Titanium compounds TiC–C and TiO2–C supported Pd catalysts for formic acid electrooxidation

In this work, Pd nanoparticles supported on TiC–C and TiO₂–C as novel and efficient supports for formic acid electrooxidation are investigated. The Pd/TiC–C and Pd/TiO₂–C catalysts have been synthesized by microwave-assisted polyol process. The Pd nanoparticles in the Pd/TiC–C and Pd/TiO₂–C catalysts are found to disperse more uniformly and have smaller sizes on the TiC–C and TiO₂–C supports than that on carbon support alone. The addition of titanium compounds (TiC and TiO₂) significantly increases catalytic activity and stability of Pd for formic acid electrooxidation because of outstanding oxidation and acid corrosion resistance of titanium compounds (TiC and TiO₂), and metal-support interaction between Pd nanoparticles and titanium compound (TiC or TiO₂). The Pd/TiC–C catalyst displays the best performance among all the samples. The effect of TiC:C mass ratio on the catalytic activity is also investigated. It is found that the maximal catalytic activity and stability for formic acid electrooxidation is observed at the Pd/TiC–C catalyst with TiC:C mass ratio of 1:2.     

Synthesis of an active and stable Ptshell–Pdcore/C catalyst for the electro-oxidation of methanol

A Pt_shell–Pd_core/C catalyst is prepared via electroless deposition and galvanic displacement. The catalyst is active toward the electro-oxidation of methanol and is more stable against CO_ad-poisoning than a commercial Pt/C catalyst. The stable activity of Pt_shell–Pd_core/C is ascribed to the tuned electronic property of the Pt over-layer in the Pt_shell–Pd_core/C, which leads to weak binding with CO_ad and increases the kinetics of OH_ad formation. The weakened binding property of the surface Pt with CO_ad and the facile oxidation of CO_ad by OH_ad were confirmed by a spectroscopic analysis and in a CO_ad-stripping experiment, respectively. The electro-oxidation of CO_ad by OH_ad is the rate-determining step of methanol oxidation. Therefore, the accelerated formation of OH_ad contributes to the overall oxidation reaction, preventing CO_ad-poisoning. In addition, Pt_shell–Pd_core/C maintains its activity longer than Pt/C does during a prolonged cycle experiment.     

Evaluation of the stability and durability of Pt and Pt–Co/C catalysts for polymer electrolyte membrane fuel cells

Carbon supported Pt and Pt–Co nanoparticles were prepared by reduction of the metal precursors with NaBH₄. The activity for the oxygen reduction reaction (ORR) of the as-prepared Co-containing catalyst was higher than that of pure Pt. 30 h of constant potential operation at 0.8 V, repetitive potential cycling in the range 0.5–1.0 V and thermal treatments were carried out to evaluate their electrochemical stability. Loss of non-alloyed and, to a less extent, alloyed cobalt was observed after the durability tests with the Pt–Co/C catalyst. The loss in ORR activity following durability tests was higher in Pt–Co/C than in Pt/C, i.e. pure Pt showed higher electrochemical stability than the binary catalyst. The lower stability of the Pt–Co catalyst during repetitive potential cycling was not ascribed to Co loss, but to the dissolution–re-deposition of Pt, forming a surface layer of non-alloyed pure Pt. The lower activity of the Pt–Co catalyst than Pt following the thermal treatment, instead, was due to the presence of non-alloyed Co and its oxides on the catalyst surface, hindering the molecular oxygen to reach the Pt sites.     

Preparation and electrochemical properties of composite LaNix/Ni–S–Co alloy film

The composite LaNi_x/Ni–S–Co film with considerable stability and high HER activity (η₁₅₀ = 70 mV, 353 K) was obtained by molten salt electrolysis combined with aquatic electrodeposition. LaNi_x film was prepared by galvanostatic electrolysis at 100 mA cm⁻² under 1273 K. The results showed that the La³⁺ ions could be reduced on the nickel cathode and the LaNi_x film could form, i.e. La³⁺ + 3e + xNi = LaNi_x (x = 5 or 3) at ca. −0.6 V, which is much lower than that of the decomposition potential of lanthanum, due to the strong depolarization effect of nickel. Furthermore, compared with the traditional amorphous Ni–S film, the composite LaNi_x/Ni–S–Co film could absorb large amount of H atoms, which would be oxidized and avoid the dissolution of the Ni–S–Co film under the state of open-circuit effectively and increase the HER activity.     

Synthesis of nano-tube CoNi/N–C complex and its catalytic properties for highly efficient oxygen reduction

Electrochemical energy storage systems such as fuel cells and metal air cells can be used as clean energy. In these systems, an essential reaction on the cathode is the oxygen reduction reaction (ORR). As ORR catalyst, non noble metal based catalyst is an important substitute for commercial Pt/C catalyst due to its rich reserves, low cost, good stability and high catalytic activity. Herein, CoNi alloy supported on nitrogen doped carbon, CoNi/N–C nanotubes, prepared by hydrothermal method and high-temperature pyrolysis method, shows excellent ORR catalytic activity and stability in 0.1 M KOH solution. In particular, the obtained CoNi/N-C-800 demonstrates the highest ORR activity of the prepared samples, with a half wave potential of 0.81V, which was equivalent to the commercially available Pt/C (0.82V). At the same time, it exhibits approximate 4e^- pathway with a comparable electron transfer number to the commercial Pt/C, and is much higher tolerant in methanol than the latter. Co and Ni alloying can induce the internal electron interaction of the catalyst, thus exposing more active sites. Furthermore, nano-tube CoNi exhibits appropriate size and hollow geometry, and its large surface area and strong conductivity improve its catalytic activity. The results may possibly provide a new impetus to the rational design of non noble metal based nanocomposite catalysts. Moreover, it is also of great significance to improve the performance of electrocatalysis and energy storage applications.     

Ni–SiO2 and Ni–Fe–SiO2 catalysts for methane decomposition to prepare hydrogen and carbon filaments

Active and stable Ni–Fe–SiO₂ catalysts prepared by sol–gel method were employed for direct decomposition of undiluted methane to produce hydrogen and carbon filaments at 823 K and 923 K. The results indicated that the lifetime of Ni–Fe–SiO₂ catalysts was much longer than Ni–SiO₂ catalyst at a higher reaction temperature such as 923 K, however, a reverse trend was shown when methane decomposition took place at a lower reaction temperature such as 823 K. XRD studies suggested that iron atoms had entered into the Ni lattice and Ni–Fe alloy was formed in Ni–Fe–SiO₂ catalysts. The structure of the carbon filaments generated over Ni–SiO₂ and Ni–Fe–SiO₂ was quite different. TEM studies showed that “multi-walled” carbon filaments were formed over 75%Ni–25%SiO₂ catalyst, while “bamboo-shaped” carbon filaments generated over 35%Ni–40%Fe–25%SiO₂ catalysts at 923 K. Raman spectra of the generated carbons demonstrated that the graphitic order of the “multi-walled” carbon filaments was lower than that of the “bamboo-shaped” carbon filaments.     

Cu/MnOx–CeO2 and Ni/MnOx–CeO2 catalysts for the water–gas shift reaction: Metal–support interaction

Monometallic copper and nickel catalysts supported on cerium-manganese mixed oxides are prepared, characterized and evaluated for the Water–Gas Shift (WGS) reaction. Active metal loading of 2.5 wt% and 7.5 wt% are used to impregnate MnO_x–CeO₂ supports with 30% and 50% Mn:Ce molar ratio. The structure of the samples strongly depends on both the active metal employed and the manganese content in the mixed support. For both Cu and Ni samples, the best catalytic behavior is found in samples supported on the MnO_x–CeO₂ oxides with 30% Mn:Ce molar ratio, as a result of the presence of Cu_xMn_yO₄ spinel-type phases in the case of copper catalysts and the presence of a NiMnO₃ mixed oxide with defect ilmenite structure in the case of nickel catalysts.     

Electrocatalytic performance of Ni modified MnOx/C composites toward oxygen reduction reaction and their application in Zn–air battery

A series of Ni modified MnO_x/C composites were synthesized by introducing NaBH₄ to MnO₂/C aqueous suspension containing Ni(NO₃)₂. The physical properties and the activity of the composites toward the oxygen reduction reaction (ORR) were investigated via transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and the electrochemical techniques. The results show that the higher activity of the composites toward the ORR is correlated with the higher content of MnOOH species transformed from Mn(II) on the surface of the composite. The main nickel species in the composites is Ni(OH)₂, while Ni(OH)₂ shows little activity toward the ORR. However, introducing Ni(OH)₂ with proper amount into the MnO_x/C improves the distribution of the active material MnO_x, which contributes to a surface with more MnOOH. The optimal composite is of the Ni/Mn atomic ratio of 1:2 and the MnO_x loading of 28 wt.%. The maximum power density of the zinc–air battery with the optimized Ni modified MnO_x/C as the cathode catalyst reaches up to 122 mW cm⁻², much higher than the one with the MnO_x/C as the air cathode catalyst (89 mW cm⁻²), and slightly higher than those with the Pd/C and Pt/C as the cathode catalysts.     

Decomposition and coupling of methane over Pd–Au/Al2O3 catalysts to form COx-free hydrogen and C2 hydrocarbons

Catalytic decomposition of methane (CDM; CH₄ → C + 2H₂) is expected to be used for clean hydrogen production because CDM does not emit carbon dioxide. Recently, it was reported that Pd–based catalysts promotes CDM, simultaneously facilitating coupling of CH₄ to form C₂ hydrocarbons. In this study, varieties of supported Pd–M alloy catalysts (M = Fe, Co, Ni, Cu, Zn, Ga, In, Sn, Au, Pb, and Bi) were synthesized and their activities for the CDM and CH₄ coupling were examined. The catalytic activity for CH₄ strongly depended on the types of Pd–M. Pd–M/Al₂O₃ (M = Ni, Fe, Co, Au) showed high activity for CDM. In addition to the production of hydrogen by the CDM, Pd–Au/Al₂O₃ formed C₂ hydrocarbons such as ethane and ethylene via the coupling of CH₄. Effects of Pd/Au ratio and reaction temperatures were examined and the role of Au for the CH₄ conversion reaction was discussed.     

Hydrogen production from ethanol steam reforming over core–shell structured NixOy–, FexOy–, and CoxOy–Pd catalysts

The present work focused on the investigation of the hydrogen generation through the ethanol steam reforming over the core–shell structured Ni_xO_y–, Fe_xO_y–, and Co_xO_y–Pd loaded Zeolite Y catalysts. The transmission electron microscopy (TEM) image of Ni_xO_y–Pd represented a very clear core–shell structure, but the other two catalysts, Co_xO_y– and Fe_xO_y–Pd, were irregular and non-uniform. The catalytic performances differed according to the added core metal and the support. The core–shell structured Co_xO_y–Pd/Zeolite Y provided a significantly higher reforming reactivity compared to the other catalysts. The H₂ production was maximized to 98% over Co_xO_y–Pd(50.0 wt%)/Zeolite Y at the conditions of reaction temperature 600 °C, CH₃CH₂OH:H₂O = 1:3, and GHSV (gas hourly space velocity) 8400 h⁻¹. In the mechanism that was suggested in this work, the cobalt component played an important role in the partial oxidation and the CO activation for acetaldehyde and CO₂ respectively, and eventually, cobalt increased the hydrogen yield and suppressed the CO generation.     

Direct Ethanol Fuel Cells: The influence of structural and electronic effects on Pt–Sn/C electrocatalysts

Carbon-supported platinum-tin electrocatalysts (Pt–Sn/C) are known to be the most efficient fuel cell anode material to oxidize ethanol in the so-called Direct Ethanol Fuel Cells (DEFC). However, the platinum-tin binary system presents distinct phases depending on the amount of Sn (i.e., the Pt:Sn ratio) and on the thermal annealing temperatures, as well as the presence of oxides (e.g. SnO₂) whose influence on the performance of DEFCs is not well understood. In this work, Pt–Sn catalysts presenting distinct Pt:Sn ratios were prepared, characterized and tested in a single DEFC. The combined results from DEFC tests and structural characterization techniques showed that increasing the amount of Sn dissolved into the Pt structure enhances DEFC performance but also that Sn content alone does not explain the overall behavior. Microstructural effects on the DEFC response was further investigated by performing a comprehensive study using high intensity X-ray Diffraction and in situ–X-Ray Absorption Spectroscopy provided by synchrotron light on Pt₃Sn₁/C samples subjected to thermal treatments in a reducing H₂ atmosphere at temperatures of 100, 200, 300, 400, and 500 °C. The results showed that best DEFC performance depends on a balance between the amount of Sn dissolved in Pt, the formation of a new phase (PtSn) and also on the presence of tin oxides, yielding a material with an optimized modified 5d-band electronic structure, which was obtained with a thermal treatment at 200 °C.     

Tuning morphology and structure of Fe–N–C catalyst for ultra-high oxygen reduction reaction activity

Exploring efficient and durable non-precious metal catalysts for oxygen reduction reaction (ORR) has long been pursued in the field of metal-air batteries, fuel cells, and solar cells. Rational design and controllable synthesis of desirable catalysts are still a great challenge. In this work, a novel approach is developed to tune the morphologies and structures of Fe–N–C catalysts in combination with the dual nitrogen-containing carbon precursors and the gas-foaming agent. The tailored Fe–N₁/N₂–C-A catalyst presents gauze-like porous nanosheets with uniformly dispersed tiny nanoparticles. Such architectures exhibit abundant Fe-N_x active sites and high-exposure surfaces. The Fe–N₁/N₂–C-A catalyst shows extremely high half-wave potential (E_1/2, 0.916 V vs. RHE) and large limiting current density (6.3 mA cm⁻²), far beyond 20 wt% Pt/C catalyst for ORR. This work provides a facile morphological and structural regulation to increase the number and exposure of Fe-N_x active sites.     

Tunable microstructure,de-/hydrogenation kinetics and thermodynamics performance of Mg–Ni–La–Ti–H systems

In the light of positive effects of rare earth and transition metals on the hydrogen absorption/desorption properties of magnesium, the Mg20La–5TiH₂, Mg20Ni–5TiH₂ and Mg10Ni10La–5TiH₂ composites have been prepared in this work to ameliorate the de-/hydrogenation kinetics and thermodynamic performance. The results indicate that the as-prepared composites are mainly composed of Mg, Mg₂Ni/LaH₃ and TiH₂ phases after activation, and LaH₃ and TiH₂ are stable during de-/hydrogenation cycles. The morphology observations give evidences that LaH₃ with size about ~20 nm and Mg₂Ni with size about ~1 μm are uniformly distributed in the composites. It is noted that the de-/hydriding kinetics of the as-prepared composites are significantly improved after internal and surface modification, of which the Mg10Ni10La–5TiH₂ composite can desorb as high as 5.66 wt% hydrogen within 3 min at 623 K. Moreover, the thermodynamic properties of the experimental composites have also been investigated and discussed according to the pressure-composition isothermal curves and corresponding calculation by Van't Hoff equation. The improved hydrogen storage properties of the as-prepared composites are mainly attributed to the uniformly distributed LaH₃, Mg₂Ni and TiH₂ phases, which provide a large amount of phase boundaries, diffusion paths and nucleation sites for de-/hydrogenation reactions.     

Decomposition of hydrogen iodide over Pt–Ir/C bimetallic catalyst

Decomposition of hydrogen iodide (HI) is one of the key reactions in the sulfur–iodine (S–I) thermochemical water splitting promising for the massive hydrogen production. Much effort has been made to explore the preparation of high performance catalyst for this hydrogen-producing reaction. Although platinum has long been found to be an efficient metallic catalyst, it was prone to agglomerate at elevated temperature resulting in a decrease in the hydrogen yield. A series of bimetallic Pt–Ir/C catalysts were prepared by electroless plating to investigate the effect of Ir/Pt molar ratio on the HI conversion compared with Pt/C and Ir/C catalysts. The physical properties and morphology of the catalysts were characterized by BET, XRD, TEM and ICP-AES. The synergistic effect of platinum and iridium with respect to HI decomposition was confirmed by the fact that the bimetallic Pt–Ir/C-0.77 catalyst with 1 wt% Pt loading and 0.77 wt% Ir loading showed much higher catalytic activity and thermostability compared with Pt/C and Ir/C catalyst. Based on the experimental results obtained, it may be concluded that the bimetallic Pt–Ir/C catalyst was supposed to be a cost-effective and high performance catalyst promising to be employed for the hydrogen production via the S–I thermochemical water splitting cycle.     

Durability study of Pt–Pd/C as PEMFC cathode catalyst

In this paper, Pt–Pd/C and Pt/C catalysts were evaluated and compared. The catalysts were evaluated as oxygen reduction reaction (ORR) catalysts in half cell test under potential cycling, and cathode catalysts in single cell test under dynamic loading simulating the vehicle operation. Physical and electrochemical techniques were applied to investigate the structure, performance and durability of those catalysts. The electrochemical active surface area (ECA) loss, particle size distribution, polarization behavior and electrochemistry impedance spectroscopy (EIS) suggested that the Pt–Pd/C showed a better durability than Pt/C.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

Electrochemical preparation and characterization of C/Ni–NiIr composite electrodes as novel cathode materials for alkaline water electrolysis

The binary NiIr coatings as novel and effective catalysts were electrochemically prepared on a Ni-modified carbon felt electrode (C/Ni–NiIr) in view of their possible application as cathode materials for the alkaline water electrolysis. The surface morphology and chemical composition of the electrodes were investigated by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) techniques. Their hydrogen evolution activity was assessed by electrochemical techniques. It was found that, the preparation of NiIr co-deposits on the Ni-modified C substrate enhances the hydrogen evolution activity. The electrodes have wide space, which is an advantage for diffusion of ions and hydrogen bubbles through inner zones and reduction of diffusion resistance. The high hydrogen evolution activity of the C/Ni–NiIr electrode was mainly attributed to the finer surface structure, high surface area and the higher numbers of the catalytically active centers.     

Design an in-situ reduction of Ni/C–SiO2 catalyst and new insights into pretreatment effect for CH4–CO2 reforming reaction

A series of Ni/C–SiO₂ catalysts with high Ni⁰ dispersion were prepared through impregnation method with glucose as the carbon source as well as the reduction agent. During the calcination process under N₂ atmosphere, the generated reductive substances, like CO, H₂ and carbon derived from decomposition and carbonization of glucose, which could transform NiO into Ni⁰ particles completely, according to XRD and H₂-TPR analysis. To improve the catalytic performance of CH₄–CO₂ reforming reaction, the Ni/C–SiO₂ catalyst was further pretreated under N₂, H₂ and CO₂ atmosphere prior to the reaction. The CO₂ pretreated catalyst exhibited excellent catalytic activity and superior stability comparing with other catalysts. A rapid deactivation occurred on the Ni/SiO₂ catalyst prepared by traditional impregnation method during 10 h test. Reversely, the CO₂ pretreated catalyst maintained a high CH₄, CO₂ and C_total conversion (71.1, 81.1 and 77.1%, respectively) during a 40 h time-on-stream test, which was attributed to homogenous Ni particles dispersion and strong interaction between metal and support. This methodology opens up a possibility for diversification in carbon-silica composite catalysts. The working catalyst without further reduction process will give the required metal-support interaction for the novel synthesis.