Effective TiO2 supported Cu-Complex catalyst in NaBH4 hydrolysis reaction to hydrogen generation

This paper reports the experimental results on using TiO₂ based Cu(II)-Schiff Base complex catalyst for hydrolysis of NaBH₄. In the presence of Cu-Schiff Base complex which we reported in advance [1] and with titanium dioxide supports a novel catalyst named TiO₂ supported 4-4′-Methylenbis (2,6-diethyl)aniline-3,5-di-tert-buthylsalisylaldimine-Cu complex is prepared, successfully. The synthesized catalyst was characterized by means of X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Brunauer-Emmett-Teller Surface Area Analysis (BET) and Fourier Transform Infrared Spectroscopy (FT-IR). The as prepared catalyst was employed to generate hydrogen through hydrolysis reaction of NaBH₄. Effects of different parameters (e.g. amount of Cu-Schiff Base complex in all catalyst, percentage of NaBH₄, percentage of NaOH, amount of TiO₂ supported Cu-Schiff Base complex catalyst and different temperatures) are also investigated. A high apparent activation energy (Ea), 25,196 kJ.mol^-1 is calculated for hydrolysis of NaBH₄ at 20–50 °C. Hydrogen generation rate was 14,020 mL H₂/g_cat.min and 22,071 mL H₂/g_cat.min in order of 30 °C and 50 °C.     

Steam reforming of n-dodecane over mesoporous alumina supported nickel catalysts: Effects of metal-support interaction on nickel catalysts

Developing a highly active and stable Ni-based catalyst is still a challenge for the generation of on-site hydrogen through steam reforming of long-chained hydrocarbons, such as kerosene fuels. Ni nanoparticles (ca. 5 nm) on mesoporous alumina prepared by atomic layer deposition (ALD) were employed in steam reforming of n-dodecane, and exhibited a turnover frequency (TOF) of 477.6 h⁻¹, whereas Ni nanoparticles on commercial alumina support prepared by impregnation method exhibited a TOF of 100 h⁻¹. The high activity of ALD Ni catalysts was ascribed to high reduction degree, as confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM), and H₂-chemisorption. A deactivation was also observed on the ALD prepared catalysts, which was ascribed to the weak metal-support interaction, as confirmed by H₂ temperature-programmed reduction (TPR). The ALD Ni/Al₂O₃ catalysts were further modified with CeO₂ and they showed enhanced stability with 8% deactivation degree in steam reforming of n-dodecane. Further characterizations of spent catalysts showed that the presence of CeO₂ was favorable for stabilizing Ni nanoparticles by enhancing moderate metal-support interaction, and reducing the formation of coke on the interfaces of NiCeO₂.     

Macaroon-like FeCo2O4 modified activated carbon anode for enhancing power generation in direct glucose fuel cell

Macaroon-like FeCo₂O₄ nanomaterial was prepared and used as electrocatalyst in direct glucose alkaline fuel cell (DGAFC), which exhibited high catalytic activity towards glucose oxidation reaction. Maximum power density of 35.91 W m⁻² was achieved in the DGAFC equipped with a FeCo₂O₄ modified activated carbon (AC) anode, which was almost 151% higher than the control. Physical and electrochemical characterizations were performed to provide further understanding of the origin of its high activity. Our results show that the introduction of FeCo₂O₄ into the AC anode remarkably increase the exchange current density and reduce the charge transfer resistance. It is supposed that there is a synergistic effect between Fe (III) and Co (III), which accelerates electron transfer from glucose to external circuits. This study will promote the development of cost effective and environmentally benign catalysts for electrochemical energy applications.     

Study of the crystal structure effect and mechanism during chemical looping gasification of coal

Chemical looping gasification (CLG) of coal, in which oxygen is provided to coal by oxygen carriers directly, is a clean and efficient way to generate syngas. Thermo-gravimetric analysis (TGA) of lignite char with oxygen carriers was conducted in this work, and the experimental results indicated that the oxygen carriers, Ti_0·5Mn_0·5Fe₂O₄, MnFe₂O₄, FeTiO₃ and Fe₂TiO₄, had a positive effect on CLG of lignite char. The effect of these oxygen carriers was discussed in the perspective of the crystal structure. XPS experiment was performed and the spectra of O 1s revealed the effect of different element on reactivity of spinel-based oxygen carriers. Five kinetic models, including Uniform Reaction (UR), Integrated Model (IM), Modified Random Pore Model (MRPM), Random Pore Model (RPM) and Modified Volumetric Model (MVM), were employed for revealing the reaction mechanism. MRPM had the highest correlation coefficient for each oxygen carrier, which means the introduction of the oxygen carriers effectively increases the active site of the reaction surface.     

Facile synthesis of IrO2 nanoparticles decorated @ WO3 as mixed oxide composite for outperformed oxygen evolution reaction

Oxygen evolution reaction (OER) electrocatalysts play the critical role in efficiency and durability for different hydrogen production systems. We have successfully synthesized the earth abundant WO₃ coupled with IrO₂ as mixed oxide composite by a facile two-step chemical method. 50% reduction in noble metal contents (IW-50) followed by two times enhancement in activity, four-folds increase in bulk mass specific activity along with the stability of mixed oxide composite as compared to state –of –the art IrO₂ catalyst are affirmed. Superior performance of mixed oxide composites are perceived due to four times increase in electrochemical surface area, reduction of Tafel slope, four-fold increase of turn over frequency, electronic distortion in Ir-4f spectrum of IW-50 along with the bridging of lattice oxygen atoms between iridium and tungsten metals. We believe that it would open up the new avenues for effective utilization of noble metal with high valence tungsten metal in corrosive environment.     

In-situ hydrogen-induced evolution and de-/hydrogenation behaviors of the Mg93Cu7-xYx alloys with equalized LPSO and eutectic structure

Nanosizing is efficient as the dual-tuning of thermodynamics and kinetics for Mg-based hydrogen storage materials. The in-situ synthesis of nanocomposites through hydrogen-induced decomposition from long-period stacking ordered phase is proved effective to achieve active nano-sized catalysts with uniform dispersion. In this study, the Mg₉₃Cu_7-xY_x (x = 0.67, 1.33, and 2) alloys with equalized Mg–Mg₂Cu eutectic and 14H long-period stacking ordered phase of Mg₉₂Cu_3.5Y_4.5 are prepared. Its solidification path is determined as α-Mg, 14H–Mg₂Cu pair and Mg–Mg₂Cu eutectic. The increased Y/Cu atomic ratio lowers the first-cycle hydrogenation rate of the alloys due to the increased 14H–Mg₂Cu structure and reduced Mg–Mg₂Cu eutectic interfaces. After the hydrogen-induced decomposition of the long-period stacking ordered phase, MgCu₂ and YH₃ nanoparticles are in-situ formed, and the following activation process significantly accelerates. The YH₃ nanoparticles partly decompose to YH₂ at 300 °C in vacuum and Mg–Mg₂Cu-YH_x nanocomposites are in-situ formed. The nano-sized YH₂ helps catalyze H₂ dissociation and the YH_x/Mg interfaces stimulate H diffusion and the nucleation of MgH₂. Therefore, the Mg₉₃Cu₅Y₂ composite shows the fastest absorption rates. However, due to the positive effect of YH_x/Mg interfaces on H diffusion and the negative effect of YH₃ nanophases on the hydride decomposition, the minimum activation energy of 115.43 kJ mol⁻¹ is obtained for the desorption of the Mg₉₃Cu_5.67Y_1.33 hydride.     

Sequential hydrothermal synthesized Co–Mn-oxide/C electrocatalysts for oxygen reduction in alkaline media

In order to design and synthesize oxygen reduction reaction catalysts with high activity and low cost, a series of Co–Mn-oxide/C catalysts with different Co:Mn ratios have been prepared using a hydrothermal method applied in sequential steps. The monotonically systematic trends of the catalysts’ phases, morphologies and particle sizes have been verified, and the trending of Mn ions and Co ions in different valence states follows the increasing Co:Mn ratio. Electrochemical performance of the catalysts in oxygen reduction reaction results in a volcano-type trend with an optimal Co:Mn ratio of 3 giving the best performance, which is comparable to that of commercial Pt/C. Lastly, a Koutecky-Levich approach has been employed to deduce the electron transfer values, in an attempt to rationalize their selectivity towards the varying 2 and 4 electron pathways. The systematic research is significant for understanding and designing a new generation of non-noble metal oxygen reduction reaction catalysts.     

Hydrogen uptake of manganese oxide-multiwalled carbon nanotube composites

Hydrogen uptake of pristine multi-walled carbon nanotubes is increased more than three-fold at 298 K and hydrogen pressure of 4.0 MPa, upon addition of hydrogen spillover catalyst manganese oxide, from 0.26 to 0.94 wt%. Simple and convenient in situ reduction method is used to prepare Mn-oxide/MWCNTs composite. XRD, FESEM, and TEM demonstrates nanostructural characterization of pristine MWCNTs and composite. TGA analysis of Mn-oxide/MWCNTs composites showed a single monotonous fall related to MWCNTs gasification. Enhancement of hydrogen storage capacity of composite is attributed to spillover mechanism owing to decoration of Mn-oxide nanoparticles on outer surface of MWCNTs. Hydrogen uptake follows monotonous dependence on hydrogen pressure. Oxide-MWCNTs composite not only shows high hydrogen storage capacity as compared to pristine, but also exhibit significant cyclic stability upon successive adsorption–desorption cycles.     

Hydrogen production via CO2 dry reforming of glycerol over ReNi/CaO catalysts

The present work investigates the performance of Re-promoted Nickel-based catalyst supported on calcium oxide for glycerol dry reforming reaction. The catalysts were prepared using wet impregnation method and their catalytic performance was tested in a packed bed reactor with CO₂ to glycerol ratio (CGR) of 1–5, reaction temperature of 600–900 °C and gas hourly specific velocity (GHSV) of 1.44 × 10⁴–7.20 × 10⁴ ml g_cat⁻¹ s⁻¹. The optimum operating temperature for both Ni/CaO and ReNi/CaO is 800 °C, with the GHSV of 3.6 × 10⁴ mL g_cat⁻¹s⁻¹. The optimum CGR for Ni/CaO and ReNi/CaO is 1.0 and 3.0, respectively. At this condition, hydrogen gas is directly produced from glycerol decomposition and indirectly from water-gas-shift reaction. After 2 h at the optimum conditions, 5% ReNi/CaO gives optimal glycerol conversion and hydrogen yield of approximately 61% and 56%, respectively, while in comparison to 15% Ni/CaO, the conversion and yield are 35 and 30%, respectively. Characterization of the spent catalysts showed the existence of whisker carbon from the CO₂ hydrogenation and methanation processes. By comparing to 15% Ni/CaO, the addition of Re increases the acidic sites of the catalyst and enhanced the surface adsorption of OH group of the glycerol. The adsorbed glycerol on the catalyst surface would further react with the adsorbed CO₂ to yield gases products. Thus, the catalytic activity improved significantly.     

Three-dimensional ordered microporous silica supported p-lanthanum ferrite and n-ceria as heterojunction photocatalyst to activate peroxymonosulfate for bisphenol a degradation

In this study, three-dimensional ordered microporous silica supported p-lanthanum ferrite and n-ceria (n-CeO₂@p-LaFeO₃/3DOM SiO₂) was successfully synthesized as a visible light-driven photocatalyst for activating peroxymonosulfate (PMS) to degrade Bisphenol A (BPA). In a wide pH range (2–12), the BPA degradation efficiency maintained at a high level, organic matter and natural inorganic ions had no significant negative impact. When the BPA concentration was as low as 2 mg·L⁻¹, the removal rate in 60 min still reached 95.56%, indicating that the novel photocatalyst has potential application in the treatment of trace pollutants. The pore confinement effects of catalysts and the synergistic effect between LaFeO₃ and CeO₂ result in the excellent photocatalytic performance. We proposed the possible mechanism of BPA degradation, specifically involving the recognition and generation mechanism of reactive oxygen species (ROSs), adsorption processes and diffusion processes. In summary, the novel n-CeO₂@p-LaFeO₃/3DOM SiO₂ would be a promising candidate photocatalytic material for practical sewage treatment.