Multicomponent Bismuth Molybdate Research Articles

Selective oxidation of biomass‐based 5‐hydroxymethylfurfural to 2,5‐diformylfuran catalyzed by multicomponent molybdenum‐based catalyst

AbstractBACKGROUNDOn the way to convert biomass‐derived products as a renewable and environment‐friendly source to high‐value added chemicals, one great challenge is the effective control of selectivity in the reaction. Here, we contribute a heterogeneous catalysis method for selective transformation of biomass‐based 5‐hydroxymethylfurfural (HMF) into 2,5‐diformylfuran (DFF) via multicomponent bismuth molybdate catalyst. The influence of the different pH value on the catalytic activity of the catalyst were investigated. In addition, to evaluate the catalytic performance of the catalyst in the selective oxidation of HMF, a variety of important reaction parameters such as the reaction temperature, catalyst amount, atmosphere, and solvent were examined.RESULTSThe catalyst prepared with pH value in the range of 1–2 exhibits the optimal catalytic activity in the selective aerobic oxidation of the hydroxy group of HMF. As a result, the target compound of DFF could be obtained with excellent yield (99%) and high selectivity (> 99%) in the presence of 0.25 mg Co9Fe3BiMo12O51 (pH = 1–2) in DMSO at 130 °C under O2 atmosphere. In addition, the catalyst Co9Fe3BiMo12O51 could be reused several times without a significant loss of its catalytic activity.CONCLUSIONIn this work, a heterogeneous catalytic approach to oxidizing HMF to DFF using Co9Fe3BiMo12O51 as catalyst and molecular oxygen as oxidant was established. The O2 temperature‐programmed desorption (O2‐TPD) characterization indicated that the pH value of co‐precipitation obviously affected the oxygen mobility and storage capacities in the catalysts, which is related to the catalytic performance in the selective aerobic oxidation. © 2022 Society of Chemical Industry (SCI).

Redox Behavior Analysis of Multicomponent Bismuth Molybdate Catalyst by Using In-situ XAFS

Redox Behavior Analysis of Multicomponent Bismuth Molybdate Catalyst by Using In-situ XAFS

Effects of zirconium content on the catalytic performance of BiMoZrx in the oxidative dehydrogenation of 1‐butene to 1,3‐butadiene

AbstractBACKGROUNDOxidative dehydrogenation (ODH) of 1‐butene has been considered as a potential process for manufacturing 1,3‐butadiene (BD). The introduction of metal oxides to pure bismuth molybdate, a promising catalyst for the ODH reaction, can be expected to improve the catalysts performance. In this work, multicomponent bismuth molybdate oxide (BiMoZrx) catalysts for ODH of 1‐butene were prepared by a co‐precipitation method with variation of zirconium content (x = 0–0.5), and the influence of zirconium on catalytic performance was investigated.RESULTSThe zirconium content has a significant effect on the structure and performance of the catalyst. The conversion of 1‐butene and the BD yield over BiMoZrx catalysts display volcano curves with respect to zirconium content. Among the catalysts tested, BiMoZr0.4 exhibits superior activity.CONCLUSION1‐butene temperature‐programmed re‐oxidation (TPRO) and X‐ray photoelectron spectroscopy (XPS) characterizations demonstrate that zirconium content is related to the oxygen mobility of BiMoZrx catalysts, and oxygen mobility is a crucial factor determining catalytic performance in the ODH reaction. © 2014 Society of Chemical Industry

Mesostructural Bi-Mo-O catalyst: correct structure leading to high performance

Structure-activity relationship has been one of the main topics of research on catalysts all the time. Component and structure are the two moieties governing the performance of solid materials as catalysts. Multicomponent bismuth molybdates are well known catalysts for propene oxidation but pure crystalline phases of bismuth molybdate are inactive for the reaction. We have designed mesostructural Bi-Mo-O catalyst with pure bismuth molybdate nanocrystals attached to molybdenum oxide nanobelts and found it is a high performance catalyst for the reaction, though the two domains themselves are inactive. The strongly expitaxial interaction between the two domains causes the lattice shrinkage and distortion of the bismuth molybdate nanocrystals and extremely promotes their catalytic activity toward propene oxidation while keeping high selectivity at the same time. The results are instructive for design of nano oxide catalysts with mesostructures leading to high performance.

Catalytic conversion of urea to biuret: A catalyst screening study

Biuret was synthesized from urea in a batch reactor using various homogeneous and heterogeneous catalysts, with the aim of searching for efficient catalyst in converting non-catalytic reaction to catalytic reaction. For this purpose, zeolite, heteropolyacid, organic acid and base, multicomponent bismuth molybdate, and multicomponent bismuth molybdate-alumina mixed catalysts were tested. It was revealed that the performance of catalytic reaction was better than that of non-catalytic reaction in the synthesis of biuret from urea. Among the homogeneous acid and base catalysts tested, thionyl chloride (SOCl2) showed the best catalytic performance. Among the heterogeneous catalysts tested, on the other hand, a mixed catalyst comprising multicomponent bismuth molybdate (Co8Fe3Bi1Mo12O50) and alumina showed the best catalytic performance.

Production of 1,3-Butadiene From C4 Raffinate-3 Through Oxidative Dehydrogenation of n-Butene Over Bismuth Molybdate Catalysts

Recent progress on the bismuth molybdate catalysts for oxidative dehydrogenation of n-butene to 1,3-butadiene was reported in this review. A number of bismuth molybdate catalysts, including pure bismuth molybdates (α-Bi2Mo3O12, β-Bi2Mo2O9, and γ-Bi2MoO6) and multicomponent bismuth molybdates, were prepared by a co-precipitation method for use in the production of 1,3-butadiene from C4 raffinate-3 through oxidative dehydrogenation of n-butene. It was observed that multicomponent bismuth molybdate catalyst was more efficient than pure bismuth molybdate catalyst in the oxidative dehydrogenation of n-butene. Various experimental measurements such as temperature-programmed reoxidation, X-ray photoelectron spectroscopy, and O2-temperature-programmed desorption analyses were carried out to elucidate the different catalytic activity of bismuth molybdate catalysts. It was revealed that a bismuth molybdate catalyst with a higher oxygen mobility showed a better catalytic performance in terms of conversion of n-butene and yield for 1,3-butadiene. We have successfully demonstrated from experimental findings that oxygen mobility of bismuth molybdate catalyst played a key role in determining the catalytic performance in the oxidative dehydrogenation of n-butene to 1,3-butadiene.

Preparation, characterization and catalytic activity of Bi−Mo-based catalysts for the oxidative dehydrogenation ofn-butene to 1,3-butadiene

Multicomponent bismuth molybdates were prepared by a co-precipitation method for use in the oxidative dehydrogenation ofn-butene to 1,3-butadiene. The effect of divalent and trivalent metals on the catalytic performance of multicomponent bismuth molybdate catalysts was investigated. It was found that the metal ratio of Fe/Bi/Mo=3∶1∶12 was favorable for the reaction. The successful formation of Ni X Co8−X Fe3Bi1Mo12O50 (X=0−8) catalysts was well confirmed by XRD and ICP-AES measurements. The multicomponent bismuth molybdate catalysts showed a better catalytic performance than the pure γ-Bi2MoO6 catalyst. Among the Ni X Co8−X Fe3Bi1Mo12O50 (X=0−8) catalysts, Ni3Co5Fe3Bi1Mo12O50 showed the highest yield of 1,3-butadiene.

Oxidative dehydrogenation of n-butene to 1,3-butadiene over multicomponent bismuth molybdate (M II9Fe 3Bi 1Mo 12O 51) catalysts: Effect of divalent metal (M II)

Multicomponent bismuth molybdate (M II 9Fe 3Bi 1Mo 12O 51) catalysts with different divalent metal (M II = Mg, Mn, Co, Ni, and Zn) were prepared by a co-precipitation method, and were applied to the oxidative dehydrogenation of n-butene to 1,3-butadiene. Effect of divalent metal (M II) on the catalytic performance of M II 9Fe 3Bi 1Mo 12O 51 catalysts was investigated. X-ray photoelectron spectroscopy (XPS) measurements were conducted to determine the oxygen mobility of M II 9Fe 3Bi 1Mo 12O 51 catalysts. It was found that the catalytic performance of M II 9Fe 3Bi 1Mo 12O 51 catalysts was closely related to the oxygen mobility of the catalysts. The yield for 1,3-butadiene was monotonically increased with increasing oxygen mobility of the catalysts. Among the catalysts tested, the Co 9Fe 3Bi 1Mo 12O 51 catalyst with the highest oxygen mobility showed the best catalytic performance in the oxidative dehydrogenation of n-butene.

Effect of Oxygen Capacity and Oxygen Mobility of Pure Bismuth Molybdate and Multicomponent Bismuth Molybdate on their Catalytic Performance in the Oxidative Dehydrogenation of n-Butene to 1,3-Butadiene

Pure bismuth molybdate (γ-Bi2MoO6) and multicomponent bismuth molybdate (Co9Fe3Bi1Mo12O51) catalysts were prepared by a co-precipitation method, and were applied to the oxidative dehydrogenation of n-butene to 1,3-butadiene. The Co9Fe3Bi1Mo12O51 catalyst showed a better catalytic performance than the γ-Bi2MoO6 catalyst in terms of conversion of n-butene and yield for 1,3-butadiene, indicating that the multicomponent bismuth molybdate was more efficient than the pure bismuth molybdate in the oxidative dehydrogenation of n-butene. It was revealed that the crucial factor determining the catalytic performance of Bi–Mo-based catalyst in the oxidative dehydrogenation of n-butene is not the amount of oxygen in the catalyst involved in the reaction (oxygen capacity) but the intrinsic mobility of oxygen in the catalyst involved in the reaction (oxygen mobility). The enhanced catalytic performance of Co9Fe3Bi1Mo12O51 was due to its facile oxygen mobility.

Reactivity of n-butene isomers over a multicomponent bismuth molybdate (Co9Fe3Bi1Mo12O51) catalyst in the oxidative dehydrogenation of n-butene

Abstract Oxidative dehydrogenation of n- butene isomers to 1,3-butadiene was carried out over a multicomponent bismuth molybdate (Co 9 Fe 3 Bi 1 Mo 12 O 51 ) catalyst. The yield for 1,3-butadiene over the catalyst decreased in the order of 1-butene > mixture of 1-butene and 2-butene > 2-butene. The oxidative dehydrogenation of n- butene to 1,3-butadiene favorably occurred with increasing 1-butene content, while the total oxidation of n- butene to CO 2 was promoted with increasing 2-butene content. It is believed that the Co 9 Fe 3 Bi 1 Mo 12 O 51 catalyst retained more selective oxygen species for the reaction with 1-butene than for the reaction with 2-butene, leading to the facile oxidative dehydrogenation of 1-butene to 1,3-butadiene.

Catalytic performance of multicomponent bismuth molybdates (Ni Fe3Bi1Mo12O42+) in the oxidative dehydrogenation of C4 raffinate-3 to 1,3-butadiene: Effect of nickel content and acid property

Abstract Multicomponent bismuth molybdate (Ni X Fe 3 Bi 1 Mo 12 O 42+ X ) catalysts were prepared by a co-precipitation method with a variation of nickel content, and were applied to the oxidative dehydrogenation of C 4 raffinate-3 to 1,3-butadiene. Conversion of n -butene and selectivity for 1,3-butadiene over Ni X Fe 3 Bi 1 Mo 12 O 42+ X catalysts showed volcano-shaped curves with respect to nickel content. As a consequence, yield for 1,3-butadiene also showed a volcano-shaped curve with respect to nickel content. Among the catalysts tested, Ni 9 Fe 3 Bi 1 Mo 12 O 51 showed the best catalytic performance. Acid properties of Ni X Fe 3 Bi 1 Mo 12 O 42+ X catalysts were measured by NH 3 -TPD experiments, with the aim of correlating the catalytic performance with the acid property of the catalysts. It was observed that either total acidity or acid strength was not directly correlated with the catalytic performance of Ni X Fe 3 Bi 1 Mo 12 O 42+ X catalysts. However, the conversion of n -butene was increased with increasing surface acidity of the catalyst. The largest surface acidity of the Ni 9 Fe 3 Bi 1 Mo 12 O 51 catalyst was responsible for its enhanced catalytic performance in the oxidative dehydrogenation of C 4 raffinate-3. The facile oxygen mobility of the γ-Bi 2 MoO 6 phase in the Ni 9 Fe 3 Bi 1 Mo 12 O 51 catalyst also played an important role in enhancing the catalytic performance of the Ni 9 Fe 3 Bi 1 Mo 12 O 51 catalyst.

Effect of alumina in multicomponent bismuth phosphate catalyst supported on silica-alumina for propylene ammoxidation reaction

The effect of compositions of silica-alumina support on multicomponent bismuth phosphate catalyst (MBP) was investigated for the propylene ammoxidation. It is appears that small amounts of Al2O3 cause retardation of the ammoxidation reaction, which would be due to activation of the selective oxidation pathway. It is understood from such results that the catalytic action of the MBP is essentially different with that of the multicomponent bismuth molybdate catalyst (MBM), which is generally used as propylene ammoxidation catalyst.

Transient Kinetics from the Tap Reactor System: Application to the Oxidation of Propylene to Acrolein

Transient kinetic data have been extracted by use of the Temporal Analysis of Products (TAP) reactor system. In the TAP reactor high resolution transient pulse experiments are performed under vacuum conditions. A rigorous model is developed and applied to the determination of Knudsen diffusivities from experiments with inert pulses. The model was applied to the catalytic oxidation of propylene over an industrial multicomponent bismuth molybdate catalyst. By fitting simulated curves to the experimentally observed response curves, kinetic parameters for the different elementary steps of the reaction were determined. It was shown that the adsorption of propylene is practically irreversible at reaction temperature and that CO 2 and acrylic acid are formed in consecutive reactions from propylene via acrolein. From the values for the kinetic parameters it is proven that under industrial conditions the adsorption of propylene is rate determining. The surface coverage under typical conditions is shown to be quite low. The kinetic model is successfully used for the simulation of a steady state reactor operating under industrial conditions.

Role of Mechanical Treatment in Preparation of Multicomponent Bismuth Molybdate Catalyst for Propylene Ammoxidation

The multicomponent catalyst Mo12Bi1Fe3Co4.5Ni2.5K0.1P0.5Ox/SiO2 (50% w/w) for propylene ammoxidation was prepared by mechanical treatment of the initial components and compared with the catalyst obtained by co-precipitation. Data on its catalytic activity, selectivity and texture (surface area and porosity) are reported. X-Ray study of the samples subjected to mechanical treatment for different times (from 0.5 to 12 h) showed that the treatment leads to changes in phase composition of the catalyst which become more pronounced on prolonged grinding time. The increase of grinding time results also in reduction of the surface area and porosity of the catalysts. Notwithstanding, data obtained demonstrate that mechanical treatment exerts favourable effect on the activity of Fe-Bi-Mo oxide catalysts.

Promotion effect of molybdate support on Bi2Mo3O12 catalyst in the selective oxidation of propylene

Catalytic behavior of Bi2Mo3O12 supported on CoMoO4 or CO11/12Fe1/12MoOx was investigated in the oxidation of propylene to acrolein. A drastic promotion effect was observed only in the catalyst supported on Co11/12Fe1/12MoOx. but not on CoMoO4. Promotion effect of cobalt and iron in the multicomponent bismuth molybdate catalyst, Mo-Bi-MII-MIII-O was discussed.

REACTIVE LATTICE OXYGEN IN MULTICOMPONENT BISMUTH MOLYBDATE CATALYST FOR OLEFIN OXIDATION

Abstract Position of the reactive lattice oxygen in the multicomponent bismuth molybdate catalyst was determined based on the isotope shift in Mo–O stretching vibration by measuring infrared and Raman spectra of the 18O-substituted catalyst with propylene oxidation using 18O2 tracer. It was proven that the oxidation reaction of olefin proceeds in accordance with the “water tank model” proposed by Moro-oka.