In the field of nanoscale magnetocaloric materials, novel concepts like micro-refrigerators, thermal switches, microfluidic pumps, energy harvesting devices and biomedical applications have been proposed. However, reports on nanoscale (Mn,Fe)2(P,Si)-based materials, which are one of the most promising bulk materials for solid-state magnetic refrigeration, are rare. In this study we have synthesized (Mn,Fe)2(P,Si)-based nanoparticles, and systematically investigated the influence of crystallite size and microstructure on the giant magnetocaloric effect. The results show that the decreased saturation magnetization (Ms) is mainly attributed to the increased concentration of an atomically disordered shell, and with a decreased particle size, both the thermal hysteresis and Tc are reduced. In addition, we determined an optimal temperature window for annealing after synthesis of 300–600 °C and found that gaseous nitriding can enhance Ms from 120 to 148 Am2kg−1 and the magnetic entropy change (ΔSm) from 0.8 to 1.2 Jkg−1K−1 in a field change of Δμ0H = 1 T. This improvement can be attributed to the synergetic effect of annealing and nitration, which effectively removes part of the defects inside the particles. The produced superparamagnetic particles have been probed by high-resolution transmission electron microscopy, Mössbauer spectra and magnetic measurements. Our results provide important insight into the performance of giant magnetocaloric materials at the nanoscale.@en

Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. Mössbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH− and the adsorbed P. OH− molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, Mössbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.@en

Cobalt oxidation is a relevant deactivation pathway of titania-supported cobalt catalysts used in Fischer-Tropsch synthesis (FTS). To work towards more stable catalysts, we studied the effect of the surface area of the titania support and noble metal promotion on cobalt oxidation under simulated high conversion conditions. Mössbauer spectroscopy was used to follow the evolution of cobalt during reduction and FTS operation as a function of the steam pressure. The reduction of the oxidic cobalt precursor becomes more difficult due to stronger metal-support interactions when the titania surface area is increased. The reducibility was so low for cobalt on GP350 titania (surface area 283 m2/g) that the catalytical activity was negligible. Although cobalt was more difficult to reduce on P90 titania (94 m2/g) than on commonly used P25 titania (50 m2/g), the Co/P90 catalyst showed increased resistance against cobalt sintering and higher FTS performance than Co/P25. The addition of platinum to Co/P90 led to a higher reduction degree of cobalt and a higher cobalt dispersion, representing a catalyst with promising performance at relatively low steam pressure. Nevertheless, the stronger cobalt-titania interactions result in more extensive deactivation at high steam pressure due to oxidation.@en

The presence of soluble iron and phosphorus in wastewater sludge can lead to vivianite scaling. This problem is not often reported in literature, most likely due to the difficult identification and quantification of this mineral. It is usually present as a hard and blue deposit that can also be brown or black depending on its composition and location. From samples and information gathered in 14 wastewater treatment plants worldwide, it became clear that vivianite scaling is common and can cause operational issues. Vivianite scaling mainly occurred in 3 zones, for which formation hypotheses were discussed. Firstly, iron reduction seems to be the trigger for scaling in anaerobic zones like sludge pipes, mainly after sludge thickening. Secondly, pH increase was evaluated to be the major cause for the formation of a mixed scaling (a majority of oxidized vivianite with some iron hydroxides) around dewatering centrifuges of undigested sludge. Thirdly, the temperature dependence of vivianite solubility appears to be the driver for vivianite deposition in heat exchanger around mesophilic digesters (37 °C), while higher temperatures potentially aggravate the phenomenon, for instance in thermophilic digesters. Mitigation solutions like the use of buffer tanks or steam injections are discussed. Finally, best practices for safe mixing of sludges with each other are proposed, since poor admixing can contribute to scaling aggravation. The relevance of this study lays in the occurrence of ironphosphate scaling, while the use of iron coagulants will probably increase in the future to meet more stringent phosphorus discharge limits.@en

It was recently discovered that vivianite (Fe3(PO4)2.8H2O) could be magnetically extracted from digested activated sludge which opened a new route for phosphorus recovery (Wijdeveld et al. 2022). While its formation in digested sludge is regularly reported, it is not yet studied for fresh, undigested activated sludge. In particular, the extent to which vivianite could form during sludge storage is missing. The current research showed that iron reduction was completed after 2–4 days of anaerobic storage, and the vivianite appeared to form quickly from the pool of reduced iron made available. After sludge thickening at the wastewater treatment plant (30 h retention time), around 11% of the iron was vivianite. With subsequent 1–3 days of anaerobic storage, this fraction increased to 50–55%. After this storage, almost all the vivianite that could potentially form did form. This research concluded that efficient vivianite formation can be achieved without a sludge digester, showing phosphorus recovery potential from undigested sludge via vivianite recovery. Besides, the recovery of vivianite from undigested sludge presents advantages like the reduction of the sludge to dispose of and mitigation of the vivianite scaling formation.@en

The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo2C decorated carbon nanosheets, α-Mo2C nanoparticles, θ-Fe3C nanoparticles, and χ-Fe5C2 nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NOx impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.@en

Transition metals supported on carbons play an important role in catalysis and energy storage. By pyrolysis of metal alginate, highly active catalysts for the Fischer-Tropsch synthesis (FTS) can be produced. However, the evolution of the carbon (alginate) and transition metal (Fe3+) during pyrolysis remains largely unknown and was herein corroborated with several advanced in situ techniques. Initially, Fe3+ was reduced to Fe2+, while bound to alginate. FeO nucleated above 300 °C, destabilizing the alginate functional groups. Increasing temperatures improved carbonization of the carbon support, which facilitated reduction of FeO to α-Fe at 630 °C. Catalysts were produced by pyrolysis between 400 and 700 °C, where the highest FTS activity (612 µmolCO gFe−1 s−1) was achieved for the sample pyrolyzed at low temperature. Lower metal loading, due to less decomposition of alginate, moderated sintering and yielded larger catalytic surface areas. The results provide valuable knowledge for rational design of metal-alginate-based materials.@en

The fundamentals of structure sensitivity and promoter effects in the Fischer–Tropsch synthesis of lower olefins have been studied. Steady state isotopic transient kinetic analysis, switching 12CO to 13CO and H2 to D2, was used to provide coverages and residence times for reactive species on supported iron carbide particles of 2–7 nm with and without promoters (Na + S). CO coverages appeared to be too low to be measured, suggesting dissociative adsorption of CO. Fitting of CH4 response curves revealed the presence of parallel side-pools of reacting carbon. CHx coverages decreased with increasing particle size, and this is rationalized by smaller particles having a higher number of highly active low coordination sites. It was also established that the turnover frequency increased with CHx coverage. To calculate H coverages, new equations were derived to fit HD response curves, again leading to a parallel side-pool model. The H coverages appeared to be lower for bigger particles. The H coverage was suppressed upon addition of promoters in line with lower methane selectivity and higher lower olefin selectivity. Density functional theory (DFT) was applied on H adsorption for a fundamental understanding of this promoter effect on the selectivities, with a special focus on counterion effects. Na2S is a better promoter than Na2O due to both a larger negative charge donation and a more effective binding configuration. On the unpromoted Fe5C2 (111) surface, H atoms bind preferably on C after dissociation on Fe. On Na2S-promoted Fe5C2 surfaces, adsorption on carbon sites weakens, and adsorption on iron sites strengthens, which fits with lower H coverage, less CH4 formation, and more olefin formation.@en

Magnetic refrigeration (MR) is a cutting-edge technology that promises high energy efficiency and eco-friendliness, making it an exciting alternative to traditional refrigeration systems. However, the main challenge to its widespread adoption is cost competitiveness. In this context, the use of liquid metals as heat transfer liquids in the MR has been proposed as a game-changing solution. Unfortunately, the toxicity and flammability of these liquid metals have raised serious concerns, limiting their practical use. In this study, we investigate the compatibility of a nontoxic and nonflammable GaInSn-based liquid metal with a magnetocaloric material, La(Fe,Mn,Si)13Hz, over a 1.5 year period. Our findings reveal nearly a 14% reduction in specific cooling energy and peak-specific isothermal magnetic entropy change for the considered magnetocaloric material. Our study provides valuable insights into the long-term stability of magnetocaloric materials and their compatibility with liquid metals, facilitating the development of more cost-effective and sustainable MR systems.@en

Adsorption is often suggested for to reach very low phosphate levels in municipal wastewater effluent and even to recover phosphate. Adsorbent performance is usually associated with surface area but the exact role of the pore size distribution (PSD) is unclear. Here, we show the effect of the PSD on phosphate adsorption. Granular activated carbons (GACs) with varying PSDs were treated with potassium permanganate followed by reaction with ferric chloride to form iron oxide coated GACs (Fe-GACs). Energy dispersive X-ray and kinetics experiments confirmed that manganese anchored on the GAC is important for subsequent iron attachment. Mössbauer spectroscopy showed presence of ferrihydrite in Fe-GAC. Transmission electron microscopy showed that the iron oxide particles are not present in the micropores of the GACs. Phosphate adsorption isotherms were performed with the Fe-GACs and adsorption at lower phosphate concentrations correlated with the porous area of >3 nm of the adsorbents, a high fraction of which is contributed by mesopores. These results show that high surface areas of GACs resulting from micropores do not contribute to adsorption at low phosphate concentrations. This can be explained by the micropores being difficult to coat with iron oxide nanoparticles, but in addition the diffusion of phosphate into these pores could also be hindered. It is therefore recommended to use backbones having high mesoporous areas. This information is useful for developing adsorbents particularly for applications treating low phosphate concentrations, for e.g. in municipal wastewater effluent polishing.@en

The effect of Co and Ni doping on the structure, magnetic and magnetocaloric properties of Fe-rich (Mn,Fe)2(P,Si) compounds was studied. With increasing Co and Ni content, both the Curie temperature (Tc) and the thermal hysteresis (ΔThys) decreased, whereas the hexagonal P-62 m crystal structure was maintained. A pronounced reduction in hysteresis was observed upon Co doping, while a significant reduction in Curie temperature was found upon Ni doping. Mössbauer spectroscopy measurements and DFT calculations indicated the substitution of Fe at the 3f site for both Co and Ni doping. Rietveld refinement of the X-ray diffraction data showed that Co substitute atoms in the main phase and the impurity phase, while Ni exhibits an affinity to the main phase. Magnetization measurements on the Co doped samples revealed an increase in magnetization for 2 at.% of Co, followed by a decrease for higher concentrations. DFT calculations showed that the magnetic moment on the 3f site is enhanced by Co substitution, whereas an opposite trend was observed for Ni substitution.@en

A set of doped iron oxides (chromium, aluminum, gallium, indium, manganese, zinc, niobium) were prepared by a one-step coprecipitation/calcination approach evaluated for their WGS activity under industrially relevant conditions and characterized in detail. The WGS activity after ageing the doped catalyst for 4 days at 25 bar follows the order chromium ≈ aluminum > gallium > indium > manganese > zinc > niobium for copper-codoped catalysts. The activated catalysts predominantly consist of magnetite, irrespective of the dopant. Mössbauer spectra of aged catalysts showed that aluminum and zinc occupy both tetrahedral and octahedral sites of magnetite, while chromium, gallium, indium, manganese, and niobium preferentially substitute octahedral iron. The incorporation of trivalent metal ions of similar size to octahedral Fe3+ (i.e., chromium, aluminum, gallium) results in moderate to high CO conversion, irrespective of incorporation in tetrahedral or octahedral sites. The substitution of Fe2+ with Mn2+ results in an increased Fe3+/Fe2+ ratio. Incorporation of Zn2+ in tetrahedral sites (replacing Fe3+ ions) leads to a complex structure where the charge balance is compensated from the octahedral sites. Separate dopant metal oxide phases were observed in indium- and niobium-doped catalysts. XPS shows that copper is present as a separate phase in activated copper-codoped catalysts. Aluminum is identified as the most promising promoter for substituting chromium in commercial high-temperature WGS catalysts on the basis of their similar high CO conversion although incorporation of these dopants into the magnetite structure differed substantially. @en

The transition-metal based Laves phase materials represent an extended family of alloys with rich and fascinating physical properties. In this work, we have investigated the negative thermal expansion and magnetocaloric effect in arc-melted and melt-spun Fe2Hf1-xTix (x = 0.15, 0.27, 0.30, 0.33, 0.36, 0.40) alloys. For x = 0.30–0.40, two hexagonal phases with different compositions share the same P63/mmc lattice symmetry, but have slightly different lattice parameters. The saturation magnetization and Curie temperature both follow a decreasing trend with the average unit-cell volume. For Fe2Hf0.6Ti0.4 melt spinning improves the saturation magnetization from 48.7 to 59.6 Am2/kg and the magnetic entropy change from 0.46 to 0.54 J/kgK at a magnetic field change of 2 T. These enhanced values are attributed to an improved homogeneity caused by a suppression of phase segregation during rapid solidification. We have utilized neutron powder diffraction and Mössbauer spectroscopy to illustrate the correlation between the magnetic order and the negative thermal expansion in single-phase Fe2Hf0.85Ti0.15. The magnetic moments of Fe align below 400 K in the a-b plane and a moment change for the Fe atoms is responsible for the large volumetric coefficient of thermal expansion of −25 × 10−6 K−1 over a wide temperature range of 300–400 K.@en

Understanding the deactivation mechanism of cobalt-based Fischer-Tropsch catalysts is of significant practical importance. Herein, we explored the role of manganese as a structural promoter on silica-supported cobalt nanoparticles under simulated high CO conversion conditions, i.e., high relative humidity. The structural changes in cobalt dispersion and oxidation state were followed by in situ Mössbauer emission spectroscopy. Adding manganese oxide to silica-supported cobalt enhanced the dispersion of metallic cobalt in the reduced catalysts. This higher cobalt dispersion, however, led to a stronger tendency of cobalt silicate formation under humid conditions. Without manganese, the cobalt particles sintered, and the larger ones were prone to transformation into cobalt carbide under high conversion conditions. As such, silica is not preferred as a support for practical FTS.@en

Iron is an important element for modern sewage treatment, inter alia to remove phosphorus from sewage. However, phosphorus recovery from iron phosphorus containing sewage sludge, without incineration, is not yet economical. We believe, increasing the knowledge about iron-phosphorus speciation in sewage sludge can help to identify new routes for phosphorus recovery. Surplus and digested sludge of two sewage treatment plants was investigated. The plants relied either solely on iron based phosphorus removal or on biological phosphorus removal supported by iron dosing. Mössbauer spectroscopy showed that vivianite and pyrite were the dominating iron compounds in the surplus and anaerobically digested sludge solids in both plants. Mössbauer spectroscopy and XRD suggested that vivianite bound phosphorus made up between 10 and 30% (in the plant relying mainly on biological removal) and between 40 and 50% of total phosphorus (in the plant that relies on iron based phosphorus removal). Furthermore, Mössbauer spectroscopy indicated that none of the samples contained a significant amount of Fe(III), even though aerated treatment stages existed and although besides Fe(II) also Fe(III) was dosed. We hypothesize that chemical/microbial Fe(III) reduction in the treatment lines is relatively quick and triggers vivianite formation. Once formed, vivianite may endure oxygenated treatment zones due to slow oxidation kinetics and due to oxygen diffusion limitations into sludge flocs. These results indicate that vivianite is the major iron phosphorus compound in sewage treatment plants with moderate iron dosing. We hypothesize that vivianite is dominating in most plants where iron is dosed for phosphorus removal which could offer new routes for phosphorus recovery.@en

Hydrogenation of levulinic acid to γ-valerolactone is a key reaction in the valorization of carbohydrates to renewable fuels and chemicals. State-of-the-art catalysts are based on supported noble metal nanoparticle catalysts. We report the utility of a bimetallic Fe-Re supported on TiO2 for this reaction. A strong synergy was observed between Fe and Re for the hydrogenation of levulinic acid in water under mild conditions. Fe-Re/TiO2 shows superior catalytic performance compared to monometallic Fe and Re catalysts at similar metal content. The hydrogenation activity of the bimetallic catalysts increased with Re content. H2-TPR, XPS, XANES, EXAFS, Mössbauer spectroscopy, TEM, and low-temperature CO IR spectroscopy show that the bimetallic catalysts contain metallic Re nanoparticles covered by FeOx species and small amounts of a Fe-Re alloy. Under reaction conditions, the partially reduced surface FeOx species adsorb water and form Brønsted acidic OH groups, which are involved in dehydration of reaction intermediates. Under optimized conditions, nearly full conversion of levulinic acid with a 95 % yield of γ-valerolactone could be achieved at a temperature as low as 180 °C in water at a H2 pressure of 40 bar.@en

The formation of Fe-carbide phases is relevant to the synthesis of Fischer-Tropsch synthesis catalysts. We investigated the carburization of Raney Fe as a model catalyst using spectroscopic and temperature-programmed techniques. IR spectroscopy shows that CO dissociation already occurs at −150 °C, while C diffusion into metallic Fe requires much higher temperature (~180 °C). The carburization rate increases with increasing H2/CO ratio, which can be attributed to the lower overall barrier for O removal as H2O as compared to CO2. O removal frees vacancies that are needed for CO dissociation. The resulting higher C coverage increases the driving force for Fe-carbide formation. A higher driving force leads to predominant formation of the more carbon-rich ε(́)-carbide, while χ-Fe5C2 is formed at lower H2/CO ratio. The removal of surface O appears to be the rate-limiting step under all conditions. Initially, most of deposited C is used for Fe-carbide formation with a small contribution to hydrocarbons formation.@en

We report a comparison of different common synthetic strategies for preparation of Prussian blue analogues (PBA). PBA are promising as cathode material for a number of different battery types, including K-ion and Na-ion batteries with both aqueous and non-aqueous electrolytes. PBA exhibit a significant degree of structural variation. The structure of the PBA determines the electrochemical performance, and it is, therefore, important to understand how synthesis parameters affect the structure of the obtained product. PBA are often synthesized by co-precipitation of a metal salt and a hexacyanoferrate complex, and parameters such as concentration and oxidation state of the precursors, flow rate, temperature and additional salts can all potentially affect the structure of the product. Here, we report 12 different syntheses and compare the structure of the obtained PBA materials. @en

Hydrogenation into light olefins is an attractive strategy for CO2fixation into chemicals. In this article, high throughput experimentation and extended characterization were employed to identify the most efficient promoters and to elucidate structure-performance correlations and reaction paths in the CO2hydrogenation to light olefins over zirconia-supported iron catalysts. K, Cs, Ba, Ce, Nb, Mo, Mn, Cu, Zn, Ga, In, Sn, Sb, Bi, and V were added in the same molar concentrations to zirconia-supported iron catalyst and evaluated as promoters. The CO2hydrogenation proceeds via intermediate formation of CO followed by surface polymerization. Over the iron catalysts containing alkaline promoters, initially higher selectivity to light olefins shows a significant decrease with the CO2conversion, because of further surface polymerization and the formation of longer chain hydrocarbons. A relatively low selectivity to light olefins over the promoted catalysts, without potassium, is not much affected by the CO2conversion. Essential characteristics of iron catalysts to obtain a higher yield of light olefins seem to be a higher iron dispersion, a higher extent of carbidization, and optimized basicity. The strongest promoting effect is reported for the alkaline metals. A further increase in the light olefin selectivity is observed after simultaneous addition of potassium with copper, molybdenum, gallium, or cerium.@en