α-Al2O3 Surface Research Articles

Structural defect and activated alumina of spheric α-Al2O3 improving alumina ceramics density from the industrial coarse gibbsite

The quality of alumina ceramics generally depends on alumina powder. High-density alumina ceramics were prepared from industrial coarse gibbsite. Near-spheric α-Al2O3 with particles smaller than 500 nm was produced via the synergy of B and F from NH4BF4. The near-spheric α-Al2O3 calcined at low temperature generated alumina ceramics with high density and low porosity. Meanwhile, the wet pretreatment yielded smaller particles with structural distortion and high microstrain and aluminum hydroxide, notably increasing the relative density of alumina ceramics. 99.18% relative density, 0.017% porosity, and 27.54 GPa Vickers hardness of alumina ceramics were achieved at 1650°C for 2 h without additives and pressed sintering. In addition, the early stage of sintering of alumina green body followed particle boundary diffusion with reduced activation energy in the sintering process. The close packing of the spheric α-Al2O3, high microstrain of α-Al2O3, structural defects with considerable AlO4 units calcined at low temperature, structural distortion in the alumina, and activated alumina on the α-Al2O3 surface collectively promoted the densification of alumina ceramics, achieving remarkable hardness, high density, and tiny porosity.

First-Principles computation-driven mechanism study of tungsten growth on alumina surfaces with TiN nano-islands

Strong comprehension of the tungsten film deposition process on Al2O3 substrate with TiN adhesion layer is essential to achieve high quality metal gate, but the fundamental mechanism of this process is yet to be fully understood. This study employs first-principles density functional theory (DFT) calculations to explore the mechanisms of tungsten film growth on alumina surfaces while focusing on amorphous/α-Al2O3 and interfaces with TiN nano-islands. Tungsten atoms are strongly bonded on the Al2O3/TiN interface compared to their bonding on the Al2O3 or TiN surface, regardless of the crystallinity of Al2O3. Moreover, amorphous Al2O3 surfaces exhibit stronger adsorption energies and present higher diffusion barriers for tungsten atoms compared to their crystalline counterparts, α-Al2O3, and TiN surfaces, which were also confirmed by electronic structure analysis. This enhanced adhesion on amorphous substrates suggests a potential pathway through which improve the step coverage and uniformity of tungsten thin films while addressing common issues such as void formation and non-uniform layering in high-aspect-ratio structures. Post-deposition annealing can help create crystalline tungsten films with superior conductivity. The insights gained from this work offer a computational perspective on the atomic-level interactions governing tungsten deposition, and they are expected to help producing high-quality thin films in semiconductor technologies.

α-Al2O3-loaded promoted the N-desorption reaction and inhibited NH3 decomposition in chemical looping ammonia generation: Experiments and DFT simulations

Chemical looping ammonia generation is a promising, efficient, and environmentally friendly synthesis of ammonia by cycling N-absorption and N-desorption reactions. A portion of the generated NH3 decomposes at the reaction temperature of the N-desorption reaction. In order to promote the N-desorption reaction and inhibit the decomposition of NH3, the effect of α-Al2O3 loading on the N-desorption reaction was investigated in this paper by fixed-bed experiments. The mechanism was revealed using Density functional theory (DFT) calculations. The results showed that when the reaction temperature increased, the conversion of AlN and the yield of NH3 increased, but the actual NH3 conversion decreased. When the steam concentration increased, the conversion of AlN, the yield of NH3, and the actual NH3 conversion increased. The loading of α-Al2O3 could facilitate the N-desorption reaction and inhibit the decomposition of NH3. The 40 wt% α-Al2O3 had the highest conversion of AlN. The 80 wt% α-Al2O3 had the highest yield of NH3. The actual efficiency of ammonia production at 1075 °C with 80 wt% load increased from 45.5% without load to 58.5%. The DFT calculations revealed the mechanism: α-Al2O3 surface promotes the dissociation of H2O molecules to make more hydroxyl groups in the reaction system, which promotes the transfer of H+ and the N-desorption reaction. Meanwhile, the adsorption of NH3 by the α-Al2O3 surface protected NH3 and inhibited its decomposition.

Hydrogen atom scattering at the Al2O3(0001) surface: a combined experimental and theoretical study.

Investigating atom-surface interactions is the key to an in-depth understanding of chemical processes at interfaces, which are of central importance in many fields - from heterogeneous catalysis to corrosion. In this work, we present a joint experimental and theoretical effort to gain insights into the atomistic details of hydrogen atom scattering at the α-Al2O3(0001) surface. Surprisingly, this system has been hardly studied to date, although hydrogen atoms as well as α-Al2O3 are omnipresent in catalysis as reactive species and support oxide, respectively. We address this system by performing hydrogen atom beam scattering experiments and molecular dynamics (MD) simulations based on a high-dimensional machine learning potential trained to density functional theory data. Using this combination of methods we are able to probe the properties of the multidimensional potential energy surface governing the scattering process. Specifically, we compare the angular distribution and the kinetic energy loss of the scattered atoms obtained in experiment with a large number of MD trajectories, which, moreover, allow to identify the underlying impact sites at the surface.

A universal and accurate LPMI method for calculating mismatch in heterogeneous ice nucleation.

The interfacial correlation factor f(m,x), where m refers to the interaction among ice, water and the substrate and x refers to the ratio of the critical nucleation size to the surface topography characteristic size of the substrate, plays a crucial role in the classical theory of heterogeneous ice nucleation as it significantly impacts the energy of nucleation. Generally, a smaller value of f(m,x) indicates a higher propensity for ice nucleation. The degree of structural compatibility between ice and the substrate greatly influences f(m,x), particularly on specific substrates. Several approaches have been proposed to calculate the lattice matching based on this idea, which allows whether a surface is favorable for nucleation to be determined. However, none of these methods adequately correlates the mismatch index with ice growth phenomena. In this paper, we embarked on a new attempt to calculate the mismatch index by combining the lattice parameter and Miller index (LPMI). Droplet freezing experiments have been carried out on α-Al2O3 and silicon surfaces with different Miller indices to verify the rationality of the LPMI method. Furthermore, we validated the LPMI method extensively against other works and further demonstrated its readiness, accuracy and universality for freezing problems. The results consistently show that δd = 2|di - ds|/(di + ds) with interplanar spacing more accurately predicts heterogeneous ice nucleation rates across a wide range of substrates than δ1 = (ai - as)/ai with the lattice parameter of ice and the substrate and is more generally applicable than δ2D = (di - di)/di with the distances between two adjacent and congener atoms on the same plane. We believe that the proposed approach will aid in the selection of substrates for promoting or inhibiting heterogeneous nucleation on a specific substrate.

Experimental investigation and molecular simulations of adsorption of MeOH-DMC Azeotrope onto α-Al2O3 (0 0 1) Surface

In this paper, the adsorption behaviours of the MeOH-DMC azeotropic system onto α-Al2O3 were investigated from both practical and theoretical aspects for the first time. The experimental results showed that the static MeOH- and DMC-adsorption capacities of α-Al2O3 were 325.52 and 70.32 mg·g−1, respectively. The selectivity S was 4.63 and the dynamic separation factor α was 4.2. Then, density functional theory (DFT) was used to reveal possible interactions between the constructed azeotrope clusters and the α-Al2O3 (0 0 1) surface. Molecular simulation results indicated that although there were different azeotropic clusters in the bulk liquid, most of the H-bonds were destroyed when they approached the solid surface. The MeOH dimers were adsorbed onto both Al and O sites via chemisorption and H-bonds, while DMC monomers mainly occupied the Al sites. Thus, chemisorption on Al sites and multi-layer adsorption played a critical role in selective adsorption. Moreover, the competition between MeOH and DMC for adsorption sites might also cause a big difference between the MeOH- and DMC-adsorption capacities of α-Al2O3.

Characterization of Ag/α-Al2O3 olefin epoxidation catalysts containing promoters and co-promoters using pulse hydrogen titration methods

A series of Cs and Cs + Re promoted 12 wt% Ag/α-Al2O3 catalysts were prepared and characterized by H2 pulse titration of O-precovered Ag to measure active Ag site concentrations. Temperature programmed reduction (TPR) at temperatures up to 500 °C was performed on α-Al2O3 supported 3–4 wt% Cs, Re, or Mo only catalysts to confirm the metal–oxygen bonds of the promoters were not reactive during titration of Ag-O surface at 170 °C; absence of H2 uptake during H2 titration for these samples confirmed the TPR results. H2 pulse titration results of 0 to 7.5 μmol Cs promoted, 12 wt% Ag/α-Al2O3 catalysts showed non-preferential deposition of Cs on Ag and α-Al2O3 surfaces. However, when Cs (2.6 μmol)–12 wt% Ag/α-Al2O3 catalyst was promoted with ≥1.3 μmol of Re, titration results showed preferential deposition of Re on Ag sites, presumably to lower overall surface free energy of the Re-Ag-Al2O3 system.

Creation of a Highly Active Small Cu-Based Catalyst Derived from Copper Aluminium Layered Double Hydroxide Supported on α-Al2 O3 for Acceptorless Alcohol Dehydrogenation.

A highly dispersed carbonate-intercalated Cu2+ -Al3+ layered double hydroxide (CuAl LDH) was created on an unreactive α-Al2 O3 surface (CuAl LDH@α-Al2 O3 ) via a simple coprecipitation method of Cu2+ and Al3+ under alkaline conditions in the presence of α-Al2 O3 . A highly reducible CuO nanoparticles was generated, accompanied by the formation of CuAl2 O4 on the surface of α-Al2 O3 (CuAlO@α-Al2 O3 ) after calcination at 1073 K in air, as confirmed by powder X-ray diffraction (XRD) and Cu K-edge X-ray absorption near edge structure (XANES). The structural changes during the progressive heating process were monitored by using in-situ temperature-programmed synchrotron XRD (tp-SXRD). The layered structure of CuAl LDH@α-Al2 O3 completely disappeared at 473 K, and CuO or CuAl2 O4 phases began to appear at 823 K or 1023 K, respectively. Our synthesised CuAlO@α-Al2 O3 catalyst was highly active for the acceptorless dehydrogenation of benzylic, aliphatic, or cyclic aliphatic alcohols; the TON based on the amount of Cu increased to 163 from 3.3 of unsupported CuAlO catalyst in 1-phenylethanol dehydrogenation. The results suggested that Cu0 was obtained from the reduction of CuO in the catalyst matrix during the reaction without separate reduction procedure and acted as a catalytically active species.

Functionalized α-Al2O3 supported gold catalyst for photocatalytic oxidative esterification of benzyl alcohol with methanol to corresponding esters

Alpha-alumina (α-Al2O3) is traditionally considered to be unsuitable as a support for high performance gold-based catalysts because of its small specific surface area. Herein, a highly active α-Al2O3-supported nearly sub-nanometer Au particles photocatalyst for oxidative esterification of benzyl alcohol under visible-light irradiation in a mild condition was synthesized via the electronic interaction between gold precursor and a layer of 3-aminopropyltriethoxysilane (APTES) pre-grafted on the α-Al2O3 called as functionalized α-Al2O3. APTES could serve as a linker to strongly anchor Au nanoparticles (NPs) to α-Al2O3 surface, leading to nearly sub-nanometer Au particles (1.8 ± 0.1 nm). The enhanced metal-support interaction reinforces the interaction of plasmonic hot holes of Au NPs and intermediate molecules, which promote the rate-limiting step of C-H bond cleavage and facilitate the activation of oxygen molecules due to the increased electron cloud density around Au NPs. Meanwhile, α-Al2O3 support can play a synergistic role because of the reactant adsorption can be improved by the acid-base pairs contained.

Removal of Acid Orange G Azo Dye by Polycation-Modified Alpha Alumina Nanoparticles.

Highly positively charged poly(vinyl benzyl trimethylammonium chloride) (PVBMA) was successfully synthesized with approximately 81.8% of yield. The PVBMA was characterized by the molecular weight (Mw) of 343.45 g·mol-1 and the molecular weight distribution, (Đ) of 2.4 by 1H NMR and SEC measurements. The PVBMA was applied as an effective agent for α-Al2O3 surface modification in the adsorptive removal of the azo dye acid orange G (AOG). The AOG removal performance was significantly enhanced at all pH compared to without surface modification. The experimental parameters were optimal at pH 8, free ionic strength, 15 min of adsorption time, and 5 mg·mL-1 α-Al2O3 adsorbents. The AOG adsorption which was mainly controlled by the PVBMA-AOG electrostatic attractions was better applicable to Langmuir isotherm and pseudo-second kinetic model. The PVBMA-modified α-Al2O3 demonstrates a high-performance and highly reusable adsorbent with great AOG performances of approximately 90.13 % after 6 reused cycles.

Adhesion and electronic properties of 4H-SiC/α-Al2O3 interfaces with different terminations calculated via first-principles methods

To comprehensively reveal the microscopic properties of the 4H-SiC/α-Al2O3 interface, not only the properties of 4H-SiC and α-Al2O3 surfaces, but also the interface separation work, interface energies, band offsets, charge transfer, interfacial bonding, and partial density of states for different types of 4H-SiC/α-Al2O3 interfaces were studied using the first-principles method. Considering the two distinct crystal faces of 4H-SiC (Si-terminated and C-terminated surfaces) and the three distinct terminal configurations on the α-Al2O3 side (single Al (Al1-terminated), double Al (Al2-terminated), and O-terminated surface), we built six different types SiC/Al2O3 interfaces (Si-Al1, Si-Al2, Si-O, C-Al1, C-Al2, and C-O interfaces). The results of the interface separation work for the O-terminated interfaces (Si-O and C-O interfaces) revealed that the O-terminated interfaces were significantly greater compared to Al1- and Al2-terminated interfaces, indicating the pronounced dominance of O-terminated interfaces in terms of bonding strength across the six interfacial structures. Moreover, the charge transfer, interfacial bonding, and electronic properties for the interfaces showed that the O-terminated interfaces had larger charge transfer and more interfacial bonds. Additionally, the larger charge transfer at the O-terminated (especially Si-O interface) interfaces caused the larger conduction band offsets (CBOs), which could effectively prevent leakage current and improve the reliability of SiC/Al2O3 devices.

DFT study of mercury adsorption on Al2O3 with presence of HCl

mercury emission control from flue gas is a crucial issue for environment protection. Alumina is an important alkali metal oxide for mercury adsorption in particulate, meanwhile is the potential adsorbent for mercury removal. The cognition on mercury heterogeneous reaction mechanism with alumina in presence of hydrogen chloride is inadequate. In this work, the DFT calculation was applied to detect mercury's chlorides adsorption on α-Al2O3 (001) surface, the Bader charge analysis was used to estimate electron transfer and the transition state theory was used to clarify reaction pathway and energy barrier, besides, the kinetic analysis based on Gibbs free energy was conducted to study the impact of temperature on chemical reaction. The results show that Hg can be captured by weak chemisorption on α-Al2O3 (001) surface with the adsorption energy of −56.37 kJ/mol, HgCl, HgCl2 are intensively bonded on surface with adsorption energies of −276.90 kJ/mol and −231.87 kJ/mol, the surface unsaturated Al and O atoms are the active sites. Charge transfer and PDOS analysis prove that the forming of covalent bonding is responsible for Hg species adsorption. Two possible reaction pathways of Hg oxidization to HgCl2 are discussed, in which a smaller energy barrier of 0.1 eV implies the dominant pathway 1 via Eley-Rideal mechanism: two adsorbed HCl molecules dissociate on surface and then react with one Hg atom. High temperature can promote the reaction rate constants of pathway 1 and 2, but is only favorable for reducing energy barrier of pathway 2.

Atomic-scale modelling of organic matter in soil: adsorption of organic molecules and biopolymers on the hydroxylated α-Al2O3 (0001) surface.

Binding of organic molecules on oxide mineral surfaces is a key process which impacts the fertility and stability of soils. Aluminium oxide and hydroxide minerals are known to strongly bind organic matter. To understand the nature and strength of sorption of organic carbon in soil, we investigated the binding of small organic molecules and larger polysaccharide biomolecules on α-Al2O3 (corundum). We modelled the hydroxylated α-Al2O3 (0001) surface, since these minerals' surfaces are hydroxylated in the natural soil environment. Adsorption was modelled using density functional theory (DFT) with empirical dispersion correction. Small organic molecules (alcohol, amine, amide, ester and carboxylic acid) were found to adsorb on the hydroxylated surface by forming multiple hydrogen bonds with the surface, with carboxylic acid as the most favourable adsorbate. A possible route from hydrogen-bonded to covalently bonded adsorbates was demonstrated, through co-adsorption of the acid adsorbate and a hydroxyl group to a surface aluminium atom. Then we modelled the adsorption of biopolymers, fragments of polysaccharides which naturally occur in soil: cellulose, chitin, chitosan and pectin. These biopolymers were able to adopt a large variety of hydrogen-bonded adsorption configurations. Cellulose, pectin and chitosan could adsorb particularly strongly, and therefore are likely to be stable in soil. This article is part of a discussion meeting issue 'Supercomputing simulations of advanced materials'.

Synthesis and Properties of Vanadium Oxide Nanocoatings on the Surface of Polycrystalline α-Al2O3

Synthesis and Properties of Vanadium Oxide Nanocoatings on the Surface of Polycrystalline α-Al2O3

Adsorption of HF and H2S on α-Al2O3 (0001) Surfaces: A DFT Study

Ex-service SF6 adsorbents in SF6 gas-insulated electric equipment contain many toxic substances. Inside, HF and H2S are two typical toxic gases. Based on the first principle, the interaction process between HF/H2S and α-Al2O3 (0001) surfaces was calculated using the density functional theory (DFT). The results showed that the adsorption of HF on α-Al2O3 (0001) is stronger than that of H2S. Under the five adsorption sites, the adsorption effect of HF-H and HF-F was similar. At O-2 site, the adsorption energy of H2S-H adsorption configuration is significantly higher than that of the other four sites. The density of states (DOS) indicated that new peaks appeared after adsorption. The DOS and partial density of states (PDOS) indicated that the adsorption of HF and H2S occurs via chemical adsorption. The DOS and PDOS shifted to the right when the S atom was approaching, proving that the system shifts to instability. Compared with the energy gap of α-Al2O3 (0001), HF and H2S adsorption systems decreased significantly. The energy gap of the HF adsorption system was 1.173 eV larger than that of the H2S system and the geometry was relatively stable, which is consistent with the DOS and PDOS adsorption calculation results. Thus, the adsorption of HF and H2S on α-Al2O3 (0001) surfaces was clearly different. The findings of this study may provide theoretical guidance for the adsorption of other gases or developing a new adsorbent.

The mechanism of ethanol steam reforming on Co10|α-Al2O3 (0001) surface: A DFT study

ESR (Ethanol steam reforming) seems to be a promising way to produce hydrogen which has been proposed as the most desirable energy carriers to overcome the problem of fossil fuels shortage. The ESR mechanism on the optimized Co10|α-Al2O3 (0001) surface is investigated by means of DFT calculations. The results show that oxidation state of Co cluster and micro-chemical environment play important roles in the ESR reaction. C-C bond scission is favored on the Co0 site while C-O bond scission is likely to happen on the Cox+ site, and the energy barrier is influenced by the number of hydrogen and oxygen atoms that are bonded with C/O atom. ESR reaction is initiated by the O-H bond scission of ethanol on the Cox+ site: CH3CH2OH*→ CH3CH2O*→CH3*+CH2O*→CH2O*+OH*→H2COOH*→COOH*+H2*→CO*+H2*with the dehydrogenation of H2COO* as the rate-determining step.

Potential of nickel nanoclusters supported on [formula omitted]-Al[formula omitted]O[formula omitted](0001) surface for CO[formula omitted] capture, energy production, and dry reforming of methane

The structural, electronic and magnetic properties of Nin@α-Al2O3(0001) (with n = 1 to 7) systems have been studied using density functional theory. Grafting energies, Bader charges and DOS analysis showed that the nickel clusters strongly interact with the α-Al2O3(0001) surface. In a second step, the adsorption performances of these materials towards CH4, CO2, CO, H2 gases have been evaluated. Pure alumina surface and supported Ni systems weakly interact with methane, which are therefore promising for an efficient purification of methane. Additionally, it was found that the pure alumina surface and Ni5/α-Al2O3(0001) selectively adsorb the CO2, facilitating its storage and utilization. A selective adsorption was also observed for CO on Ni3/α-Al2O3(0001). Looking now at the dry reforming of methane, a strong adsorption of CO was shown in all supported systems. The dissociative adsorption of hydrogen on all supported systems (except for n = 4) was observed. A high resistance against carbon deposition was observed on our modeled systems compared to those reported in the literature, which is a promising result since the rapid deactivation by coke deposition is the main problem for the catalysts used in the dry reforming of methane process.

Adsorption and transformation of tetracyclines on alpha alumina particles with surface modification by anionic surfactant

The adsorption and transformation of tetracyclines (TCs) antibiotics, including oxytetracycline (OTC), chlortetracycline (CTC), and tetracycline (TC), on the sodium dodecyl sulfate (SDS) surfactant-modified α-Al2O3 particles were comprehensively investigated in this study. The TCs adsorption was significantly enhanced by using the modified adsorbents compared with the use of the unmodified adsorbents. The experimental conditions were systematically optimized and found to be pH 4, NaCl 1 mM, the contact time of 180 min, and the adsorbent dosage of 25 mg. mL−1. The high maximum adsorption capacities were approximately 320, 85, and 91 mg. g−1 for TC, OTC, and CTC, respectively. Meanwhile, the great removal efficiencies of the three antibiotics TC, OTC, and CTC were correspondingly 91.85, 88.4, and 98.3%. The TCs adsorption isotherm and kinetics on the SDS-modified α-Al2O3 particles mainly governed by the electrostatic and hydrophobic interactions were clarified by a suitable two-step model, the Fourier transform infrared spectroscopy (FT-IR) and zeta potential measurements. Meanwhile, the TCs structural transformation determined by the liquid chromatography with tandem mass spectrometry (LC-MS/MS) measurement was promoted through the adsorption on the α-Al2O3 surface. The TCs transformation rates strongly affected by the TCs adsorption were in the order of CTC > TC > OTC. The found results are promised that the SDS-modified α-Al2O3 particles might behave as high-performance adsorbents to remove the TCs from aqueous solutions.

Unexpected catalytic influence of atmospheric pollutants on the formation of environmentally persistent free radicals.

Environmentally persistent free radicals (EPFRs) have been recognized as harmful and persistent environmental pollutants. In polluted regions, many acidic and basic atmospheric pollutants, which are present at high concentrations, may influence the extent of the formation of EPFRs. In the present paper, density functional theory (DFT) and ab-initio molecular dynamics (AIMD) calculations were performed to investigate the formation mechanisms of EPFRs with the influence of the acidic pollutants sulfuric acid (SA), nitric acid (NA), organic acid (OA), and the basic pollutants, ammonia (A), dimethylamine (DMA) on α-Al2O3 (0001) surface. Results indicate that both acidic and basic pollutants can enhance the formation of EPFRs by acting as "bridge" or "semi-bridge" roles by proceeding via a barrierless process. Acidic pollutants enhance the formation of EPFRs by first transferring its hydrogen atom to the α-Al2O3 surface and subsequently reacting with phenol to form an EPFR. In contrast, basic pollutants enhance the formation of EPFRs by first abstracting a hydrogen atom from phenol to form a phenoxy EPFR and eventually interacting with the α-Al2O3 surface. These new mechanistic insights will inform in understanding the abundant EPFRs in polluted regions with high mass concentrations of acidic and basic pollutants.

Theoretical study on the stability mechanism of a high energy system composed of molecules containing C[sbnd]O[sbnd]C or –N3 groups and aluminum hydride

The stability of aluminum hydride(AlH3) based high-energy propellants is important for its large-scale application. In this work, to explore the stability mechanism of systems composed of AlH3 and a binder containing COC or –N3 groups, molecular dynamics simulations were carried out to explore the thermal expansion properties of AlH3, and density functional theory calculations were employed to study the micro-interactions between molecules containing COC or –N3 groups and AlH3. More specifically, CH3OC2H5 and CH3N3 were used to model polyethylene glycol and glycidyl azide polyether, respectively. It is found that AlH3 is more sensitive to temperature changes than its oxide layer. Upon contact between the alumina layer and CH3OC2H5 or CH3N3, these compounds exist stably on the α-Al2O3(0001) and γ-Al2O3(110) surfaces. Upon direct contact with the α-AlH3(010) surface, CH3OC2H5 is relatively stable, while CH3N3 can trigger the surface hydrogen transfer reaction due to the low energy barrier(5.0 kcal/mol). The current work provides a theoretical basis for understanding the sensitivity of AlH3 and binders containing COC or –N3 groups, and is useful in the research and development of superior composite energetic propellants.