Building Fe atom–cluster composite sites using a site occupation strategy to boost electrochemical oxygen reduction

The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.

The effects of amino groups and open metal sites of MOFs on polymer-based electrolytes for all-solid-state lithium metal batteries

Metal-organic frameworks(MOFs) are becoming more and more popular as the fillers in polymer electrolytes in recent years. In this study, a series of MOFs(NH_(2)-MIL-101(Fe), MIL-101(Fe), activated NH_(2)-MIL-101(Fe) and activated MIL-101(Fe)) were synthesized and added to PEO-based solid composite electrolytes(SCEs). Furthermore, the role of the —NH_(2) groups and open metal sites(OMSs) were both examined. Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations. At last, we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO, Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries. This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.

Spatial distribution and potential ecological and health risks associated with heavy metals in the Ijero-Ekiti mining site,Nigeria

Artisanal gold mining,a labor-intensive and antiquated technique,is a growing industry and the source of income for rural communities all over the world.However,artisanal gold mining has potential negative and long-term effects on economy,environment,and society.This study collected soil samples from 16 sample points including a control point to examine the pollution degrees and spatial distribution of heavy metals,as well as ecological and health risks associated with heavy metal pollution in the Ijero-Ekiti mining site,Nigeria.Geographical Information System(GIS)and remote sensing technologies were used to identify regions with high concentrations of heavy metals and assess the environmental impact of gold mining activities.The results show that the mean heavy metal concentrations of 16 soil pointa are 8.94(±5.97)mg/kg for As,0.18(±0.54)mg/kg for Cd,0.11(±1.06)mg/kg for Co,14.32(±3.43)mg/kg for Cr,6.89(±0.64)mg/kg for Cu,48.92(±11.77)mg/kg for Fe,135.81(±30.75)mg/kg for Mn,5.92(±0.96)mg/kg for Ni,5.72(±1.66)mg/kg for Pb,and 13.94(±1.38)mg/kg for Zn.The study reveals that heavy metal concentration in soils follows the order of Mn>Fe>Cr>Zn>As>Cu>Ni>Pb>Co>Cd.An analysis of soil samples indicates that 3 principal components(PCs)account for 70.008%of the total variance and there are strong positive correlations between various pairs of heavy metals.The total potential ecological risk index(309.599)in the study area is high.Non-carcinogenic risk suggests that there may be long-term health impacts on people who work in the mining areas due to chronic exposure to the environment.Based on the study,the hazard index of carcinogenic health risks associated with heavy metals through ingestion is 520.00×10^(–4).Dermal contact from As and Cr also increases the risk of cancer,with the highest hazard index value of 18.40×10^(–4).The lowest exposure pathway,with the hazard index value of 0.68×10^(–4),indicates that the inhalation of heavy metals has a comparatively low risk of cancer.This study recommends the formulation of policies to monitor the Ijero-Ekiti mining site and other regions in Nigeria where indiscriminate artisanal gold mining activities exist.

Tailoring local structures of atomically dispersed copper sites for highly selective CO_(2) electroreduction

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon(Cu–N–C)can provide novel possibilities to enable highly selective and active electrochemical CO_(2) reduction reactions.However,the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites(Cu–N_(4))on carbon remains challenging.Here,we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N_(4) sites(Cu–N_(4)C_(8))located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor.Edge‐hosted Cu–N_(4)C_(8) catalysts outperformed the previously reported M–N–C catalysts for CO_(2)‐to‐CO conversion,achieving a maximum CO Faradaic efficiency(FECO)of 96%,a CO current density of–8.97 mA cm^(–2) at–0.8 V versus reversible hydrogen electrode(RHE),and over FECO of 90%from–0.6 to–1.0 V versus RHE.Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N_(4)C_(8) sites causes the d‐orbital energy level of the Cu atom to shift upward,which in return decreases the occupancy of antibonding states in the*COOH binding.This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.

Homogenous metallic deposition regulated by abundant lithiophilic sites in nickel/cobalt oxides nanoneedle arrays for lithium metal batteries

Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.

Atomically dispersed metal sites in COF-based nanomaterials for electrochemical energy conversion

Atomically dispersed metal sites(ADMSs)play key roles in electrochemical energy conversion.The covalent organic frameworks(COFs)enable the precise control of the chemical compositions and structures at the molecular level,making them ideal substrates for supporting ADMSs.In this review,we systematically summarize the recent progress on the design and synthesis of ADMSs in COFs,including embedding molecular catalysts into COFs,immobilizing ADMSs on heteroatom-containing COFs,and preparing COF-derived carbon materials through pyrolysis.The electrocatalytic performance of the resulting catalysts is presented for various electrochemical reactions,involving oxygen reduction reaction(ORR),carbon dioxide reduction reaction(CO_(2)RR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and nitrogen reduction reaction(NRR).The modulation strategies of AMDSs in COFs for enhanced activity,selectivity,and stability are highlighted,together with a perspective of the current challenges and the future opportunities in this field.

Doping sites modulation of T-Nb_(2)O_(5) to achieve ultrafast lithium storage

Heteroatoms doping has been regarded as a promising route to modulate the physiochemical properties of electrode materials,in which the doping sites greatly influence the electrochemical performances.However,very few reports focus on enhancing the lithium storage performances of Nb_(2)O_(5) via heteroatoms doping,yet the effect of different doping sites remains unclear.Herein,nitrogen doping has been proposed to improve the fast-charging capability of orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))via a urea-assisted annealing process.Experimental data and theoretical calculation demonstrate that the N doping sites in T-Nb_(2)O_(5) can be tuned by the heating rate,in which substitutional N can increase the spacing of the Li^(+)transport layer as well as reduce the band gap,while interstitial N can provide an electron-rich environment for Li^(+)transport layer and then reduce the Li^(+)diffusion barrier.Arising from the synergistic effect of N doping at different sites,the N-doped T-Nb_(2)O_(5) without carbon coating delivers impressive rate performance(104.6 mA h g^(-1) at 25 C)as well as enhanced cycle stability with a retention of 70.5%over1000 cycles at 5 C.In addition,the assembled lithium ion capacitor exhibits a high energy density of46.6 Wh kg^(-1) even at high power density of 8.4 kW kg^(-1).

Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase‑Like Activity for Sensitive Biosensing

Although nanozymes have been widely developed,accurate design of highly active sites at the atomic level to mimic the electronic and geometrical structure of enzymes and the exploration of underlying mechanisms still face significant challenges.Herein,two functional groups with opposite electron modulation abilities(nitro and amino)were introduced into the metal–organic frameworks(MIL-101(Fe))to tune the atomically dispersed metal sites and thus regulate the enzymelike activity.Notably,the functionalization of nitro can enhance the peroxidase(POD)-like activity of MIL-101(Fe),while the amino is poles apart.Theoretical calculations demonstrate that the introduction of nitro can not only regulate the geometry of adsorbed intermediates but also improve the electronic structure of metal active sites.Benefiting from both geometric and electronic effects,the nitro-functionalized MIL-101(Fe)with a low reaction energy barrier for the HO*formation exhibits a superior POD-like activity.As a concept of the application,a nitro-functionalized MIL-101(Fe)-based biosensor was elaborately applied for the sensitive detection of acetylcholinesterase activity in the range of 0.2–50 mU mL−1 with a limit of detection of 0.14 mU mL−1.Moreover,the detection of organophosphorus pesticides was also achieved.This work not only opens up new prospects for the rational design of highly active nanozymes at the atomic scale but also enhances the performance of nanozyme-based biosensors.

High-throughput computational screening of Cu-MOFs with open metal sites for efficient C_2H_2/C_2H_4 separation

Cost effective separation of acetylene(C_2H_2)and ethylene(C_2H_4)is of key importance to obtain essential chemical raw materials for polymer industry.Due to the low compression limit of C_2H_2,there is an urgent demand to develop suitable materials for efficiently separating the two gases under ambient conditions.In this paper,we provided a high-throughput screening strategy to study porous metal-organic frameworks(MOFs)containing open metal sites(OMS)for C_2H_2/C_2H_4 separation,followed by a rational design of novel MOFs in-silico.A set of accurate force fields was established from ab initio calculations to describe the critical role of OMS towards guest molecules.From a large-scale computational screening of 916 experimental Cu-paddlewheel-based MOFs,three materials were identified with excellent separation performance.The structure-performance relationships revealed that the optimal materials should have the largest cavity diameter around 5-10?and pore volume in-between 0.3-1.0 cm^3 g^(-1).Based on the systematic screening study result,three novel MOFs were further designed with the incorporation of fluorine functional group.The results showed that Cu-OMS and the-F group on the aromatic rings close to Cu sites could generate a synergistic effect on the preferential adsorption of C_2H_2 over C_2H_4,leading to a remarkable improvement of C_2H_2 separation performance of the materials.The findings could provide insight for future experimental design and synthesis of high-performance nanostructured materials for C_2H_2/C_2H_4 separation.

Controllable active sites and facile synthesis of cobalt nanoparticle embedded in nitrogen and sulfur co-doped carbon nanotubes as efficient bifunctional electrocatalysts for oxygen reduction and evolution reactions

Development of efficient and promising bifunctional electrocatalysts for oxygen reduction and evolutionreactions is desirable. Herein, cobalt nanoparticles embedded in nitrogen and sulfur co-doped carbonnanotubes(Co@NSCNT) were prepared by a facile pyrolytic treatment. The cobalt nanoparticles and co-doping of nitrogen and sulfur can improve the electron donor-acceptor characteristics of the carbon nan-otubes and provide more active sites for catalytic oxygen reduction and evolution reactions. The preparedCo@NSCNT, annealed at 900℃, showed excellent electrocatalytic performance and better durability thancommercial platinum catalysts. Additionally, Co@NSCNT-900 catalysts exhibited comparable onset poten-tials and Tafel slopes to ruthenium oxide. Overall, Co@NSCNT showed high activity and improved dura-bility for both oxygen evolution and reduction reactions.

A Universal Principle to Accurately Synthesize Atomically Dispersed Metal–N_4 Sites for CO_2 Electroreduction

Atomically dispersed metal-nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction(CO2 ER),but they still suffer from the imprecisely control of type and coordination number of N atoms bonded with central metal.Herein,we develop a family of single metal atom bonded by N atoms anchored on carbons(SAs-M-N-C,M=Fe,Co,Ni,Cu)for CO2 ER,which composed of accurate pyrrole-type M-N4 structures with isolated metal atom coordinated by four pyrrolic N atoms.Benefitting from atomically coordinated environment and specific selectivity of M-N4 centers,SAs-Ni-N-C exhibits superior CO2 ER performance with onset potential of-0.3 V,CO Faradaic efficiency(F.E.) of 98.5%at-0.7 V,along with low Tafel slope of 115 mV dec-1 and superior stability of 50 h,exceeding all the previously reported M-N-C electrocatalysts for CO2-to-CO conversion.Experimental results manifest that the different intrinsic activities of M-N4 structures in SAs-M-N-C result in the corresponding sequence of Ni> Fe> Cu> Co for CO2 ER performance.An integrated Zn-CO2 battery with Zn foil and SAs-Ni-N-C is constructed to simultaneously achieve CO2-to-CO conversion and electric energy output,which delivers a peak power density of 1.4 mW cm-2 and maximum CO F.E.of 93.3%.

d-Orbital steered FeN_(4)moiety through N,S dual-site adjustation for zinc-air flow battery

The implementation of pristine covalent organic polymer(CO_(2)P)with well-defined structure as air electrode may spark fresh vitality to rechargeable zinc-air flow batteries(ZAFBs),but it still remains challenges in synergistically regulating their electronic states and structural porosity for the great device performance.Here,we conquer these issues by exploiting N and S co-doped graphene with COP rich in metal-ligand nitrogen to synergistically construct an effective catalyst for oxygen reduction reaction(ORR).Among them,the N and S co-doped sites with high electronegativity properties alter the number of electron occupations in the d orbital of the iron centre and form electron-transfer bridges,thereby boosting the selectivity of the ORR-catalysed four-electron pathway.Meanwhile,the introduction of COP materials aids the formation of pore interstices in the graphene lamellae,which both adequately expose the active sites and facilitate the transport of reactive substances.Benefiting from the synergistic effect,as-prepared catalyst exhibits excellent half-wave potentials(E_(1/2)=912 mV)and stability(merely 8.8%drop after a long-term durability test of 50000 s).Further,ZAFBs assembled with the N/SG@CO_(2)P catalyst demonstrate exceptional power density(163.8 mW cm^(-2))and continuous charge and discharge for approximately 140 h at 10 mA cm^(-2),outperforming the noble-metal benchmarks.

Synergistic interaction of metal–acid sites for phenol hydrodeoxygenation over bifunctional Ag/TiO_2 nanocatalyst

The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero turnover frequency for HDO owing to its high C\\O bond breaking energy barrier and low carbon and oxygen binding energies.Herein this work, titania supported silver catalysts were synthesized and firstly used to examine its phenol HDO activity via experimental reaction runs. BET, XRD, FESEM, TEM, EDX, ICP–OES, Pyridine-FTIR, NH_3-TPD and H_2-TPD analyses were done to investigate its physicochemical properties. Phenomena of hydrogen spillover and metal–acid site synergy were examined in this study. With the aid of TiO_2 reducible support, hydrogen spillover and metal–acid site interactions were observed to a certain extent but were not as superior as other Pt, Pd, Ni-based catalysts used in other HDO studies. The experimental findings showed that Ag/TiO_2 catalyst has mediocre phenol conversion but high benzene selectivity which confirms the explanation from other computational studies.

Role of local coordination in bimetallic sites for oxygen reduction: A theoretical analysis

Understanding of the oxygen reduction reaction(ORR)mechanism for single atom catalysts is pivotal for the rational design of non-precious metal cathode materials and the commercialization of fuel cells.Herein,a series of non-precious metal electrocatalysts based on nitrogen-doped bimetallic(Fe and Co)carbide were modeled by density functional theory calculations to predict the corresponding reaction pathways.The study elucidated prior oxygen adsorption on the Fe atom in the dual site and the modifier role of Co atoms to tune the electronic structures of Fe.The reaction activity was highly correlated with the bimetallic center and the coordination environment of the adjacent nitrogen.Interestingly,the preadsorption of*OH resulted in the apparent change of metal atoms'electronic states with the d-band center shifting toward the Fermi level,thereby boosting reaction activity.The result should help promote the fundamental understanding of active sites in ORR catalysts and provide an effective approach to the design of highly efficient ORR catalysts on an atomic scale.

Comparison of Soil Samples from Selected Anthropogenic Sites within Enugu Metropolis for Physicochemical Parameters and Heavy Metal Levels Determination

This study compared the physicochemical parameters and heavy metal levels in soil samples from selected anthropogenic sites within Enugu metropolis, Enugu State, Nigeria using standard analytical methods. Soil samples at depths (0 - 20 cm) and (20 - 40 cm) were collected from waste dump sites, metal scrap dumps, fuel filling stations and auto-mechanic workshops and analyzed for physicochemical characteristics and heavy metal levels. Atomic absorption spectrophotometer was used for heavy metal determination while conventional analytical methods were employed for physicochemical parameters evaluation of the soil samples. At soil depths 0 - 20 cm and 20 - 40 cm the respective mean range of pH, electrical conductivity, organic matter and organic carbon contents in the soil samples were, 6.33 - 6.74, 101.46 - 123.21 μS/cm, 6.41% - 8.35% and 13.73% - 16.14% for auto-mechanic workshops;6.92 - 7.43, 56.46 - 60.02 μS/cm, 1.53% - 2.20% and 11.93% - 12.60% for fuel filling stations;7.14 - 7.84, 70.81 - 77.71 μS/cm, 3.81% - 4.12% and 8.57% - 9.24% for metal scrap dumps;6.54 - 6.81, 94.40 - 100.71 μS/cm, 8.83% - 10.75% and 18.26% - 20.81% for waste dump sites. The pH of the top soil samples from auto-mechanical workshop was below the WHO recommended limits for agricultural purposes. The physic-chemical characteristics of the soil samples decreased with soil depths indicating therefore that anthropogenic activities greatly influence the soil characteristics at the top soils than the sub-soils. The electrical conductivity values of top and sub-soil samples from the studied auto-mechanical workshops were above the recommended limits. At soil depths 0 - 20 cm and 20 - 40 cm, the respective mean range of Zn, Pb and Cd in the soil samples were 17.29 - 19.16 μg/g, 0.704 - 0.96 μg/g and 0.26 - 0.33 μg/g for auto-mechanic workshops;4.13 - 4.88 μg/g, 0.21 - 0.32 μg/g and 0.03 - 0.11 μg/g for fuel filling stations;30.02 - 36.11 μg/g, 0.43 - 0.48 μg/g and 0.15 - 0.19 μg/g for metal scrap dumps;9.30 - 10.84 μg/g, 0.53 - 0.60 μg/g and 0.38 - 0.45 μg/g for waste dump sites. The mean levels of Pb in soil samples from mechanic workshops and waste dump sites were above the recommended permissible limits for agricultural purposes. The study therefore indicated that these sites (auto-mechanic workshops and waste dump sites) could be major sources of Pb pollution to nearby farmlands, streams and the general environment. Plants grown on or around these sites may not produce high yields and could be severely contaminated with heavy metals which portend health danger to food consumers within the environment.

Structural transformation of metal–organic framework with constructed tetravalent nickel sites for efficient water oxidation

A mixture of Ni and Fe oxides is among the most commonly active catalysts for the oxygen evolution reaction(OER)during the water oxidation process.In particular,Ni oxide incorporated with even a small amount of Fe leads to substantively enhanced OER activity.However,the critical role of Fe species during the electrocatalytic process is still under evaluation.Herein,we report nickel(oxy)hydroxide incorporated with Fe through the surface reconstruction of a bimetallic metal-organic framework(NiFe-MOF)during the water oxidation process.The spectroscopic investigations with theoretical calculations reveal the critical role of Fe in promoting the formation of highly oxidized Ni^(4+),which directly correlates with an enhanced OER activity.Both the geometric and electronic structu res of the as-reconstructed Ni_(1-x)Fe_(x)OOH electrocatalysts can be delicately tuned by the Ni-Fe ratio of the bimetallic NiFe-MOF,further affecting the catalytic activity.As a result,the Ni_(1-x)Fe_(x)OOH derived from Ni_(0.9)Fe_(0.1)-MOF delivers low overpotentials of 260 mV at 10 mA cm^(-2)and 400 mV at 300 mA cm^(-2).

Surface BrØnsted-Lewis dual acid sites for high-efficiency dinitrogen photofixation in pure water

As is known to all, nitrogen not only plays an important role in the industrial development of human society but also plays an important part in the proteins that constitute the essence of life[1]. In 1910, the Haber-Bosch process was first used to synthesize ammonia.

DFT Study of Metal Atoms Adsorbed at Low-coordinated Sites of MgO (001) Surface

The adsorption of metal atoms, Ni, Pd, Pt, Cu, Ag and Au, at low-coordinated edge and corner oxygen sites of MgO (001) surface has been studied theoretically by using density functional method with cluster models embedded in a large array of point charges. For comparison, the interaction of metal atoms with perfect regular oxygen site of MgO (001) surface was also calculated. As regards these metal atoms adsorbed at perfect oxygen sites of MgO (001) surface, Cu, Ag and Au are very weakly bonded to the surface of MgO; Ni, Pd and Pt, on the other hand, exhibit strong interactions with perfect oxygen sites of MgO (001) surface; the large adsorption energy shows that there exist strong bonds formed between these metal atoms with surface oxygen sites. For the metal atoms adsorbed at edge and corner sites, the adsorption energy is much increased, consistent with our previous study of CO and Cl2 adsorption on MgO (001) surface. This illustrates that the low-coordinated sites, especially corner site, are more advantageous positions for those metal atoms adsorbed on MgO (001) surface. The Mulliken population analysis indicates that the electron transferred from MgO to the metal atoms were increased with the decrease of the coordination numbers, which may be one of the reasons for changing catalytic efficiency and selectivity of the metal particles supported by MgO.

Fabrication and sintering behavior of high-nitrogen nickel-free stainless steels by metal injection molding

High-nitrogen nickel-free stainless steels were fabricated by the metal injection molding technique using high nitrogen alloying powders and a mixture of three polymers as binders.Mixtures of metal powders and binders with various proportions were also investigated, and an optimum powder loading capacity was determined as 64vol%.Intact injection molded compacts were successfully obtained by regulating the processing parameters.The debinding process for molded compacts was optimized with a combination of thermo-gravimetric analysis and differential scanning calorimetry analysis.An optimum relative density and nitrogen content of the specimens are obtained at 1360℃,which are 97.8%and 0.79wt%,respectively.

In situ reaction mechanism of MgAlON in Al–Al2O3–MgO composites at 1700°C under flowing N2

The Al–AlO–MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M, M, and M, respectively, were prepared at 1700°C for 5 h under a flowing Natmosphere using the reaction sintering method. After sintering, the Al–AlO–MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen Mwas composed of MgO and MgAlO. Compared with specimen M, specimens Mand Mpossessed MgAlON, and its production increased with increasing aluminum addition. Under an Natmosphere, MgO, AlO, and Al in the matrix of specimens Mand Mreacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al–AlO–MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an Natmosphere, the partial pressure of oxygen is quite low; thus, when the Al–AlO–MgO composites were soaked at 580°C for an extended period, aluminum metal was transformed into AlN. With increasing temperature, AlOdiffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with AlOto form MgAlO. When the temperature was greater than(1640 ± 10)°C, AlN diffused into AlOand formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and Mg AlOat high temperatures because of their similar spinel structures.