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At least 19 records

In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

The catalytic activity and surface reactivity of monometallic Pt and bimetallic Pt-Ir and Pt-Ru nanoparticles, supported on two distinct Engineered Catalyst Supports (ECSs), were investigated for the Ammonia Electrooxidation Reaction (AmER) in alkaline media. XRD measurements confirmed alloy formation between Pt-Ir and Pt-Ru nanoparticles, as indicated by the shift of the (111) reflection to higher 2θ values. Cyclic voltammetry, linear sweep voltammetry, and chronoamperometry experiments were conducted to assess the catalytic activity of the Pt, Pt-Ir, and Pt-Ru electrocatalysts. All bimetallic catalysts exhibited lower onset potentials compared to Pt. The differing Tafel slopes between Pt (74 mV dec⁻¹), Pt-Ir (152 mV dec⁻¹), and Pt-Ru (118–197 mV dec⁻¹) suggest that alloying Pt with Ir or Ru alters the reaction mechanisms. Furthermore, the bimetallic Pt-Ir and Pt-Ru catalysts demonstrated greater tolerance for concentrated ammonia solutions relative to Pt. In-situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) provided insights into the formation of N-H species, azide anions (N₃⁻), and N-O compounds. For the Pt-Ru catalyst, an additional peak around ~3600 cm⁻¹ was observed, corresponding to OH⁻ species. The PM-IRRAS results align with the Gerischer–Mauerer mechanism, indicating that partially dehydrogenated ammonia adsorbates act as active intermediates in the oxidation of ammonia over Pt-Ir and Pt-Ru catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO and H 2 adsorption on Au-Ni bimetallic surfaces: a combined experimental and DFT theoretical study

Au-Ni bimetallic thin films were grown on refractory metal substrates. CO and H 2 adsorption on Au-Ni bimetallic surfaces have been studied by a combination of in situ polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. It is found CO desorption peak shifts from 413 K on pure Ni surfaces to 293 K on the isolated Ni atoms formed by alloying with Au atoms. The sharp decrease of CO desorption temperature on Au-Ni surfaces with increasing Au coverage is caused by the change of the favored CO adsorption sites from bridge/hollow sites on pure Ni surfaces to Ni top sites on Au-Ni bimetallic surfaces. In situ PM-IRRAS shows two CO adsorption bands on Au sites at 2119 cm −1 and 2103 cm −1 on Au-Ni surfaces at 80 K, which are due to CO bound on under-coordinated Au atoms and electron negatively charged Au sites modified with nearby Ni atoms, respectively. Even with the Au-Ni surface temperature at as low as 100 K, CO adsorption induced Ni surface segregation has been observed by in situ PM-IRRAS. Furthermore, DFT calculation results discover the adsorption energy of CO on Ni top sites continues to decrease with increasing Au coverage due to the geometric ensemble effect and the lowered d-band center after Ni alloying with Au. H 2 desorption temperature decreases from 363 K on pure Ni thin films to 302 K with increasing Au coverage to 0.6 ML. A new H 2 peak appears at around 170 K on the Au-Ni surfaces with Au coverages between 0.6 ML and 0.9 ML. This new H 2 TPD peak is assigned to H 2 desorption from the totally isolated Ni sites. With Au coverage above 1.5 ML, there is no any H 2 desorption detected. Finally, the combined surface science studies and DFT calculations provide new insights into the surface structure-activity correlation of Ni-base bimetallic surface alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (−C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H 2 /N 2 and CO 2 /CH 4 ideal selectivities and an eightfold enhancement for CO 2 /N 2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

IRRAS↗

Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid-to-Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen

A large jump of proton transfer rates across solid-to-solid interfaces by inserting an ultrathin amorphous silica layer into stacked metal oxide nanolayers is discovered using electrochemical impedance spectroscopy and Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS). The triple stacked nanolayers of Co 3 O 4 , SiO 2 , and TiO 2 prepared by atomic layer deposition (ALD) enable a proton flux of 2400 ± 60 s -1 nm -2 (pH 4, room temperature), while a single TiO 2 (5 nm) layer exhibits a threefold lower flux of 830 s -1 nm -2 . Based on FT-IRRAS measurements, this remarkable enhancement is proposed to originate from the sandwiched silica layer forming interfacial SiOTi and SiOCo linkages to TiO 2 and Co 3 O 4 nanolayers, respectively, with the O bridges providing fast H + hopping pathways across the solid-to-solid interfaces. Finally, together with the complete O 2 impermeability of a 2 nm ALD-grown SiO 2 layer, the high flux for proton transport across multi-stack metal oxide layers opens up the integration of incompatible catalytic environments to form functional nanoscale assemblies such as artificial photosystems for CO 2 reduction by H 2 O.

36 MATERIALS SCIENCE↗

Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration

Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO x infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO x infiltration, especially one that is initiated by AlO x priming, has not received much attention because highly reactive hydroxyl groups generated by AlO x -priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO x VPI. Here, we interrogate the ZnO x infiltration mechanism in AlO x -primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO x -only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO x network can quickly saturate the AlO x infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO x infiltration using divalent DEZ precursor, once activated via AlO x -priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO x -priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO x .

36 MATERIALS SCIENCE↗

Infrared reflection absorption spectroscopy and temperature-programmed desorption studies of CO adsorption on Ni/CeO 2 (111) thin films: The role of the ceria support

Ceria-supported Ni has shown unique catalytic activity due to unique properties of small Ni particles and strong metal-support interaction. Identification of adsorption sites and understanding the chemical interaction over Ni-ceria at the fundamental level provide crucial insights into the reaction pathways of complex catalytic processes. In this study, to probe the surface sites, the adsorption of CO was carried out with model Ni/ceria systems consisting of Ni nanoparticles vapor-deposited on well-ordered CeO x (111) (1.5 < x < 2) thin films using infrared reflection absorption spectroscopy (IRRAS) and temperature-programmed desorption (TPD) under ultrahigh vacuum (UHV) conditions. Fully oxidized CeO 2 (111) (Ce 4+ ) and partially reduced CeO 1.75 (111) (Ce 4+ /Ce 3+ ) thin films were grown on Ru(0001) to examine the role of the ceria support. Additionally, Ni with low coverages (e.g., 0.2 ML) grows forming small two-dimensional particles on ceria at 300 K, which develop into three-dimensional clusters after heating to 700 K. In the absence of Ni, CO adsorption at 1 mTorr at 100 K shows distinct IR bands at 2158 cm -1 on CeO 2 and 2165 cm -1 on CeO 1.75 . Bridging and atop IR bands associated with CO adsorption over metallic Ni were observed on the Ni-CeO 1.75 surface at 300 K under UHV conditions. CO adsorption over Ni 0 was also observed over as-deposited Ni on CeO 2 . However, a new IR band at 2146 cm -1 due to CO adsorption over Ni 2+ species was detected at 100 K over the annealed Ni particles on CeO 2 . CO IRRAS data suggest the oxidation of Ni to Ni 2+ on CeO 2 and the formation of predominant Ni 2+ species with heating, which is further confirmed with CO TPD data and previous x-ray photoelectron spectroscopy results.

36 MATERIALS SCIENCE↗

Correlation between infrared spectra features and coverage of different adsorption sites for the NO/Pd(111) system

This study investigates the adsorption of nitric oxide (NO) on Pd(111) surfaces at 200 K using infrared reflection absorption spectroscopy (IRRAS). Peak positions and areas are used as proxies for tracking coverage of different species, serving as groundwork for in-situ experiments that need real-time tracking of surface species. Here, we derived a mathematical model correlating NO coverage with dose, consistent with the Molecular Langmuir Model. Distinct correlations are observed between coverage and spectral features (peak position and peak area for the NO vibration): at lower coverages (θ<0.6), the total integrated peak areas are linearly corelated to coverage; at higher coverages (θ>0.6), the peak center for a compressed-hollow site becomes the primary coverage indicator, showing a linear relationship between wavenumber and coverage. Note that this study addresses coverages below saturation. These findings refine our understanding of NO adsorption and establish a foundation for real-time in situ transient kinetics studies of chemical reactions involving NO on Pd(111).

25 ENERGY STORAGE↗

Controlling and Optimizing Photoinduced Charge Transfer across Ultrathin Silica Separation Membrane with Embedded Molecular Wires for Artificial Photosynthesis

Ultrathin amorphous silica membranes with embedded organic molecular wires (oligo( p -phenylenevinylene), three aryl units) provide chemical separation of incompatible catalytic environments of CO 2 reduction and H 2 O oxidation while maintaining electronic and protonic coupling between them. For an efficient nanoscale artificial photosystem, important performance criteria are high rate and directionality of charge flow. Here, the visible-light-induced charge flow from an anchored Ru bipyridyl light absorber across the silica nanomembrane to Co 3 O 4 water oxidation catalyst is quantitatively evaluated by photocurrent measurements. Charge transfer rates increase linearly with wire density, with 5 nm -2 identified as an optimal target. Accurate measurement of wire and light absorber densities is accomplished by the polarized FT-IRRAS method. Guided by density functional theory (DFT) calculations, four wire derivatives featuring electron-donating (methoxy) and -withdrawing groups (sulfonate, perfluorophenyl) with highest occupied molecular orbital (HOMO) potentials ranging from 1.48 to 0.64 V vs NHE were synthesized and photocurrents evaluated. Charge transfer rates increase sharply with increasing driving force for hole transfer from the excited light absorber to the embedded wire, followed by a decrease as the HOMO potential of the wire moves beyond the Co 3 O 4 valence band level toward more negative values, pointing to an optimal wire HOMO potential around 1.3 V vs NHE. Comparison with photocurrents of samples without nanomembrane indicates that silica layers with optimized wires are able to approach undiminished electron flux at typical solar intensities. Combined with the established high proton conductivity and small-molecule blocking property, the charge transfer measurements demonstrate that oxidation and reduction catalysis can be efficiently integrated on the nanoscale under separation by an ultrathin silica membrane.

photocurrent measurements↗

Direct Evidence of Graphene-Induced Molecular Reorientation in Polymer Films

For the first time, direct evidence of graphene-induced molecular reorientation in polymer films using polarization modulated infrared reflection absorption spectroscopy (PMIRRAS) are presented. By creating favorable electrostatic interactions, graphene-polymer interfaces can be controlled by varying polymer and solvent composition. After trans of unmodified graphene from copper onto a polymer substrate, polymer chain rearrangement relative to the orientation at the polymer-copper interface is observed using PM-IRRAS. Transfer success is characterized using both optical transmission measurements and Raman spectroscopy to quantify the transfer fidelity, i.e. graphene coverage fraction. Taken together, oxygencontaining poly(ethylene-co-vinyl acetate) shows more polymer chain rearrangement and better graphene coverage compared to oxygen-free polyethylene. Polymer composition seems to dominate graphene-polymer interactions while solvent choice has a smaller effect on transfer quality. These results are the first direct measurement of this effect and point towards the possibility of engineering graphene-polymer interactions for specific applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electropolymerized-molecularly imprinted polymers (E-MIPS) as sensing elements for the detection of dengue infection

Here, a straightforward in situ detection method for dengue infection was demonstrated through the molecular imprinting of a dengue nonstructural protein 1 (NS1) epitope into an electropolymerized molecularly imprinted polyterthiophene (E-MIP) film sensor. The key enabling step in the sensor fabrication is based on an epitope imprinting strategy, in which short peptide sequences derived from the original target molecules were employed as the main template for detection and analysis. The formation of the E-MIP sensor films was facilitated using cyclic voltammetry (CV) and monitored in situ by electrochemical quartz crystal microbalance (EC-QCM). Surface properties were analyzed using different techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and polarization modulation-infrared reflection-adsorption (PM-IRRAS). The standard calibration curve (R = 0.9830) was generated for the detection of the epitope, Ac-VHTWTEQYKFQ-NH 2 , with a linear range of 0.2 to 30 μg/mL and detection limit of 0.073 μg/mL. A separate calibration curve (R = 0.9786) was obtained using spiked buffered solutions of dengue NS1 protein, which resulted in a linear range of 0.2 to 10 μg/mL and a detection limit of 0.056 μg/mL. The fabricated E-MIP sensor exhibited long-term stability, high sensitivity, and good selectivity towards the targeted molecules. These results indicated that the formation of the exact and stable cavity imprints in terms of size, shape, and functionalities was successful. In our future work, we aim to use our E-MIP sensors for NS1 detection in real-life samples such as serum and blood.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Formation of Silanol Groups in Two-Dimensional Siliceous Nanomaterials under Mild Hydrothermal Conditions

Monitoring the effects of mild hydrothermal conditions, in situ, on siliceous materials remains challenging using surface science techniques, which often require electrically conductive substrates. The emergence of two-dimensional (2-D) siliceous nanomaterials deposited on metal single crystals overcomes this limitation. Here, we use infrared reflection absorption spectroscopy (IRRAS) to study the effects of mild hydrothermal conditions, in situ, on 2-D model systems, namely, all-Si MFI nanosheets supported on Au(111) and a polymorphous bilayer silicate supported on Ru(0001). We find that the formation of silanol groups (SiOH) occurs at 473 and 573 K under a H 2 O pressure of 3 mbar in the MFI nanosheets, but not in the polymorphous bilayer silicate. The effects of mild hydrothermal conditions are reversible in the MFI nanosheets and do not result in framework degradation. Implications shown here provide a fundamental understanding of the impact of mild hydrothermal conditions on the 2-D siliceous nanomaterials and serve as a starting point when considering these effects on three-dimensional (3-D) ones.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Origin of hydroxyl pair formation on reduced anatase TiO 2 (101)

The interaction of water with metal oxide surfaces is of key importance to several research fields and applications. Because of its ability to photo-catalyze water splitting, reducible anatase TiO 2 (a-TiO 2 ) is of particular interest. Here, we combine experiments and theory to study the dissociation of water on bulk-reduced a-TiO 2 (101). Following large water exposures at room temperature, point-like protrusions appear on the a-TiO 2 (101) surface, as shown by scanning tunneling microscopy (STM). These protrusions originate from hydroxyl pairs, consisting of terminal and bridging OH groups, OH t /OH b , as revealed by infrared reflection absorption spectroscopy (IRRAS) and valence band experiments. Utilizing density functional theory (DFT) calculations, we offer a comprehensive model of the water/a-TiO 2 (101) interaction. In conclusion, this model also explains why the hydroxyl pairs are thermally stable up to ~480 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Review—In Situ X-ray and Infrared Spectroscopic Studies of Electrochemical Systems

Despite of intense research and a wealth of data, the phenomena occurring during electrocatalysis are still a major obstacle in many chemical processes. Molecular analysis of the electrode/electrolyte interface is needed to correctly describe the reaction through identifying the species involved, their interaction with the environment and kinetics in situ, i.e. while the reaction is taking place. That can be done by coupling the electrochemical system with complementary non-electrochemical techniques. Particularly revealing are in situ X-ray spectroscopic techniques to analyze the electrode itself, providing the information on the changes in the catalyst during the reaction. The synergy of the traditional electrochemical techniques with the complementary spectroscopic methodologies offer understanding of the electrode/electrolyte interface above and beyond traditional experimental mainframe. Here we demonstrate how in situ X-ray absorption spectroscopy (XAS), in situ infrared reflection/absorption spectroscopy (IRRAS), and traditional voltammetric studies can increase our understanding of electrochemical processes during oxidation of ethanol. The results show the pronounced role of electrode surface in determining reaction kineticks and revealed the selectivity of the catalyst to complete oxidation pathway. They further provide understanding of the parameters that enhance its oxidation for future designing catalysts for alcohol oxidation fuel cells.

30 DIRECT ENERGY CONVERSION↗

Rocket engine system reliability analyses using probabilistic and fuzzy logic techniques

The reliability of rocket engine systems was analyzed by using probabilistic and fuzzy logic techniques. Fault trees were developed for integrated modular engine (IME) and discrete engine systems, and then were used with the two techniques to quantify reliability. The IRRAS (Integrated Reliability and Risk Analysis System) computer code, developed for the U.S. Nuclear Regulatory Commission, was used for the probabilistic analyses, and FUZZYFTA (Fuzzy Fault Tree Analysis), a code developed at NASA Lewis Research Center, was used for the fuzzy logic analyses. Although both techniques provided estimates of the reliability of the IME and discrete systems, probabilistic techniques emphasized uncertainty resulting from randomness in the system whereas fuzzy logic techniques emphasized uncertainty resulting from vagueness in the system. Because uncertainty can have both random and vague components, both techniques were found to be useful tools in the analysis of rocket engine system reliability.

Hardy, Terry L.↗

Sulfur and Oxygen Isotopic Analysis of a Cosmic Symplectite from a Comet Wild 2 Stardust Terminal Particle

Introduction: Analyses of comet 81P/Wild 2 samples re-turned from the Stardust mission have uncovered surprising simi-larities to meteoritic material, including the identification of inner solar system grains [1-3]. The TEM characterization of terminal particle (TP) 4 from Stardust track #147 revealed an assemblage consisting of symplectically intergrown pentlandite and nanocrys-talline maghemite coexisting with high-Ca pyroxene [4]. Mineral-ogically similar cosmic symplectites (COS) containing pentlandite and magnetite in the primitive Acfer 094 meteorite are highly de-pleted in 16O (17O, 18O ~ 180 per mille) [5-7]. This isotopic signature is proposed to record alteration with primordial solar nebula water. Conversely, the normal O isotopic composition of the Stardust COS indicates alteration by a different aqueous reservoir, perhaps on the comet [8]. In this study, we analyzed the Wild 2 COS for S isotopes to further constrain its origin. Experimental: Thin sections of TP4 (12 m) were produced and their mineralogy was thoroughly characterized by TEM. Two of the sections were analyzed for O isotopes by isotopic imaging in the JSC NanoSIMS 50L. The sample in one of the slices was completely consumed. The remaining material in the adjacent slice was analyzed simultaneously for 16O, 32S, 33S, 34S, and 56Fe16O in electron multipliers using a Cs+ primary ion beam. Quasi-simulta-neous arrival (QSA) can have a significant effect on S isotopic ra-tios when using electron multipliers, resulting in undercounting of 32S [9]. Canyon Diablo troilite (CDT) was measured numerous times to deduce a correction factor for QSA and ensure measure-ment reproducibility. Isotopic ratios are reported relative to CDT. Results and Discussion: The Wild 2 COS is enriched in the heavy S isotopes relative to CDT (33S = 6.5 +/- 1.6 per mille; 34S = 5.1 +/- 0.7 per mille; 1). The degree of 33S enrichment indicates mass-inde-pendent fractionation (MIF) with 33S = 3.9 +/- 1.7 per mille. MIF of S has been observed in some chondrules (33S up to 0.11per mille) [10], but this effect has not been identified in sulfides from carbonaceous chondrites [11] or IDPs [12]. S isotopic analysis of Stardust impact craters also did not reveal MIF or anomalies, save for one potential 32S-rich presolar sulfide [13]. Measurement errors on these impact craters were much larger than those in this study, however. MIF of S has been proposed to result from heterogeneities in the solar neb-ula from nucleosynthetic components [14] or photochemical irra-diation of solar nebula gas [10]. Presolar SiC grains are observed to have 32S enrichments [15, 16] contrary to the S isotopic compo-sition of the cometary COS. The S isotopic composition more likely reflects irradiation of nebular gas.

Nguyen, A. N.↗

Cryogenic Carbon Monoxide Oxidation on Cuprous Oxide

Performing oxidation reactions at low temperatures using earth-abundant materials is crucial for advancing solutions for sustainable chemistry. CO oxidation serves as a benchmark reaction to characterize oxidation and to advance fundamental concepts in surface chemistry. While there are several examples of CO oxidation occurring on metal oxides at low temperatures, from 300 K to ∼200 K, reactivity in the cryogenic temperature regime typically requires a metal nanoparticle on a metal oxide. Here, we show oxygen atoms on the (111) facet of Cu 2 O react with CO to form CO 2 at temperatures below 100 K. Combining spectroscopic experimental evidence with calculations, we propose a low barrier path for CO oxidation at reconstructed surface sites on Cu 2 O(111). This finding is a rare example of an earth-abundant metal oxide, in this case copper, that can provide highly reactive multifunctional sites, enabling both adsorption and reaction fundamental steps toward the efficient heterogeneous oxidation of chemicals.

36 MATERIALS SCIENCE↗

Addition of transient kinetics capabilities to an infrared reflection absorption spectroscopy system through synchronized gas pulsing and data acquisition

Surface science methodologies for understanding thermodynamic aspects of surface processes are at an advanced level. However, instrumentation and approaches for extracting kinetic parameters from elementary steps are far less accessible. In this work, we present an approach combining the use of a fast gas pulsing valve synchronized with data acquisition to enable surface transient kinetics studies using infrared reflection absorption spectroscopy. This methodology applies to the study of reversible processes and borrows concepts and ideas from molecular beam scattering and temporal analysis of products. Here, a temporal resolution of ~67 ms is achieved, and this is illustrated through the study of CO adsorption and desorption on a Pd(111) crystal in the presence and absence of background O 2 . The same approach can be extended to other surface spectroscopies, such as X-ray photoelectron spectroscopy, to obtain spectra with high temporal resolution and signal-to-noise ratio and enable future multimodal surface transient kinetic studies aiming at elucidating reaction mechanisms.

36 MATERIALS SCIENCE↗