Mono-, Bi-, and Tri-Metallic DES Are Prepared from Nb, Zr, and Mo for n-Butane Selective Oxidation via VPO Catalyst

In recent work, deep eutectic solvents (DESs) as ionic liquid analogues have been abundantly used in catalysis. Herein, vanadium phosphorus oxide (VPO) catalysts were synthesized from mono-, bi-, and tri- metallic DES of Nb, Zr, and Mo metal dopants as structure-directing agents and electronic promoters for n-butane selective oxidation towards maleic anhydride. Higher MA selectivity and larger n-butane conversion was successfully obtained using the newly developed catalysts, while oxidation by-product COx (CO, CO2) was minimized. Characterization techniques including FTIR, DSC, XRD, TEM, SEM, EDS, Raman spectroscopy, TGA, XPS, and NH3-TPD were employed to fully characterize the DESs, precursors and catalysts. This work led to an increase of 7.8% in MA mass yield with 16% more n-butane conversion as compared to an unpromoted VPO catalyst. Moreover, the utilization of a low-carbon alkane brought in a green impact on the chemical plant as well as the environment.

Phosphorus-Doped Carbon Supported Vanadium Phosphate Oxides for Catalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran

2,5-diformylfuran (DFF) is an important downstream product obtained by selective oxidation of the biomass-based platform compound 5-hydroxymethylfurfural (HMF). In this study, a phosphorus-doped carbon (P-C) supported vanadium phosphate oxide (VPO) catalyst was successfully prepared and showed remarkably high catalytic activity in the selective oxidation of HMF to produce DFF with air as an oxidant. The effects of the reaction temperature, reaction time, solvent, catalyst amount, and VPO loading amount were investigated. The results showed that an HMF conversion rate of 100% and a DFF yield of 97.0% were obtained under suitable conditions, and DMSO was found to be the most suitable solvent under an air atmosphere.

The obtaining of the anhydride products by oxidation of n-pentane on the VPO catalysts

It was investigated VPMeO catalysts (Me=Fe, Mo, Te, W, Ni, Ti, La, Bi, Zr і Ag) in oxidation of n-pentane. On these catalytic samples the main products of reaction are maleic (MA), phthalic (PhA), citraconic (CA) anhydrides, carbon oxides and in-significant quantity of acetic and of acrylic acids. It was established that a change of physical-chemical properties of the VPMeO catalysts affects a course of reaction of n-pentane oxidation. It was determined that the introduction of additives into the basic VPO composition and its content influences a phase composition, a morphol-ogy, acidic properties of catalyst surface, a crystallization temperature of active component and a oxidation degree of vanadium in it. It was established that addi-tives in the VPO sample may be distributed in two ways: a) evenly, high disperse (Fe, Te, Ni, Ag ions), b) with formation of X-ray amorphous additive phosphate phase (Ti, Bi, La, W, Zr ions). Additives that decrease temperature of the active phase formation of a catalyst and increase temperature of its oxidation (Fe, Ti, Bi, Zr ions) positively influence the life of exploitation of catalytic pattern without losing its se-lectivity in the n-pentane oxidation. Additives that reduce the O 1s-electrons energy and increase an oxygen content (O/(V+P+Me)) on the VPO composition surface en-hance the specific rate of the hydrocarbon oxidation. A growth of phosphorous con-tent on the surface of synthesized compositions also contributes to the increase of the time of their stable work. The influence of ratio of Bronsted and Lewis acid cen-ters on surface of the VPМеO pattern on a selectivity of anhydrides production was established. The growth of acidic centers content on the surface of patterns increas-es the CA selectivity. The rise of quantity of Lewis centers favors the PhA formation while the MA selectivity reduces in the reaction products. According to experimental data the modification of the VPO catalyst is affect its physical-chemical and cata-lytic properties. The change of defined physical-chemical properties allows to regu-late a process of the n-pentane oxidation in the direction of formation of one of the anhydrides.

Direct ultrasound synthesis of vanadyl pyrophosphate catalyst for partial oxidation of n-butane to maleic anhydride

Three VPO catalyst were prepared via direct ultrasound technique using organic, sesquihydrate and dihydrate routes, denoted as VPOuo, VPOus and VPOud respectively. These catalysts were synthesised solely on direct ultrasound technique and calcined in n-butane/air mixture. All catalysts exhibited well-crystallised (VO)2P2O7 phase. VPOus and VPOud showed αII-VOPO4, which led to an increase in average oxidation state of vanadium. All catalysts were showing O1s approx. 530 eV, similar P2p value and V2p3/2 at approx. 517 eV, giving vanadium oxidation state of approx. 4.0 – 4.2. FE-SEM micrographs showed the secondary structure consisting of thin plate-like crystals in different sizes agglomerate to each other due to cavitation effect. HR-TEM demonstrated the existence of polycrystalline phase. The nature of the oxidants was investigated by TPR in H2. VPOus showed highest amount of total removal of oxygen species suggesting that it had highest activity compared to VPOuo and VPOud. The XANES measurement of these catalysts showed the occurrence of vanadium oxide reductions in flowing hydrogen gas, which indicates the presence of V4+ and V5+ species. Catalytic tests demonstrated that the activity and selectivity to maleic anhydride increased with direct ultrasound technique. This study showed that catalyst synthesis time can be reduced to only 2 hours and giving polycrystalline particles compared to conventional method.

Vapour phase dehydration of glycerol to acrolein over vanadium phosphorous oxide (VPO) catalyst

X-ray diffraction patterns of pure and spent VPO samples.

Influence of Intercalation-Exfoliation-Reduction Technique towards the Physico-Chemical of VPO Catalysts

Four VPO catalysts were synthesized through intercalation and exfoliation in various alcohols and subsequent reduction of the exfoliated VOPO4sheets with various alcohols to produce VOHPO4⋅0.5H2O. The resulting VOHPO4⋅0.5H2O that undergoes the intercalation-exfoliation-reduction (IER) process will be further activated into VPO catalysts, and addition of 1 mole % Bi(NO3)3⋅5H2O in the first stage of this experiment has also being investigated. The synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and temperature-programmed reduction (TPR) in H2. Catalytic evaluation of the IER-treated and Bi-doped VPO catalysts was also studied on microreactor. The VPO catalyst produced through IER using 2-butanol and ethanol with addition of Bi, IERC(2Bu-Et)RBi1, gave the highest MA selectivity due to reactive O2−species released from the additional crystalline V5+phase formed by doping 1% bismuth as promoter (O2−-V5+pair) at relative lower temperature. Nevertheless, the VPO catalyst produced through IER using isobutanol, IERC(isoBu), gave the highest activity due to high amount of reactive O−species released from V4+phase (O−-V4+pair) whereby the IERC(isoBu) catalyst synthesized consists of high percentage of V4+(93 %).