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1.
Pt/CeMgAl layered double hydroxides with different Ce contents were prepared by one-step co-precipitation method, which underwent calcination and reduction with hydrogen and were finally converted into Pt/CeMgAlO catalysts. These catalysts were tested in the dehydrogenation of methylcyclohexane (MCH) into toluene to produce hydrogen. The addition of CeO2 promoted the dispersion of Pt and decreased the Pt particle size. During the dehydrogenation reaction, toluene was the only liquid product and its selectivity was higher than 99.9%. MCH conversion increased with the reaction temperature rising. The conversion and hydrogen evolution rate on Pt/Ce14MgAlO350 reached up to 98.5% and 1358.6 mmol/gPt/min at 350 °C. Moreover, Pt/CeMgAlO catalysts exhibited no acidity and presented a high anti-coking ability and good stability. These results suggest that Pt/CeMgAlO catalysts have potential industrial application for hydrogen energy utilization.  相似文献   

2.
Ni/Al2O3, NiCo/Al2O3MgO and NiCo/Al2O3MgO/NbZr nanocatalysts were prepared by the sol-gel technique with citric acid and tested in the dry reforming of methane (DRM). In this paper, the effects of Nb and Zr addition as promoters in Al2O3MgO supported catalysts on the physicochemical characteristics and the reaction performance in the DRM were investigated. The NbZr promoters are expected to enhance the activity and performance of the catalyst due to its high thermal stability and also improvement in the metal dispersion of the catalyst. The catalysts samples were characterized by FESEM, BET, XRD, TEM, H2-TPR and CO2-TPD techniques. FESEM results demonstrated that NiCo/Al2O3MgO/NbZr has more uniform and well-dispersion of metal than NiCo/Al2O3MgO. The BET results unravel that the addition of NbZr promoters increase the surface area of the synthesized catalyst due to the high surface area of the promoters. There is a formation of MgAl2O4 spinel-type solid solution proved by the XRD and CO2-TPD analysis due to the interaction between alumina lattice and magnesium metal which has high resistance to carbon formation. The DRM reaction is performed in the tubular furnace reactor at 1073.15 K, 1 atm and a CH4/CO2 ratio of unity. The sol-gelled NiCo/Al2O3MgO/NbZr was found to be the most proper choice for DRM which illustrates much higher conversion (86.96% for CH4 conversion and 87.84% for CO2 conversion) compared to the other catalysts. This is due to the strong interaction between active metals and supports, resistance to coke formation and higher stability in DRM reaction.  相似文献   

3.
At present, there is an urgent need for plentiful non-noble metal catalyst to substitute for valuableness platinum based metal catalyst in electrochemical water splitting. Here, we fabricated a three-demensional (3D) NiCoNiCo2O4 nanosheets electrocatalyst that directly grew on Ni foam firstly and then were reduced in 0.1 mol dm−3 sodium borohydride solution. This electrode exhibited high activity in 1.0 mol dm−3 KOH solution with an onset potential of ∼40 mV and a tafel slope of 77 mV dec−1. Furthermore, the NiCoNiCo2O4/NF electrode showed a splendid durability during long-playing electrochemical test. Our work may provide an inexpensive, easy-to-obtain and excellent catalyst candidate for future electrolytic water research and industry studies that may involve hydrogen applications in the future.  相似文献   

4.
It is attractive to design and develop a low-cost and environment friendly material preparation route for the catalysts used in alkaline hydrogen evolution reaction. Mineral reconstruction in chlorination roasting and electrodeposition in deep eutectic solvent have been combined in this work. The electrodeposition of NiMoCu coatings from roasted nickel matte precursor in choline chloride (ChCl)-urea deep eutectic solvent (DES) has been investigated. Cyclic voltammetry (CV) implies that the electrodeposition process of NiMoCu coatings in ChCl-urea DES consists of a one-step reaction of Ni(II), a two-step reaction of Cu(II) and Ni/Mo inductive co-deposition. The hydrogen evolution performance parameters of deposited NiMoCu coatings have been systematically studied in alkaline solution by linear sweep voltammetry (LSV), and the electrochemical surface area (ECSA) has been tested by CV. The hydrogen evolution kinetics of deposited NiMoCu coatings has been further investigated by electrochemical impedance spectroscopy (EIS). Owing to its high electrochemical surface area, the NiMoCu coating deposited on Ni foam at −1.2 V can deliver a current density of 10 mA cm−2 at an overpotential of 93 mV in 1 M KOH. It is suggested that NiMoCu coating can be a promising candidate for water splitting in alkaline solution.  相似文献   

5.
With the aid of computer simulation, we have designed four covalent-organic frameworks based on tetrakis(4-aminophenyl)silsesquioxane (taps-COFs) and their hydrogen storage properties were predicted with grand canonical Monte Carlo (GCMC) simulation. The structural parameters and physical properties were investigated after the geometrical optimization. The accessible surface for H2 molecule (5564.68–6754.78 m2/g) were estimated using the numerical Monte Carlo integration and the pore volume (4.06–10.74 cm3/g) was evaluated by the amounts of the containable nonadsorbing helium molecules at low pressures and room temperature. GCMC simulation reveals that at 77 K, tapsCOF1 has the highest gravimetric H2 adsorption capacity of 51.43 wt% and tapsCOF3 possesses the highest volumetric H2 adsorption capacity of 58.51 g/L. Excitedly, at room temperature of 298 K, the gravimetric hydrogen adsorption capacities of tapsCOF1 (8.58 wt%) and tapsCOF2 (8.20 wt%) have exceeded the target (5.5 wt%) of onboard hydrogen storage system for 2025 set by the U.S Department of Energy.  相似文献   

6.
To improve the hydrogen storage properties of YZrFe alloys, the alloying with Ti was carried out to obtain Y0.7Zr(0.3-x)TixFe2 (x = 0.03, 0.09, 0.1, 0.2) alloys by different processes. It was expected that Ti would substitute Zr and decrease the lattice constant of YFe2-based C15 Laves phase. All YZrTiFe quaternary alloys consist of the main Y(Zr)Fe2 phase and the minor YFe3 phase. Despite the large solubility of Ti in Zr or Zr in Y, the Ti incorporation into YZrFe alloys results in the inhomogeneity of Y and the segregation of Ti, and thus decreases the hydrogen storage capacity. Only the alloy Y0.7Zr0.27Ti0.03Fe2 containing very few Ti shows the substitution of Ti to Zr and the resultant improvement in the dehydriding equilibrium pressure.  相似文献   

7.
In this work, hydrogen production from partial oxidation (POX) of propane over composite Ni/Al2O3SiC catalyst was investigated. In order to utilize the high thermal conductivity and chemical stability of SiC, the composite Al2O3SiC support of the catalyst was synthesized by precipitation technique, then Ni component was loaded using impregnation method. The as-prepared samples were characterized by X-ray diffraction, BET, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements. As observed, stacking porous structures were appeared after calcination process by doping SiC with certain ratios. According to the stiochiometric ratio, a C3H8O2 (1:1.5) gas mixture was used to study the catalytic activity for hydrogen production from POX of propane. From the results, local overheat of the catalyst bed generated by the exothermic reactions was relieved by doping SiC and Ni/Al2O3SiC (30 wt%) catalyst performed a higher hydrogen production. Aggregation and carbon deposition of Ni/Al2O3SiC (30 wt%) catalyst were reduced compared to Ni/Al2O3 from the observation of SEM and TEM with H2 production up to around 236 μmol/gcat·s and kept stable for 26 h at 600 °C. By means of TGA, non-isothermal oxidative decarburizations of the spent catalysts were studied. It was found that less carbon deposit and lower activation energy for oxidative decarburization were found by doping SiC to Ni/Al2O3.  相似文献   

8.
PdAgFe, FePdAg and FeAgPd trimetallic nanoparticles were synthesized by seedless and step-wise simultaneous chemical reduction of Fe3+, Ag+ and Pd2+ by using hydrazine in presence of cetyltrimethylammonium bromide and used as a catalyst for the degradation of formic acid. The effects of nanoparticle composition, presence of sodium format (promoter), [catalyst], [formic acid] and temperature play key roles in the hydrogen generation. The Ba(OH)2 trap experiment and water displacement technique were used to determine the generation of CO2 and H2, respectively. The decomposition of formic acid followed complex-order kinetics with respect to [formic acid]. It was found that FeAgPd showed a maximum catalytic activity (turn over frequency) of 75 mol H2 per mol catalyst per h. The activation energy (Ea = 51.6 kJ/mol), activation enthalpy (ΔH = 48.9 kJ/mol) and activation entropy (ΔS = −151.0 JK-1 mol−1) were determined and discussed for the catalytic reaction. The reusability of the FeAgPd at 50 °C shows an efficient degree of activity for six consecutive catalytic cycles.  相似文献   

9.
Here, novel polyvinyl alcohol (PVA) nanofibers with incorporated CuO and Co3O4 nanoparticles (PVA-CuOCo3O4) were synthesized through a conventional single-nozzle electrospinning technique and characterized by atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX), fourier-transform infrared spectroscopy (FT-IR), elemental analysis, transmission electron microscopy (TEM), differential thermal analysis (DTA), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Novel Pt/polyvinyl alcohol-CuOCo3O4/chitosan (Pt/PVA-CuOCo3O4/CH) catalyst was successfully prepared. EDX, TEM, and FT-IR spectroscopy techniques were used to characterize the prepared catalysts. The electrocatalytic activity of Pt/PVA-CuOCo3O4/CH catalyst was investigated for methanol electrooxidation through cyclic voltammetry, chronoamperometry, CO stripping voltammetry, and electrochemical impedance spectroscopy techniques. The effects of some experimental factors for methanol electrooxidation were studied on the prepared catalysts and the optimum conditions were determined. Pt/PVA-CuOCo3O4/CH catalyst had extraordinary electrocatalytic activity for methanol electrooxidation. It exhibited better stability, higher electrochemically active surface area, and better antipoisoning effect than Pt/PVA-CuOCo3O4 and Pt/PVA/CH catalysts indicating that Pt/PVA-CuOCo3O4/CH could be a promising catalyst for direct methanol fuel cell (DMFC) applications. A real DMFC was designed, assembled and tested with Pt/PVA-CuOCo3O4/CH as anodic catalyst.  相似文献   

10.
The effect of LiCe(BH4)3Cl on the hydrogen storage properties of Mg(NH2)22LiH system was studied systematically, which has a high Li ion conductivity. The hydrogen desorption temperatures for LiMgNH system shift to lower temperatures by 0.05LiCe(BH4)3Cl doping with the onset temperature of dehydrogenation decreasing by 40 °C and the peak temperature decreasing by 30 °C. The Mg(NH2)22LiH–0.03LiCe(BH4)3Cl composite exhibits an improved comprehensive hydrogen storage properties, which can reversibly store about 5.0 wt% hydrogen at 160 °C, and released hydrogen as much as 8.6 times faster than that of the Mg(NH2)22LiH composite at 160 °C. The results indicated that the LiCe(BH4)3Cl-containing sample exhibited much better cycling properties than that of Mg(NH2)22LiH sample. XRD and FTIR results show that the structure of LiCe(BH4)3Cl does not change before and after hydrogen absorption/desorption, indicating it plays the catalytic effect. The hydrogen desorption activation energy of Mg(NH2)22LiH doped with 0.03LiCe(BH4)3Cl was reduced by 37.5%. The rate-controlling step of desorption shifted from the diffusion to the chemical reaction by the addition of LiCe(BH4)3Cl, indicating that the diffusion rates of small ions like H+, Li+ and Mg2+ in LiMgNH system are significantly enhanced, which could be well explained by the improved ionic conductivity of LiCe(BH4)3Cl doped sample.  相似文献   

11.
Designing and synthesizing of efficient and inexpensive bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is one of the current research topics. In this study, NiFeCMo film in nickel mesh substrate is prepared by one-step direct-current electrodeposition method. The obtained NiFeCMo film shows the excellent electrocatalytic activity, which only requires overpotentials of 254 mV for HER and 256 mV for OER to drive current density of 10 mA cm−2, with corresponding Tafel slopes of 163.9 and 60.3 mV·dec−1 in 30% KOH medium, respectively. Moreover, NiFeCMo film only needs a low cell voltage of 1.61 V to drive current density of 10 mA cm−2 in an alkaline electrolyzer. Such remarkably HER and OER properties of NiFeCMo alloy is attributed to the increased effective electrochemically active surface area and the synergy effect among Ni, Fe, C and Mo.  相似文献   

12.
In this work, a spherical spider web-like structure RuNi/Ni foam catalyst was prepared for hydrogen evaluation from sodium borohydride (NaBH4) by a combination of electroless plating and electroplating. Microstructure, surface morphology, surface area and elemental composition of the RuNi/Ni foam catalyst were analyzed by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM-EDS and X-ray Photoelectron Spectroscopy (XPS), Brunauere-Emmette-Teller method (BET, AS-1C-VP), respectively. The influences of RuNi with different molar ratios, NaOH concentration, NaBH4 concentration, and solution temperature on the hydrogen production rate were investigated in this paper. The results showed that the RuNi metals were arrayed densely and uniformly on the surface of Ni foam. The average hydrogen production rate is 360 mL min −1 g−1 in 20 wt % of NaBH4, 1 wt% of NaOH at 30 °C in the presence of the RuNi/Ni foam catalysts. The calculated activation energy was 39.96 kJ mol−1 for hydrogen production from sodium borohydride using the RuNi/Ni foam catalyst.  相似文献   

13.
Here, a simple two-step solvothermal approach has been employed to synthesize PtFe alloy (or Pt)/CeO2/C with PtFe (or Pt) selective loading on CeO2 nanoparticles. In addition, the selective loading of PtFe alloy or Pt nanoparticles on the surface of CeO2 is achieved under weak alkaline environment, which is mainly attributed to the opposite electrostatic force between H+ enriched on the surface of CeO2 particles and OH covered with carbon supporters. As-prepared PtFe alloy (or Pt)/CeO2/C catalysts with two-stage loading structures show more excellent electro-catalytic efficiency for methanol oxidation as well as duration compared with commercial Pt/C and PtCeO2/C with random loading structure. Further, single-cell assembly based on Pt3Fe/CeO2/C as the anode catalyst exhibits a maximum power density of 31.1 mW cm−2, which is 1.95 times that of an analogous cell based on the commercial Pt/C. These improved performances with considerable low Pt content (<0.3 mg cm−2) are mainly ascribed to the abundant three phase interfaces (PtCeO2 carbon) induced by the selective and efficient dispersion of Pt nanoparticles on ceria.  相似文献   

14.
Recently, the application of magnesium-based gasochromic switchable mirror has been baffled by the low optical dynamic range due to the insufficient conversion between Mg and MgH2. Based on the excellent catalytic property of Nb2O5 for the magnesium-hydrogen reaction, we fabricated fluorocarbon (FC)/Pd/MgNb2O5 switchable films via magnetron sputtering and low-temperature inductively coupled plasma chemical vapor deposition technologies in this study, and the optical performance and microstructure of the films were investigated. The results show that the FC/Pd/Mg-3 mol% Nb2O5 film exhibits the higher dynamic ranges of the luminous (49.4%) and solar transmittance (54.7%), compared with most of reported Mg-based alloys and MgTiO2 systems. The addition of Nb2O5 and covering a FC layer on the Pd/Mg film could effectively accelerate the switching response and improve such optical properties as transmittance at transparent state and dynamic range. The microstructural analysis reveals that the Nb2O5 and appropriate amount of ternary MgNbO phase in the Mg-based layer are supposed to facilitate rapid and sufficient hydrogen absorption and desorption. Furthermore, the high-valence Nb ions scattering around Mg atoms may act as a transfer station for catalyzing the reversible reaction between Mg and H. The excellent optical modulation performance and enhanced hydrophobicity of the FC/Pd/MgNb2O5 films signify an application prospect for gasochromic switchable mirror.  相似文献   

15.
The Ba modified ZrO2 materials were prepared and loaded Ru nanoparticles for ammonia decomposition to COx-free hydrogen reaction. The catalytic activity of Ru supported on BaZrO2 derived from sol-gel process (Ru/BaZrO2) is found to be several times of those for Ru/ZrO2 without any promoter and RuBa/ZrO2 catalysts prepared by conventional immersion method at the identical conditions. It is found that the formation of BaZrO3 phase in BaZrO2 can enhance the electron-donating ability of the support and Ru nanoparticles dispersion. Therefore, mobile electrons would be transferred from BaZrO3 to the surface Ru particles, facilitating the recombinative desorption of N over Ru particles, leading to the increase of activity for ammonia decomposition sufficiently. Additionally, the suitable size of spherical Ru particles with average size of 2.4 nm for the formation of active sites are also responsible factors for the higher activity of this catalyst. The catalytic performance of Ru/BaZrO2 catalyst can also be further improved by introducing of K and Cs promoters, and the apparent activation energies over Ru/BaZrO2 of 94.1 kJ/mol decrease to 70.7 kJ/mol and 64.2 kJ/mol for K and Cs promoted Ru/BaZrO2, respectively.  相似文献   

16.
Based on first-principles calculations, we investigated the hydrogen adsorption dissociation on the LaFeO3 (010) surface with an O vacancy. It was confirmed that H2 molecules have four kinds of adsorption modes on LaFeO3 (010) surfaces with an O vacancy. First, H atoms are adsorbed on O atoms to form an OH group. Second, H atoms are adsorbed on Fe atoms to form FeH bonds. Third, two H atoms are adsorbed on the same O atom to form H2O. Fourth, two H atoms are adsorbed on the same Fe atom and it is a new type of adsorption, which does not exist in the ideal surface. The main channel of dissociative adsorption is the fourth adsorption mode of OH and FeH, where the H atoms adsorbed on the surface of Fe can be easily diffused into O atoms. Charge population analysis showed that increasing the O vacancy enhanced the interaction between FeH. In the system containing O vacancies adsorbed H atoms in the top of Fe to diffuse to the top of O need to overcome the energy barrier decreased from 0.968 eV to 0.794 eV. So the existence of an O vacancy enhances the hydrogen absorption properties of Fe atoms in LaFeO3.  相似文献   

17.
The effect of Fe content in electroless-deposited CoNi-Fex-P alloy catalysts (x = 5.5–11.8 at.%) from the hydrolysis of NaBH4 is investigated in alkaline sodium borohydride solution. The electroless-deposited CoNiFe5.5-P and CoNiFe7.6-P alloy catalysts are composed of flake-like micron particles; however, with an increase in Fe content to 11.8 at.%, the flake-like morphology is changed to a spherical shape and the crystal structure of the electroless-deposited CoNiFeP catalyst is transformed from FCC to BCC. Among all the CoNi-Fex-P alloy catalysts, the CoNi-Fex-P (x = 7.6 at.%) catalyst has the highest hydrogen production rate of 1128 ml min−1 g−1catalyst in alkaline solution containing 1 wt% NaOH + 10 wt% NaBH4 at 303 K. For the optimized catalyst, the activation energy of the hydrolysis of NaBH4 is calculated to be 54.26 kJ mol−1. Additionally, in this work, we report a new hydrolysis using Mg(BH4)2 and Ca(BH4)2. As a result, the Mg(BH4)2 is stored unstably in an alkaline solution, whereas the Ca(BH4)2 is stored stably. When optimizing the hydrogen production kinetics from the hydrolysis of Ca(BH4)2, the rate is 784 ml min−1 g−1catalyst in 10 wt% NaOH + 3 wt% Ca(BH4)2 solution.  相似文献   

18.
In this study, MgH2 and Co powders were mechanically milled in the molar ratio 2:1 and compressed to hard-packed cylindrical pellets. The microstructure, phase changes, and hydrogen storage properties of the mechanically milled 2MgH2Co powder and the 2MgH2Co compressed pellet were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and synchronous thermal (DSC/TG) analyses. Dehydrogenation of the 2MgH2Co compressed pellet is mainly due to the decomposition of Mg2CoH5 while it is the dehydriding of MgH2 for the milled 2MgH2Co powder. Pressure composition absorption isotherms of the 2MgH2Co powder and 2MgH2Co compressed pellet show two and three plateaus, respectively, corresponding to the formation of Mg6Co2H11 and Mg2CoH5 hydride phases. For the compressed 2MgH2Co pellet, enthalpies of formation/decomposition were measured to be −58.11±7.69 kJ/mol H2/55.70±3.34 kJ/mol H2 for Mg2CoH5 and -81.89±10.39 kJ/mol H2/74.47±5.27 kJ/mol H2 for Mg6Co2H11. In contrast, hydrogenation/dehydrogenation enthalpies of Mg2CoH5 and Mg6Co2H11 mechanically milled 2MgH2Co powder were −73.98±10.1 kJ/mol H2/71.67±1.38 kJ/mol H2 and -96.86±8.73 kJ/mol H2/89.95±10.81 kJ/mol H2, respectively. Fast hydrogenation was observed in the dehydrided 2MgH2Co compressed pellet with about 2.75 wt% absorbed in less than 1 min at 300 °C and a maximum hydrogen storage capacity of 4.43 wt% (2.32 wt% for the 2MgH2Co powder) was achieved. The hydrogen absorption activation energy of the 2MgH2Co compressed pellet (64.34 kJ-mol−1 H2) is lower than the mechanically milled 2MgH2Co powder (73.74 kJ-mol−1 H2). The results show that mechanical milling followed by high-pressure compression is an efficient method for the synthesis of Mg-based complex hydrides with superior hydrogen sorption properties.  相似文献   

19.
At present, it is difficult for electrocatalytic electrode materials with high-Performance to be prepared at low cost and large area under mild conditions. Therefore, we adopt a facile electroless plating method to deposit the FeCoP alloys on the nickel foam (NF) with different areas of 1 cm2, 4 cm2, 8 cm2 and 16 cm2. The FeCoP/NF catalysts exhibit extraordinary catalytic activity for the oxygen evolution reaction (OER) in alkaline media and are comparable to the state-of-the-art IrO2 in 1.0 M KOH, capable of yielding a current density of 10 mA cm−2 at an overpotential of only 250 mV. Furthermore, the FeCoP/NF catalysts show efficient activity towards the hydrogen evolution reaction (HER) with an overpotential of 163 mV at j = 10 mA cm−2 as well. Remarkably, when used as both the anode and cathode, a low potential of 1.68 V (vs. RHE) is required to reach the current density of j = 10 mA cm−2, making the FeCoP/NF alloys as an active bifunctional electrocatalyst for overall water splitting. The FeCoP/NF alloy catalysts with high catalytic activity, facile preparation and low cost would provide a new pathway for the design and large-scale application of high-performance bifunctional catalysts for electrochemical water splitting.  相似文献   

20.
Cerium oxide nanorods treated at 200 (CeO2-NR2) and 400 °C (CeO2-NR4) were used to synthesize of PdCeO2-NR2/C and PdCeO2-NR4/C nanocatalysts to promote the Methanol, Ethanol, Ethylene Glycol and Glycerol Oxidation Reactions (MOR, EOR, EGOR and GOR, respectively). The crystalline nanocatalysts had morphology of agglomerated Pd nanoparticles dispersed on Vulcan and on the nanorods as well. The polarization curves in 0.5 M KOH showed that the catalytic activity decreases in all reactions in the order PdCeO2-NR4/C > PdCeO2-NR2/C > Pd/C, which confirmed the synergetic effect of the nanorods on the catalytic behavior of Pd, particularly after heat treatment at 400 °C. The highest mass current density has been obtained from the EGOR (jf = 6661 mA mgPd−1) with the PdCeO2-NR4/C nanocatalyst, which catalyzed the reaction with an onset potential (Eonset) of −0.26 V/SHE. Meanwhile, the EOR was promoted with the most negative Eonset (−0.40 V/SHE), delivering 5719 mA mgPd−1, also using PdCeO2-NR4/C. Therefore, considering electrocatalysis parameters for fuel cells applications, the oxidation of C2H6O2 and C2H5OH showed advantages using PdCeO2-NR4/C.  相似文献   

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