Thermal and photon effects on the reaction of H2 and O2 to water over Ag–Pd/TiO2

The reaction of H₂ and O₂ to water are studied over a Ag–Pd/TiO₂ anatase catalyst, under dark and photo-irradiation conditions in the gas and liquid phases. The catalyst consisted of metal particles of mean size of ca.1 nm dispersed over 10–15 nm TiO₂ particles. Kinetic parameters including order of reaction (n), rate constant (k), and activation energy (E_a), were evaluated. E_a for the thermal reaction was found to be 49-47 kJ mol^?1. The oxidation reaction rate constant was found to be ca. 3 times higher in the presence of photons when compared to dark reaction at room temperature. The overall quantum yield of the reaction in the slurry phase was found to be 0.09. Considering the number of metal particles on TiO₂, the photon yield per metal particle was found to be 0.16. A possible explanation of the changes in kinetics with respect to experimental conditions is given.     

An infinite chain, {[Ni(tn)2]3[Fe(CN)4(μ-CN)2]2}n,a new catalyst for electrochemical-driven water splitting and photochemical-driven hydrogen evolution from water under blue light

A new catalyst for both water reduction and oxidation, based on an infinite chain, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n, is formed by the reaction of NiCl₂, 1,3-propanediamine (tn) and K₃ [Fe(CN)₆]. {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can electro-catalyze hydrogen evolution from a neutral aqueous buffer (pH 7.0) with a turnover frequency (TOF) of 1561 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) at an overpotential (OP) of 837 mV {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n also can electro-catalyze O₂ production from water with a TOF of ～45 mol O₂ (mol cat)^?1s^?1 at an OP of 591 mV. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H₂A) as a sacrificial electron donor, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can photo-catalyze hydrogen generation from an aqueous buffer (pH 4.0) with a turnover number (TON) of 11,450 mol H₂ per mole of catalyst (mol of H₂ (mol of cat)^?1) during 10 h irradiation. The average of apparent quantum yield (AQY) is as high as 40.96% during 10 h irradiation. Studies indicate that {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n exists in two forms: a cyano-bridged chain ({[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n) in solid, and a salt ([Ni(tn)₂]₃ [Fe(CN)₆]₂) in aqueous media; Catalytic reaction occurs on the nickel center of [Ni(tn)₂]²⁺, and the introduction of [Fe(CN)₆]^3- can improve the catalytic efficiency of [Ni(tn)₂]²⁺ for H₂ or O₂ generation. We hope these findings can afford a new method for the design of catalysts for both water reduction and oxidation.     

Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Increased hydroxyl concentration by tungsten oxide modified h-BN promoted catalytic performance in partial oxidation of methane

Hexagonal boron nitride (h-BN) as a layered inorganic nonmetallic material has been widely used. Hydrogen peroxide (H₂O₂) modification can trigger exfoliation and afford abundant B–OH active sites at edge of h-BN, which can enhance methane activation ability. Introducing tungsten oxide (WO₃) to h-BN produces a similar effect, because doping WO₃ into h-BN resulted in electron transfer to N, inducing fracture of B–N bond, resulting in N vacancy (triboron center), exposing more B sites and promoting the generation of B–OH. Significantly, the introduction of WO₃ on the modified h-BN dramatically increased the concentration of B–OH compared with the unmodified h-BN, because H₂O₂ modification weakened B–N bond. By means of XRD, TEM, XPS,EPR, FT-IR, it is proved that the high concentration of B–OH active sites contributed to activating C–H bond, thus methane conversion and CO and H₂ selectivity were significantly improved.     

A dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanopaticles showing significant electrocatalytic activity towards ethanol oxidation reaction (EOR)

To the best of our knowledge, this is the first time to report the preparation of a dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as Pd_xNi_y NPs) via a hydrothermal method using NU and PdO·H₂O as the starting materials. The samples prepared at the mass ratio of NU to PdO·H₂O 1:1, 1:2 and 2:1 were, respectively, nominated as catalyst c₁, c₂ and c₃. The chemical compositions of all synthesized catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c₁. More importantly, when being used as electrocatalysts for EOR, all prepared catalysts exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV) test, the peak current density of the forward peak of EOR on catalyst c₁ measured at 50 mV s^?1 was as high as 56.1 mA cm^?2, being almost 9 times higher than that of EOR on catalyst c₃ (6.3 mA cm^?2). Particularly, the polarized current density of EOR on catalyst c₁ at 3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be around 1.47 mA cm^?2, a value higher than the latest reported data of 1.3 mA cm^?2 (measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted nanowires arranged by 5 nm sized nanoparticles and showing the significant eletrocatalytic activities of the newly prepared dotted nanowires towards EOR were the major contributions of this preliminary work.     

Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia

Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH₃) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi⁰/Bi³⁺ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900  ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH₃ yield rate and remarkable Faradaic efficiency of 15.10  ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis.     

High-temperature oxidation behavior of monolithic Zr3[Al(Si)]4C6 and its composite incorporating 30vol% ZrB2-SiC: Providing a basis for broadening the service temperature

To provide a basis for the high-temperature oxidation of ultra-high temperature ceramics (UHTCs), the oxidation behavior of Zr₃[Al(Si)]₄C₆ and a novel Zr₃[Al(Si)]₄C₆-ZrB₂-SiC composite at 1500 °C were investigated for the first time. From the calculation results, the oxidation kinetics of the two specimens follow the oxidation dynamic parabolic law. Zr₃[Al(Si)]₄C₆ exhibited a thinner oxide scale and lower oxidation rate than those of the composite under the same conditions. The oxide scale of Zr₃[Al(Si)]₄C₆ exhibited a two-layer structure, while that of the composite exhibited a three-layer structure. Owing to the volatilization of B₂O₃ and the active oxidation of SiC, a porous oxide layer formed in the oxide scale of the composite, resulting in the degradation of its oxidation performance. Furthermore, the cracks and defects in the oxide scale of the composite indicate that the reliability of the oxide scale was poor. The results support the service temperature of the obtained ceramics.     

Unipolar plasma electrolytic oxidation: Waveform optimisation for corrosion resistance of commercially pure titanium

This study deals with the anodisation of titanium grade 2 in 0.5-M sulphuric acid using a pulsed signal in a unipolar regime. The electrical parameters investigated are voltage, frequency and duty cycle. The use of duty cycles with a high percentage of anodic polarisation (90%), combined with high frequencies (1000 Hz) and the higher voltage tested (220 V), favoured the establishment of a plasma regime involving strong dielectric discharges, allowing the growth of thicker oxides but with rough architecture. The corrosion resistance of the formed film has been characterised by potentiodynamic tests in 0.5-M NaBr for localised corrosion resistance and by immersion tests in 10% v/v sulphuric acid solution for a uniform corrosion assessment. Current–time curves, visual observations and electron microscope analysis (scanning electron microscopy, energy-dispersive X-ray spectroscopy) were the tools selected to provide a correlation between technological parameters and oxide growth mechanism. For localised and uniform corrosion, anodisation at 220 V with a high level of anodic polarisation (90%) and frequency (1000 Hz) was verified to be particularly advantageous.     

Structure,mechanical and thermal properties of Y-doped CrAlN coatings

CrAlYN coatings with different Y contents (0, 5 and 12 at.%) were deposited by cathodic arc evaporation to investigate the influence of Y-addition on the structure, mechanical and thermal properties of CrAlN coatings by using X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermal gravimetric analysis and nanoindentation. The structural transformation of single phase cubic Cr_0.42Al_0.58N and Cr_0.39Al_0.56Y_0.05N coatings to cubic–wurtzite mixed Cr_0.32Al_0.56Y_0.12N coating leads to a drop in hardness from (30.2±0.7) GPa of Cr_0.42Al_0.58N and (32.0±1.0) GPa of Cr_0.39Al_0.56Y_0.05N to (25.2±0.7) GPa of Cr_0.32Al_0.56Y_0.12N. The incorporation of 5 at.% Y retards the thermal decomposition of CrAlN, verified by the postponed precipitation of w-AlN and N-loss upon annealing. Correspondingly, Cr_0.39Al_0.56Y_0.05N coating consistently exhibits the highest hardness value during thermal annealing. Nevertheless, alloying with Y exerts an adverse effect on the oxidation resistance of CrAlN.     

Mesoporous SmMnO3/CuMnOx catalyst for photothermal synergistic degradation of gaseous toluene

Mesoporous SmMnO₃/CuMnO_x catalyst was prepared by a two-step method using flaky CuMnO_x with high specific surface and excellent catalytic ability as the carrier, which was further applied to photothermal synergistic degradation of gaseous toluene. Quantitative analysis of O₂-TPD and H₂-TPR showed that SmMnO₃/CuMnO_x exhibited abundant of the surface oxygen species and oxygen vacancies content, which enabled it to convert free oxygen to lattice oxygen more quickly during the reaction, and thus improving the reaction process. I-t and photoluminescence experiments demonstrated the improvement of photogenerated electron and hole separation ability of SmMnO₃/CuMnO_x catalyst. UV–Vis analysis manifested the full spectral range of absorption. XPS analysis verified the unequal positions of valence band of the two materials, which can facilitate the separation of photogenerated electrons from holes and improve the ability of better electron transfer. SmMnO₃/CuMnO_x catalyst has higher adsorbed oxygen content and light absorption capacity, which is beneficial to the catalytic oxidation. In situ DRIFTs proved that the oxidation reaction on the catalyst followed the Mars-van Krevelen redox cycle. The VOCs test found that SmMnO₃/CuMnOx composite catalyst is with lower onset reaction temperature (T₉₀ = 190 °C, T₉₀, corresponding to 90% conversion) and good mineralization (100% at 275 °C).