The Future of Chemical Sciences is Sustainable.

Chemistry, a vital tool for sustainable development, faces a challenge due to the lack of clear guidance on actionable steps, hindering the optimal adoption of sustainability practices across its diverse facets from discovery to implementation. This Scientific Perspective explores established frameworks and principles, proposing a conciliated set of triple E priorities anchored on Environmental, Economic, and Equity pillars for research and decision making. We outline associated metrics, crucial for quantifying impacts, classifying them according to their focus areas and scales tackled. Emphasizing catalysis as a key driver of sustainable synthesis of chemicals and materials, we exemplify how triple E priorities can practically guide the development and implementation of processes from renewables conversions to complex customized products. We summarize by proposing a roadmap for the community aimed at raising awareness, fostering academia-industry collaboration, and stimulating further advances in sustainable chemical technologies across their broad scope.

CO2 Electroreduction To Syngas With Tunable Composition In An Artificial Leaf.

Invited for this month's cover is the group of Javier Pérez-Ramírez at ETH Zürich, which collaborated with the group of Tsvetelina Merdzhanova at Forschungszentrum Jülich. The image shows how artificial leaves, able to recycle carbon dioxide into syngas of variable composition, could be integrated with chemical plants. The Research Article itself is available at 10.1002/cssc.202301398.

CO2 Electroreduction To Syngas With Tunable Composition In An Artificial Leaf.

Artificial leaves (a-leaves) can reduce carbon dioxide into syngas using solar power and could be combined with thermo- and biocatalytic technologies to decentralize the production of valuable products. By providing variable CO : H2 ratios on demand, a-leaves could facilitate optimal combinations and control the distribution of products in most of these hybrid systems. However, the current design procedures of a-leaves concentrate on achieving high performance for a predetermined syngas composition. This study demonstrates that incorporating the electrolyte flow as a design variable enables flexible production without compromising performance. The concept was tested on an a-leaf using a commercial cell, a Cu2 O:Inx cathodic catalyst, and an inexpensive amorphous silicon thin-film photovoltaic module. Syngas with CO : H2 ratio in the range of 1.8-2.3 could be attained with only 2 % deviation from the optimal cell voltage and controllable solely by catholyte flow. These features could be beneficial for downstream technologies such as Fischer-Tropsch synthesis and anaerobic fermentation.

Consumer Grade Polyethylene Recycling via Hydrogenolysis on Ultrafine Supported Ruthenium Nanoparticles.

Catalytic hydrogenolysis has the potential to convert high-density polyethylene (HDPE), which comprises about 30 % of plastic waste, into valuable alkanes. Most investigations have focused on increasing activity for lab grade HDPEs displaying low molecular weight, with limited mechanistic understanding of the product distribution. No efficient catalyst is available for consumer grades due to their lower reactivity. This study targets HDPE used in bottle caps, a waste form generated globally at a rate of approximately one million units per hour. Ultrafine ruthenium particles (1 nm) supported on titania (anatase) achieved up to 80 % conversion into light alkanes (C1 -C45 ) under mild conditions (498 K, 20 bar H2 , 4 h) and were reused for three cycles. Small ruthenium nanoparticles were critical to achieving relevant conversions, as activity sharply decreased with particle size. Selectivity commonalities and peculiarities across HDPE grades were disclosed by a reaction modelling approach applied to products. Isomerization cedes to backbone scission as the reaction progresses. Within this trend, low molecular weight favor isomerization whilst high molecular weight favor cleavage. Commercial caps obeyed this trend with decreased activity, anticipating the influence of additives in realistic processing. This study demonstrates effective hydrogenolysis of consumer grade polyethylene and provides selectivity patterns for product control.

The Environmental Feasibility of Decentralised Solar Ammonia.

Intense efforts have been devoted to developing green and blue centralised Haber-Bosch processes (gHB and bHB, respectively), but the feasibility of a decentralised and sustainable scheme has yet to be assessed. Here we reveal the conditions under which small-scale systems based on the electrocatalytic reduction of nitrogen (eN2R) powered by photovoltaic energy (NH3-leaf) could become a competitive technology in terms of environmental criteria. To this end, we calculated energy efficiency targets based on solar irradiation atlases to guide research in the incipient eN2R field. Even under this germinal state, the NH3-leaf technology would compete favourably in sunny locations relative to the business-as-usual production scenario. The disclosed sustainability potential of NH3-leaf makes it a strong ally of gHB toward a non-fossil ammonia production.

Environmental and economic potential of decentralised electrocatalytic ammonia synthesis powered by solar energy.

Intense efforts have been devoted to developing green and blue centralised Haber-Bosch processes (gHB and bHB, respectively), but the feasibility of a decentralised and more sustainable scheme has yet to be assessed. Here we reveal the conditions under which small-scale systems (NH3-leaves) based on the electrocatalytic reduction of nitrogen (eN2R) powered by photovoltaic energy could realise a decentralised scheme competitive in terms of environmental and economic criteria. For this purpose, we calculated energy efficiency targets worldwide, providing clear values that may guide research in the incipient eN2R field. Even at this germinal stage, the NH3-leaf technology would compete favourably in sunny locations for CO2-related Earth-system processes and human health relative to the business-as-usual production scenario. Moreover, a modest 8% gain in energy efficiency would already make them outperform the gHB in terms of climate change-related impacts in the sunniest locations. If no CO2 taxation is enforced, the lowest estimated ammonia production cost would be 3 times the industrial standard, with the potential to match it provided a substantial decrease of investment costs and very high selectivity toward ammonia in eN2R are achieved. The disclosed sustainability potential of NH3-leaf makes it a strong ally of gHB toward defossilised ammonia production.

ZrO2-Promoted Cu-Co, Cu-Fe and Co-Fe Catalysts for Higher Alcohol Synthesis.

The development of efficient catalysts for the direct synthesis of higher alcohols (HA) via CO hydrogenation has remained a prominent research challenge. While modified Fischer-Tropsch synthesis (m-FTS) systems hold great potential, they often retain limited active site density under operating conditions for industrially relevant performance. Aimed at improving existing catalyst architectures, this study investigates the impact of highly dispersed metal oxides of Co-Cu, Cu-Fe, and Co-Fe m-FTS systems and demonstrates the viability of ZrO2 as a general promoter in the direct synthesis of HA from syngas. A volcano-like composition-performance relationship, in which 5-10 mol % ZrO2 resulted in maximal HA productivity, governs all catalyst families. The promotional effect resulted in a 2.5-fold increase in HA productivity for the optimized Cu1Co4@ZrO2-5 catalyst (Cu:Co = 1:4, 5 mol % ZrO2) compared to its ZrO2-free counterpart and placed Co1Fe4@ZrO2-10 among the most productive systems (345 mgHA h-1 gcat-1) reported in this category under comparable operating conditions, with stable performance for at least 300 h. ZrO2 assumes an amorphous and defective nature on the catalysts, leading to enhanced H2 and CO activation, facilitated formation of metallic and carbide phases, and structural stabilization.

NMR-based quantification of liquid products in CO2 electroreduction on phosphate-derived nickel catalysts.

Recently discovered phosphate-derived Ni catalysts have opened a new pathway towards multicarbon products via CO2 electroreduction. However, understanding the influence of basic parameters such as electrode potential, pH, and buffer capacity is needed for optimized C3+ product formation. To this end, rigorous catalyst evaluation and sensitive analytical tools are required to identify potential new products and minimize increasing quantification errors linked to long-chain carbon compounds. Herein, we contribute to enhance testing accuracy by presenting sensitive 1H NMR spectroscopy protocols for liquid product assessment featuring optimized water suppression and reduced experiment time. When combined with an automated NMR data processing routine, samples containing up to 12 products can be quantified within 15 min with low quantification limits equivalent to Faradaic efficiencies of 0.1%. These developments disclosed performance trends in carbon product formation and the detection of four hitherto unreported compounds: acetate, ethylene glycol, hydroxyacetone, and i-propanol.

Controlled Formation of Dimers and Spatially Isolated Atoms in Bimetallic Au-Ru Catalysts via Carbon-Host Functionalization.

The introduction of a foreign metal atom in the coordination environment of single-atom catalysts constitutes an exciting frontier of active-site engineering, generating bimetallic low-nuclearity catalysts often exhibiting unique catalytic synergies. To date, the exploration of their full scope is thwarted by (i) the lack of synthetic techniques with control over intermetallic coordination, and (ii) the challenging characterization of these materials. Herein, carbon-host functionalization is presented as a strategy to selectively generate Au-Ru dimers and isolated sites by simple incipient wetness impregnation, as corroborated by careful X-ray absorption spectroscopy analysis. The distinct catalytic fingerprints are unveiled via the hydrogen evolution reaction, employed as a probe for proton adsorption properties. Intriguingly, the virtually inactive Au atoms enhance the reaction kinetics of their Ru counterparts already when spatially isolated, by shifting the proton adsorption free energy closer to neutrality. Remarkably, the effect is magnified by a factor of 2 in dimers. These results exemplify the relevance of controlling intermetallic coordination for the rational design of bimetallic low-nuclearity catalysts.

Long-term recurrences and mortality in patients with noncardiac syncope.

INTRODUCTION AND OBJECTIVES: There are no in-depth studies of the long-term outcome of patients with syncope after exclusion of cardiac etiology. We therefore analyzed the long-term outcome of this population. METHODS: For 147 months, we included all patients with syncope referred to our syncope unit after exclusion of a cardiac cause. RESULTS: We included 589 consecutive patients. There were 313 (53.1%) women, and the median age was 52 [34-66] years. Of these, 405 (68.8%) were diagnosed with vasovagal syncope (VVS), 65 (11%) with orthostatic hypotension syncope (OHS), and 119 (20.2%) with syncope of unknown etiology (SUE). During a median follow-up of 52 [28-89] months, 220 (37.4%) had recurrences (21.7% ≥ 2 recurrences), and 39 died (6.6%). Syncope recurred in 41% of patients with VVS, 35.4% with OHS, and 25.2% with SUE (P=.006). In the Cox multivariate analysis, recurrence was correlated with age (P=.002), female sex (P <.0001), and the number of previous episodes (< 5 vs ≥ 5; P <.0001). Death occurred in 15 (3.5%) patients with VVS, 11 (16.9%) with OHS, and 13 (10.9%) with SUE (P=.001). In the multivariate analysis, death was associated with age (P=.0001), diabetes (P=.007), and diagnosis of OHS (P=.026) and SUE (P=.020). CONCLUSIONS: In patients with noncardiac syncope, the recurrence rate after 52 months of follow-up was 37.4% and mortality was 6.6% per year. Recurrence was higher in patients with a neuromedial profile and mortality was higher in patients with a nonneuromedial profile.

Analog Lock-In Amplifier Design Using Subsampling for Accuracy Enhancement in GMI Sensor Applications.

A frequency downscaling technique for enhancing the accuracy of analog lock-in amplifier (LIA) architectures in giant magneto-impedance (GMI) sensor applications is presented in this paper. As a proof of concept, the proposed method is applied to two different LIA topologies using, respectively, analog and switching-based multiplication for phase-sensitive detection. Specifically, the operation frequency of both the input and the reference signals of the phase-sensitive detector (PSD) block of the LIA is reduced through a subsampling process using sample-and-hold (SH) circuits. A frequency downscaling from 200 kHz, which is the optimal operating frequency of the employed GMI sensor, to 1 kHz has been performed. In this way, the proposed technique exploits the inherent advantages of analog signal multiplication at low frequencies, while the principle of operation of the PSD remains unaltered. The circuits were assembled using discrete components, and the frequency downscaling proposal was experimentally validated by comparing the measurement accuracy with the equivalent conventional circuits. The experimental results revealed that the error in the signal magnitude measurements was reduced by a factor of 8 in the case of the analog multipliers and by a factor of 21 when a PSD based on switched multipliers was used. The error in-phase detection using a two-phase LIA was also reduced by more than 25%.

Microfabrication Enables Quantification of Interfacial Activity in Thermal Catalysis.

A myriad of heterogeneous catalysts comprises multiple phases that need to be precisely structured to exert their maximal contribution to performance through electronic and structural interactions at their peripheries. In view of the nanometric, tridimensional, and anisotropic nature of these materials, a quantification of the interface and the impact of catalytic sites located there on the global performance is a highly challenging task. Consequently, the true origin of catalysis often remains subject of debate even for widely studied materials. Herein, an integrated strategy based on microfabricated catalysts and a custom-designed reactor is introduced for determining interfacial contributions upon catalytic activity assessment under process-relevant conditions, which can be easily implemented in the common catalysis research infrastructure and will accelerate the rational design of multicomponent heterogeneous catalysts for diverse applications. The method is validated by studying the high-pressure continuous-flow hydrogenation of CO and CO2 over Cu-ZnO catalysts, revealing linear correlations between the methanol formation rate and the interface between the metal and the oxide. Characterization of fresh and used materials points to the model catalyst preparation as the current challenge of the methodology that can be addressed through further development of nanotechnological tools.

Direct Conversion of Polypropylene into Liquid Hydrocarbons on Carbon-Supported Platinum Catalysts.

Efforts to selectively convert polypropylene (≈30 % of all plastic waste) have not been particularly successful. Typical distributions span from gas to solid products, highlighting a challenging cleavage control. Here, carbon-supported platinum nanoparticles were designed for complete hydrocracking into liquid hydrocarbons (C5 -C45 ). The metal and carrier phases operated synergistically. The cleavage activity depended on platinum and its rate rose with decreasing particle size. The carbon carrier controlled selectivity via hydrocarbon binding strength, which depended on the chain length and on the surface oxygen concentration. An optimal binding provided by carbons with high oxygen content promoted both adsorption of long chains and desorption of short products. This strategy achieved an unprecedented 80 % selectivity toward motor oil (C21 -C45 ). Carbons exhibiting too strong binding (low oxygen content) hindered product desorption, while non-binding materials (e. g., silica or alumina) did not promote plastic-Pt contact, leading in both cases to low performance. This work pioneers design guidelines in a key process towards a sustainable plastic economy.

Ultrastructural Characterization of Human Oligodendrocytes and Their Progenitor Cells by Pre-embedding Immunogold.

Oligodendrocytes are the myelinating cells of the central nervous system. They provide trophic, metabolic, and structural support to neurons. In several pathologies such as multiple sclerosis (MS), these cells are severely affected and fail to remyelinate, thereby leading to neuronal death. The gold standard for studying remyelination is the g-ratio, which is measured by means of transmission electron microscopy (TEM). Therefore, studying the fine structure of the oligodendrocyte population in the human brain at different stages through TEM is a key feature in this field of study. Here we study the ultrastructure of oligodendrocytes, its progenitors, and myelin in 10 samples of human white matter using nine different markers of the oligodendrocyte lineage (NG2, PDGFRα, A2B5, Sox10, Olig2, BCAS1, APC-(CC1), MAG, and MBP). Our findings show that human oligodendrocytes constitute a very heterogeneous population within the human white matter and that its stages of differentiation present characteristic features that can be used to identify them by TEM. This study sheds light on how these cells interact with other cells within the human brain and clarify their fine characteristics from other glial cell types.

Head-up tilt test diagnostic yield in syncope diagnosis.

BACKGROUND: The European Syncope Guidelines (ESG) recommend the use of Head-up tilt test (HUT) in case of suspicion of vasovagal syncope (VVS) or orthostatic hypotensive syncope (OHS) after an adequate initial inconclusive evaluation. We report a single center experience in the scenario of suspected VVS or OHS, who underwent HUT in patients referred to a Syncope Clinic after ruling out high-risk causes. METHODS: We prospectively and consecutively included all syncopal patients that were referred for HUT, by their attending physician after performing a series of diagnostic tests to rule out cardiac etiology. The clinical history and diagnostic tests performed were reviewed prior to HUT. Patients were pre-classified according to the recommendations from the ESG as; VVS, OHS or Syncope of Unknown Etiology (SUE). RESULTS: We studied 1058 patients, 558 (52.7%) males, mean age 46.5 ±â€¯20.1 yr. There were no gender differences in age, risk factors, previous heart diseases, ECG findings or number of previous tests. Based on the ESG criteria a significant number of diagnostic tests were probably unnecessarily performed. HUT was positive in 609 patients (57.5%). The rate of positive HUT according to pre-classification was significantly different among groups: 60% VVS, 46.1% OHS and 54.3% SUE (p = 0.037). Combining ESG recommendations and HUT results of the 1058 resulted in 762 (72%) diagnosed as VVS, 89 (8.4%) as OHS and 207 (19.5%) as SUE. CONCLUSIONS: Appropriate application of ESG recommendations combined with HUT, identified 81% of patients with non-cardiogenic syncope, potentially avoiding a significant number of unnecessary diagnostic tests.

Electrochemical Reduction of Carbon Dioxide to 1-Butanol on Oxide-Derived Copper.

The electroreduction of carbon dioxide using renewable electricity is an appealing strategy for the sustainable synthesis of chemicals and fuels. Extensive research has focused on the production of ethylene, ethanol and n-propanol, but more complex C4 molecules have been scarcely reported. Herein, we report the first direct electroreduction of CO2 to 1-butanol in alkaline electrolyte on Cu gas diffusion electrodes (Faradaic efficiency=0.056 %, j1-Butanol =-0.080 mA cm-2 at -0.48 V vs. RHE) and elucidate its formation mechanism. Electrolysis of possible molecular intermediates, coupled with density functional theory, led us to propose that CO2 first electroreduces to acetaldehyde-a key C2 intermediate to 1-butanol. Acetaldehyde then undergoes a base-catalyzed aldol condensation to give crotonaldehyde via electrochemical promotion by the catalyst surface. Crotonaldehyde is subsequently electroreduced to butanal, and then to 1-butanol. In a broad context, our results point to the relevance of coupling chemical and electrochemical processes for the synthesis of higher molecular weight products from CO2 .

Hybridization of Fossil- and CO2 -Based Routes for Ethylene Production using Renewable Energy.

Carbon capture and utilization (CCU) has recently gained broad interest in the chemical industry. Direct electro- and thermocatalytic technologies are currently the focus of intense research, where the former employs electricity directly to reduce the CO2 molecule, while the latter comprises hydrogenation of CO2 in tandem with electrocatalytic water splitting. So far, it remains unclear which of the two is superior, yet this information is considered critical. Focusing on the platform chemical ethylene, the two CCU routes were compared using state-of-the-art performances with the fossil technology considering different power and CO2 sources. The thermo-route was found to be, at present, economically and environmentally better, yet under the same electrolyzer efficiencies, the electro-route would become superior. CCU routes could substantially improve the carbon footprint of the fossil ethylene (by 236 %) while decreasing at the same time impacts on human health, ecosystem quality, and resources (64, 140, and 80 %, respectively). However, they are economically unattractive even when considering externalities (indirect cost of environmental impacts), that is, 1.7- to 3.9-fold more expensive compared to the current fossil-based analogue. Acknowledging this limitation, the concept of hybridization was applied as a means to smooth the transition towards more sustainable chemicals. Accordingly, it was found that an optimal hybrid plant could produce carbon-neutral (cradle-to-gate) ethylene with a premium of only 30 % over the current market prices by judiciously combining CCU routes with fossil technologies.

Nitride-Derived Copper Modified with Indium as a Selective and Highly Stable Catalyst for the Electroreduction of Carbon Dioxide.

The lack of efficient catalysts prevents the electrocatalytic reduction of carbon dioxide from contributing to the pressing target of a carbon-neutral economy. Indium-modified copper nitride was identified as a stable electrocatalyst selective toward CO. In2 O3 /Cu3 N showed a Faradaic efficiency of 80 % at 0.5 V overpotential for at least 50 h, in stark contrast to the very limited stability of the benchmark In2 O3 /Cu2 O. Microfabricated systems allowed to correlate activity with highly stable interfaces in indium-modified copper nitride. In contrast, fast diffusion of indium resulted in rapidly evolving interfaces in the case of the system based on oxide-derived Cu. A metastable nitrogen species observed by spectroscopic means was proposed as the underlying cause leading to the unchanging interfaces. This work reveals the stabilizing properties of nitride-derived copper toward high-performance multicomponent catalysts.

Origin of the Selective Electroreduction of Carbon Dioxide to Formate by Chalcogen Modified Copper.

The electrochemical reduction of atmospheric CO2 by renewable electricity opens new routes to synthesize fuels and chemicals, but more selective and efficient catalysts are needed. Herein, by combining experimental and first-principles studies, we explain why chalcogen modified copper catalysts are selective toward formate as the only carbon product. On the unmodified copper, adsorbed CO2 is the key intermediate, yielding carbon monoxide and formate as carbon products. On sulfur, selenium, or tellurium modified copper, chalcogen adatoms are present on the surface and actively participate in the reaction, either by transferring a hydride or by tethering CO2 thus suppressing the formation of CO. These results highlight the active role of chalcogen centers via chemical steps and point toward basicity as the key descriptor for the stability and selectivity of these catalysts.