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The Norway lobster (Nephrops norvegicus) is one of the most important decapod crustacean seafood species in the Adriatic Sea. Previous research has identified significant differences in growth rates and maturation timing of Nephrops in the Pomo/Jabuka Pits area compared to other subpopulations in Adriatic fishing grounds. Here, we use 1,623 genome-wide single nucleotide polymorphisms (SNPs) to investigate whether the Pomo Pits subpopulation is genetically different from other sites in the Adriatic and neighbouring seas. We found no genetic differentiation among all sampled Adriatic sites, suggesting high gene flow between Pomo Pits Nephrops and those of surrounding areas. We also found genetic homogeneity between the Adriatic sites and single-site samples from the Aegean and Tyrrhenian Seas. However, we detected distinct genetic differentiation between all Mediterranean sites and an Atlantic site in western Scotland, which provides evidence for a phylogenetic break between the Atlantic and the Mediterranean. Our results indicate that Pomo Pits Nephrops are not genetically different from others sampled in the Adriatic and that key biological parameters in Pomo Pits Nephrops could be driven by spatial variation in fishing pressure and/or environmental factors rather than geographic isolation.

Although fishing is considered the primary cause of the decline in fish populations, increasing evidence of the significant role of climate change has been provided recently in the Mediterranean Sea, which shows one of the highest warming trends in the world. In this area, the most important environmental driver is represented by the increase in seawater temperature. Though several studies have addressed the effects of sea warming on thermophilic species, little attention has been paid to cold-water species. Among these, blue whiting (Micromesistius poutassou) constitutes one of the most important traditional fisheries resources in the northern part of the basin, particularly in the central Adriatic Sea. This area has experienced intense fishing exploitation by the Italian and Croatian fishing fleets. Since 2015, the Pomo/Jabuka Pits area, the fleets’ main fishing ground, has been subject to a series of fishing regulations over time and space. In the present study, we investigated the age structure and growth performance (by means of otoliths) of blue whiting, comparing samples collected during 1985–86 and 2020–21 in the Pomo/Jabuka Pits. Our results show that the 2020–21 blue whiting specimens had a lower length-at-age compared to 1985–86. The asymptotic length estimate decreased from 29 cm TL in 1985–86 to 25 cm TL in 2020–21. The pattern observed might be related to a modification in the cold and dense water formation dynamics in the northern Adriatic Sea, as a consequence of climate change, resulting in higher temperatures and lower nutrient and oxygen exchange, which may have hampered the optimal growth of the species. Moreover, data on the historical trend of landings from the Adriatic Sea reveals a clear decline in catches starting from 2000 onwards. Although the introduction of a fishing ban in the Pomo/Jabuka Pits was an important milestone, the abundance of this species in the area remains at low levels, highlighting a potentially alarming situation for the stock of blue whiting in the central Adriatic Sea.

Ocean observations are the foundation of our understanding of ocean processes. Improving these observations has critical implications for our ability to sustainably derive food from the ocean, predict extreme weather events that take a toll on human life, and produce the goods and services that are needed to meet the needs of a vast and growing population. While there have been great leaps forward in sustained operational monitoring of our oceans there are still key data gaps which result in sub-optimal ocean management and policy decisions. The global fishing industry represents a vast opportunity to create a paradigm shift in how ocean data are collected: the spatio-temporal extent of ocean data gaps overlaps significantly with fishers’ activities; fishing vessels are suitable platforms of opportunity to host communications and sensor equipment; and many fishing vessels effectively conduct a depth-profile through the water column in the course of normal fishing activities, representing a powerful subsurface data collection opportunity. Fishing vessel-collected ocean data can complement existing ocean observing networks by enabling the cost-effective collection of vast amounts of subsurface ocean information in data-sparse regions. There is an emerging global network of fishing vessels participating in collaborative efforts to collect oceanographic data accelerated by innovations in enabling technologies. While there are clear opportunities that arise from partnering with fishing vessels, there are also challenges ranging from geographic and cultural differences in fleets, fishing methods and practices, data processing and management for heterogeneous data, as well as long term engagement of the fishers. To advance fishing vessel-based ocean observation on a global scale, the Fishing Vessel Ocean Observing Network (FVON) aims to maximize data value, establish best practices around data collection and management, and facilitate observation uptake. FVON’s ultimate goals are to foster collaborative fishing vessel-based observations, democratize ocean observation, improve ocean predictions and forecasts, promote sustainable fishing, and power a data-driven blue economy.

Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO2. In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO2 and H2. Alkali-doping of 2 wt% Pt/m-ZrO2 increases catalyst basicity, which weakens the formate CH bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate ν(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H- to D-labeled formaldehyde in TP-reaction/MS.

In this contribution, we examine the effect of the promoter´s ionic charge and valence orbital energy on the catalytic activity of Fe-based catalysts, based on in situ synchrotron X-ray powder diffraction (SXRPD), temperature-programmed-based techniques (TPR, TPD, CO-TP carburization), and Fischer–Tropsch synthesis catalytic testing studies. We compared the promoting effects of K (a known promoter for longer-chained products) with Ba, which has a similar ionic radius but has double the ionic charge. Despite being partially “buried” in a crystalline BaCO3 phase, the carburization of the Ba-promoted catalyst was more effective than that of K; this was primarily due to its higher (2+) ionic charge. With Ba2+, higher selectivity to methane and lighter products were obtained compared to the K-promoted catalysts; this is likely due to Ba´s lesser capability of suppressing H adsorption on the catalyst surface. An explanation is provided in terms of a more limited mixing between electron-filled Ba2+ 5p and partially filled Fe 3d orbitals, which are expected to be important for the chemical promotion, as they are further apart in energy compared to the K+ 3p and Fe 3d orbitals.

The Norway lobster, Nephrops norvegicus, supports a key European fishery. Stock assessments for this species are mostly based on trawling and UnderWater TeleVision (UWTV) surveys. However, N. norvegicus are burrowing organisms and these survey methods are unable to sample or observe individuals in their burrows. To account for this, UWTV surveys generally assume that “1 burrow system = 1 animal”, due to the territorial behavior of N. norvegicus. Nevertheless, this assumption still requires in-situ validation. Here, we outline how to improve the accuracy of current stock assessments for N. norvegicus with novel ecological monitoring technologies, including: robotic fixed and mobile camera-platforms, telemetry, environmental DNA (eDNA), and Artificial Intelligence (AI). First, we outline the present status and threat for overexploitation in N. norvegicus stocks. Then, we discuss how the burrowing behavior of N. norvegicus biases current stock assessment methods. We propose that state-of-the-art stationary and mobile robotic platforms endowed with innovative sensors and complemented with AI tools could be used to count both animals and burrows systems in-situ, as well as to provide key insights into burrowing behavior. Next, we illustrate how multiparametric monitoring can be incorporated into assessments of physiology and burrowing behavior. Finally, we develop a flowchart for the appropriate treatment of multiparametric biological and environmental data required to improve current stock assessment methods.

Na in Fe-based catalysts can be used to increase CO conversion and C2-C4 olefins and decrease the conversion of H2 and C1 selectivity, but its behaviour at different reaction temperatures is of importance in Fischer-Tropsch synthesis (FTS). The dependency of the C1 formation rate, the conversions of H2 and CO, the water-gas shift reaction, the olefins and paraffins of the C2-C4 and C5-C12 hydrocarbons, and C13+ hydrocarbons on the reaction temperature for prepared Fe/Al2O3 and FeNa/Al2O3 catalysts was evaluated in a tubular fixed-bed reactor. This was done to investigate the effects of Na in Fe-based catalyst at different reaction temperatures (250 – 310 °C). The results show that the effects of Na in Fe-based catalysts to increase CO conversion and decrease H2 conversion are dependent on the reaction temperature in FTS. The Na-promoted Fe-based catalyst (FeNa/Al2O3) gave a lower C1 formation rate at certain lower reaction temperatures (250 °C and 270 °C) compared to the unpromoted Fe-based catalyst (Fe/Al2O3). The presence of Na in the Fe-based catalyst improved the C1 formation rate at certain higher reaction temperatures (290 °C and 310 °C). Na was found to hinder the selectivity towards C2-C4 paraffins and C13+ hydrocarbons, including the oxygenates, and improve the formation of C2-C4 olefins and C5-C12 hydrocarbons at different reaction temperatures.

Marine resources exploitation through bottom trawling affects marine ecosystems; thus, management should consider the presence of sensitive species as ecosystem health indicators. Epibenthic organisms such as sea pens are widely used to assess benthic conditions, as their populations are declining where trawling is intense. The Pomo/Jabuka Pits fishing ground in the Adriatic Sea, subject to various management measures over the years, is a nursery for European hake and hosts a small, but dense, population of Norway lobster and a remarkable abundance of pink shrimp. The sea pen Funiculina quadrangularis shares its habitat (sandy-muddy bottoms) with these crustaceans. Through UnderWater TeleVision surveys conducted from 2012 to 2019, F. quadrangularis abundance and distribution were quantified in relation to changes in the spatiotemporal distribution of fishing efforts. The average density (n/m2) of colonies was calculated for three periods: BEFORE implementation of measures (before 1 July 2015), during an INTERMEDIATE period in which limitations changed (2 July 2015 to 31 August 2017), and AFTER the implementation of a Fishery Restricted Area (from 1 September 2017). F. quadrangularis revealed an increase in density where fisheries were closed, even after a short period. This showed how management measures can positively influence epibenthic communities and that sea pens can be indicators of impact and/or recovery of habitats.

Different low-cost cobalt precursors (acetate, chloride) and thermal treatments (air calcination/H2 reduction versus direct H2-activation) were investigated to alter the interaction between cobalt and silica. H2-activated catalysts prepared from cobalt chloride had large Co0 particles (XRD, chemisorption) formed by weak interactions between cobalt chloride and silica (temperature programmed reduction (TPR), TPR with mass spectrometry (TPR-MS), TPR with extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES) techniques) and retained Cl-blocked active sites, resulting in poor activity. In contrast, unpromoted Co/SiO2 catalysts derived from cobalt acetate had strong interactions between Co species and silica (TPR/TPR-MS, TPR-EXAFS/XANES); adding Pt increased the extent of the Co reduction. For these Pt-promoted catalysts, the reduction of uncalcined catalysts was faster, resulting in larger Co0 clusters (19.5 nm) in comparison with the air-calcined/H2-activated catalyst (7.8 nm). Both catalysts had CO conversions 25% higher than that of the Pt-promoted catalyst prepared in the traditional manner (air calcination/H2 reduction using cobalt nitrate) and three times higher than that of the traditional unpromoted Co/silica catalyst. The retention of residual cobalt carbide (observed in XANES) from cobalt acetate decomposition impacted performance, resulting in a higher C1–C4 selectivity (32.2% for air-calcined and 38.7% for uncalcined) than that of traditional catalysts (17.5–18.6%). The residual carbide also lowered the α-value and olefin/paraffin ratio. Future work will focus on improving selectivity through oxidation–reduction cycles.

Abstract Underwater Television (UWTV) surveys provide fishery-independent stock size estimations of the Norway lobster (Nephrops norvegicus), based directly on burrow counting using the survey assumption of “one animal = one burrow”. However, stock size may be uncertain depending on true rates of burrow occupation. For the first time, 3055 video transects carried out in several Functional Units (FUs) around Ireland were used to investigate this uncertainty. This paper deals with the discrimination of burrow emergence and door-keeping diel behaviour in Nephrops norvegicus, which is one of the most commercially important fisheries in Europe. Comparisons of burrow densities with densities of visible animals engaged in door-keeping (i.e. animals waiting at the tunnel entrance) behaviour and animals in full emergence, were analysed at time windows of expected maximum population emergence. Timing of maximum emergence was determined using wave-form analysis and GAM modelling. The results showed an average level of 1 visible Nephrops individual per 10 burrow systems, depending on sampling time and depth. This calls into question the current burrow occupancy assumption which may not hold true in all FUs. This is discussed in relation to limitations of sampling methodologies and new autonomous robotic technological solutions for monitoring.

Sodium-promoted monoclinic zirconia supported ruthenium catalysts were tested for CO2 hydrogenation at 20 bar and a H2:CO2 ratio of 3:1. Although increasing sodium promotion, from 2.5% to 5% by weight, slightly decreased CO2 conversion (14% to 10%), it doubled the selectivity to both CO (~36% to ~71%) and chain growth products (~4% to ~8%) remarkably and reduced the methane selectivity by two-thirds (~60% to ~21%). For CO2 hydrogenation during in situ DRIFTS under atmospheric pressure, it was revealed that Na increases the catalyst basicity and suppresses the reactivity of Ru sites. Higher basicity facilitates CO2 adsorption, weakens the C–H bond of the formate intermediate promoting CO formation, and inhibits methanation occurring on ruthenium nanoparticle surfaces. The suppression of excessive hydrogenation increases the chain growth probability. Decelerated reduction during H2-TPR/TPR-MS and H2-TPR-EXAFS/XANES at the K-edge of ruthenium indicates that sodium is in contact with ruthenium. A comparison of the XANES spectra of unpromoted and Na-promoted catalysts after H2 reduction showed no evidence of a promoting effect involving electron charge transfer.

Abundance and distribution of commercial marine resources are influenced by environmental variables, which together with fishery patterns may also influence their catchability. However, Catch Per Unit Effort (CPUE) can be standardized in order to remove most of the variability not directly attributable to fish abundance. In the present study, Generalized Additive Models (GAMs) were used to investigate the effect of some environmental and fishery covariates on the spatial distribution and abundance of the Norway lobster Nephrops norvegicus within the Pomo/Jabuka Pits (Central Adriatic Sea) and to include those that resulted significant in a standardization process. N. norvegicus is a commercially important demersal crustacean, altering its catchability over the 24-h cycle and seasons according to its burrowing behavior. A historically exploited fishing ground for this species, since 2015 subject to specific fisheries management measures, is represented by the meso-Adriatic depressions, which are also characterized by particular oceanographic conditions. Both the species behaviour and the features of this study area influence the dynamics of the population offering a challenging case study for a standardization modelling approach. Environmental and catch data were obtained during scientific trawl surveys properly designed to catch N. norvegicus, thus improving the quality of the model input data. Standardization of CPUE from 2 surveys from 2012 to 2019 was conducted building two GAMs for both biomass and density indices. Bathymetry, fishing pressure, dissolved oxygen and salinity proved to be significant drivers influencing catch distribution. After cross validations, the tuned models were then used to predict new indices for the study area and the two survey series by means of informed spatial grids, composed by constant surface cells, to each of which are associated average values of environmental parameters and specific levels of fishing pressure, depending on the management measures in place. The predictions can be used to better describe the structure and the spatio-temporal distribution of the population providing valuable information to evaluate the status of such an important marine resource.

The burrowing crustacean decapod Nephrops norvegicus is a significant species in European Atlantic and Mediterranean fisheries. Research over the decades has mainly focused on behavioral and physiological aspects related to the burrowing lifestyle, since animals can only be captured by trawls when engaged in emergence on the seabed. Here, we performed a global bibliographic survey of all the scientific literature retrieved in SCOPUS since 1965, and terminology maps were produced with the VOSviewer software to reveal established and emerging research areas. We produced three term-map plots: term clustering, term citation, and term year. The term clustering network showed three clusters: fishery performance, assessment, and management; biological cycles in growth, reproduction, and behavior; and finally, physiology and ecotoxicology, including food products. The term citation map showed that intense research is developed on ecotoxicology and fishery management. Finally, the term year map showed that the species was first studied in its morphological and physiological aspects and more recently in relation to fishery and as a food resource. Taken together, the results indicate scarce knowledge on how burrowing behavior and its environmental control can alter stock assessment, because of the poor use of current and advanced monitoring technologies.

The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO2 temperature programmed desorption results, as well as a greater splitting observed between the formate νasym(OCO) and νsym(OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer.

Iron-based catalysts are the most suitable candidates for converting CO2 or CO2-rich syngas to hydrocarbons. However, several issues about the mechanism of CO2 hydrogenation are still unclear. In this work, we investigated the performance of an iron-based catalyst with H2/CO2, H2/CO/N2 and H2/CO/13CO2/N2 gas mixtures at the same process conditions (T = 270°C, P = 175 psi and SV = 3 NL/h/gcat). The CO2 hydrogenation rate was much lower than that observed for CO hydrogenation. 13CO2 tracer experiments indicated that CO2 is hydrogenated to hydrocarbons via the reverse water-gas shift even when present in small concentration (1.8 vol%). 13C enrichment was observed in both CO and C1-C4 hydrocarbons.

While the observation of the open ocean is well achieved by automated ocean measurement instruments, coastal and shelf seas suffer the lack of sub-surface collection platforms. Commercial fishing gear such as bottom trawls, pots, traps and long lines can act as platforms for sensors, which collect physical oceanographic data concurrently with normal fishing operations. The lack of observed in situ ocean data in coastal and shelf seas limits operational oceanography, weather forecasting, maritime industries, and climate change monitoring. In addition, using fishing gear as an ocean observation platform has auxiliary benefits for fisheries management including stakeholder involvement. This study quantifies and compares the existing sub-surface in situ data coverage with the spatial distribution of fishing activities. The results show that integration with fishing could contribute to filling some of the most pressing gaps in existing ocean observation systems in coastal and shelf seas. There are limitations related to opportunistic data collection, mainly related to spatial and temporal heterogeneity of fishing activities. However, we make the case that fishery-based observations have the potential to complement existing ocean observing systems in areas where oceanographic data are lacking and needed most in order to ensure long term sustainability of ocean monitoring.

The decarboxylation pathway in ethanol steam reforming ultimately favors higher selectivity to hydrogen over the decarbonylation mechanism. The addition of an optimized amount of Cs to Pt/m-ZrO2 catalysts increases the basicity and promotes the decarboxylation route, converting ethanol to mainly H2, CO2, and CH4 at low temperature with virtually no decarbonylation being detected. This offers the potential to feed the product stream into a conventional methane steam reformer for the production of hydrogen with higher selectivity. DRIFTS and the temperature-programmed reaction of ethanol steam reforming, as well as fixed bed catalyst testing, revealed that the addition of just 2.9% Cs was able to stave off decarbonylation almost completely by attenuating the metallic function. This occurs with a decrease in ethanol conversion of just 16% relative to the undoped catalyst. In comparison with our previous work with Na, this amount is—on an equivalent atomic basis—just 28% of the amount of Na that is required to achieve the same effect. Thus, Cs is a much more efficient promoter than Na in facilitating decarboxylation.

The ethanol steam reforming reaction (ESR) was investigated on unpromoted and potassium- and rubidium-promoted monoclinic zirconia-supported platinum (Pt/m-ZrO2) catalysts. Evidence from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization indicates that ethanol dissociates to ethoxy species, which undergo oxidative dehydrogenation to acetate followed by acetate decomposition. The acetate decomposition pathway depends on catalyst composition. The decarboxylation pathway tends to produce higher overall hydrogen selectivity and is the most favored route at high alkali loading (2.55 wt.% K and higher or 4.25 wt.% Rb and higher). On the other hand, decarbonylation is a significant route for the undoped catalyst or when a low alkali loading (e.g., 0.85% K or 0.93% Rb) is used, thus lowering the overall H2 selectivity of the process. Results of in situ DRIFTS and the temperature-programmed reaction of ESR show that alkali doping promotes forward acetate decomposition while exposed metallic sites tend to facilitate decarbonylation. In previous work, 1.8 wt.% Na was found to hinder decarbonylation completely. Due to the fact that 1.8 wt.% Na is atomically equivalent to 3.1 wt.% K and 6.7 wt.% Rb, the results show that less K (2.55% K) or Rb (4.25% Rb) is needed to suppress decarbonylation; that is, more basic cations are more efficient promoters for improving the overall hydrogen selectivity of the ESR process.

Certain alkali metals (Na, K) at targeted loadings have been shown in recent decades to significantly promote the LT-WGS reaction. This occurs at alkali doping levels where a redshift in the C-H band of formate occurs, indicating electronic weakening of the bond. The C-H bond breaking of formate is the proposed rate-limiting step of the formate associative mechanism, lending support to the occurrence of this mechanism in H2-rich environments of the LT-WGS stage of fuel processors. Continuing in this vein of research, 2%Pt/m-ZrO2 was promoted with various levels of Cs in order to explore its influence on the rate of formate intermediate decomposition, as well as that of LT-WGS in a fixed bed reactor. In situ DRIFTS experiments revealed that Cs promoter loadings of 3.87% to 7.22% resulted in significant acceleration of the forward formate decomposition in steam at 130 °C. Of all of the alkali metals tested to date, the redshift in the formate ν(CH) band with the incorporation of Cs was the greatest. XANES difference experiments at the Pt L2 and L3 edges indicated that the electronic effect was not likely due to an enrichment of electronic density on Pt. CO2 TPD experiments revealed that, unlike Na and K promoters, Cs behaves more like Rb in that the decomposition of the second intermediate in LT-WGS, carbonate species, is hindered due to (1) increased basicity of Cs, (2) the tendency of Cs to cover Pt sites that facilitate CO2 decomposition, and (3) the tendency of Cs to increase Pt particle size as shown by EXAFS results, resulting in fewer Pt sites that facilitate CO2 decomposition. As such, the LT-WGS rate was hindered overall and the rate-limiting step shifted to carbonate decomposition (CO2 removal). Like its Rb counterpart, low levels of added Cs (e.g., 0.72%Cs) were found to improve the stability of the catalyst relative to the unpromoted catalyst; the stability comparison was made at similar CO conversion level as well as similar space velocity.

Recent studies have shown that appropriate levels of alkali promotion can significantly improve the rate of low-temperature water gas shift (LT-WGS) on a range of catalysts. At sufficient loadings, the alkali metal can weaken the formate C–H bond and promote formate dehydrogenation, which is the proposed rate determining step in the formate associative mechanism. In a continuation of these studies, the effect of Rb promotion on Pt/ZrO2 is examined herein. Pt/ZrO2 catalysts were prepared with several different Rb loadings and characterized using temperature programmed reduction mass spectrometry (TPR-MS), temperature programmed desorption (TPD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), an X-ray absorption near edge spectroscopy (XANES) difference procedure, extended X-ray absorption fine structure spectroscopy (EXAFS) fitting, TPR-EXAFS/XANES, and reactor testing. At loadings of 2.79% Rb or higher, a significant shift was seen in the formate ν(CH) band. The results showed that a Rb loading of 4.65%, significantly improves the rate of formate decomposition in the presence of steam via weakening the formate C–H bond. However, excessive rubidium loading led to the increase in stability of a second intermediate, carbonate and inhibited hydrogen transfer reactions on Pt through surface blocking and accelerated agglomeration during catalyst activation. Optimal catalytic performance was achieved with loadings in the range of 0.55–0.93% Rb, where the catalyst maintained high activity and exhibited higher stability in comparison with the unpromoted catalyst.

The effect of cobalt substitution with nickel was investigated for the Fischer−Tropsch synthesis reaction. Catalysts having different Ni/Co ratios were prepared by aqueous incipient wetness co-impregnation, characterized, and tested using a continuously stirred tank reactor (CSTR) for more than 200 h. The addition of nickel did not significantly modify the morphological properties measured. XRD, STEM, and TPR-XANES results showed intimate contact between nickel and cobalt, strongly suggesting the formation of a Co-Ni solid oxide solution in each case. Moreover, TPR-XANES indicated that nickel addition improves the cobalt reducibility. This may be due to H2 dissociation and spillover, but is more likely the results of a chemical effect of intimate contact between Co and Ni resulting in Co-Ni alloying after activation. FTS testing revealed a lower initial activity when nickel was added. However, CO conversion continuously increased with time on-stream until a steady-state value (34%−37% depending on Ni/Co ratio) was achieved, which was very close to the value observed for undoped Co/Al2O3. This trend suggests nickel can stabilize cobalt nanoparticles even at a lower weight percentage of Co. Currently, the cobalt price is 2.13 times the price of nickel. Thus, comparing the activity/price, the catalyst with a Ni/Co ratio of 25/75 has better performance than the unpromoted catalyst. Finally, nickel-promoted catalysts exhibited slightly higher initial selectivity for light hydrocarbons, but this difference typically diminished with time on-stream; once leveling off in conversion was achieved, the C5+ selectivities were similar (≈ 80%) for Ni/Co ratios up to 10/90, and only slightly lower (≈ 77%) at Ni/Co of 25/75.

Trifluoromethyl propargylamines react with various azide derivatives to afford 1,4-disubstituted 1,2,3-triazoles through a Huisgen 1,3-dipolar cycloaddition. The reaction is catalyzed by a Cu(I) species in acetonitrile, and the corresponding products are obtained in good yields. This process thus offers an entry to new trifluoromethyl peptidomimetics as interesting scaffolds.