Matrix Atoms Research Articles

Origin of the distinct site occupations of H atom in hcp Ti and Zr/Hf

The location of the H atoms in Ti, Zr, and Hf is crucial to the formation of the hydrides in these metals as it influences the crystal lattice transformation and the hydrogen diffusion involved in the hydride formation process. Although Ti, Zr, and Hf are all of hexagonal close-packed structure with similar lattice parameters, the solute H atom occupies the octahedral interstice in Ti but the tetragonal interstice in Zr and Hf, of which the origin is still mysterious. In the present work, the origin of the distinct site occupation behavior of H atom in Ti and Zr/Hf is investigated through first principles calculations. The calculated solution energies confirm that H prefers the octahedral interstice in Ti but the tetrahedral interstice in Zr and Hf. We ascribe the distinct site occupations of H in Ti and Zr/Hf to the varying Coulomb repulsion between the H (as a screened proton in the metals) and the matrix atoms against the interstitial size. The competition between the H-induced electron accumulation effect and the matrix atom debonding effect might matter as well. We propose that, as a general rule, a H atom prefers the site with a trade-off between a large space and a high electron density in metals.

Enhancing corrosion fatigue performance of 17-4 PH stainless steel by simultaneous aging and plasma nitriding

This study investigated the effects of simultaneous aging and low-temperature plasma nitriding on the corrosion fatigue performance of 17-4 PH stainless steel. Plasma nitriding was conducted under two temperatures of 400 and 500 °C and, for comparison, some other specimens were subjected to aging treatment at the same temperatures and times. Microstructural characterization by scanning electron microscope (FESEM) and electron backscatter diffraction (EBSD) confirmed similar structures at the core in the nitrided and aged specimens, thereby, the influence of nitrogen at the surface of 17-4 alloy could be carefully investigated. X-ray diffraction and grazing incidence X-ray diffraction (GIXRD) identified expanded martensite as the matrix within the nitrided layer, accompanied by CrN, Fe3N, and Fe4N phases. X-ray photoelectron spectroscopy (XPS) analysis revealed high nitrogen concentration, in regions very close to the surface, after nitriding at 500 °C. The N1s spectra shifted towards lower binding energies, indicating interaction between nitrogen and the matrix atoms, and the formation of nitrides in the nitrided layer. The nitrided thicknesses experienced close values at 400 °C (10 h) and 500 °C (5 h), provided at 400 °C the layer was mostly a supersaturated solid solution but at 500 °C it was composed of iron nitrides and chromium nitride. High hardness values of above 1600 HV0.1 were obtained after optimum plasma nitriding as the result of combined effects of solution strengthening induced by nitrogen atoms and the presence of dispersed nitride phases. EBSD results indicated residual stress within the nitrided layer, which would affect the corrosion fatigue resistance. Experimental findings demonstrated that both aging and plasma nitriding substantially enhanced the corrosion fatigue resistance of 17-4 PH stainless steel in 3.5 wt% NaCl. Moreover, simultaneous aging and plasma nitriding proved superior behavior in corrosion fatigue, primarily due to delayed crack initiation and improved fatigue resistance, without the risk of overaging which is detrimental to mechanical properties.

Copper cluster regulated by N, B atoms for enhanced CO2 electroreduction to formate

Electrochemical CO2 conversion into formate by intermittent renewable electricity, presents a captivating prospect for both the storage of renewable electrical energy and the utilization of emitted CO2. Typically, Cu-based catalysts in CO2 reduction reactions favor the production of CO and other by-products. However, we have shifted this selectivity by incorporating B, N co-doped carbon (BNC) in the fabrication of Cu clusters. These Cu clusters are regulated with B, N atoms in a porous carbon matrix (Cu/BN-C), and Zn2+ ions were added to achieve Cu clusters with the diameter size of ∼1.0 nm. The obtained Cu/BN-C possesses a significantly improved catalytic performance in CO2 reduction to formate with a Faradaic efficiency (FE) of up to 70 % and partial current density (jformate) surpassing 20.8 mA cm−2 at −1.0 V vs RHE. The high FE and jformate are maintained over a 12-hour. The overall catalytic performance of Cu/BN-C outperforms those of the other investigated catalysts. Based on the density functional theory (DFT) calculation, the exceptional catalytic behavior is attributed to the synergistic effect between Cu clusters and N, B atoms by modulating the electronic structure and enhancing the charge transfer properties, which promoted a preferential adsorption of HCOO* over COOH*, favoring formate formation.

Effect of rare earth elements scandium on Sn-0.7Cu brazing metal: First-principles calculation

In this paper, the effects of rare earth element Sc on the thermal and mechanical properties of precipitates (Cu6Sn5), (Cu3Sn) and Sn matrix in Sn-0.7Cu brazing metal, as well as the interface bonding strength between stable precipitates (Cu6Sn5) and Sn matrix were investigated based on first-principles calculations. The results show that the electronic structure of the precipitated phase and the matrix changes to a certain extent, the atomic bonding mode recombines, and the electron orbitals of the matrix atoms and the rare earth elements hybridize. In addition, rare earth elements improve the mechanical properties of precipitated phase and matrix, increase the plasticity of precipitated phase and enhance the strength of matrix. Rare-earth elements improve the thermodynamic properties of the matrix and precipitated phase to some extent, increase the heat capacity of the precipitated phase and the matrix, and reduce the melting point. At the same time, rare earth elements enhance the mechanical properties and thermodynamic stability of the interface between the precipitated phase and the matrix, and improve the oxidation resistance of the matrix. Transmission electron microscope (TEM) observation shows that there is a segregation of Cu atoms at the interface between precipitated phase and matrix. Other experimental results show that: Rare-earth element Sc has a positive effect on the mechanical properties, melting characteristics and oxidation resistance of the filler metal alloy. When the addition of Sc is 0.1 % (wt), the tensile strength and elongation of the alloy are significantly increased, the melting point is reduced, the surface oxidation resistance is increased, and the comprehensive properties of the alloy are the best.

Effects of Ar ion bombardment on the structure and properties of β-quartz

β-quartz is an important component that affects the physical and chemical properties of glass-ceramics. The material removal process of ion beam machining is complicated as one of the ultra-precision machining forms. Therefore, it is important to understand the removal mechanism of ion beam machining materials. The methods of molecular dynamics (MD) and first-principles were adopted to investigate the microscopic mechanism of ion beam bombardment of the β-quartz structure. The damage evolution of structures and the evolution of material properties caused by defects respectively from the atomic and electronic levels. Through MD analysis, we find that the random collision between incident ions and matrix atoms can lead to the formation of sputtered atoms. The incidence of ions will increase the disorder degree of the matrix, and the influence on the disorder degree at different depths of the matrix is different. The degree of disorder increases obviously in the range of 50–70 Å from the surface of the matrix. It has a significant impact on the surface topology of the matrix, the number of defects, surface roughness, and matrix density. The results of first-principle calculation show that the refraction, absorption and other characteristics of the system are significantly different with different doping forms, and the energy loss is most affected by substituted doping. And the substituted doping defects have the most significant effects on the structural energy loss. Among, the Ar-substituted O doping structure leads to higher energy loss, and the peak energy loss intensity reaches 5.146. In contrast, the Ar-substituted Si doping structure causes the least energy loss, the intensity is 2.543. This study provides a theoretical basis for the selection of parameters and the realization of ultra-smooth surface in actual ion beam machining.

Overcoming the strength-ductility trade-off dilemma in austenitic lightweight steel via stepwise controllable intragranular dual nanoprecipitation

The strength-ductility trade-off is an inevitable scenario in precipitation-hardened austenitic lightweight steels. The reduction in ductility is due to the shearing of κ′-carbides by dislocations, resulting in limited work hardening capability. Conversely, non-shearable B2 particles can effectively improve the work hardening rate. However, these B2 particles tend to precipitate along grain boundaries and coarsen due to their incompatibility with the austenite matrix, resulting in negligible strengthening effect or even brittleness. We propose a stepwise controllable dual nanoprecipitation strategy to overcome the strength-ductility trade-off. To implement this strategy, we develop a manufacturing process that includes a high-temperature annealing treatment and a three-step aging process (700 °C/15min + 900 °C/15min + 450 °C/1 h). The higher annealing temperature increases the supersaturation of solute atoms in the austenite matrix, which improves the chemical driving force for the precipitation of intragranular B2 particles during aging at 900 °C. Additionally, the coarsened κ′-carbides (30–35 nm) formed during aging at 700 °C provide heterogeneous nucleation sites for the formation of intragranular B2 particles. Further aging at 450 °C promotes the precipitation of nano-sized κ′-carbides (5 nm) within the austenite matrix. The dual nanoparticles provide a significant precipitation strengthening contribution of 400 MPa without sacrificing ductility. The multiple deformation mechanisms of nanoscale “planar slip and Orowan bowing” provide an efficient source of work hardening capability. The present work aims to overcome the strength-ductility trade-off in austenitic lightweight steels by tailoring the precipitation process, which may provide insight into producing high-performance lightweight steels.

R-Phase Transformation Evolution in NiTi SMA Wires Studied via the Internal Friction Technique

The specific damping capacity variation of heat-treated NiTi was observed during a pseudoelasticity test. The detailed B2 → R-phase transformation process in cold-drawn NiTi wires undergoing middle-temperature aging was studied via X-ray diffraction, transmission electron microscope, and internal friction technique. Results show that, as aging time increased at 450 °C, the dynamic phase transition splitting from B2 → R to B2 → R1 and B2 → R2 became evident. However, such a splitting process was not observed for the sample after aging at 400 °C. The reason for R-phase generation is attributed to non-uniformly distributed stress fields. The splitting of the internal friction peak, in conjunction with high-resolution transmission electron microscope and mechanic results, suggests a substantial occurrence of short-range segregation of Ni atoms in the B2-NiTi matrix. Furthermore, the specific damping capacity (SDC) exhibits a gradual increase with prolonged annealing time. Specifically, the sample with significant dynamic phase transition splitting reaches an SDC value of 0.60.

The effective polymeric macromolecule as peroxymonosulfate activator as an alternative to metal oxides in the treatment of organic dye pollutants

Catalyst efficiency is affected by inhomogeneous catalyst atom placement on the substrate, leading to nano-level aggregation and reduced performance. Research on single-atom catalysts aims to place them at the atomic level to maximize efficiency, but faces challenges and high costs. This study presents a cost-effective approach using polymeric phthalocyanine Co(II) complex (poly-CoPc) prepared by a simple method. Poly-CoPc shows superior catalytic activity by acting as a catalyst without requiring additional processing. Co(II) atoms in the polymer matrix are covalently coordinated into single atoms and inhibit nanoparticle growth. The poly-CoPc/PMS system outperforms Co3O4 and unsubstituted cobalt phthalocyanine, achieving 97.06% Rhodamine B degradation in 20 min. Furthermore, the poly-CoPc proves to be the most effective, with a degradation efficiency of 69.94% for tap water and 95.76% for seawater, producing predominantly 1O2. These results position poly-CoPc as a promising PMS activator for environmental treatment that surpasses metal oxide derivatives in terms of activity and properties.

Theoretical modeling of defect diffusion in wide bandgap semiconductors

Since the 1940s, it has been known that diffusion in crystalline solids occurs due to lattice defects. The diffusion of defects can have a great impact on the processing and heat treatment of materials as the microstructural changes caused by diffusion can influence the material qualities and properties. It is, therefore, vital to be able to control the diffusion. This implies that we need a deep understanding of the interactions between impurities, matrix atoms, and intrinsic defects. The role of density functional theory (DFT) calculations in solid-state diffusion studies has become considerable. The main parameters to obtain in defect diffusion studies with DFT are formation energies, binding energies, and migration barriers. In particular, the utilization of the nudged elastic band and the dimer methods has improved the accuracy of these parameters. In systematic diffusion studies, the combination of experimentally obtained results and theoretical predictions can reveal information about the atomic diffusion processes. The combination of the theoretical predictions and the experimental results gives a unique opportunity to compare parameters found from the different methods and gain knowledge about atomic migration. In this Perspective paper, we present case studies on defect diffusion in wide bandgap semiconductors. The case studies cover examples from the three diffusion models: free diffusion, trap-limited diffusion, and reaction diffusion. We focus on the role of DFT in these studies combined with results obtained with the experimental techniques secondary ion mass spectrometry and deep-level transient spectroscopy combined with diffusion simulations.

Cyclable CuⅠ-Ov-Mn sites accelerate O2 activation to enhance photo-driven catalytic oxidation performance

Molecular oxygen activation (MOA) plays a crucial function in various oxidation reactions. Nonetheless, facile, continuous and efficient MOA remains challenging. Herein, we have successfully constructed recyclable CuⅠ-Ov-Mn sites (Ov: oxygen vacancy) for MOA by incorporating Cu single atoms in MnO2 matrix. The localized photogenerated electron at CuⅡ site drives the generation of electron-rich CuⅠ species and an adjacent photoinduced Ov, which possesses stronger O2 affinity and affords a durable O2 activation site. The CuⅡ/CuⅠ cycle accelerates the separation of charge carriers to supply adequate photogenerated electrons and assures the renewability of photoinduced Ov, thus realizing rapid and sustained O2 activation and generating abundant monatomic oxygen ions (O-). Consequently, Cu-MnO2 catalyst performed extraordinarily high activity in O2-involved reactions. For instance, in toluene oxidation, toluene conversion reached as high as 96 %, comparable to that on the state-of-the-art supported Pt catalysts. This work will bring more possibilities for modulating the O2-involved oxidative reactions.

Oxidized phosphorus linking promotes the activity of a cobalt molecular assembly for electrochemical oxygen evolution

Molecular assemblies represent a classical type of active electrocatalysts for oxygen evolution reaction (OER), while the practical application is limited by the relatively low electrical conductivity. Herein, a cobalt molecular assembly was synthesized and supported by a conductive phosphorus doped graphene. It served as a potential OER electrocatalyst by affording a current density of 10 mA cm−2 at a small overpotential of 390 mV, and the turnover frequency of cobalt sites was increased by 21.5 times comparing to the assembly supported by the pristine graphene. Our observations unveil that the potential linking of oxidized phosphorus atoms in the carbon matrix is mainly responsible for the high activity of cobalt molecular assembly. The overall OER catalytic cycle was analyzed by in situ attenuated total reflectance-surface enhanced infrared absorption spectroscopy, suggesting that the formation of *OOH species on the cobalt sites could be critical for the final evolution of oxygen. These results open a potential avenue into the exploration of highly active OER electrocatalysts toward replacing the noble metals based electrocatalysts.

Quantifying the energy of vacancy mediated diffusion of solute Cu, Mg, Ag and Zn atoms in an aluminum Matrix: An insight from ab initio calculations

In this work, a consistent and accurate set of energy barrier values for the migration process, assisted by a vacancy, of atoms of different chemical elements belonging to the two most relevant families of age-hardenable Al-Cu and Al-Zn-based alloys is given. These values were calculated using the Nudged Elastic Band method within the Density Functional Theory framework for a vacancy diffusing in simple configurations of solute atoms, specifically the main alloying elements Cu and Zn involving a single solute atom or more complex configurations, such as pairs of elements of the same or different chemical species. In both cases, in our calculations, the presence of Mg and/or Ag solute atoms is also considered. The results obtained are analyzed in terms of the energetic interaction among vacancies and the different solute atoms. The advantage of having a set of vacancy diffusion energy barrier values calculated under the same criteria is that it can be used as reliable input parameters for future kinetic Monte Carlo simulations to study the precipitation kinetics in a wide type of age-hardenable alloys.

Wear mechanism of diamond-cutting tool in nano-cutting polycrystalline γ-TiAl alloy based on molecular dynamics simulation

The machining of γ-TiAl is susceptible to tool wear, and investigations into tool-wear mechanisms can contribute to enhancing machining efficiency and optimizing the surface integrity of workpieces. In this study, a molecular-dynamics method is employed to simulate the cutting process of polycrystalline titanium–aluminum alloys using a single-crystal diamond tool. The findings suggest that tool wear is induced by cutting forces and plastic deformation, with amorphization and diffusive wear as the primary mechanisms. Plastic deformation within the matrix facilitates interactions between internal dislocations in the grains, thus resulting in work hardening at the surface layer, increased cutting forces, and heightened susceptibility of the cutting edge to wear due to plastic deformation. Moreover, elevated temperatures and pressures in the cutting contact area induce atomic amorphization, which reduces both the strength and hardness of the tool while triggering structural phase transitions for certain atoms. Consequently, lattice distortion occurs within this region, thus causing matrix atoms to diffuse into the tool. The combined effect of amorphization and diffusion significantly exacerbates tool wear. This investigation provides valuable insights into wear mechanisms and guidance for enhancing the quality of γ-TiAl alloy.

Direct evidence of melting and decomposition of TiC particles in laser powder bed fusion processed 316L-TiC composite

Recent advancements have shown the effectiveness of strengthening 316L with TiC particles addition through the laser powder bed fusion (LPBF) process. However, the question remains whether TiC undergoes decomposition into Ti and C atoms, primarily because of the challenges associated with measuring C at low concentrations. In this study, we employed atom probe tomography (APT) to provide evidence of decomposition by observing the presence of Ti and C atoms in the 316L matrix. The fast cooling rate of the LPBF process results in the supersaturation of Ti and C in the 316L matrix. Adding 3 wt% TiC particles increased the yield strength of LPBF-processed 316L from 599 MPa to 832 MPa. The subsequent annealing treatment resulted in the formation of more TiC nanoparticles as a result of precipitation from the supersaturated Ti and C in the 316L matrix. Consequently, the yield strength was further enhanced to 959 MPa after annealing at 700 °C for 1 h. This study marks the first direct demonstration of the decomposition of TiC in metal matrix composites.

Reconstructing the 3D Coordinates of Guest:Host OLED Blends with Single Atom Resolution.

The performance of electronic and semiconductor devices is critically dependent on the distribution of guest molecules or atoms in a host matrix. One prominent example is that of organic light-emitting diode (OLED) displays containing phosphorescent emitters, now ubiquitous in handheld devices and high-end televisions. In such OLEDs the phosphorescent guest [normally an iridium(III)-based complex] is typically blended into a host matrix, and charge injection and transport, exciton formation and decay, and hence overall device performance are governed by the distribution of the emissive guest in the host. Here high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is used with depth sectioning to reconstruct the 3D distribution of emissive iridium(III) complexes, fac-tris(2-phenylpyridine)iridium(III) [Ir(ppy)3], blended into the amorphous host material, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), by resolving the position of each single iridium(III) ion. It is found that most Ir(ppy)3 complexes are clustered with at least one other, even at low concentrations, and that for films of 20wt.% Ir(ppy)3 essentially all the complexes are interconnected. The results validate the morphology of blend films created using molecular dynamics simulations which mimic the evaporation film-forming process and are also consistent with the experimentally measured charge transport and photophysical properties.

Explainable machine learning accelerated density functional theory prediction for diffusive transport behaviour of elements in aluminium matrix and graphene/aluminium interface

In this paper, the diffusive migration behaviour of alloy atoms in aluminium matrix and different types of graphene/aluminium interfaces is systematically investigated by using a machine learning accelerated density functional theory. A small sample dataset is established by first principles calculation, the types of input and output eigenvalues are determined by feature engineering, and the number of input features for perfect interfaces, defective interfaces, and aluminium matrix are finally determined to be 6, 5, and 4 by taking into account the effects of model complexity and prediction accuracy. With a five-fold crossover and by comparing more than a dozen machine learning models, the CatBoost algorithm possesses the lowest error as well as a better coefficient of determination. We further optimized the CatBoost algorithm with further parameters and adjusted the regularization term coefficients to avoid the risk of overfitting. The impact of each feature on the model prediction results was quantitatively described by constructing a matrix of SHAP values. The best performing Catboost model was used to predict the full periodic table data, which in turn was used to screen out the elemental species that are easy to move towards the graphene/aluminium composite interface. Those alloying elements are beneficial for modifying the defective graphene in the composite by comparing the results of elemental diffusive migration in the aluminium matrix as well as at different graphene/aluminium interfaces. The results of machine learning accelerated first principles calculations can provide a theoretical basis for further development of new aluminium alloy composite.

Effects of Ni Content and Heat Treatment on the Properties, Microstructures, and Precipitates of Cu-0.2 wt% Be-x wt% Ni Alloys.

Cu-Be alloys exhibit excellent comprehensive performance in electrics, thermotics, and mechanics, and hence, they attract much attention. Among them, low-Be copper alloys are more environmentally friendly and promising. This study explores the effects of different Ni contents and heat treatment parameters on the properties, microstructures, and precipitates of Cu-0.2 wt% Be-x wt% Ni (0 < x < 2.0) alloys. The experimental results demonstrate that the fast cooling rate of cast alloys during solidification contributes to retention of the solute atoms in the copper matrix, which is beneficial for subsequent solid solution treatment. Furthermore, solid solution treatment slightly reduces the electrical conductivities, microhardness values, and compressive yield strengths of Cu-0.2 wt% Be-1.0/1.6 wt% Ni alloys. The optimal solution temperature and time are about 925 ℃ and 60 min, respectively. Aging treatment significantly increases the electrical conductivities, microhardness values, and compressive yield strengths of Cu-0.2 wt% Be-1.0/1.6 wt% Ni alloys. The best aging temperature is around 450 ℃. However, the properties of Cu-0.2 wt%Be-0.4 wt%Ni alloys remain unaffected by solution and aging treatments. Around x = 1.0, Cu-0.2 wt% Be-x wt% Ni alloys possess the best comprehensive properties, which are about 72%IACS of electrical conductivity, 241 HV of microhardness, and 281MPa of compressive yield strength, respectively. TEM and EDS analyses reveal that the precipitate evolution of Cu-0.2 wt% Be-1.0 wt% Ni alloys with aging time is GP zones → γ″ → γ'. Notably, a distinct double-peak age strengthening phenomenon emerges with Cu-0.2 wt% Be-1.0/1.6 wt% Ni alloys. The precipitation of plenty of GP zones at the early stage of aging should account for the first strengthening peak, and the strengthening mechanism transformation of the γ″ or γ' phase from shear to Orowan should induce the second strengthening peak. This work may help to design new low-Be copper alloys and their preparation processes.

Boosted hydrogen evolution kinetics of heteroatom-doped carbons with isolated Zn as an accelerant

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present a practical strategy to rationally design a model catalyst with a single zinc (Zn) atom coordinated with nitrogen and sulfur atoms in a multilevel carbon matrix. The Zn site exhibits an atomic interface configuration of ZnN4S1, where Zn's electron injection effect enables thermal-neutral hydrogen adsorption on neighboring atoms, pushing the activity boundaries of carbon electrocatalysts toward electrochemical hydrogen evolution to an unprecedented level. Experimental and theoretical analyses confirm the low-barrier Volmer-Tafel mechanism of proton reduction, while the multishell hollow structures facilitate the hydrogen evolution even at high current intensities. This work provides insights for understanding the actual active species during hydrogen evolution reaction and paves the way for designing high-performance electrocatalysts.

Rapid PL Enhancement in Cd doped Alq3 Nanowires

Aluminium tris (8-hydroxyquinoline) (Alq3) is a popular coordination complex extensively used in organic luminescent devices as the emissive layer. Metal doping in Alq3 and its nanoscale synthesis are two strategies which are widely adopted to enhance the functional properties of Alq3. In the present work, Cadmium (Cd) doped Alq3 films having 1-dimensional morphology have been successfully synthesised using thermal vapor transport method. These films have been subjected to different analytical studies to study their functional properties. Scanning Electron Microscopy (SEM) images reveal the dendritic nature of Cd-doped Alq3 nanowires while Energy Dispersive X-ray Spectroscopy (EDAX) analysis confirms the presence of Cd in Cd-doped Alq3 nanowires. X-ray Diffraction (XRD) study reveals the polycrystalline nature of Cd-doped Alq3 nanowires. X-ray Photoelectron Spectroscopy (XPS) analysis of Cd-doped Alq3 nanowires samples indicates the replacement of some Al atoms with Cd atoms in Alq3 matrix. UV–visible spectroscopy study of the Cd-doped Alq3 nanowires shows enhancement in the optical absorbance with increasing Cd concentration while Photoluminescence (PL) spectroscopy analysis shows a 7-fold enhancement in PL intensity for 0.5 mol% Cd-doping. This rapid enhancement in the PL is explained on the basis of electronic charge transfer from Cd ions to Alq3 molecules.

Downshift of the Ni d band center over Ni nanoparticles in situ confined within an amorphous silicon nitride matrix.

Herein, nanocomposites made of Ni nanoparticles in situ distributed in an amorphous silicon nitride (Ni/a-Si3N4) matrix, on the one hand, and within an amorphous silicon dioxide (Ni/a-SiO2) matrix, on the other hand, were synthesized from the same Ni-modified polysilazane precursor. In both compounds, the Ni/Si atomic ratio (0.06-0.07), average Ni nanocrystallite size (7.0-7.6 nm) and micro/mesoporosity of the matrix were rigorously fixed. Hydrogen (H2)-temperature-programmed desorption (TPD) profile analysis revealed that the activation energy for H2 desorption at about 100-130 °C evaluated for the Ni/a-Si3N4 sample (47.4 kJ mol-1) was lower than that for the Ni/a-SiO2 sample (68.0 kJ mol-1). Mechanistic study with X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculations revealed that, at Ni nanoparticle/matrix heterointerfaces, Ni becomes more covalently bonded to N atoms in the a-Si3N4 matrix compared to O atoms in the a-SiO2 matrix. Therefore, based on experimental and theoretical studies, we elucidated that nickel-nitrogen (Ni-N) interactions at the heterointerface lead to remarkable Ni d band broadening and downshifting of the d band center relative to those generated by Ni-oxygen (Ni-O) interactions at the heterointerface. This facilitates H2 desorption, as experimentally observed in the Ni/a-Si3N4 sample.