2,5-Dimethylfuran Production by Catalytic Hydrogenation of 5-Hydroxymethylfurfural Using Ni Supported on Al2O3-TiO2-ZrO2 Prepared by Sol-Gel Method: The Effect of Hydrogen Donors.

5-Hydroxymethylfurfural (5-HMF) has been described as one of the 12 key platform molecules derived from biomass by the US Department of Energy, and its hydrogenation reaction produces versatile liquid biofuels such as 2,5-dimethylfuran (2,5-DMF). Catalytic hydrogenation from 5-HMF to 2,5-DMF was thoroughly studied on the metal nickel catalysts supported on Al2O3-TiO2-ZrO2 (Ni/ATZ) mixed oxides using isopropanol and formic acid (FA) as hydrogen donors to find the best conditions of the reaction and hydrogen donor. The influence of metal content (wt%), Ni particle size (nm), Nickel Ni0, Ni0/NiO and NiO species, metal active sites and acid-based sites on the catalyst surface, and the effect of the hydrogen donor (isopropanol and formic acid) were systematically studied. The structural characteristics of the materials were studied using different physicochemical methods, including N2 physisorption, XRD, Raman, DRS UV-Vis, FT-IR, SEM, FT-IR Pyad, H2-TPD, CO2-TPD, H2-TPR, TEM and XPS. Second-generation 2,5-DMF biofuel and 5-HMF conversion by-products were analyzed and elucidated using 1H NMR. It was found that the Ni0NiO/ATZ3WI catalyst synthesized by the impregnation method (WI) generated a good synergistic effect between the species, showing the best catalytic hydrogenation of 5-HMF to 2,5-DMF using formic acid as a hydrogen donor for 24 h of reaction and temperature of 210 °C with 20 bar pressure of Argon (Ar).

γ-Valerolactone Production from Levulinic Acid Hydrogenation Using Ni Supported Nanoparticles: Influence of Tungsten Loading and pH of Synthesis.

γ-Valerolactone (GVL) has been considered an alternative as biofuel in the production of carbon-based chemicals; however, the use of noble metals and corrosive solvents has been a problem. In this work, Ni supported nanocatalysts were prepared to produce γ-Valerolactone from levulinic acid using methanol as solvent at a temperature of 170 °C utilizing 4 MPa of H2. Supports were modified at pH 3 using acetic acid (CH3COOH) and pH 9 using ammonium hydroxide (NH4OH) with different tungsten (W) loadings (1%, 3%, and 5%) by the Sol-gel method. Ni was deposited by the suspension impregnation method. The catalysts were characterized by various techniques including XRD, N2 physisorption, UV-Vis, SEM, TEM, XPS, H2-TPR, and Pyridine FTIR. Based on the study of acidity and activity relation, Ni dispersion due to the Lewis acid sites contributed by W at pH 9, producing nanoparticles smaller than 10 nm of Ni, and could be responsible for the high esterification activity of levulinic acid (LA) to Methyl levulinate being more selective to catalytic hydrogenation. Products and by-products were analyzed by 1H NMR. Optimum catalytic activity was obtained with 5% W at pH 9, with 80% yield after 24 h of reaction. The higher catalytic activity was attributed to the particle size and the amount of Lewis acid sites generated by modifying the pH of synthesis and the amount of W in the support due to the spillover effect.

Chemical and Structural Changes by Gold Addition Using Recharge Method in NiW/Al2O3-CeO2-TiO2 Nanomaterials.

NiWAu trimetallic nanoparticles (NPs) on the surface of support Al2O3-CeO2-TiO2 were synthesized by a three-step synthetic method in which Au NPs were incorporated into presynthesized NiW/Al2O3-CeO2-TiO2. The recharge method, also known as the redox method, was used to add 2.5 wt% gold. The Al2O3-CeO2-TiO2 support was made by a sol-gel method with two different compositions, and then two metals were simultaneously loaded (5 wt% nickel and 2.5 wt% tungsten) by two different methods, incipient wet impregnation and ultrasound impregnation method. In this paper, we study the effect of Au addition using the recharge method on NiW nanomaterials supported on mixed oxides on the physicochemical properties of synthesized nanomaterials. The prepared nanomaterials were characterized by scanning electron microscopy, BET specific surface area, X-ray diffraction, diffuse reflectance spectroscopy in the UV-visible range and temperature-programmed desorption of hydrogen. The experimental results showed that after loading of gold, the dispersion was higher (46% and 50%) with the trimetallic nanomaterials synthesized by incipient wet impregnation plus recharge method than with impregnation plus ultrasound recharge method, indicating a greater number of active trimetallic (NiWAu) sites in these materials. Small-sized Au from NiWAu/ACTU1 trimetallic nanostructures was enlarged for NiWAu/ACT1. The strong metal NPs-support interaction shown for the formation of NiAl2O4, Ni-W-O and Ni-Au-O species simultaneously present in the surface of trimetallic nanomaterial probably plays an important role in the degree of dispersion of the gold active phase.

Bimetallic M-Cu (M = Ag, Au, Ni) Nanoparticles Supported on γAl2O3-CeO2 Synthesized by a Redox Method Applied in Wet Oxidation of Phenol in Aqueous Solution and Petroleum Refinery Wastewater.

Three bimetallic catalysts of the type M-Cu with M = Ag, Au and Ni supports were successfully prepared by a two-step synthesized method using Cu/Al2O3-CeO2 as the base monometallic catalyst. The nanocatalysts were characterized using X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), N2 adsorption-desorption, scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy with diffuse reflectance (DR-UV-Vis) techniques. This synthesized methodology allowed a close interaction between two metals on the support surface; therefore, it could have synthesized an efficient transition-noble mixture bimetallic nanostructure. Alloy formation through bimetallic nanoparticles (BNPs) of AgCuAlCe and AuCuAlCe was demonstrated by DR-UV-Vis, EDS, TEM and H2-TPR. Furthermore, in the case of AgCuAlCe and AuCuAlCe, improvements were observed in their reducibility, in contrast to NiCuAlCe. The addition of a noble metal over the monometallic copper-based catalyst drastically improved the phenol mineralization. The higher activity and selectivity to CO2 of the bimetallic gold-copper- and silver-copper-supported catalysts can be attributed to the alloy compound formation and the synergetic effect of the M-Cu interaction. Petroleum Refinery Wastewater (PRW) had a complex composition that affected the applied single CWAO treatment, rendering it inefficient.