Pressureless consolidation of boron nitride fiber ceramics via a chemical bonding approach

Hexagonal boron nitride (h-BN) materials with excellent physicochemical stability and processibility have been considered as promising engineering materials. However, their practical applications are rather limited by the difficulty in constructing the well-bonded h-BN ceramic. Herein, we present a reaction welding strategy for facile preparation of well-bonded h-BN fibers (BNFs) network by using ethanolamine (ETA) containing alcoholic hydroxyl and primary amine groups as crosslinking agent. The formed >B-O-H₂C-H₂C-H₂N|→B< bond bridges through the esterification and intramolecular coordination (N|→B) reactions between ETA molecules and BNFs containing surface hydroxyls, play an essential role in the construction of the thermodynamically stable >B-N-B< covalent bond between BNFs. Based on this synthetic strategy and a room-temperature molding process followed by a calcination step, a series of resilient BNFs ceramics with high processibility, typical diamagnetism, low dielectric constant (∼ 2.1) and loss, good resistance to temperature different, corrosion, oxidation and abrasion are produced. Besides, they also exhibit excellent strain and damage tolerance, the maximum compression strain and strength can reach up to 38% and ∼ 33 MPa, respectively. Significantly, the deliberately designed BNFs vessel can be successfully used for the alloying of high melting point metals, showing both structural/chemical robustness and good reusability. This ingenious design for well-bonded BNFs network not only is a good model for exploring the welding way for h-BN powders, but also opens up numerous opportunities for practical applications.     

Al2O3 coated glass by aerosol deposition with excellent mechanical properties for mobile electronic displays

Al₂O₃ thin film was deposited on Gorilla glass using an aerosol deposition method to improve the mechanical property of cover glass for mobile electronic device. The deposited Al₂O₃ film (approximately 1 μm thick) was a polycrystalline structure and showed a high light transmittance of approximately 90% in the visible light region. The CIE color space (L*a*b) measurement also showed a characteristic corresponding to the acceptable optical range of the cover glass. Further, it was confirmed that the bending strength improved by 10 %, as compared with bare Gorilla glass (from 6970 kgf/cm² to 7704 kgf/cm²), and the Vickers hardness increased to approximately 1700–2000 HV, as compared with that of Gorilla glass (<700 HV). Owing to the improved mechanical properties, the Al₂O₃ thin film exhibited good anti-scratch properties and is expected to be applied to the cover glass of various display products.     

A study of reaction between palladium,palladium silver alloy and silicon carbide ceramics at high temperature

The reactions between palladium (Pd), palladium-silver alloy (Pd-Ag) and silicon carbide (SiC) from 1200 °C to 1400 °C have been studied to investigate the impact of liquid phases on reaction products formation. The liquid phases were generated in Pd/SiC reactions at 1400 °C and in Pd-Ag/SiC reactions above 1300 °C. An increase in the amount of liquid associated with higher temperatures or Ag presence strongly affected the reaction mechanism and was responsible for the inhomogeneous dissolution of SiC grains and grain boundaries by Pd-rich phase at reaction front. This study helps understand Pd’s role on Ag release through SiC layer in Tri-structural isotropic (TRISO) fuel particles.     

Sintering characteristics and microwave dielectric properties of ultralow-loss SrY2O4 ceramics

A SrY₂O₄ microwave dielectric ceramic suitable for 5G systems is synthesised via a solid-state reaction in a sintering temperature range of 1425–1525 °C. X-ray diffraction patterns and Rietveld refinement analysis show that the ceramic has an antispinel orthorhombic crystal structure belonging to the Pnma space group. Scanning electron microscopy images show that the ceramic particles are closely connected, the grain boundaries are clear, and the particles are uniform at the optimal sintering temperature of 1475 °C. The optimal microwave dielectric performances are ε_r = 14.78, Q × f = 84090 GHz, τ_? = ?14.98 ppm/°C. The relatively low dielectric constant, high Q × f value, low τ_? value, and easily available raw materials indicate that it is a good choice for 5G equipment.     

Room-temperature densification of MgO bulk ceramics with dispersed nitride phosphor particles

Wave conversion materials with high thermal conductivity are necessary for high-power semiconductor lighting. Ceramics have higher thermal conductivity than existing matrices such as resin or glass in which phosphor particles are dispersed. However, the high densification of ceramics generally requires high-temperature sintering, which degrades and alters the phosphor particles. In this study, we aimed to achieve the high densification of MgO ceramics at room temperature. Applying high hydrostatic pressure with water addition improved the sample packing ratio and promoted the formation of Mg(OH)₂. As a result, the relative density was ≥95%. Additionally, various nitride phosphor particles (CaAlSiN₃:Eu²⁺, β-SiAlON:Eu²⁺, and α-SiAlON:Eu²⁺) were dispersed in the MgO matrix at room temperature without degrading the luminescence property. The thermal conductivity of the obtained sample was about 8 W m^?1K^?1, 40 times higher than that of the epoxy matrix.     

Fabrication of Al2O3/AlN composite ceramics with enhanced performance via a heterogeneous precipitation coating process

To improve the thermal and mechanical properties of Al₂O₃/AlN composite ceramics, a novel heterogeneous precipitation coating (HPC) approach was introduced into the fabrication of Al₂O₃/AlN ceramics. For this approach, Al₂O₃ and AlN powders were coated with a layer of amorphous Y₂O₃, with the coated Al₂O₃ and AlN powders found to favor the formation of an interconnected YAG second phase along the grain boundaries. The interconnected YAG phase was designed to act as a diffusion barrier layer to minimize the detrimental interdiffusion between Al₂O₃ and AlN particles. Compared with samples prepared by a conventional ball-milling method, the HPC Al₂O₃/AlN composites exhibited less AlON formation, a higher relative density, a smaller grain size and a more homogeneous microstructure. The thermal conductivity, bending strength, fracture toughness and Weibull modulus of the HPC Al₂O₃/AlN composite ceramics were found to reach 34.21 ± 0.34 W m⁻¹ K⁻¹, 475.61 ± 21.56 MPa, 5.53 ± 0.29 MPa m^1/2 and 25.61, respectively, which are much higher than those for the Al₂O₃ and Al₂O₃/AlN samples prepared by the conventional ball-milling method. These results suggest that HPC is a more effective technique for preparing Al₂O₃/AlN composites with enhanced thermal and mechanical properties, and is probably applicable to other composite material systems as well.     

Mechanical and dielectric properties of porous magnesium aluminate (MgAl2O4) spinel ceramics fabricated by direct foaming-gelcasting

Porous ceramic materials have been broadly applied in various fields due to their multifunctional properties. Optimization of their microstructural characteristics, such as pore morphology, total porosity, and pore size distribution, which determine various properties of the final products, is crucial to improve their performances and thus extend their applications. In this study, single-phase porous MgAl₂O₄ materials were fabricated by direct foaming–gelcasting. With an increase in the foam volume from 260 to 350 mL, the total porosity and pore size of the porous ceramic increased, and its microstructure varied from mostly closed cells to open cells containing interconnected large pores (40–155 μm) and small circular windows (10–40 μm) in the ceramic skeleton. The total porosity could be tailored from 84.91% to 76.08% by modulating the sintering temperature and foam volume and the corresponding compressive strengths were in the range of 2.8–15.0 MPa. The compressive strength exhibited a power-law relationship with the relative density with indices of approximately 3.409 and 3.439, respectively. Porous MgAl₂O₄ ceramics exhibited low dielectric constants in the range of 1.618–1.910 at room temperature, which are well matched with theoretical calculations on account of a modified Bruggeman model. The porous MgAl₂O₄ ceramics with good mechanical and dielectric properties controlled easily by various sintering temperatures and foam volumes are promising for practical applications.     

Migration,transformation and solidification/stabilization mechanisms of heavy metals in glass-ceramics made from MSWI fly ash and pickling sludge

In consideration of recycling solid waste to achieve high value-added products, glass-ceramics have been fabricated from municipal solid waste incineration (MSWI) fly ash, pickling sludge (PS), and waste glass (WG) by melting at 1450 °C firstly to achieve parent glass and then crystallizing at 850 °C. Results demonstrated that heavy metals have been well solidified in the prepared glass-ceramics, and relatively/extremely low leaching concentrations of heavy metals have been detected. The synthetic toxicity index of heavy metals has been greatly reduced from 7-18 to <3.2 after crystallization treatment, and the leaching concentrations of Cr, Ni, Zn, Cu, and Pb are 0.15, 0.05, 0.26, 0.12, 0.19 mg L^-1 respectively. Chemical morphology analysis, principal component analysis, TEM and EPMA were utilized to clarify the migration, transformation, and solidification mechanism of heavy metals from the as-received solid wastes. The major heavy metals, Cr and Ni which is responsible for the most toxicity, mainly exist in form of the oxidation state and residual state in parent glass, while the residual state in the glass-ceramics. The solidification performance was mostly positively correlated with the form of residue state, which the stability of heavy metals in glass-ceramics is improved. The solidification mechanism of heavy metals in glass-ceramics could be explained by the combination of chemical solidification/stabilization and physical coating. The TEM and EPMA confirmed that Cr and Ni mainly exist in the spinel crystalline (NiCr₂O₄, Fe_0.99Ni_0.01Fe_1.97Cr_0.03O₄) by solid solution or chemical substitution, and a small amount of Cr in the diopside phase. Pb, Cu, and Zn are homogenously dispersed in the glass-ceramics, which is considered as physical coating solidification.     

Shrinkage behavior and mechanical properties of alkali activated mortar incorporating nanomaterials and polypropylene fiber

Blended ground granulated blast slag (GGBS), low-calcium fly ash (FA), nano silica (NS), and nano alumina (NA) with/without polypropylene fiber (PPF) had a significant effect on the development length of alkali activated mortar (AAM) cured at various humidity levels and curing ages. This paper presents the behavior of alkali activated mortar with 50% FA and 50% GGBFS binder materials and the alkali ratio of sodium silicate to sodium hydroxide (SS/SH) is 2.5. The molar concentration of sodium hydroxide (NaOH) used was 12 M. Feasibility Comparisons between the different humidity 60%–98% of at 23 ± 3 C° were examined. The strength behavior of alkali-activated mortar with different curing ages was also evaluated. Scanning electron microscopy (SEM) analysis and X-ray diffractions (XRD) were also conducted to clarify the effect of nanomaterials and PPF on the microstructures of AAM. It was found that the shrinkage values of AAM were decreased with the addition of polypropylene fiber and nanomaterials. The combined use of both nanomaterials had better performance than the use of nano SiO₂ and/or nano Al₂O₃ alone. The combined use of PPF with nanomaterials had a superior reduction in shrinkage and expansion and increment on strength values; the minimum shrinkage, expansion values, and maximum strength were found at AAM mix incorporating 2%NS-1%NA-0.5%PPF. The SEM analysis and XRD evaluation indicates the significant effect of nanomaterials on the microstructures and bond strength of AAM. The microstructure of the mixes incorporating both nanomaterials and PPF was denser than other mixes without nanomaterials and/or PPF and showed lower micro cracks.     

Ultra-high-temperature tantalum-hafnium carbonitride ceramics fabricated by combustion synthesis and spark plasma sintering

We report the fabrication of dense single-phase (Ta,Hf)CN carbonitride ceramics using a combination of combustion synthesis (CS) and spark plasma sintering (SPS). The ceramic powder was produced by high-energy ball milling of the reactants (Ta, Hf, C) in different atomic ratios followed by CS of the obtained nanostructured composites in a nitrogen atmosphere. X-ray diffraction analysis of the combustion products revealed the formation of (Ta,Hf)CN with cubic B1 structures as the dominant phases for all investigated compositions. The SPS of the as-synthesized powders allowed both homogenization of the composition and consolidation of the bulk single-phase carbonitride ceramics with a relative density of 98 ± 1 %. Ta₂₅Hf₇₅CN showed the highest hardness (19.4 ± 0.2 GPa) and fracture toughness (5.4 ± 0.4 MPa m^1/2) among the investigated composites and excellent oxidation resistance in air.     

Interface properties of Ti3SiC2/Al2O3 ceramics: Combined experiments and first-principles calculations

The synthesis, characterization, and first-principles calculations of Ti₃SiC₂/Al₂O₃ ceramics were reported. X-ray diffraction measurements showed that the composite ceramics were highly pure. Scanning electron microscopy and transmission electron microscopy were used to characterize the interface information for Ti₃SiC₂ and Al₂O₃ crystals. Surface energies and interface properties were calculated using the first-principles method. The results suggested that Ti₃SiC₂ with Ti terminations and Al₂O₃ with O terminations are more stable than other terminations crystals. Thus powerful attraction between the coordinatively unsaturated Ti and O atoms on the Ti₃SiC₂∥Al₂O₃ interface would result in higher work of adhesion (Wad) and shorter boundary distance, demonstrating the intercrystalline strengthening of Ti₃SiC₂/Al₂O₃ composite ceramics.     

Highly compressible ceramic/polymer aerogel-based piezoelectric nanogenerators with enhanced mechanical energy harvesting property

Ceramic piezoelectric materials have orders of magnitude higher piezoelectric coefficients compared to polymers. However, their brittleness precludes imposition of large strains in mechanical energy harvesting applications. We report here that ice templating affords low bulk modulus lead-free aerogel piezoelectric nanogenerators (PENG) with unprecedented combination of flexibility and high piezoelectric response (voltage and power density). A modified ice templating protocol was used to fabricate piezoelectric nanocomposites of surface modified BaTiO₃ (BTO) nanoparticles in crosslinked polyethylene imine. This protocol allowed incorporating a significantly high fraction of BTO particles (up to 83 wt %) in the aerogel, while retaining remarkably high compressibility and elastic recovery up to 80% strain. The output voltage, at an applied compressive force of 20 N (100 kPa), increased with BTO loading and a maximum output voltage of 11.6 V and power density of 7.22 μW/cm² (49.79 μW/cm³) was obtained for PENG aerogels containing 83 wt% BTO, which is orders of magnitude higher than previously reported values for foam-based piezoelectric energy harvesters. The BTO/PEI PENGs also showed cyclic stability over 900 cycles of deformation. PENGs with higher porosity showed better elastic recovery and piezoelectric properties than lower porosity and higher BTO content aerogels. To the best of our knowledge, this is the first report to demonstrate the piezoelectric properties of high ceramic content aerogels having very high compressibility and elastic recovery.     

Evaluation of mechanical properties of YSZ TBCs doped by different ratios of Eu3+ ions after isothermal oxidation

Thermal barrier coatings (TBCs) are essential to improve the thermal insulation performance of high-temperature components. Rare earth element (Eu³⁺) doped yttrium stabilized zirconia (YSZ) TBCs have been proved to be an ideal solution for non-destructive testing of internal damages. Based on this theory, two types of coatings deposited by air plasma spray (APS) on Hastelloy-X were investigated: (1) Eu³⁺ doped YSZ (dopant ratios 1 mol%, 2 mol%, 4 mol%, respectively), (2) traditional undoped 8YSZ. Isothermal oxidation treatment at 1100 °C, in increments of 10h until the failure of the coatings are conducted to evaluate the mechanical properties of different coatings. The microscopic morphology and phase of the coatings were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) patterns, respectively. The indentation testing methods were used to study the apparent interfacial fracture toughness and the hardness of the ceramic top coat. Results show that the Vickers hardness of the top coat increases with the decrease of porosity in the early stage and then decreases with the heat treatment time increasing in the long-term stage. Simultaneously, compared with the undoped 8YSZ coating, the fracture toughness increased with the dopant of Eu³⁺ ions increasing, from 1 mol% to 2 mol%, nevertheless, that of 4 mol% Eu³⁺ doped YSZ decreased compared with in the undoped 8 YSZ. For all types of specimens, the interfacial fracture toughness decreases with the increase of isothermal oxidation time. Results also indicate that the content of Eu³⁺ doping does not affect the microstructure and interfacial morphology of the YSZ coating as well as the growth law of thermally grown oxides (TGO). Furthermore, EDS detection found that the Eu³⁺ ions almost do not diffuse inside the TBCs system after isothermal oxidation treatment.     

Study on the microstructure and mechanical properties of microwave sintered NbC–Ni cermets reinforced by multilayer graphene

In recent years, NbC–Ni cermets has been proposed as a potential substitute for WC-Co cemented carbide in machining and other fields because of its economy and good performance, which has attracted extensive attention of scholars. Research on improving its mechanical properties will help to explore its application potential. Graphene-reinforced NbC–Ni cermets were prepared using a microwave sintering technique, and the effects of multilayer graphene (MLG) on its mechanical properties and microstructure were investigated. The experimental results show that the addition of a certain content of graphene contributes to the densification of the material and inhibits the grain growth. The Vickers hardness, toughness, and bending strength increased and then decreased with an increase in the MLG content. When 0.75 wt% MLG was added, the comprehensive mechanical properties of NbC–Ni cermets were optimal, with a Vickers hardness, fracture toughness, and bending strength of 1297.5 kg/mm², 18.23 MPa m^1/2, and 1464.5 MPa, respectively, which were 12.01%, 38.95%, and 18.97% higher than those without MLG. At low MLG content, the graphene sheet layers were well dispersed in the matrix grain boundaries, whereas graphene agglomerates and pores appeared in cermets with 1 wt% MLG, which degraded their mechanical properties. The strengthening and toughening mechanisms of MLG include grain refinement, large-angle deflection of cracks, crack bridging, and pullout of graphene sheet layers.     

Effect of grain boundary state and grain size on the microstructure and mechanical properties of alumina obtained by SPS: A case of the amorphous layer on particle surface

The work was aimed at the investigation of kinetics of Spark Plasma Sintering (SPS) of the α-Al₂O₃ particles with amorphous surface layers and investigation of the effect of the amorphous layers on the grain growth and on the mechanical properties of alumina. The objects of investigations comprised:(i) submicron α-Al₂O₃ powder, (ii) submicron α-Al₂O₃ powder with the amorphous layers on the particles' surfaces, and (iii) the fine-grained α-Al₂O₃ powder. The submicron powders (i) and (ii) were used to analyze the effect of the amorphous layers on the sintering kinetics. Powders (i) and (iii) were used to analyze the effect of the initial particle sizes on the shrinkage kinetics. The effect of the temperature regime and of the rate (V_h) on the shrinkage kinetics of the submicron and fine alumina powders has been studied. The shrinkage curves were analyzed using the Young–Cutler and Coble models. The sintering kinetics was shown to be determined by the intensity of grain boundary diffusion for the submicron powders and by simultaneous lattice diffusion and grain boundary one for the fine powders. The amorphous layers on the surfaces of the submicron α-Al₂O₃ particles were found to affect the grain boundary migration rate and the Coble equation parameters at the final stages of SPS. The abnormal characteristics of the alumina ceramics sintered from the submicron powder with the amorphous layers on the particles’ surfaces were suggested to originate from the increased concentration of the defects and of the excess free volume at the grain boundaries formed during crystallization of the amorphous layers.     

A comprehensive exploration on the development of nano Y2O3 dispersed in AA 7017 by mechanical alloying and hot-pressing technique

The main objective of the present study is to develop AA 7017 alloy matrix reinforced with yttrium oxide (Y₂O₃, rare earth element) nanocomposites by mechanical alloying (MA) and hot pressing (HP) techniques for armor applications. AA 7017+10 vol % Y₂O₃ nanocomposites were synthesized in a high-energy ball mill with different milling times (0, 5, 10, and 20 h) to explore the structural refinement effect. The phase analysis and homogeneous dispersion of Y₂O₃ in AA 7017 nanocrystallite matrix were investigated by X-ray diffraction (XRD), various electron microscopes (HRSEM, and HRTEM), Particle Size Analyzer (PSA), and Differential Thermal Analysis (DTA). The nanostructured powders were hot-pressed at 500 MPa pressure with a temperature of 673k for 1hr. The consolidated sample results revealed significant grain refinement and the enhanced mechanical properties with the function of milling time in which the 20h sample exhibited improvement in the hardness (142 VHN - 260 VHN) and ultimate compressive strength (514 MPa–906.45 MPa) due to effective dispersion of Y₂O₃. The various strengthening mechanisms namely, grain boundary (27.02–32.69 MPa), solid solution (57.21 MPa), precipitate (189.79–374.62 MPa), Orowan (135.68–206.92 MPa), and dislocation strengthening (84.99–149.82 MPa) were determined and correlated to the total strength.     

Effects of ceramic-based CrN,TiN, and AlCrN interlayers on wear and friction behaviors of AlTiSiN+TiSiN PVD coatings

In this study, the wear and friction behavior of cathodic arc physical vapor deposited AlTiSiN+TiSiN coatings on H13 tool steels were investigated by using CrN, TiN and AlCrN interlayers with tribometer tests both under unlubricated and boundary lubricated conditions. 6 mm alumina balls were used as counter surfaces to test ceramic hard coatings. Surface coatings were characterized through nanoindentation, scanning electron microscopy coupled with an energy-dispersive X-ray spectrometer (SEM/EDXS), optical profilometry, and atomic force microscopy (AFM) techniques. The results showed that especially AlTiSiN+TiSiN coating with TiN interlayer resulted in a much more enhanced tribological performance of the tool steels at both unlubricated and the boundary lubricated conditions even at elevated contact pressures.     

Microstructural and main mechanical properties of novalac based carbon–carbon composites as the pyrolysis heating rate

In this study, the effects of pyrolysis heating rate on microstructural and main mechanical properties of Novalac-based carbon/carbon composites were investigated by CHNS, optical microscope, FE-SEM, BET N₂ adsorption, XRD, Raman, FT-IR, wear analyzing, three-point bending test, tensile and Vickers micro-hardness tests. Firstly, PAN-derived carbon nanofibers (reinforcing agent) was synthesized using electrospinning followed by the functionalizing via the wet chemical oxidation to improve the strength of nanofiber bonding to the matrix of composites. Firstly, novalac resin (acting as a matrix), hexamethylenetetramine (hardener agent) and carbon nanofibers (reinforcing agent) were mixed and hot-pressed at 180 °C under the compression load of 40 kN to produce compressed CNFs-Novolac composites. Carbon/Carbon composites were obtained from the pyrolysis of CNFs-Novolac composites up to 1000 °C by the various heating rates under the compression press of 400 bar, finally. Structural and mechanical studies confirmed that the heating rates below or equal to 10 °C.min⁻¹ resulted in the production of low porosity (≤17%) carbon composite with high carbon content (>90 wt%), high fracture strength (≥270 MPa), high toughness (≥9 MPa m^1/2), high hardness (≥156 Hv), and low friction coefficient (<0.6).     

Optimized pore structure and high permeability of metakaolin/fly-ash-based geopolymer foams from Al– and H2O2–sodium oleate foaming systems

Geopolymer foams have been widely studied as adsorbents owing to their high specific surface areas, high heavy metal immobilization efficiencies, low cost, environmental friendliness, and resource-recycling benefits. In this study, geopolymer foams with different pore structures were prepared from Al– and H₂O₂–sodium oleate foaming systems, and their chemical properties, pore structures, and permeabilities were characterized. The effects of the foaming agent type and surfactant content on the crystal structure and chemical bonding of the materials were analyzed by X-ray diffraction analysis and Fourier-transform infrared spectroscopy, and the pore morphology and structural characteristics were characterized by morphological observations, three-dimensional (3D) reconstruction, and compression tests. Numerical simulations were also carried out to study the structural characteristics of the 3D-reconstructed pores. Furthermore, variations in the permeability coefficient and flow characteristics were tested and analyzed by experiments and simulations. The pores in the geopolymer from the H₂O₂–sodium oleate foaming system tended to be more connected, whereas those in the Al–sodium oleate geopolymers were more complete and closed. The highly connected pore structure facilitates the even diffusion of the solution and effectively increases the amount of adsorption sites. These properties are significant for adjusting the adsorption capacity of geopolymer foams as adsorption monoliths.     

Tetragonal multilayered ZnO/CuO composites derived from Zn- and Cu-containing metal-organic framework: Effect of calcination temperature on physicochemical properties and photocatalytic activity

Tetragonal multilayered ZnO/CuO composites prepared by the annealing of a Zn- and Cu-containing pillar-layered metal-organic framework were characterized by using instrumental techniques and investigated as catalysts for the degradation of 4-nitrophenol (4-NP) under irradiation with UV–vis light. The as synthesized samples contained p-n junctions, amorphous-crystalline heterojunctions, which benefitted light absorption and charge separation. The calcination temperature significantly influenced both the physicochemical properties and photocatalytic activities of these composites. The sample obtained at 400 °C (TL-ZC-400) exhibited the best photocatalytic performance, achieving a 4-NP degradation efficiency of 93.93% after 40 min of illumination. The TL-ZC-400 still showed high photodegradation ability (97.2%) after four times recycling. Furthermore, the recombination of ZnO and CuO adjusted the band gap structure of TL-ZC-400. Radical trapping experiments showed that the degradation of 4-NP was mainly mediated by hydroxyl radicals and holes. A possible photocatalytic mechanism was also proposed in this study.