Ni-Supported Pd Nanoparticles with Ca Promoter: A New Catalyst for Low-Temperature Ammonia Cracking.
ABSTRACT: In this paper we report a new nanometallic, self-activating catalyst, namely, Ni-supported Pd nanoparticles (PdNPs/Ni) for low temperature ammonia cracking, which was prepared using a novel approach involving the transfer of nanoparticles from the intermediate carrier, i.e. nano-spherical SiO2, to the target carrier technical grade Ni (t-Ni) or high purity Ni (p-Ni) grains. The method that was developed allows a uniform nanoparticle size distribution (4,4±0.8 nm) to be obtained. Unexpectedly, the t-Ni-supported Pd NPs, which seemed to have a surface Ca impurity, appeared to be more active than the Ca-free (p-Ni) system. A comparison of the novel PdNPs/Ni catalyst with these reported in the literature clearly indicates the much better hydrogen productivity of the new system, which seems to be a highly efficient, flexible and durable catalyst for gas-phase heterogeneous ammonia cracking in which the TOF reaches a value of 2615 mmolH2/gPd min (10,570 molNH3/molPd(NP) h) at 600°C under a flow of 12 dm3/h (t-Ni).
Project description:The development of efficient catalysts for hydrogen generation via ammonia decomposition is crucial for the use of ammonia as an energy carrier. Here, we report the effect of pore confinement of NaNH2 and KNH2 on ammonia decomposition catalysis. For the first time, Ni- or Ru-doped NaNH2 and KNH2 were confined in carbon nanopores using a combination method of solution impregnation and melt infiltration. Structure characterization indicates the nanoscale intimacy between transition metals and alkali metal amides inside the pores of the carbon support. As a result, 8 wt % Ni-doped NaNH2 and KNH2 nanocomposites give NH3 conversions of 79 and 60%, respectively at 425 °C, close to the performance of a 5 wt % Ru/C reference catalyst. 0.8 wt % Ru-doped nanocomposites exhibit even better catalytic performance, with about 95% NH3 conversion at a moderate temperature of 375 °C. The hydrogen production rates of these Ni- and Ru-doped nanocomposites in a pure NH3 flow are about 3-4 times higher than for the recently reported novel catalysts such as Ni-Li2NH and Ru-Li2NH/MgO. Interestingly, the apparent activation energies of the Ru- or Ni-based catalysts decrease 20-30 kJ mol-1 by co-confinement with alkali metal amides. The strategy of nanoconfinement of alkali metal amides in porous hosts may open a new avenue for effectively generating H2 from NH3 at low temperatures.
Project description:A Ni-based catalyst (Ni-PVP/PFC3R) with polyvinyl pyrrolidone (PVP) as a dispersant supported in a pretreated fluid catalytic cracking catalyst residue (PFC3R) was synthesized and applied to C9 petroleum resin (C9 PR) hydrogenation. For comparison, a Ni catalyst without PVP (Ni/PFC3R) was prepared in the same way. Ni-PVP/PFC3R exhibited higher activity and better stability. The catalysts were characterized by X-ray diffraction, scanning electron microscope, H2-temperature programmed reduction/temperature programmed desorption, Fourier transform infrared spectroscopy and the Brunauer-Emmett-Teller method. The catalysts had a smaller crystallite size and stronger interactions between the Ni species and the PFC3R support in the presence of PVP. The effects of nickel loading, H2 pressure, temperature and reaction time for C9 PR hydrogenation over Ni-PVP/PFC3R were investigated. The bromine number was reduced to 1.25 under the following conditions: nickel content of 12 wt%, PVP amount of 1.5 wt%, temperature of 270°C, H2 pressure of 8 MPa and reaction time of 240 min.
Project description:Polymer inclusion membranes (PIMs) doped with ethylenodiamino-bis-acetylacetone as fixed carrier was applied for the investigation of the facilitated transport of Zn(II), Cr(III), and Ni(II) ions from an aqueous nitrate feed phase (cM = 0.001 mol/dm3). The optimal membrane composition (amount of carrier and o-NPPE-plasticizer) was determined. For the optimal polymer inclusion membranes doped with ethylenodiamino-bis-acetylacetone, the following patterns of transport selectivity were found: Zn(II) > Cr(III) > Ni(II). The initial flux of Zn(II), Cr(III), and Ni(II) ions was 6.37 µmol/m2?s, 5.53 µmol/m2?s, and 0.40 µmol/m2?s, respectively. The selectivity coefficients equal to 1.2 and 15.9 were found for Zn(II)/Cr(III) and Zn(II)/Ni(II), respectively. After 24-h transport, the recovery factor of Zn(II), Cr(III), and Ni(II) were 90%, 65%, and 6%, respectively. The polymer inclusion membranes doped with ethylenodiamino-bis-acetylacetone were characterized by scanning electron microscopy and non-contact atomic force microscopy. The influence of membrane morphology on transport process was discussed.
Project description:Fluid catalytic cracking (FCC) is the main conversion process used in oil refineries. An X-ray microscopy method is used to show that metal poisoning and related structural changes in the zeolite active material lead to a non-uniform core–shell deactivation of FCC catalyst particles. The study links the detrimental effect of V and Ni poisoning with zeolite destruction and dealumination in a spatial manner within a single FCC catalyst particle.
Project description:The catalytic cycle of allylic arylation in water catalyzed by linear polystyrene-stabilized Pd or PdO nanoparticles (PS-PdNPs or PS-PdONPs) was investigated. Stoichiometric stepwise reactions indicated that the reaction did not proceed stepwise on the surface of the catalyst. In the case of the reaction with PS-PdNPs, the leached Pd species is the catalytically active species and the reaction takes place through a similar reaction pathway accepted in the case of a complex catalyst. In contrast, allylic arylation using PS-PdONPs as a catalyst occurs via a Pd(II) catalytic cycle.
Project description:Hexavalent chromium is extremely toxic and increasingly prevalent owing to industrialisation, thereby posing serious human health and environmental risks. Therefore, new approaches for detoxifying high concentrations of Cr (VI) using an ultralow amount of catalyst with high recyclability are increasingly being considered. The catalytic conversion of Cr (VI) into Cr (III) was previously reported; however, it required a large amount of catalyst to reduce a low concentration of Cr (VI); further, pH adjustment and catalyst separation had to be performed, causing issues with large-scale remediation. In this study, an unprecedented eco-friendly and cost-effective method was developed for the synthesis of Pd nanoparticles (PdNPs) with a significantly narrow size distribution of 3-25 nm. PdNPs demonstrated the presence of elemental Pd with the zero oxidation state when analysed by energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy. The PdNPs could detoxify a high concentration of Cr (VI), without the need to adjust the pH or purify the nanoparticles for reusability. The reusability of the PdNPs for the catalytic conversion of Cr (VI) into Cr (III) was >90% for subsequent cycles without the further addition of formic acid. Thus, the study provides new insights into the catalytic reclamation of Cr (VI) for industrial wastewater treatment.
Project description:Selective reduction of ketone/aldehydes to alcohols is of great importance in green chemistry and chemical engineering. Highly efficient catalysts are still demanded to work under mild conditions, especially at room temperature. Here we present a synergistic function of single-atom palladium (Pd1) and nanoparticles (PdNPs) on TiO2 for highly efficient ketone/aldehydes hydrogenation to alcohols at room temperature. Compared to simple but inferior Pd1/TiO2 and PdNPs/TiO2 catalysts, more than twice activity enhancement is achieved with the Pd1+NPs/TiO2 catalyst that integrates both Pd1 and Pd NPs on mesoporous TiO2 supports, obtained by a simple but large-scaled spray pyrolysis route. The synergistic function of Pd1 and PdNPs is assigned so that the partial Pd1 dispersion contributes enough sites for the activation of C=O group while PdNPs site boosts the dissociation of H2 molecules to H atoms. This work not only contributes a superior catalyst for ketone/aldehydes hydrogenation, but also deepens the knowledge on their hydrogenation mechanism and guides people to engineer the catalytic behaviors as needed.
Project description:The recovery of La(III) and Ni(II) ions by a macroporous cation exchanger in sodium form (Lewatit Monoplus SP112) has been studied in batch experiments under varying HNO3 concentrations (0.2-2.0 mol/dm3), La(III) and Ni(II) concentrations (25-200 mg/dm3), phase contact time (1-360 min), temperature (293-333 K), and resin mass (0.1-0.5 g). The experimental data revealed that the sorption process was dependent on all parameters used. The maximum sorption capacities were found at CHNO3 = 0.2 mol/dm3, m = 0.1 g, and T = 333 K. The kinetic data indicate that the sorption followed the pseudo-second order and film diffusion models. The sorption equilibrium time was reached at approximately 30 and 60 min for La(III) and Ni(II) ions, respectively. The equilibrium isotherm data were best fitted with the Langmuir model. The maximum monolayer capacities of Lewatit Monoplus SP112 were equal to 95.34 and 60.81 mg/g for La(III) and Ni(II) ions, respectively. The thermodynamic parameters showed that the sorption process was endothermic and spontaneous. Moreover, dynamic experiments were performed using the columns set. The resin regeneration was made using HCl and HNO3 solutions, and the desorption results exhibited effective regeneration. The ATR/FT-IR and XPS spectroscopy results indicated that the La(III) and Ni(II) ions were coordinated with the sulfonate groups.
Project description:Decarboxylation of fatty acids over non-noble metal catalysts without added hydrogen was studied. Ni/C catalysts were prepared and exhibited excellent activity and maintenance for decarboxylation. Thereafter, the effects of nickel loading, catalyst loading, temperature, and carbon number on the decarboxylation of fatty acids were investigated. The results indicate that the products of cracking increased with high nickel loading or catalyst loading. Temperature significantly impacted the conversion of stearic acid but did not influence the selectivity. The fatty acids with large carbon numbers tend to be cracked in this reaction system. Stearic acid can be completely converted at 370 °C for 5 h, and the selectivity to heptadecane was around 80%.
Project description:Poly(tetrafluoroethylene)-stabilized Pd nanoparticles (PTFE-PdNPs) were prepared in water with 4-methylphenylboronic acid as a reductant and characterized using powder X-ray diffraction, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Small PdNPs with a fairly uniform size were obtained in the presence of PTFE, whereas aggregation of palladium was observed in the absence of PTFE. PTFE-PdNPs showed high catalytic activity for the Suzuki coupling reaction in water and were reused without any loss of activity. No palladium species were observed by ICP-AES analysis in the reaction solution after the reaction, nor was any change in particle size observed after the recycle experiment. PTFE-PdNPs also exhibited excellent catalytic activity and reusability for the Heck reaction in water. Although palladium species were not detected in the reaction solution after the reaction, aggregates and smaller sizes of PdNPs were observed in the TEM image of the recovered catalyst. PTFE was also useful as the stabilizer of rhodium nanoparticles (RhNPs) prepared by reduction with NaBH4. PTFE-RhNPs showed high catalytic activity and reusability toward arene hydrogenation under mild conditions.