Titanium Nitride Nanorod Research Articles

Reduced Graphene Oxide Decorated Titanium Nitride Nanorod Array Electrodes for Electrochemical Applications

This work describes the fabrication and characterization of a new high surface area nanocomposite electrode containing reduced graphene oxide (rGO) and titanium nitride (TiN) for electrochemical applications. This approach involves electrochemically depositing rGO on a high surface area TiN nanorod array electrode to form a new nanocomposite electrode. The TiN nanorod array was first formed by the glancing angle deposition technique in a DC (Direct Current) sputtering system. GO flakes of ~1.5 μm in diameter, as confirmed by Dynamic Light Scattering (DLS), were electrodeposited on the nanostructured TiN electrode via the application of a fixed potential for one hour. The surface morphology of the as-prepared rGO/TiN electrode was evaluated by scanning electron microscopy (SEM) and the presence of rGO on TiN was confirmed by Raman Microscopy. The CV shows an increase in the capacitive current at rGO/TiN as compared to TiN. The rGO decorated TiN electrode was then used for analyzing the electrocatalytic oxidation of ascorbic acid and dopamine, and the reduction of nitrate by CV and linear sweep voltammetry (LSV), respectively. CV or LSV show that the electrochemical kinetics of these three analytes are significantly faster on rGO/TiN than TiN itself. Overall, the rGO/TiN electrode showed better electrochemical behavior for biomolecules like ascorbic acid and dopamine as well as another target analyte, nitrate ions, compared to TiN by itself.

The photothermal coupling of TiN@Au core-shell nanorods applied to near-infrared photothermal therapy

Thermal plasmonic nanoparticles offer a novel and significant approach for photothermal therapy in the medical field, which is photothermal therapy of cancer. This study introduces a type of core-shell nanorods with internal coupling of titanium nitride (TiN) and gold (Au) nanomaterials. The photothermal properties of these nanorods in the near infrared (NIR) band were investigated using COMSOL Multiphysics software and the finite element method. Results indicate that TiN@Au and Au@TiN core-shell nanorods exhibit superior photothermal properties in the NIR band compared to pure TiN nanorods of similar volume. Furthermore, core-shell nanorods with polarization angles of 0° and 45° demonstrate enhanced optical absorption properties in the near infrared range. Furthermore, the study on the tunability of localized surface plasmon resonance with variations in core diameter, shell thickness, and combined changes of core diameter and shell thickness for core-shell nanorods of equal volume suggests that TiN@Au core-shell nanorods with a 10 nm Au shell offer increased optical absorption efficiency and photothermal conversion capability. Ultimately, the TiN and Au core-shell nanorods proposed in this research offer valuable insights for the structural design and heat transfer control of nanoparticle heat generators to enhance fluid temperature, as well as provide practical guidance for the preparation of core-shell nanoparticles.

Chiro-plasmon responses of x-shaped titanium nitride (TiN) nanoarrays by numerical simulations

Titanium nitride (TiN) has recently been taken as a potential candidate for plasmonic material, which supports surface plasmon resonances and exhibits excellent thermal stability. In this article, we proposed a novel chiral metamaterial with TiN, which consists of X-shaped TiN nanorods periodically arranged on a glass substrate. Its extinction, circular dichroism (CD) spectra, and g-factors were calculated and regulated by the detailed geometry through numerical simulations using the finite element method to further boost the application of TiN in chiro-plasmonic system. We show that it presents chiral responses both in visible and near infrared (NIR) ranges. Under the optimized geometric parameters and NIR incidence, it predicts ∼4 and 2 fold E-field enhancement and g-factor, respectively, than that of experimental reports of TiN nanohelices. The obtained excellent chiro properties are elucidated well in terms of the obtained superchiral field and charge distributions, whose origin was analyzed by a linear superposition method. Moreover, the influence of dielectric environments is discussed as well. Overall, the findings underscore the potential of TiN as a chiro-plasmonic refractory metamaterial and shed light on the design of alternative chiro-plasmon metamaterials for NIR applications in the future.

Analysis of photothermal coupling of titanium nitride nanorods applied to near-infrared photothermal therapy

Titanium nitride (TiN) serves as an ideal reagent for photothermal therapy due to its cost-effectiveness, stability, and biocompatibility. This study investigates the optical and thermal properties of TiN nanoparticles in the near-infrared (NIR) region. Specifically, we employ the COMSOL Multiphysics software to solve Maxwell's equations using a finite element method, enabling us to investigate the photothermal characteristics of individual TiN nanorods. To ensure accurate photothermal coupling calculations, we utilize the Fourier steady-state heat conduction equation. The results demonstrate that the nanorod photothermal properties exhibit significantly enhanced effects when the incident light is polarized along the long axis of the rod, while the thermal properties of the nanorods are primarily influenced by their optical absorption efficiency. The tunability investigation of the nanorods demonstrates that an increase in aspect ratio (AR) results in a red-shift of the absorption peaks. Concurrently, there is an expansion in the bandwidth corresponding to the absorption peak, accompanied by an augmentation in its peak value. It is evident that at AR = 5, the TiN nanorods exhibit enhanced photothermal properties in the NIR region, resulting in a temperature increase of 43 K in the surrounding medium through efficient heat transfer. Consequently, this accomplishment enables achieving the desired temperature range for effective photothermal therapy. The significance of this study lies in providing a valuable reference and theoretical guidance for exploring the utilization of TiN nanorods in photothermal therapy, with a specific focus on attaining a more precise understanding of temperature elevation and distribution during the treatment process.

Titanium nitride nanorod array/carbon cloth as flexible integrated host for highly stable lithium–sulfur batteries

Titanium nitride nanorod array/carbon cloth as flexible integrated host for highly stable lithium–sulfur batteries

Titanium Nitride Nanorods Array-Decorated Graphite Felt as Highly Efficient Negative Electrode for Iron-Chromium Redox Flow Battery.

Iron-chromium redox flow batteries have attracted widespread attention because of their low cost. However, the performance of these batteries is still lower than that of vanadium redox flow batteries due to the poor electrochemical activity of Cr3+ /Cr2+ redox couples on graphite felt electrodes. Herein, binder-free TiN nanorods array-decorated 3D graphite felt composite electrode-is demonstrated. The dendrite-like TiN nanorods array increases the specific surface area of the electrode. The nitrogen and oxygen elements on the surface provide more adsorption sites and electrochemically active sites for Cr3+ /Cr2+ . The contact resistance of the composite electrode is effectively reduced and its homogeneity and stability are improved by avoiding the use of a binder and mixing process. A battery prepared using the TiN nanorods array-decorated 3D graphite felt electrode has enabled the maximum power density to be 427 mW·cm-2 , which is 74.0% higher than a battery assembled with TiN nanoparticles bonded to graphite felt. At a current density of 80 mA·cm-2 , the TiN nanorods battery exhibits the highest coulombic efficiency of 93.0%, voltage efficiency of 90.4%, and energy efficiency of 84.1%. Moreover, the battery efficiency and composite electrode structure remains stable during a redox flow battery cycle test.

Spectroscopic study on alternative plasmonic TiN-NRs film prepared by R-HiPIMS with GLAD technique

In this study, we investigate the structural and optical property of alternative plasmonic titanium nitride nanorods (TiN-NRs) films. The TiN-NRs films were deposited by reactive high-power impulse magnetron sputtering (R-HiPIMS) with glancing angle deposition (GLAD) technique at room temperature. The effect of operating pressure on the film crystalline and morphology have been characterized by grazing-incident X-ray diffraction (GIXRD) and field-emission scanning electron microscope (FE-SEM). The sputtered TiN films contain the nanocolumnar structure with the cubic crystalline structure. The optical property, as well as real and imaginary parts of the dielectric function, were measured by the spectroscopic ellipsometry technique. The atomic concentration and distribution of nitrogen atoms were examined by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. In addition, the TiN-NRs films show the great potential of promising in surface-enhanced fluorescence substrate application.

Preparation of TiN nanorods for SERS substrate by controlling pulse frequency of high power impulse magnetron sputtering

The surface-enhanced Raman scattering (SERS) substrate was fabricated using titanium nitride nanorods structures (TiN NRs) which were prepared by the combination of high-power impulse magnetron sputtering (HiPIMS) and glancing angle depositions (GLAD) techniques. The surface morphology, crystalline structures and chemical composition of TiN NRs were characterized by field-emission scanning electron microscopy (FE-SEM), grazing incidence X-ray diffraction (GIXRD) and X-ray photoelectron spectroscopy, (XPS) respectively. Additionally, a portable Raman spectroscopy at 532 nm was used to inspect the performance of Raman signal enhancement. The cubic phase of TiN NRs was shown on (111), (200) and (220) planes. The efficiency of the generated Raman signal of Rhodamine 6 G be measured at a detection limit of 10–6 M with a long shelf-life of TiN NR SERS of more than 28 days. According to the experimental results, TiN NRs are a promising candidate for SERS substrates fabricated cost effectively.

Capacitive heavy metal ion removal of 3D self-supported nitrogen-doped carbon-encapsulated titanium nitride nanorods via the synergy of faradic-reaction and electro-adsorption

Recently, the highly efficient, low-cost and environment-friendly capacitive deionization (CDI) hold great promise in the field of wastewater purification. In this paper, we report an N-doped carbon nanolayer (N-C) encapsulated ultrafine titanium nitride (TiN) nanorod-assembled flower-like framework anchored on the carbon cloth (CC) matrix (N-C@TiN@CC) as the self-supported electrode for robust CDI-based heavy metal ion wastewater purification. Benefitting from the synergistic effects of specific structure features (i.e., high porosity, 3D open framework and hierarchical pore arrangement), surface doping strategy of high-conductivity carbon nanolayer and integrated electrode processing, the resultant N-C@TiN@CC hybrid electrode proves superior deionization performance and excellent cycling stability, yielding an outstanding average removal efficiency up to ca. 98 % in the simulated high-concentration single, binary and multi-component wastewater systems. Moreover, it is further revealed the effective electro-adsorption and faradic reaction coupling ion removal process in the deionization system, which may account for the significant removal efficiency promotion of N-C@TiN@CC hybrid electrode.

Boosting Nitrogen Reduction Reaction via Electronic Coupling of Atomically Dispersed Bismuth with Titanium Nitride Nanorods.

Electrocatalytic nitrogen reduction reaction (NRR) is a promising alternative to the traditional Haber–Bosch process. However, the sluggish kinetics and competitive hydrogen evolution reaction result in poor NH3 yield and low Faradaic efficiency (FE). Herein, single bismuth atoms incorporated hollow titanium nitride nanorods encapsulated in nitrogen‐doped carbon layer (NC) supported on carbon cloth (NC/Bi SAs/TiN/CC) is constructed for electrocatalytic NRR. Impressively, as an integrated electrode, it exhibits a superior ammonia yield rate of 76.15 µg mgcat −1 h−1 (9859 µg μmolBi −1 h−1) at −0.8 V versus RHE and a high FE of 24.60% at −0.5 V versus RHE in 0.1 m Na2SO4 solution, which can retain stable performance in 10 h continuous operation, surpassing the overwhelming majority of reported Bi‐based NRR catalysts. Coupling various characterizations with theory calculations, it is disclosed that the unique monolithic core‐shell configuration with porous structure endows abundant accessible active sites, outstanding charge‐transfer property, and good stability, while the cooperation effect of Bi SAs and TiN can simultaneously promote the hydrogenation of N2 into NH3* on the TiN surface and the desorption of NH3 * to release NH3 on the Bi SA sites. These features result in the significant promotion of NRR performance.

Ruthenium single atoms implanted continuous MoS2-Mo2C heterostructure for high-performance and stable water splitting

Merging metal single atoms into a nanostructure is a novel approach to motivate the number and types of active centers for boosting catalytic activities towards both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Herein, we reported a continuous molybdenum sulfide-carbide heterostructure-based nanosheets incorporated with ruthenium atoms (2.02 at%) and shelled over high-conductive 1D titanium nitride nanorod arrays (Ru-MoS 2 -Mo 2 C/TiN) to form a 3D hierarchical porous material via an effective synthesis strategy. The material with fine-tuned electronic structure and multi-integrated active sites exhibited small overpotentials of 25 and 280 mV at 10 mA cm −2 for HER and OER in 1.0 M KOH medium, respectively. An electrolyzer delivered from Ru-MoS 2 -Mo 2 C/TiN required an operating voltage of only 1.49 V at 10 mA cm −2 , surpassing that of a commercial catalyst-based system as well as earlier reports. The good performance was identified by its enlarged electroactive surface area and superior charge-transfer ability. In addition, theoretical calculations further showed its reasonable density of states near the Fermi level together with optimum adsorption free energy for reactants. The result indicated that the Ru-MoS 2 -Mo 2 C/TiN on CC is an excellent bifunctional electrocatalyst for hydrogen production by electrochemical water splitting. • A continuous Ru-doped MoS 2 -Mo 2 C heterostructure shelling over 1D TiN is synthesized. • Ru-MoS 2 -Mo 2 C/TiN demonstrates good catalytic activity for both HER and OER. • Ru-MoS 2 -Mo 2 C/TiN-based electrolyzer requires a cell voltage of 1.49 V at 10 mA cm −2 . • DFT calculation suggests the optimum DOS and free energies of Ru-MoS 2 -Mo 2 C for water electrolysis.

Deposited ultra-thin titanium nitride nanorod array as a plasmonic near-perfect light absorber

The transmittance, reflectance, and extinctance that correspond to the localized plasmonic resonance within TiN nanorods were investigated. The obliquely deposited TiN nanorod array shows polarization-independent admittance matching to air. Unlike noble metal nanorods, the near-field localized longitudinal and transverse plasmonic resonance of TiN nanorod arrays present polarization-dependent light extinction in the far field. The longitudinal plasmonic mode presents stronger extinction than transverse plasmonic mode. In order to have high efficient light absorption, an ultra-thin two-layered TiN nanorod array was fabricated with orthogonal deposition planes for upper layer and bottom layer to absorb different polarized light energy. The measured spectrum shows broadband and wide-angle light extinction.

Tunable Plasmonic Resonances in TiN Nanorod Arrays

In this work, titanium nitride (TiN) nanorod arrays were fabricated using glancing angle deposition in a magnetron sputtering system. The deposition parameters, including the bias on the substrate and the flow rate of nitrogen, were varied to deposit various TiN nanorod arrays. Before glancing angle deposition was conducted, uniform TiN films were deposited and their permittivity spectra, for various deposition parameters, were obtained. The effect of the deposition parameters on the morphology of the nanorods is analyzed here. The polarization-dependent extinctance spectra of TiN nanorod arrays were measured and compared. Extinction, which corresponds to the longitudinal mode of localized surface plasmon resonance, can be significantly changed by tuning the N2 flow rate and substrate bias voltage during deposition.

TiN Nanorods as Effective Substrate for Surface-Enhanced Raman Scattering

Owing to its well-known chemical stability, thermal stability, and complementary metal-oxide-semiconductor process compatibility, titanium nitride (TiN) has recently been demonstrated as an excelle...

Obliquely Deposited Titanium Nitride Nanorod Arrays as Surface-Enhanced Raman Scattering Substrates.

In this work, titanium nitride (TiN) nanorod arrays were prepared as surface-enhanced Raman scattering (SERS) substrates using glancing angle deposition (GLAD) in a magnetron sputtering system. The nitrogen flow rate was varied from RN2 = 1 to 3 sccm, yielding five TiN uniform thin films and five TiN nanorod arrays. The figure of merit (FOM) of each TiN uniform film was measured and compared with the SERS signal of each TiN nanorod array. Rhodamine 6G (R6G) was used as the analyte in SERS measurement. For an R6G concentration of 10−6 M, the analytical enhancement factor (AEF) of the TiN nanorod array that was prepared at RN2 = 1.5 sccm was 104. The time-durable SERS performance of TiN nanorod arrays was also investigated.

Gold-Nanoparticle-Decorated Titanium Nitride Electrodes Prepared by Glancing-Angle Deposition for Sensing Applications

Titanium nitride (TiN) and gold (Au)-decorated TiN nanorod array electrodes were fabricated on Au substrates using glancing-angle deposition (GLAD), and the electrochemical properties of these materials were investigated in potassium chloride and buffered solutions containing potassium ferricyanide, ascorbic acid, uric acid, and dopamine. Cross-sectional scanning electron microscopy images depict an array of vertical nanocolumns that are ∼30 nm in width and ∼300 nm in height with sharp pointed apexes. The atomic percent ratio of N to Ti is 40:60, as revealed by X-ray photoelectron spectroscopy. Decoration of the GLAD-produced TiN nanorods with Au nanoparticles reduces the width between nanocolumns from ∼23 to ∼15 nm and improves the electroactivity of the electrodes. The capacitive current in potassium chloride increases by a factor of 2, and the electron-transfer rate of potassium ferricyanide increased by 4. The addition of Au nanoparticles to the TiN nanorod support also significantly improves the elec...

Extinction Properties of Obliquely Deposited TiN Nanorod Arrays

Plasmonic titanium nitride (TiN) nanorod arrays (NRA) were fabricated by glancing angle deposition in a DC magnetron reactive sputtering system. The morphology of the TiN NRA was varied by collimating the vapor flux. The transmittance, reflectance, and extinctance of slanted TiN nanorods with different lengths as functions of wavelength and angle of incidence were measured and analyzed. The extinction peaks in the spectra reveal the transverse and longitudinal plasmonic modes of TiN NRA upon excitation by s-polarized and p-polarized light, respectively. The near-field simulation was performed to elucidate localized field enhancements that correspond to high extinction. The extension of the high extinction band with an increasing length of the nanorods results in broadband and wide-angle light extinction for a TiN NRA with a thickness greater than 426 nm.

Quasi-atomic-scale platinum anchored on porous titanium nitride nanorod arrays for highly efficient hydrogen evolution

Highly efficient electrocatalytic hydrogen evolution reaction (HER) is achieved by constructing uniformly dispersed quasi-atomic-scale Pt on porous conductive titanium nitride nanorod arrays (PtTiN NAs). The PtTiN NAs demonstrate high HER efficiencies both in acid (0.5 M H2SO4) and alkaline media (1 M KOH) with the overpotentials of 39.7 mV and 139 mV at the current density of 10 mA cm−2, respectively, which is comparable to that of commercial 20 wt % Pt/C under the same experimental condition. In addition, the Tafel slopes of PtTiN NAs (38.6 mV dec−1 in acid and 98.3 mV dec−1 in alkaline media) are much lower than that of commercial Pt/C. More remarkably, the PtTiN NAs display a much higher current retention of 91.6% after continuous test for 60 h in 0.5 M H2SO4 comparing to 46.9% of Pt/C after 30 h cycling. The excellent HER performance of as-prepared PtTiN NAs are attributed to the abundant available reaction sites from the uniformly distributed quasi-atomic-scale Pt, the suppressed aggregation of Pt by the strong metal-substrate interaction between Pt and TiN, and the superior electron transfer caused by high electric conductivity TiN substrate. Our designed structure provides an ideal catalytic system for efficient HER, which may inspire the design and synthesis of other high efficiency electrocatalytic systems.

Inside Back Cover: Vertically Aligned Titanium Nitride Nanorod Arrays as Supports of Platinum–Palladium–Cobalt Catalysts for Thin‐Film Proton Exchange Membrane Fuel Cell Electrodes (ChemElectroChem 5/2016)

Inside Back Cover: Vertically Aligned Titanium Nitride Nanorod Arrays as Supports of Platinum–Palladium–Cobalt Catalysts for Thin‐Film Proton Exchange Membrane Fuel Cell Electrodes (ChemElectroChem 5/2016)

Vertically Aligned Titanium Nitride Nanorod Arrays as Supports of Platinum–Palladium–Cobalt Catalysts for Thin‐Film Proton Exchange Membrane Fuel Cell Electrodes

AbstractThe degradation of the carbon supports and high platinum (Pt) loading significantly hinder the wide adoption of proton exchange membrane fuel cells. In conventional electrodes, the ionomer binders introduce an undesirable, high oxygen‐transport resistance and cover the catalysts active sites. Herein, an advanced catalytic layer based on vertically aligned titanium nitride nanorod arrays (TiN NRs) is prepared, without additional ionomer or binders in the cathode. After supporting the thin‐film platinum–palladium–cobalt (PtPdCo) catalyst (Pt loading: 66.9 μm cm−2) onto TiN NRs, the ordered electrodes were investigated as the cathode of a single cell without additional ionomer in the catalytic layer. With this electrode architecture, the as‐synthesized electrode performs with a maximum power density of 390.5 mW cm−2 and cathode mass‐specific power density of 5.84 W mgPt−1. The 2000 potential cycles accelerated degradation test shows that the PtPdCo–TiN electrode is more stable than the commercial gas diffusion electrode.