed to the complete oxidation of CH4 to CO2. Nonetheless, contact time and in situ spectroscopic studies at isothermal conditions revealed only subtle differences in the reaction scheme by surface modifications, indicating that Au affected the reactivity indirectly.

Nanoscale morphology tailoring in plasma deposited CN x layers

Magnetron discharge plasma was applied for the synthesis of CN x thin layers using methane and nitrogen gas precursors. The incorporation of nitrogen in the carbon network resulted in the dramatic evolution of growth morphology: from a ‘buried’ porous layer observed at low nitrogen incorporation to aligned bundles of nanorods grown perpendicular to the substrate surface at maximum discharge power and nitrogen flow. The films deposited at the low discharge power and high nitrogen incorporation exhibited a mesoporous sponge-like morphology after vacuum annealing. Relevant physical mechanisms responsible for the formation of nano- and mesoshaped morphology are discussed in terms of the effects of internal mechanical stresses and plasma etching. In addition, the sensing properties of the sponge-like layer were preliminarily examined in water vapor and ammonia ambients. The CN x films showed enhanced sensitivity to ammonia and reverse electrical response to moisture in comparison with a nitrogen-free nanoporous carbon film, which were assigned to modification of the electronic properties of the nitridated surface.

Deep UV transparent conductive Si-doped Ga2O3 thin films grown on Al2O3 substrates

β-Ga2O3 is attracting considerable attention for applications in power electronics and deep ultraviolet (DUV) optoelectronics owing to the ultra-wide bandgap of 4.85 eV and amendable n-type conductivity. In this work, we report the achievement of Si-doped β-Ga2O3 (Si:β-Ga2O3) thin films grown on vicinal α-Al2O3 (0001) substrates with high electrical conductivity and DUV transparency of promising potential as transparent electrodes. The use of Al2O3 substrates with miscut angles promotes step-flow growth mode, leading to substantial improvement of crystalline quality and electrical properties of the Si:β-Ga2O3 films. A high conductivity of 37 S·cm−1 and average DUV transparency of 85% have been achieved for 0.5% Si-doped film grown on a 6° miscut substrate. High-resolution x-ray and ultraviolet photoemission spectroscopy were further used to elucidate the surface electronic properties of the grown Si:β-Ga2O3 films. An upward surface band bending was found at the surface region of Si:β-Ga2O3 films. Interestingly, all the Si:β-Ga2O3 films have a very low work function of approximately 3.3 eV, which makes Si:β-Ga2O3 suitable materials for efficient electron injection. The present Si:β-Ga2O3 films with high conductivity, DUV transparency, and low work function would be useful as the DUV transparent electrode to develop advanced DUV optoelectronic devices.

Thermo- and Photocatalytic Activation of CO2 in Ionic Liquids Nano-domains.

Ionic liquids (ILs) are considered to be potential material devices for CO2 capturing and conversion to energy-adducts. They form a cage (confined-space) around the catalyst providing an ionic nano-container environment which serves as physical-chemical barrier that selectively controls the diffusion of reactants, intermediates, and products to the catalytic active sites via their hydrophobicity and contact ion pairs. Hence, the electronic properties of the catalysts in ILs can be tuned by the proper choice of the IL-cations and anions that strongly influence the residence time/diffusion of the reactants, intermediates, and products in the nano-environment. On the other hand, ILs provide driving force towards photocatalytic redox process to increase the CO2 photoreduction. By combining ILs with the semiconductor, unique solid semiconductor-liquid commodities are generated that can lower the CO2 activation energy barrier by modulating the electronic properties of the semiconductor surface. This mini-review provides a brief overview of the recent advances in IL assisted thermal conversion of CO2 to hydrocarbons, formic acid, methanol, dimethyl carbonate, and cyclic carbonates as well as its photo-conversion to solar fuels.

Thermo‐ and Photocatalytic Activation of CO2 in Ionic Liquids Nanodomains

AbstractIonic liquids (ILs) are considered to be potential material devices for CO2 capturing and conversion to energy‐adducts. They form a cage (confined‐space) around the catalyst providing an ionic nano‐container environment which serves as physical‐chemical barrier that selectively controls the diffusion of reactants, intermediates, and products to the catalytic active sites via their hydrophobicity and contact ion pairs. Hence, the electronic properties of the catalysts in ILs can be tuned by the proper choice of the IL‐cations and anions that strongly influence the residence time/diffusion of the reactants, intermediates, and products in the nano‐environment. On the other hand, ILs provide driving force towards photocatalytic redox process to increase the CO2 photoreduction. By combining ILs with the semiconductor, unique solid semiconductor‐liquid commodities are generated that can lower the CO2 activation energy barrier by modulating the electronic properties of the semiconductor surface. This mini‐review provides a brief overview of the recent advances in IL assisted thermal conversion of CO2 to hydrocarbons, formic acid, methanol, dimethyl carbonate, and cyclic carbonates as well as its photo‐conversion to solar fuels.

Stability and electronic properties of low-index surfaces of zinc stannate modulated by vacancy defect: A first-principle study

The low-index surfaces and defect structures of perovskite zinc stannate (ZTO) were studied based on the first-principles density functional theory (DFT) calculations. The geometry, stability and electronic properties of zinc stannate modulated by point defects were discussed. It is found that the 001 surface of ZTO and its oxygen defects on the surface were most stable thermodynamically among the 42 low-dimensional structures according to the energy calculations. The electronic properties near the Fermi level of low-dimensional ZTO structures can be modulated by different defects. This can be understood by electron band structure and density of states analysis. 101 surface of ZTO showed a metallic characteristic, while other low-dimensional ZTO structures were all semiconductors with a decreased band gap than that of the bulk. Defects could induce electron transfer and charge re-distribution on the ZTO surface by means of geometric and chemical bonding reconstruction on surfaces with defects.

Electrostatic Design of the Nanoscale Internal Surfaces of Porous Covalent Organic Frameworks.

It is well established that the collective action of assemblies of dipoles determines the electronic structure of surfaces and interfaces. This raises the question, to what extent the controlled arrangement of polar units can be used to also tune the electronic properties of the inner surfaces of materials with nanoscale pores. In the present contribution, state-of-the-art density-functional theory calculations are used to show for the prototypical case of covalent organic frameworks (COFs) that this is indeed possible. Decorating pore walls with assemblies of polar entities bonded to the building blocks of the COF layers triggers a massive change of the electrostatic energy within the pores. This, inevitably, also changes the relative alignment between electronic states in the framework and in guest molecules and is expected to have significant impacts on charge separation in COF heterojunctions, on redox reactions in COFs-based electrodes, and on (photo)catalysis.

Enhanced catalytic activity for methanol synthesis from CO2 hydrogenation by doping indium into the step edge of Rh(211): A theoretical study

The doping of foreign metals can modify the electronic properties of the original catalyst surfaces, thereby changing the catalytic activity. Realistic surfaces possess many defects, such as step sites. Herein, the first-principles calculation is implemented to research how indium doping on stepped Rh(211) alters the catalytic activity for methanol synthesis. The calculated substitution energy shows that the indium atom tends to be doped at the step edge of Rh(211). Almost all species prefer to adsorb at the step-edge sites because the surface atoms at the step-edge possess the lowest coordination number. The electronic structure analysis demonstrates that the activation degree of CO2* chiefly relies on the charge transfer between CO2* and catalyst. Furthermore, the doped indium atoms make In/Rh(211) expose more H* adsorption sites and promote the relative stability of adsorbed species on In/Rh(211). Besides, the doping of indium significantly inhibits the generation of by-product CO*, and enables the activation barrier to be as low as 0.98 eV for the rate-determining step on In/Rh(211), which is much lower than that of some reported catalysts. The ultrahigh catalytic activity of In/Rh(211) might be attributed to the decrease of the work function induced by the doping of indium, enhancing the relative stability of reaction species and CO2* activation degree.