Formation Of Oxynitride Research Articles

Solar driven photocatalytic colored co–TixOyNz amorphous film prepared through air plasma treatment of sputtered titanium film

Colored co–titanium oxides and oxynitride amorphous thin film were fabricated through air plasma treatment of sputtered titanium films. Air plasma treatment led to the removal of the passive film that developed on the titanium film surface, and changes in the structural and optical properties of the films. The amorphous nature, grain size, and thickness of the films remained invariant after the treatment process. The surface roughness of the films increased upon plasma treatment. UV-vis spectroscopy study showed the reduction of the bandgap energy of the films after the air plasma treatment and the maximum reduction was found for the thinner film. The 60min air plasma treatment of the thinner film (AD5: film with 5 min deposition time) leads to the changes in bandgap from 4.11 eV to 3.26 eV, and significant Urbach energy values pointed to the formation of defect states. XPS analysis highlighted that the plasma treatment process led to the formation of titanium oxides (TiO2, Ti2O3) and oxynitrides (TiON), accompanied with Ti2+ defect states in the bandgap. The degradation of methylene blue dye solution with plasma-treated film (PT5) as the photocatalyst resulted in 88% degradation efficiency under 240min irradiation of solar simulator. The degradation has also been checked with natural solar illumination and is found to have a 90% degradation efficiency in 480min.

Physicochemical and structural properties of silica films prepared from perhydropolysilazane using vacuum ultraviolet irradiation

Developing techniques to form functional films at low temperatures is crucial for enabling their application on materials with limited heat resistance. In this study, silica films were prepared by irradiating a perhydropolysilazane (PHPS) precursor, which contains reactive Si–H and N–H groups and is free from organics, with vacuum ultraviolet (VUV) light under a controlled atmosphere. To investigate the quality of the resulting films and mechanisms behind photochemical conversion, infrared and electron spectroscopic measurements were performed. The results revealed that VUV irradiation converted the top surface of the film into silica, irrespective of the atmospheric conditions. However, differences in the oxygen concentration affected both the VUV light intensity penetrating the film and the oxygen diffusion into it, leading to the formation of silica or silicon oxynitride within the film. Under irradiation, PHPS was converted to silica not only from the surface but also from the interface with the substrate. In addition, silica was formed even at long irradiation distances, in which case VUV light barely reached the PHPS surface owing to absorption by atmospheric oxygen. These findings demonstrate that the silica-film formation involved two processes: breaking of chemical bonds induced by VUV photons and oxidation due to oxygen diffusion from the surface. The spectroscopic measurements and X-ray reflectivity results indicated that the composition, chemical state, Auger parameter, and density of the prepared silica film were comparable to those of a silica film prepared through heat treatment at 500°C. Further, the prepared silica film using VUV irradiation had a smoother surface than that of the heat-treated film. The thickness of the prepared film remained unchanged before and after VUV irradiation, indicating that the formation process using VUV irradiation suppressed the shrinkage of the film during the conversion of PHPS to silica.

Oxynitride from Oxide versus Nitride: Manifesting Competitive and Synergistic Properties in Titanium Oxynitride for Solar‐Driven Water Splitting and Nitrogen Fixation

The present study investigates the phase formation of the titanium oxynitride (TiOxNy) system using the “oxide‐to‐oxynitride” and “nitride‐to‐oxynitride” synthesis strategies. The XRD patterns of both the materials show peaks corresponding to Ti–N and Ti–O lattices, confirming the formation of Ti–oxynitride system. Accordingly, the presence of Ti3+–N3− and Ti4+–2O2− signals is also confirmed by XPS analysis. The TiOxNy derived from oxide (TO‐TON) exhibits wide visible light absorption with a narrow‐bandgap energy of ≈2.30 eV, while the nitride‐derived–TiOxNy (TN‐TON) exhibits relatively a wide‐bandgap energy (≈2.92 eV) along with the plasmonic band of TiN. In line with this, an enhanced recombination resistance and charge carriers with extended lifetime are observed for TN‐TON (4.47 ns) and TO‐TON (4.33 ns) systems via photoluminescence and time‐resolved photoluminescence analysis. Consequently, the TN‐TON system demonstrates a superior H2/NH3 production at a rate of ≈1432/646 μmol g−1 h−1 under solar irradiation, while it is ≈1136/553 μmol g−1 h−1 for the TO‐TON system. These efficiencies are ≈20× and 3× times higher than the bare TiN and TiO2, respectively, toward H2/NH3 production. The insights from this study demonstrate that the nitride‐ and oxide‐based precursors likely manifest synergistic and competitive properties, respectively, in the resulting oxynitride system.

Mechanical properties and corrosion resistance of porous nickel titanium alloys synthesized in different reactive atmospheres

In the existing studies on the self-propagating high temperature synthesis of titanium nickelide, the main attention has been paid to the study of the influence of heating rate, synthesis start temperature, powder particle size, reaction gas pressure on the structure and properties of NiTi intermetallides. However, the influence of the reactive medium on the formation of surface intermetallic oxynitrides and the properties of the NiTi alloys has not been considered. In the present work, porous titanium nickelide alloys have been obtained by self-propagating high-temperature synthesis in two different reactive atmospheres, argon and nitrogen. The studies show that NiTi-(N) alloys synthesised in the nitrogen reaction atmosphere contain a large amount of brittle secondary Ti2Ni+Ti4Ni2O(N) phases which, in contrast to NiTi-(Ar), are predominantly distributed as small particles. The intergranular Ti2Ni phases in the NiTi-(Ar) alloy synthesised in the argon reaction atmosphere are observed as regions of extensive accumulation of Ti2Ni phase. The reactive nitrogen environment resulted in dispersion of the Ti2Ni phase and lower compressive strength of the porous NiTi-(N) alloy compared to NiTi-(Ar). However, both alloys have a compressive strength greater than human cancellous bone and can be successfully used for intraosseous implantation. At the same time, the porous alloys obtained in different reaction media are passive to electrochemical corrosion and resistant to dissolution in biological media containing chlorine.

Effect of alkali-metal cations on synthesis of stoichiometric layered perovskite oxynitrides

Layered perovskite oxynitrides, which contain a stoichiometric lattice N content, are promising visible-light-driven photocatalysts. However, their synthesis remains a challenge for inorganic chemists. Herein, we report the successful synthesis of layered perovskite oxynitrides A2A'2Ta3O9N with different cations at A/A′-sites (A = Na, K, Rb, Cs; A' = Ca, Sr, Ba) via thermal ammonolysis from layered Dion–Jacobson phase oxide precursors (AA'2Ta3O10). We present the first experimental study of layered oxynitride formation across the A and A′ cation size series, revealing that the A-site alkali-metal cation rather than the A′-site alkaline-earth metal cation is critical to the successful synthesis of the stoichiometric layered oxynitrides. Nitrided products with A = Na, K, or Rb exhibited structural transitions, while no structural transition was observed for Cs. Interestingly, nitrided products with A = Rb and K exhibited the same structural transition behavior, i.e., alkali-metal cations entered the interlayer to form an oxynitride with a composition A2A'2Ta3O9N·nH2O. By contrast, with A = Na, it formed an oxynitride that differs from the Ruddlesden–Popper structure but has the same composition of A2A'2Ta3O9N·nH2O. Our finding suggests that, as the cation size decreases from Cs to Na, stoichiometric A2A'2Ta3O9N compositions become more favorable than compounds with A-sites. This work provides a new perspective for the future design and synthesis of novel layered oxynitrides.

High-temperature wear and oxidation behavior of (CrNbTaMoVW)N high entropy films deposited by reactive magnetron sputtering

Rapid advancements in industrial technology necessitate mechanical parts capable of operating at high temperatures. High entropy alloy films have emerged as promising material for high-temperature resistant coatings, providing improved friction control and wear reduction. In this study, (CrNbTaMoVW)N high-entropy films were fabricated on YG6 cemented carbide substrates using reactive DC magnetron sputtering. The oxidation and tribological performance of the films were investigated across a temperature range from room temperature to 800 °C. Oxidation results revealed that (CrNbTaMoVW)N film maintained its simple Face-Centered Cubic (FCC) structure up to 600 °C for 3 h in the presence of air. At 800 °C, complete oxidation occurred, resulting in the formation of complex metal oxides and metal oxynitrides, and a structural transformation from FCC to these compounds. Following oxidation at 600 °C for 3 h, High-Entropy Alloy (HEA) film exhibited the maximum values of hardness (30.6 GPa) and modulus (301.7 GPa). Tribological results demonstrated an increase in both friction coefficient and wear rate with rising test temperature. However, (CrNbTaMoVW)N film showed a relatively low wear rate ranging from room temperature to 600 °C, approximately 10−15 m3/N•m, thus indicating excellent high-temperature tribological properties. Notably, the wear resistance of (CrNbTaMoVW)N film was significantly compromised at 800 °C due to the formation of loosely bonded metal oxides with reduced hardness, in contrast to the test temperature of 600 °C.

Catalytic activity of γ-Al2O3(110) in the NO + H2 reaction: a DFT study.

In this work, the interaction of the surface of γ-Al2O3(110) with NO and H2 was studied using density functional theory calculations. Free γ-Al2O3(110) adsorbs NO and binds H atoms, but repels the H2 molecule. A triplet of low-coordinated OII-AlIII-OII atoms provides the catalytic activity of γ-Al2O3(110) along the path: (i) the adsorption of NO/AlIII is followed by the binding of H2 to form a hydroxylamine derivative NHOH through an intermediate NO/AlIII + 2 × H/OII complex; (ii) recombination of NHOH with the release of N2 through an intermediate NHOH/AlIII + NHOH/AlIV or adsorption of NO followed by the release of N2O through the intermediate NHOH/AlIII + NO/AlIV; the pathway ends with the regeneration of γ-Al2O3(110). The calculated adsorption heats ensure the diffusion of H atoms from the deposited Pt to the surface (110), initiating the formation of the NH2/AlIII + H/OII complex, which releases NH3 endothermically and is stable enough to inhibit stage (ii) of the above reaction pathway. An excess of O2 in the NO + H2 mixture excludes H/Pt and eliminates inhibition. The formation of oxynitrides is suppressed, but not excluded by more exothermic surface processes. The N-doped conductivity of bulk and surface oxynitrides Al32O47N and the dependence of the heat of adsorption of H atoms on the band gap width were revealed, which suggests a relationship between the band gap width and catalytic activity.

Development of Corrosion Resistant and Electrically Conductive Coatings on Metallic Bipolar Plates for Applications in PEMFC

Proton exchange membrane fuel cell (PEMFC) is considered as one of the most promising alternative energy devices due to its high efficiency, low pollutants emission and possible application in automobiles. However, the application of PEMFC is still hindered by the high cost of some of its components such as bipolar plates (BPP) which are a key component in PEMFC to facilitate electron transfer, gas flow, heat and water removal. To reduce the cost, increase conductivity and durability, metallic bipolar plates, typically made of stainless steel, are normally used but they could suffer from severe corrosion in the acidic environment of PEMFC; the formation of corrosion products on the metal surface could reduce the through-plane electrical conductivity and increase the interfacial contact resistance (ICR) between the bipolar plates and gas diffusion layer, eventually causing high power loss in the fuel cell stack. Therefore, developing corrosion resistant and electrically conductive bipolar plates is of vital importance for the practical applications of PEMFC.Transition nitride coated stainless steel, such as titanium nitride (TiN) coated 316L SS, is considered as a possible solution to improve the performance metallic bipolar plates. In this work, TiN coated 316L SSs with heat treatment at different temperatures were prepared. The corrosion behaviours of the prepared samples were investigated in the simulated working environments of fuel cell. The heat treated samples exhibit the improved corrosion resistance compared with the pristine TiN coated samples and with an increase of the heat treatment temperature, the corrosion resistance tends to increase due to the formation of oxide and oxynitride on the sample surface. The ICR test results indicate that high temperature (450 ℃) heat treatment has detrimental effect on the electrical conductivity of samples due to the formation of a thick oxide dominated layer, while the samples heat treated at 300 ℃ only form the graded layers with suitable oxide amount which endows the coated specimens with a very low ICR value both before and after the corrosion tests.Moreover, TiN coatings with different amounts of Ta addition were also prepared. After the corrosion tests in the H2SO4 solution with pH=3 at 70 ℃, the results reveal that Ti150Ta30N samples exhibit the highest corrosion resistance compared with the pristine TiN coated samples and the samples with different amount of Ta addition. The steady state current density of Ti150Ta30N samples after long term potentiostatic polarization at 0.6 V (vs Ag/AgCl) is 0.02 μA/cm2 which is much lower than that of TiN coated samples. The Ti150Ta30N samples also presents a good electrical conductivity with low ICR values before and after the corrosion tests. These studies suggest that a suitable amount of oxygen or Ta incorporation into TiN is a feasible strategy to improve the corrosion resistance while maintaining considerable electrical conductivity of TiN samples.

Surface modification of titanium alloy via atmospheric pressure nitrogen plasma assisted femtosecond laser irradiation

The effect of atmospheric pressure nitrogen plasma in conjunction with femtosecond laser surface modification of Ti–6Al–4V samples was investigated. It was suggested that the superior friction and wear characteristics of the LP series (the sample subjected to both laser and plasma irradiation) were induced by the synergistic combination of the following three factors: the increased smoothness induced by homogenizing the laser-induced periodic surface groove shape structure, the high hardness caused by grain refinement and the high toughness and low friction properties conferred to the sample by the formation of oxynitride.

Effect of OH species in the oxynitride titanium formation during plasma-assisted thermochemical treatment

Currently, the study of oxynitrides surfaces emerges as one of the most promising ways to obtain improvements in several properties of titanium and expand its applications. In this context, the plasma-assisted thermochemical technique has stood out due to its versatility and easy to control precisely the structure and composition of the compound layer. In this work, titanium samples were subjected to 40%H 2 –60%N 2 and 40%H 2 –45%N 2 –15%O 2 plasma treatment for surface modification where the effect of OH species in the oxynitride formation was investigated. Grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and X-ray induced photoelectron spectroscopy (XPS) were used for structural and chemical composition analyses. Also, optical emission spectroscopy (OES) was used in order to study the plasma chemistry. Results evidenced that the addition of H 2 , which consequently increases the concentration of OH species in the plasma, during the pre-treatment and treatment was important for the cleaning and reduction of native titanium oxides. XPS results showed that the titanium surface, which had 92% Ti O bond before treatment, was totally reduced, giving rise to Ti-N-O (56%) and Ti N (44%) bonds when nitrided. When oxygen was added to the atmosphere, the Ti N bond disappeared, giving rise to the Ti O bond (27%) and Ti-N-O bond (73%). The treatments were suitable for oxynitriding the titanium surface in a predominantly diffusive process with about 290 nm thickness. Material analysis allow us to describe the main mechanisms for oxynitride formation as well as correlate this phenomenology with some investigated plasma properties by OES analysis.

Experimental Investigation on the Sputtering Process for Tantalum Oxynitride Thin Films

Metal oxynitrides are compounds between nitrides and oxides with a certain level of photocatalytic functions. The purpose of this study is to investigate an appropriate range of oxygen flow rate during sputtering for depositing tantalum oxynitride films. The sputtering process was carried out under fixed nitrogen but variable oxygen flow rates. Post rapid thermal annealing was conducted at 800 °C for 5 min to transform the as-deposited amorphous films into crystalline phases. The material characterizations of annealed films include X-ray diffraction and Raman spectroscopy for identifying crystal structures; scanning electron microscope for examining surface morphology; energy-dispersive X-ray spectroscopy to determine surface elemental compositions; four-point probe and Hall effect analysis to evaluate electrical resistivity; UV-visible-NIR spectroscopy for quantifying optical properties and optical bandgaps. To assess the photocatalytic function of oxynitride films, the degradation of methyl orange in de-ionized water was examined under continuous irradiation by a simulated solar light source for six hours. Results indicate that crystalline tantalum oxynitride films can be obtained if the O2 flow rate is chosen to be 0.25–1.5 sccm along with 10 sccm of N2 and 20 sccm of Ar. In particular, films deposited between 0.25 and 1.5 sccm O2 flow have higher efficiency in photodegradation on methyl orange due to a more comprehensive formation of oxynitrides.

Study on the Influence Mechanism of the Deficient Oxygen Fraction and the Formation of Oxysulfide and Oxynitride in Dense Zone of Circulating Fluidized Bed Boiler

Study on the Influence Mechanism of the Deficient Oxygen Fraction and the Formation of Oxysulfide and Oxynitride in Dense Zone of Circulating Fluidized Bed Boiler

Low temperature synthesis of barium oxynitridosilicates using BaCN2 and SiO2.

Barium oxynitridosilicates, Ba3Si6O12N2 and Ba3Si6O9N4, were obtained from a mixture of BaCN2 and SiO2 at 800 °C, which is several hundred degrees lower than the temperature required in solid state reactions using BaCO3, SiO2 and Si3N4. The low-temperature formation mechanism was investigated by thermogravimetry analysis in conjunction with gas chromatography and mass spectroscopy. The phase ratio between the oxynitridosilicates was controlled by tuning the reaction temperature, duration, and atmosphere. Almost single-phase Ba3Si6O12N2 was obtained by reaction at 800 °C for 15 h under a N2 atmosphere, but the product changed to Ba3Si6O9N4 after 50 h at 800 °C or by heating at 950 °C for 15 h. The photoluminescence properties of Eu-doped products obtained at 800 °C using a mixture of BaCN2 : Eu and SiO2 were investigated.

Atomic layer deposition of titanium oxide and nitride on vertically aligned carbon nanotubes for energy dense 3D microsupercapacitors

This work demonstrates the use of ALD coatings in a full-cell 3D microsupercapacitor (MSC) device for the first time. The novel device design described herein has potential to be exploited for rapid and scalable manufacturing of on-chip MSCs integrated with other electronic devices in standard semiconductor fabs or foundries. In this study, atomic layer deposition (ALD) was used to deposit conformal pseudocapacitive coatings of titanium oxide (TiO2) and titanium nitride (TiN) onto CVD-grown vertically aligned carbon nanotubes (VACNTs) to increase the area-specific capacitance (by 240× and 74× at 0.1 Vs−1 versus the as-deposited VACNT electrode and full-cell VACNT device, respectively) and thus energy density for microscale energy storage applications. The study indicated that combining TiO2 and TiN ALD layers resulted in a multilayered composite coating rich in oxygen vacancies with enhanced capacitance relative to a single TiO2 or TiN layer due to a dynamic surface chemistry that developed during charge-discharge cycling. A key component of this multilayered coating was the formation of titanium oxynitride (TiON) which we attributed to the improved performance. Further, we demonstrated that controlling the thickness and stoichiometric ratio of the TiN-TiO2 composite coating was key to enabling functionality and optimizing the symmetric 3D MSC device performance.

Alternating silicon oxy-nitride and silicon oxide stripe formation by nitric oxide (NO+) ion implantation

We report nitric oxide ion (NO+) beam induced nanoscale pattern formation on Si (100) surface. The patterns are found to be structurally as well as chemically periodic. A highly reactive 14 keV NO+ beam is developed in an Electron Cyclotron Resonance ion beam system and implanted on Si (100) surface at oblique angles to form a periodic nano-ripple pattern with specific silicon oxide and silicon oxy-nitride enriched sectors with different dielectric constants. Well-defined ripple patterns start to form at comparatively lower ion fluences due to an additional instability generation by the chemical reaction of NO+ ions with silicon. The chemical shift of the Si 2p peak in the x-ray photoelectron spectroscopy study of an ion irradiated sample confirms the formation of silicon oxide and silicon oxy-nitride, whereas the local chemical nature of the ion induced ripple patterns, probed by electron energy loss spectroscopy, approves spatially resolved silicon oxide and silicon oxy-nitride stripe pattern formation. The ion modified layer thickness measured by cross-sectional transmission electron microscopy has an excellent agreement with Monte Carlo simulations. The optical sensitivity of an NO+ bombarded chemically patterned Si surface is also studied by UV–Visible spectroscopy. Formation mechanisms and potential applications of such nano-scale spatially graded materials are discussed.

Disordered Nonlinear Metalens for Raman Spectral Nanoimaging.

Over the past decades, considerable progress has been made toward far-field optical imaging beyond the diffraction limit. However, most working proof-of-concepts are based on either time-consuming scanning of a subdiffraction focal spot over a sample or postrecovery treatment using a priori information on a sought image. To our knowledge, none of these can be regarded as being close to a perfect far-field superlensing system capable of real-time color imaging with subwavelength resolution. In this paper, we suggest a proof-of-concept for far-field nonlinear metalens that is made of a disordered metal-dielectric nanocomposite. Postoxidation of a refractory titanium nitride (TiN) thin film, used as a nonlinear plasmonic material, results in the formation of a titanium oxynitride (TiON) film comprising a mixture of multiple phases of TiOxNy. Due to a double epsilon-near-zero behavior near the percolation threshold, the TiON favors supercoupling of the incident light to surface plasmon resonance within the visible and near-infrared range. Point spread function narrowing is achieved owing to the multiplicative nature of stimulated Raman scattering (SRS) and enhanced third-order optical nonlinearity in TiN and TiO2 particle chains through plasmon resonances and Anderson localization of light, respectively. Combined with a conventional confocal optical microscope, the multimode metalens shows subwavelength resolution of λ/6NA at different visible wavelengths (SRS overtones) using multiwalled carbon nanotubes as a test sample. We are confident that our finding will bring us one step closer to developing a robust and versatile far-field super-resolution color imaging system and, eventually, implementing "eye-on-a-chip" technology.

High temperature thermoelectric properties of nitrogen doped ITO thin films

Nitrogen doped indium tin oxide (ITO) and platinum thin films were fabricated on alumina substrate by magnetron sputtering and formed thin film thermocouples (TFTCs) with stencil mask. After annealing in N2 or air, the thermoelectric properties of the TFTCs were calibrated for multiple cycles with different calibration atmospheres. The Seebeck coefficient of ITO thin films at high temperature was obtained. The element segregation and oxygen vacancy was stabilized by the formation of oxynitrides in ITO films. And their effects on the Seebeck coefficient of ITO films was discussed.

Surface characterization and formation mechanism of the ceramic TiO2-xNx spherical powder induced by annealing in air

Mechanism for the formation of titanium oxynitride (TiO2-xNx) on the surfaces of spherical Ti powder particles upon heat treatment in air at 500, 600, 700 and 800 °C was investigated. The results showed that the first at 500 °C a hexagonal closed packed (HCP) TiOx film was formed while aTiO2 film was observed after annealing at 600 °C and eventually a TiO2-x-Nx layer coated the spherical Ti particles at 700 and 800 °C due to N diffusion within the TiO2 crystal lattice. The resulting surface structure was studied by means of x-ray diffraction (XRD) while the surface morphology of the powders was characterized using the scanning electron microscope (SEM) attached with energy dispersive x-ray spectroscopy (EDS) detector. The AFM images confirmed that when the N content increases (800 °C-heat treated sample) the powder loses its triangular grains (700 °C-annealed sample) to irregular shaped grains.

Synthesis and properties of thallium nitride films

Abstract Thallium nitride, the last of nitrides in AiiiBv subgroup of nitrides, has been synthesized in a film form by DC reactive sputtering of metal thallium in nitrogen. Transmission electron microscopy (TEM) and electron diffraction investigations of as-deposited films showed that the TlN crystallizes in wurtzite type structure with a = 0.368 ± 0.001 A, c = 0.601 ± 0.002 A and c/a = 1.633 lattice parameters. Studies of optical and electrical properties of as-deposited TlN films allowed to establish that the thallium nitride is highly degenerated direct band semiconductor with Eg = 1.5 eV, ρ = 1.2·10−3 Ω cm resistivity and Hall coefficient, RH ≈ −3.7·10−9 m3·qul−1. TEM investigations of samples spent different time intervals open air revealed that TlN easily oxidizes by its oxidation in accordance with TlN + O2→TlN + Tl2O→TlN + Tl2O + Tl2O3→Tl2O3+Tl2O→Tl2O3 scheme without formation of intermediate oxynitrides. The reason for this effect is that the Tl N bonding is much weaker compared to Tl O bonding. However, TlN films may be conserved without oxidation in neutral environment like vacuum or nitrogen gas. It is supposed that appearance of unusual microstructure and growth mechanism of TlN films on initial growth stages is a result of that the film-forming species are the TlN molecules and molecular clusters rather than atoms. The change of the growth from coagulation to normal coalescence mode, revealed for thick (>100 nm) films, occurs due to increase of the surface temperature during deposition.

Enhanced Photocatalytic Hydrogen Evolution with TiO2–TiN Nanoparticle Composites

Metal nitrides have potential in energy applications because of their physical and optical properties. Nanoparticle composites of titanium nitride (TiN) and titanium dioxide (TiO2) were investigated for their photocatalytic hydrogen (H2) evolution activity via methanol reformation. Physical mixing of the nanoparticulate TiO2 and TiN was employed to prevent the oxy-nitride formation and particle aggregation observed in thermal preparations. This convenient combination of TiO2 and TiN demonstrated a substantial synergistic effect with enhanced activity (9.4 μmol/h TiO2–TiN vs 1.8 μmol/h TiO2) under combined UV/vis light. Irradiation under only UV light resulted in a similar enhancement factor compared to using combined UV/vis light, demonstrating that the enhanced activity of the composites occurs essentially for UV-driven photocatalysis. No activity/enhancement was observed with only visible light irradiation; however, minor enhancement was observed when switching between UV and UV/vis irradiation, suggesting a contribution from the TiN plasmon. We propose that the plasmonic contribution is dependent on the band gap excitation of TiO2, which reduces the degree of band bending at the TiO2/TiN interface. This promotes the migration of hot electrons from TiN away from the TiO2/TiN interface to be used for H2 evolution.