Dependence of n-butane activation on active site of vanadium phosphate catalysts

The nature and the role of oxygen species and vanadium oxidation states on the activation of n-butane for selective oxidation to maleic anhydride were investigated. Bi–Fe doped and undoped vanadium phosphate catalysts were used a model catalyst. XRD revealed that Bi–Fe mixture dopants led to formation of αII-VOPO4 phase together with (VO)2P2O7 as a dominant phase when the materials were heated in n-butane/air to form the final catalysts. TPR analysis showed that the reduction behaviour of Bi–Fe doped catalysts was dominated by the reduction peak assigned to the reduction of V5+ species as compared to the undoped catalyst, which gave the reduction of V4+ as the major feature. An excess of the oxygen species (O2−) associated with V5+ in Bi–Fe doped catalysts improved the maleic anhydride selectivity but significantly lowering the rate of n-butane conversion. The reactive pairing of V4+-O− was shown to be the centre for n-butane activation. It is proposed that the availability and appearance of active oxygen species (O−) on the surface of vanadium phosphate catalyst is the rate determining step of the overall reaction

Investigating the influence of Fe speciation on N2O decomposition over Fe–ZSM-5 catalysts

The influence of Fe speciation on the decomposition rates of N2O over Fe–ZSM-5 catalysts prepared by Chemical Vapour Impregnation were investigated. Various weight loadings of Fe–ZSM-5 catalysts were prepared from the parent zeolite H-ZSM-5 with a Si:Al ratio of 23 or 30. The effect of Si:Al ratio and Fe weight loading was initially investigated before focussing on a single weight loading and the effects of acid washing on catalyst activity and iron speciation. UV/Vis spectroscopy, surface area analysis, XPS and ICP-OES of the acid washed catalysts indicated a reduction of ca. 60% of Fe loading when compared to the parent catalyst with a 0.4 wt% Fe loading. The TOF of N2O decomposition at 600 °C improved to 3.99 × 103 s−1 over the acid washed catalyst which had a weight loading of 0.16%, in contrast, the parent catalyst had a TOF of 1.60 × 103 s−1. Propane was added to the gas stream to act as a reductant and remove any inhibiting oxygen species that remain on the surface of the catalyst. Comparison of catalysts with relatively high and low Fe loadings achieved comparable levels of N2O decomposition when propane is present. When only N2O is present, low metal loading Fe–ZSM-5 catalysts are not capable of achieving high conversions due to the low proximity of active framework Fe3+ ions and extra-framework ɑ-Fe species, which limits oxygen desorption. Acid washing extracts Fe from these active sites and deposits it on the surface of the catalyst as FexOy, leading to a drop in activity. The Fe species present in the catalyst were identified using UV/Vis spectroscopy and speculate on the active species. We consider high loadings of Fe do not lead to an active catalyst when propane is present due to the formation of FexOy nanoparticles and clusters during catalyst preparation. These are inactive species which lead to a decrease in overall efficiency of the Fe ions and consequentially a lower TOF

The formation of methanol from glycerol bio-waste over doped ceria based catalysts

A series of ceria-based solid-solution metal oxides were prepared by co-precipitation and evaluated as catalysts for glycerol cleavage, principally to methanol. The catalyst activity and selectivity to methanol were investigated with respect to the reducibility of the catalysts. Oxides comprising of Ce-Pr and Ce-Zr were prepared, calcined and compared to CeO2, Pr6O11 and ZrO2. The oxygen storage capacity of the catalysts was examined with analysis of Raman spectroscopic measurements and a temperature programmed reduction, oxidation and reduction cycle. The incorporation of Pr resulted in significant defects, as evidenced by Raman spectroscopy. The materials were evaluated as catalysts for the glycerol to methanol reaction and it was found that an increased defect density or reducibility was beneficial. The space time yield of methanol normalised to surface area over CeO2 was found to be 0.052 mmolMeOH m-2 h-1 and over CeZrO2 and CePrO2 this was to 0.029 and 0.076 mmolMeOH m-2 h-1 respectively. The inclusion of Pr reduced the surface area, however, the carbon mole selectivity to methanol and ethylene glycol remained relatively high, suggesting a shift in the reaction pathway compared to that over ceria. This article is part of a discussion meeting issue “Science to enable the circular economy”

Ammonia decomposition enhancement by Cs-Promoted Fe/Al2O3 catalysts

A range of Cs-doped Fe/Al2O3 catalysts were prepared for the ammonia decomposition reaction. Through time on-line studies it was shown that at all loadings of Cs investigated the activity of the Fe/Al2O3 catalysts was enhanced, with the optimum Cs:Fe being ca. 1. Initially, the rate of NH3 decomposition was low, typically < 10% equilibrium conversion (99.7%@500°C) recorded after 1 h. All catalysts exhibited an induction period (typically ca. 10 h) with the conversion reaching a high of 67% equilibrium conversion for Cs:Fe = 0.5 and 1. The highest rate of decomposition observed was attributed to the balance between increasing the concentration of Cs without blocking the active site. Analysis of H2-TPR and XPS measurements indicated that Cs acts as an electronic promoter. Previously, Cs has been shown to act as a promoter for Ru, where Cs alters the electron density of the active site, thereby facilitating the recombination of N2 which is considered the rate determining step. In addition, XRD and N2 adsorption measurements suggest that with higher Cs loadings deactivation of the catalytic activity is due to a layer of CsOH that forms on the surface and blocks active sites

Experimental methods in chemical engineering: Scanning electron microscopy and X-ray ultra-microscopy—SEM and XuM

Scanning electron microscopy (SEM) produces images at 500 000 times magnification and better than 1 nm resolution to characterize inorganic and organic solid morphology, surface topography, and crystallography. An electron beam interacts with the material and generates secondary electrons (SE) and backscattered electrons (BSE) that detectors capture. Coupled with X-ray energy-dispersive spectroscopy (X-EDS), SEM-EDS identifies elemental composition. X-ray ultra-microscopy (XuM) traverses particles to identify phase changes and areas of high density and voids without slicing through the solids by microtome. Although SEM instrument capability continuously evolves with higher magnification and better resolution, desktop SEMs are becoming standard in laboratories that require frequent imaging and lower magnification. Hand-held cameras (800–1500×) have the advantage of low cost, ease of use, and better colours. SEM depth of field is better than visible light microscopy, but image stacking software has narrowed the gap between the two. Modern user interfaces mean that today's SEM instruments are easier to operate and data acquisition is faster, but operators must be able to select the right technique for the application (e.g., SE vs. BSE). Furthermore, they must understand how operating parameters like probe current, accelerating voltage, spot-diameter, convergence angle, and working distance compromise sample integrity. The number of articles the Web of Science indexes that mention SEM has grown from 1000 in 1990 to over 40 000 in 2021. A bibliometric map identified four clusters of research: mechanical properties and microstructure; nanoparticles, composites, and graphene; antibacterial and green synthesis; and adsorption and wastewater

Can gold be an effective catalyst for the Deacon reaction?

The Deacon reaction is an important industrial process for the oxidation of hydrogen chloride, thereby enabling chlorine to be recycled. As gold is an efficient catalyst for reactions involving hydrogen chloride and oxygen, we have studied the use of gold as a potential catalyst for the Deacon reaction. Unfortunately, gold displays only limited activity; however, this is markedly increased if hydrogen is cofed as a reactant

Influence of Bi–Fe additive on properties of vanadium phosphate catalysts for n-butane oxidation to maleic anhydride

The physico-chemical and catalytic properties of three ways of modified catalysts were studied, i.e. (i) the addition of both Bi and Fe (nitrate form) during the refluxing VOPO4·2H2O with isobutanol (Catalyst A), (ii) the simultaneous addition of BiFe oxide powder in the course of the synthesis of precursor VOHPO4·0.5H2O (Catalyst B) and (iii) the mechanochemical treatment of precursor VOHPO4·0.5H2O and BiFe oxide in ethanol (Catalyst C). It was found that surface area of the modified catalysts has increased except Catalyst B. The reactivity of the oxygen species linked to V5+ and V4+ was studied by using H2-TPR, which also affected the catalytic performance of the catalyst. The conversion of n-butane decreases with an increment of oxygen species associated with V5+

Heterogeneous Trimetallic Nanoparticles as Catalysts

The development and application of trimetallic nanoparticles continues to accelerate rapidly as a result of advances in materials design, synthetic control, and reaction characterization. Following the technological successes of multicomponent materials in automotive exhausts and photovoltaics, synergistic effects are now accessible through the careful preparation of multielement particles, presenting exciting opportunities in the field of catalysis. In this review, we explore the methods currently used in the design, synthesis, analysis, and application of trimetallic nanoparticles across both the experimental and computational realms and provide a critical perspective on the emergent field of trimetallic nanocatalysts. Trimetallic nanoparticles are typically supported on high-surface-area metal oxides for catalytic applications, synthesized via preparative conditions that are comparable to those applied for mono- and bimetallic nanoparticles. However, controlled elemental segregation and subsequent characterization remain challenging because of the heterogeneous nature of the systems. The multielement composition exhibits beneficial synergy for important oxidation, dehydrogenation, and hydrogenation reactions; in some cases, this is realized through higher selectivity, while activity improvements are also observed. However, challenges related to identifying and harnessing influential characteristics for maximum productivity remain. Computation provides support for the experimental endeavors, for example in electrocatalysis, and a clear need is identified for the marriage of simulation, with respect to both combinatorial element screening and optimal reaction design, to experiment in order to maximize productivity from this nascent field. Clear challenges remain with respect to identifying, making, and applying trimetallic catalysts efficiently, but the foundations are now visible, and the outlook is strong for this exciting chemical field

Recent advances on the valorization of glycerol into alcohols

Glycerol, a highly functionalised polyol, can be used as a platform molecule to produce a variety of high-value chemicals. As glycerol production is projected to increase over the coming years, it’s critically important that technology and infrastructure are developed to make use of the inevitable surplus. The catalytic production of ‘green’ mono alcohols from glycerol, in the absence of H2, is an emerging area of research that, in recent years, has generated significant industrial interest. Herein, we provide an update on recent advances in this field and discuss challenges which need to be overcome if this approach is to be considered viable industrially. The economic significance of using crude glycerol as a feedstock for glycerol valorisation strategies is also addressed and suggestions for improving the impact of research conducted in this field are proposed

Advancing critical chemical processes for a sustainable future: challenges for industry and the Max Planck-Cardiff centre on the fundamentals of heterogeneous catalysis (funcat)

Catalysis is involved in around 85 % of manufacturing industry and contributes an estimated 25 % to the global domestic product, with the majority of the processes relying on heterogeneous catalysis. Despite the importance in different global segments, the fundamental understanding of heterogeneously catalysed processes lags substantially behind that achieved in other fields. The newly established Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT) targets innovative concepts that could contribute to the scientific developments needed in the research field to achieve net zero greenhouse gas emissions in the chemical industries. This Viewpoint Article presents some of our research activities and visions on the current and future challenges of heterogeneous catalysis regarding green industry and the circular economy by focusing explicitly on critical processes. Namely, hydrogen production, ammonia synthesis, and carbon dioxide reduction, along with new aspects of acetylene chemistry