Dual Doping of MoP with M(Mn,Fe) and S to Achieve High Hydrogen Evolution Reaction Activity in Both Acidic and Alkaline Media

Rational design of cost‐effective, high performance and stable hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline media holds the key to the future hydrogen‐based economy. Herein, we introduce an effective approach of simultaneous non‐metal (S) and metal (Fe or Mn) doping of MoP to achieve excellent HER performance at different pH. The catalysts show remarkable overpotentials at −10 mA cm−2 of only 65 and 68 mV in 0.5 M H2SO4, and 50 and 51 mV in 1.0 M KOH, respectively, as well as much higher turnover frequencies compared to undoped MoP. Furthermore, the catalysts exhibit outstanding long‐term stability at a fixed current of −10 mA cm−2 for 40 h. The effects of both dopants, such as electronic structure modification and enhancement of the intrinsic activity, increase of the electrochemically active surface area, and formation of coordinatively unsaturated edge sites, act cooperatively to accelerate the HER at both pH media. Additionally, the presence of oxophilic Mn and Fe at the surface results in Mn or Fe oxide/hydroxide species that promote the dissociation of water molecules in alkaline electrolyte. This work introduces a facile and effective design principle that could pave the way towards engineering highly active HER catalysts for a wide pH range.Metal (Mn or Fe) and non‐metal (S) dual doped MoP catalysts were synthesiszed by reductive pyrolysis of the corresponding Mn,Mo‐ and Fe,Mo‐phosphonates precursors, in the presence of elemental S. The derived catalysts showed remarkable hydrogen evolution reaction (HER) activity in acidic and alkaline media. The dual doping process endowed MoP with proper hydrogen binding energy thus enhancing the HER in acidic media. In addition, Mn and Fe acted as surface oxides species in alkaline medium, which facilitated the water dissociation step. imageYousef Jameel Scholarship FundPeer Reviewe

Single-Step Formation of Metal Oxide Nanostructures Wrapped in Mesoporous Silica and Silica–Niobia Catalysts for the Condensation of Furfural with Acetone

The integration of metal oxide nanomaterials with mesoporous silica is a promising approach to exploiting the advantages of both types of materials. Traditional synthesis methods typically require multiple steps. This work instead presents a fast, one-step, template-free method for the synthesis of metal oxides homogeneously dispersed within mesoporous silica, including oxides of W, Ti, Nb, Ta, Sn, and Mo. These composites have tunable metal oxide contents, large surface areas, and wide mesopores. The combination of Nb2O5 nanoparticles (NPs) with SiO2 results in an increased surface area and a larger number of acid sites compared to pure Nb2O5 NPs. The surface texture and acidity of the silica–niobia composites can be tuned by adjusting the Nb/Si molar ratio. Moreover, the silica provides protection to the niobia NPs, preventing sintering during thermal treatment at 400 °C. The silica–niobia materials exhibit superior performance as catalysts in the aldol condensation of furfural (Fur) with acetone compared to pure niobia, leading to an up to 62% in product yield. Additionally, these catalysts show remarkable stability, retaining their performance over multiple runs. This work demonstrates the potential of the proposed synthesis approach for preparing more sustainable, high-performance, durable, and stable nanoscale metal oxide-based catalysts with a tunable composition, surface area, and active site density.CICECO—Aveiro Institute of MaterialsFCTPeer Reviewe

Comparing the Performance of Nb2O5 Composites with Reduced Graphene Oxide and Amorphous Carbon in Li‐ and Na‐Ion Electrochemical Storage Devices

Two‐dimensional (2D) reduced graphene oxide (rGO) is often combined with metal oxides for energy‐storage applications, owing to its unique properties. Here, we compare the electrochemical performance of Nb2O5‐rGO and amorphous carbon‐coated‐Nb2O5 composites, synthesized in similar conditions. The composite made of Nb2O5 and amorphous carbon (using 1,3,5‐triphenylbenzene as carbon source) outperforms the Nb2O5‐rGO counterpart as a high rate anode electrode material in Li‐ion and Na‐ion half‐cells and hybrid supercapacitors, delivering specific capacities of 134 mAh g−1 at 25 C against 98 mAh g−1 for the rGO‐based composite (in Li electrolyte) and 125 mAh g−1 at 20 C against 98 mAh g−1 (in Na electrolyte). The organic molecules, which are the precursor of the amorphous carbon, control the size and coat the metal oxide particles more efficiently, leading to more extensive carbon‐oxide contacts, which benefits the energy‐storage performance.Peer Reviewe

Chemical valorisation of biomass derived furanics and carboxylic acids over niobium-based catalysts

Furfural is an industrial renewable platform chemical, which can be converted to useful furanics such as α-angelica lactone, carboxylic acids such as levulinic acid and valeric acid, or to higher carbon content products via condensation routes for producing drop-in fuel replacements and chemicals with diverse applications. These important conversion processes may be carried out in selective fashions, although they require adequate catalysts. They were successfully carried out using versatile, stable silica-wrapped niobium oxide nanostructured catalysts. For example, α-angelica lactone was converted in an integrated fashion to ethyl levulinate in 90% yield, and the esterification of levulinic and valeric acids gave ethyl levulinate in quantitative yield and ethyl valerate in 90% yield, respectively, at 140 °C. Catalytic, mechanistic and kinetic modelling studies shed light on the influence of the materials properties on the catalytic performances. These catalysts outperformed pure Nb2O5, as well as hydrothermally synthesized composites consisting of Nb2O5 nanoparticles embedded in a mesoporous siliceous matrix.CICECO-Aveiro Institute of Materials 10.13039/100007889Fundação para a Ciência e a Tecnologia 10.13039/501100001871Ministério da Ciência, Tecnologia e Ensino Superior 10.13039/501100006111Peer Reviewe

Exploiting the Condensation Reactions of Acetophenone to Engineer Carbon-Encapsulated Nb2O5 Nanocrystals for High-Performance Li and Na Energy Storage Systems

Efficient synthetic methods to produce high‐performance electrode‐active materials are crucial for developing energy storage devices for large‐scale applications, such as hybrid supercapacitors (HSCs). Here, an effective approach to obtain controllable carbon‐encapsulated T‐Nb2O5 nanocrystals (NCs) is presented, based on the solvothermal treatment of NbCl5 in acetophenone. Two separate condensation reactions of acetophenone generate an intimate and homogeneous mixture of Nb2O5 particles and 1,3,5‐triphenylbenzene (TPB), which acts as a unique carbon precursor. The electrochemical performance of the resulting composites as anode electrode materials can be tuned by varying the Nb2O5/TPB ratio. Remarkable performances are achieved for Li‐ion and Na‐ion energy storage systems at high charge–discharge rates (specific capacities of ≈90 mAh g−1 at 100 C rate for lithium and ≈125 mAh g−1 at 20 C for sodium). High energy and power densities are also achieved with Li‐ and Na‐ion HSC devices constructed by using the Nb2O5/C composites as anode and activated carbon (YPF‐50) as cathode, demonstrating the excellent electrochemical properties of the materials synthesized with this approach.Peer Reviewe

Niobium pentoxide nanomaterials with distorted structures as efficient acid catalysts

Niobium pentoxides are promising acid catalysts for the conversion of biomass into fuels and chemicals. Developing new synthesis routes is essential for designing niobium pentoxide catalysts with improved activity for specific practical processes. Here we show a synthesis approach in acetophenone, which produces nanostructured niobium pentoxides with varying structure and acidity that act as efficient acid catalysts. The oxides have orthorhombic structures with different extents of distortions and coordinatively unsaturated metal atoms. A strong dependence is observed between the type and strength of the acid sites and specific structural motifs. Ultrasmall niobium pentoxide nanoparticles, which have strong Brønsted acidity, as well as Lewis acidity, give product yields of 96% (3 h, 140 °C, 100% conversion), 85% (3 h, 140 °C, 86% conversion), and 100% (3 h, 110 °C, 100% conversion) in the reactions of furfuryl alcohol, 5-(hydroxymethyl)furfural, and α-angelica lactone with ethanol, respectively.Peer Reviewe

Mesostructured γ-Al2O3-Based Bifunctional Catalysts for Direct Synthesis of Dimethyl Ether from CO2

In this work, we propose two bifunctional nanocomposite catalysts based on acidic mesostructured γ-Al2O3 and a Cu/ZnO/ZrO2 redox phase. γ-Al2O3 was synthesized by an Evaporation-Induced Self-Assembly (EISA) method using two different templating agents (block copolymers Pluronic P123 and F127) and subsequently functionalized with the redox phase using an impregnation method modified with a self-combustion reaction. These nanocomposite catalysts and their corresponding mesostructured supports were characterized in terms of structural, textural, and morphological features as well as their acidic properties. The bifunctional catalysts were tested for the CO2-to-DME process, and their performances were compared with a physical mixture consisting of the most promising support as a dehydration catalyst together with the most common Cu-based commercial redox catalyst (CZA). The results highlight that the most appropriate Pluronic for the synthesis of γ-Al2O3 is P123; the use of this templating agent allows us to obtain a mesostructure with a smaller pore size and a higher number of acid sites. Furthermore, the corresponding composite catalyst shows a better dispersion of the redox phase and, consequently, a higher CO2 conversion. However, the incorporation of the redox phase into the porous structure of the acidic support (chemical mixing), favoring an intimate contact between the two phases, has detrimental effects on the dehydration performances due to the coverage of the acid sites with the redox nanophase. On the other hand, the strategy involving the physical mixing of the two phases, distinctly preserving the two catalytic functions, assures better performances.MIUR—National Program PON Ricerca e InnovazioneUniversity of CagliariFondazione di Sardegna (FdS)Regional Government of Sardinia ASSET projectPeer Reviewe

Assessing the role of compound drought and heatwave events on unprecedented 2020 wildfires in the Pantanal

The year 2020 had the most catastrophic fire season over the last two decades in the Pantanal, which led to outstanding environmental impacts. Indeed, much of the Pantanal has been affected by severe dry conditions since 2019, with evidence of the 2020's drought being the most extreme and widespread ever recorded in the last 70 years. Although it is unquestionable that this mega-drought contributed significantly to the increase of fire risk, so far, the 2020's fire season has been analyzed at the univariate level of a single climate event, not considering the co-occurrence of extreme and persistent temperatures with soil dryness conditions. Here, we show that similarly to other areas of the globe, the influence of land-atmosphere feedbacks contributed decisively to the simultaneous occurrence of dry and hot spells (HPs), exacerbating fire risk. The ideal synoptic conditions for strong atmospheric heating and large evaporation rates were present, in particular during the HPs, when the maximum temperature was, on average, 6 °C above the normal. The short span of the period during those compound drought-heatwave (CDHW) events accounted for 55% of the burned area of 2020. The vulnerability in the northern forested areas was higher than in the other areas, revealing a synergistic effect between fuel availability and weather-hydrological conditions. Accordingly, where fuel is not a limiting factor, fire activity tends to be more modelled by CDHW events. Our work advances beyond an isolated event-level basis towards a compound and cascading natural hazards approach, simultaneously estimating the contribution of drought and heatwaves to fuelling extreme fire outbreaks in the Pantanal such as those in 2020. Thus, these findings are relevant within a broader context, as the driving mechanisms apply across other ecosystems, implying higher flammability conditions and further efforts for monitoring and predicting such extreme events

Analysis of shared heritability in common disorders of the brain

ience, this issue p. eaap8757 Structured Abstract INTRODUCTION Brain disorders may exhibit shared symptoms and substantial epidemiological comorbidity, inciting debate about their etiologic overlap. However, detailed study of phenotypes with different ages of onset, severity, and presentation poses a considerable challenge. Recently developed heritability methods allow us to accurately measure correlation of genome-wide common variant risk between two phenotypes from pools of different individuals and assess how connected they, or at least their genetic risks, are on the genomic level. We used genome-wide association data for 265,218 patients and 784,643 control participants, as well as 17 phenotypes from a total of 1,191,588 individuals, to quantify the degree of overlap for genetic risk factors of 25 common brain disorders. RATIONALE Over the past century, the classification of brain disorders has evolved to reflect the medical and scientific communities' assessments of the presumed root causes of clinical phenomena such as behavioral change, loss of motor function, or alterations of consciousness. Directly observable phenomena (such as the presence of emboli, protein tangles, or unusual electrical activity patterns) generally define and separate neurological disorders from psychiatric disorders. Understanding the genetic underpinnings and categorical distinctions for brain disorders and related phenotypes may inform the search for their biological mechanisms. RESULTS Common variant risk for psychiatric disorders was shown to correlate significantly, especially among attention deficit hyperactivity disorder (ADHD), bipolar disorder, major depressive disorder (MDD), and schizophrenia. By contrast, neurological disorders appear more distinct from one another and from the psychiatric disorders, except for migraine, which was significantly correlated to ADHD, MDD, and Tourette syndrome. We demonstrate that, in the general population, the personality trait neuroticism is significantly correlated with almost every psychiatric disorder and migraine. We also identify significant genetic sharing between disorders and early life cognitive measures (e.g., years of education and college attainment) in the general population, demonstrating positive correlation with several psychiatric disorders (e.g., anorexia nervosa and bipolar disorder) and negative correlation with several neurological phenotypes (e.g., Alzheimer's disease and ischemic stroke), even though the latter are considered to result from specific processes that occur later in life. Extensive simulations were also performed to inform how statistical power, diagnostic misclassification, and phenotypic heterogeneity influence genetic correlations. CONCLUSION The high degree of genetic correlation among many of the psychiatric disorders adds further evidence that their current clinical boundaries do not reflect distinct underlying pathogenic processes, at least on the genetic level. This suggests a deeply interconnected nature for psychiatric disorders, in contrast to neurological disorders, and underscores the need to refine psychiatric diagnostics. Genetically informed analyses may provide important "scaffolding" to support such restructuring of psychiatric nosology, which likely requires incorporating many levels of information. By contrast, we find limited evidence for widespread common genetic risk sharing among neurological disorders or across neurological and psychiatric disorders. We show that both psychiatric and neurological disorders have robust correlations with cognitive and personality measures. Further study is needed to evaluate whether overlapping genetic contributions to psychiatric pathology may influence treatment choices. Ultimately, such developments may pave the way toward reduced heterogeneity and improved diagnosis and treatment of psychiatric disorders

MAMMALS IN PORTUGAL : A data set of terrestrial, volant, and marine mammal occurrences in P ortugal

Mammals are threatened worldwide, with 26% of all species being includedin the IUCN threatened categories. This overall pattern is primarily associatedwith habitat loss or degradation, and human persecution for terrestrial mam-mals, and pollution, open net fishing, climate change, and prey depletion formarine mammals. Mammals play a key role in maintaining ecosystems func-tionality and resilience, and therefore information on their distribution is cru-cial to delineate and support conservation actions. MAMMALS INPORTUGAL is a publicly available data set compiling unpublishedgeoreferenced occurrence records of 92 terrestrial, volant, and marine mam-mals in mainland Portugal and archipelagos of the Azores and Madeira thatincludes 105,026 data entries between 1873 and 2021 (72% of the data occur-ring in 2000 and 2021). The methods used to collect the data were: live obser-vations/captures (43%), sign surveys (35%), camera trapping (16%),bioacoustics surveys (4%) and radiotracking, and inquiries that represent lessthan 1% of the records. The data set includes 13 types of records: (1) burrowsjsoil moundsjtunnel, (2) capture, (3) colony, (4) dead animaljhairjskullsjjaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8),observation in shelters, (9) photo trappingjvideo, (10) predators dietjpelletsjpine cones/nuts, (11) scatjtrackjditch, (12) telemetry and (13) vocalizationjecholocation. The spatial uncertainty of most records ranges between 0 and100 m (76%). Rodentia (n=31,573) has the highest number of records followedby Chiroptera (n=18,857), Carnivora (n=18,594), Lagomorpha (n=17,496),Cetartiodactyla (n=11,568) and Eulipotyphla (n=7008). The data setincludes records of species classified by the IUCN as threatened(e.g.,Oryctolagus cuniculus[n=12,159],Monachus monachus[n=1,512],andLynx pardinus[n=197]). We believe that this data set may stimulate thepublication of other European countries data sets that would certainly contrib-ute to ecology and conservation-related research, and therefore assisting onthe development of more accurate and tailored conservation managementstrategies for each species. There are no copyright restrictions; please cite thisdata paper when the data are used in publications.info:eu-repo/semantics/publishedVersio