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At least 1,027 records · Page 57

High-Performance Iridium–Molybdenum Oxide Electrocatalysts for Water Oxidation in Acid: Bayesian Optimization Discovery and Experimental Testing

Ir oxides are costly and scarce catalysts for oxygen evolution reaction (OER) in acid. There has been extensive interest in developing alternatives that are either Ir-free or require smaller amounts of Ir to drive the reactions at acceptable rates. One design strategy is to identify Ir-based mixed oxides that achieve similar performance while requiring smaller amounts of Ir. The obstacle to this strategy has been a very large phase space of the Ir-based mixed metal oxides, in terms of the metals combined with Ir and the different crystallographic structures of the mixed oxides, which prevents a thorough exploration of possible materials. In this work, we developed a workflow that uses machine-learning-aided Bayesian optimization in combination with density functional theory to make the exploration of this phase space plausible. This screening identified Mo as a promising dopant for forming acid-tolerant Ir-based oxides for the OER. We synthesized and characterized the Ir–Mo mixed oxides in the form of thin-film electrocatalysts with a known surface area. We show that these mixed oxides exhibited overpotentials ~30 mV lower than a pure Ir control while maintaining 24% lower Ir dissolution rates than the Ir control. Furthermore, these findings suggest that Mo is a promising dopant and highlight the promise of machine learning to guide the experimental exploration and optimization of catalytic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polar coupling enabled nonlinear optical filtering at MoS 2 /ferroelectric heterointerfaces

Complex oxide heterointerfaces and van der Waals heterostructures present two versatile but intrinsically different platforms for exploring emergent quantum phenomena and designing new functionalities. The rich opportunity offered by the synergy between these two classes of materials, however, is yet to be charted. Here, we report an unconventional nonlinear optical filtering effect resulting from the interfacial polar alignment between monolayer MoS 2 and a neighboring ferroelectric oxide thin film. The second harmonic generation response at the heterointerface is either substantially enhanced or almost entirely quenched by an underlying ferroelectric domain wall depending on its chirality, and can be further tailored by the polar domains. Unlike the extensively studied coupling mechanisms driven by charge, spin, and lattice, the interfacial tailoring effect is solely mediated by the polar symmetry, as well explained via our density functional theory calculations, pointing to a new material strategy for the functional design of nanoscale reconfigurable optical applications.

36 MATERIALS SCIENCE↗

First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides

To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO 2 . Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used $R\bar{3}m$ structure for LiNiO 2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, $R\bar{3}m$, C2/m, P2 1 /c, and P2/c, P2/c with charge disproportionation of Ni 2+ and Ni 4+ is the most energetically stable and semiconducting structure of LiNiO 2 . Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO 2 to form Li x Ni y Mn z Co 1-y-z O 2 . In the fully lithiated (x=1.0) high Ni content NMC (y>0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 3+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni 2+ to Ni 3+ , then oxidizing Ni 3+ and Co 3+ , while Mn 4+ remains electrochemically inactive till x=0. Finally, a general relationship for the oxidation state change in each TM as a function of x is derived and shows agreement with both modeling and experimental data.

25 ENERGY STORAGE↗

A deep redox proteome profiling workflow and its application to skeletal muscle of a Duchenne Muscular Dystrophy model

Perturbation to the redox state accompanies many diseases and its effects are viewed through oxidation of biomolecules, including proteins, lipids, and nucleic acids. The thiol groups of protein cysteine residues undergo an array of redox post-translational modifications (PTMs) that are important for regulation of protein and pathway function. To better understand what proteins are redox regulated following a perturbation, it is important to be able to comprehensively profile protein thiol oxidation at the proteome level. Herein, we report a deep redox proteome profiling workflow and demonstrate its application in measuring the changes in thiol oxidation along with global protein expression in skeletal muscle from mdx mice, a model of Duchenne Muscular Dystrophy (DMD). In depth coverage of the thiol proteome was achieved with >18,000 Cys sites from 5608 proteins in muscle being quantified. Compared to the control group, mdx mice exhibit markedly increased thiol oxidation, where ~2% shift in the median oxidation occupancy was observed. Further, pathway analysis for the redox data revealed that coagulation system and immune-related pathways were among the most susceptible to increased thiol oxidation in mdx mice, whereas protein abundance changes were more enriched in pathways associated with bioenergetics. This study illustrates the importance of deep redox profiling in gaining greater insight into oxidative stress regulation and pathways/processes that are perturbed in an oxidizing environment.

60 APPLIED LIFE SCIENCES↗

Controlling the corrosion resistance of multi-principal element alloys

Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.

Scully, John R.↗

Microbial functional genes commonly respond to elevated carbon dioxide

Atmospheric CO 2 concentration is increasing, largely due to anthropogenic activities. Previous studies of individual free-air CO 2 enrichment (FACE) experimental sites have shown significant impacts of elevated CO 2 (eCO 2 ) on soil microbial communities; however, no common microbial response patterns have yet emerged, challenging our ability to predict ecosystem functioning and sustainability in the future eCO 2 environment. Here we analyzed 66 soil microbial communities from five FACE sites, and showed common microbial response patterns to eCO 2 , especially for key functional genes involved in carbon and nitrogen fixation (e.g., pcc/acc for carbon fixation, nifH for nitrogen fixation), carbon decomposition (e.g., amyA and pulA for labile carbon decomposition, mnp and lcc for recalcitrant carbon decomposition), and greenhouse gas emissions (e.g., mcrA for methane production, norB for nitrous oxide production) across five FACE sites. Also, the relative abundance of those key genes was generally increased and directionally associated with increased biomass, soil carbon decomposition, and soil moisture. In addition, a further literature survey of more disparate FACE experimental sites indicated increased biomass, soil carbon decay, nitrogen fixation, methane and nitrous oxide emissions, plant and soil carbon and nitrogen under eCO 2 . A conceptual framework was developed to link commonly responsive functional genes with ecosystem processes, such as pcc/acc vs. soil carbon storage, amyA/pulA/mnp/lcc vs. soil carbon decomposition, and nifH vs. nitrogen availability, suggesting that such common responses of microbial functional genes may have the potential to predict ecosystem functioning and sustainability in the future eCO 2 environment.

59 BASIC BIOLOGICAL SCIENCES↗

Redox Couples Control Band Bending, Photovoltage, and Quasi-Fermi Levels in Tungsten Oxide (WO 3 ) Photoanodes

Tungsten oxide (WO 3 ) is a well-known photoanode and photocatalyst for photoelectrochemical (PEC) water oxidation. Because the compound has a deep valence band, it can facilitate the oxygen evolution reaction without added cocatalysts, and it can drive the oxidation of species with much higher electrochemical potentials, including the conversion of water to hydrogen peroxide, sulfate to persulfate, and iodate to meta-periodate. Here, we use the liquid vibrating Kelvin probe surface photovoltage (liquid VK-SPV) technique in combination with open circuit potential (OCP) and photoelectrochemical (PEC) scans to assess the possibility of reaching such oxidizing potentials in aqueous electrolytes and at open circuit. Here, this is done by mapping the quasi-Fermi levels of electrons and holes at the interfaces as a function of the light intensity. Nanostructured WO 3 photoelectrodes for this purpose were fabricated by thermal annealing of a tungstic acid solution on fluorine-doped tin oxide. Electrochemical measurements are conducted at open circuit and 400 nm LED light illumination in electrolytes containing fast (O 2 /H 2 O 2 ), slow (O 2 /H 2 O), and very oxidizing (NaIO 4 /NaIO 3 ) redox couples. Photovoltage values scale with the light intensity and with the built-in potential for each redox couple and reach values up to 0.61 V under 20 mW cm –2 illumination for the NaIO 4 electrolyte. This shows that the photoelectrodes behave like Schottky-type diodes whose maximum possible energy output is determined mainly by the built-in voltage of each junction. For slow redox couples, the quasi-Fermi level of the holes increases with light intensity due to hole accumulation at the WO 3 –liquid interface. For example, for the O 2 /H 2 O electrolyte, interfacial hole accumulation and removal occur on the 90–300 s time scale. For the fast hole acceptor H 2 O 2 , on the other hand, the quasi-Fermi level of the photoholes is pinned to the electrochemical potential of the O 2 /H 2 O 2 couple. This limits the energy conversion efficiency of the electrode. Overall, these results reveal the influence of charge transfer thermodynamics and kinetics on the photovoltage of WO 3 . Furthermore, the work further establishes VK-SPV as a contactless method to observe the photovoltage, carrier dynamics, and quasi-Fermi levels of semiconductor-liquid junctions.

Electrodes↗

Lanthanide-dependent alcohol dehydrogenases require an essential aspartate residue for metal coordination and enzymatic function

The lanthanide elements (Ln 3+ ), those with atomic numbers 57–63 (excluding promethium, Pm 3+ ), form a cofactor complex with pyrroloquinoline quinone (PQQ) in bacterial XoxF methanol dehydrogenases (MDHs) and ExaF ethanol dehydrogenases (EDHs), expanding the range of biological elements and opening novel areas of metabolism and ecology. Other MDHs, known as MxaFIs, are related in sequence and structure to these proteins, yet they instead possess a Ca 2+ -PQQ cofactor. An important missing piece of the Ln 3+ puzzle is defining what features distinguish enzymes that use Ln 3+ -PQQ cofactors from those that do not. In this work, using XoxF1 MDH from the model methylotrophic bacterium Methylorubrum extorquens AM1, we investigated the functional importance of a proposed lanthanide-coordinating aspartate residue. We report two crystal structures of XoxF1, one with and another without PQQ, both with La 3+ bound in the active-site region and coordinated by Asp 320 . Using constructs to produce either recombinant XoxF1 or its D320A variant, we show that Asp 320 is needed for in vivo catalytic function, in vitro activity, and La 3+ coordination. XoxF1 and XoxF1 D320A, when produced in the absence of La 3+ , coordinated Ca 2+ but exhibited little or no catalytic activity. We also generated the parallel substitution in ExaF to produce ExaF D319S and found that this variant loses the capacity for efficient ethanol oxidation with La 3+ . These results provide evidence that a Ln 3+ -coordinating aspartate is essential for the enzymatic functions of XoxF MDHs and ExaF EDHs, supporting the notion that sequences of these enzymes, and the genes that encode them, are markers for Ln 3+ metabolism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the role of $\mathrm{Fe}$-$\mathrm{Mo}$ interactions in the metal oxide precursors for Fe promoted $\mathrm{Mo/ZSM}$-5 catalysts in non-oxidative methane dehydroaromatization

Literature shows that adding Fe as a separate phase to MoO 3 /ZSM-5 catalysts can improve benzene selectivity in methane dehydroaromatization (MDA), but only when added in small quantities, making it difficult to characterize the state of Fe in the catalyst and understand the role of Fe-Mo interactions on the catalytic properties. We explore how the nature of the Mo-Fe interactions in the catalyst precursor can influence the stability and product selectivity in MDA, by employing for the first time Fe 2 (MoO 4 ) 3 /ZSM-5 as a catalyst precursor in MDA. We have compared the activity of Fe 2 (MoO 4 ) 3 /ZSM-5 with monometallic MoO 3 /ZSM-5 and mixed MoO 3 + Fe 2 O 3 /ZSM-5 containing equivalent Mo and Fe loadings and found that Fe 2 (MoO 4 ) 3 /ZSM-5 shows higher benzene selectivity than the mixed MoO 3 + Fe 2 O 3 /ZSM-5 catalyst and exhibits higher stability in reaction compared to the monometallic MoO3/ZSM-5 catalyst. Structural characterization suggests that Fe 2 (MoO 4 ) 3 partially segregates to Fe 2 O 3 and amorphous MoO x during thermal pretreatment. The MoO x species migrate into the zeolite channels during pretreatment, while Fe oxides remain on the external surface of the zeolite. Gas adsorption/desorption techniques and density functional theory calculations demonstrate that the preexisting Fe 2 O 3 phases on the external surface of the zeolite in the mixed MoO 3 + Fe 2 O 3 /ZSM-5 precursor trap (MoO 3 ) 3 clusters preventing them from migrating into the zeolite channels during pretreatment, whereas gradual formation of amorphous MoOx together with the segregation of the Fe 2 O 3 phase when using the Fe 2 (MoO 4 ) 3 precursor diminishes trapping of (MoO 3 ) 3 and consequently enhances migration and anchoring of the MoO x species in the zeolite channels, boosting selectivity to benzene. Characterization of used catalysts suggests that the presence of Fe promotes formation of structured carbon nanofibers which reduce the rate of catalyst deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resistive AC-Coupled Silicon Detectors: principles of operation and first results from a combined analysis of beam test and laser data

This paper presents the principles of operation of Resistive AC-Coupled Silicon Detectors (RSDs) and measurements of the temporal and spatial resolutions using a combined analysis of laser and beam test data. RSDs are a new type of n-in-p silicon sensor based on the Low-Gain Avalanche Diode (LGAD) technology, where the n+ implant has been designed to be resistive, and the read-out is obtained via AC-coupling. The truly innovative feature of RSD is that the signal generated by an impinging particle is shared isotropically among multiple read-out pads without the need for floating electrodes or an external magnetic field. Careful tuning of the coupling oxide thickness and the n+ doping profile is at the basis of the successful functioning of this device. Several RSD matrices with different pad width-pitch geometries have been extensively tested with a laser setup in the Laboratory for Innovative Silicon Sensors in Torino, while a smaller set of devices have been tested at the Fermilab Test Beam Facility with a 120 GeV/c proton beam. The measured spatial resolution ranges between 2.5μm for 70–100 pad-pitch geometry and 17μm with 200–500 matrices, a factor of 10 better than what is achievable in binary read-out (bin size/12). Beam test data show a temporal resolution of ~40ps for 200 μm pitch devices, in line with the best performances of LGAD sensors at the same gain.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Inhibition of Extracellular Enzyme Activity by Reactive Oxygen Species upon Oxygenation of Reduced Iron-Bearing Minerals

The dual roles of minerals in inhibiting and prolonging extracellular enzyme activity in soils and sediments are governed by enzyme adsorption to mineral surface. Oxigenation of mineral-bound Fe(II) generates reactive oxygen species (ROS), yet it is unknown whether and how this process alters the activity and functional lifespan of extracellular enzymes. Here, the effect of mineral-bound Fe(II) oxidation on the hydrolytic activity of a cellulose-degrading enzyme ß-glucosidase (BG) was studied using two pre-reduced Fe-bearing clay minerals (nontronite and montmorillonite) and one pre-reduced iron oxide (magnetite) at pH 5 and 7. Under anoxic condition, BG adsorption to mineral surface decreased its activity but prolonged its lifespan. Under oxic condition, ROS was produced, with the amount of •OH, the most abundant ROS, being positively correlated with the extent of structural Fe(II) oxidation in reduced minerals. •OH decreased BG activity and shortened its lifespan via conformational change and structural decomposition of BG. These results suggest that under oxic condition the ROS-induced inhibitory role of Fe(II)-bearing minerals outweighed their adsorption-induced protective role in controlling enzyme activity. These results disclose a previously unknown mechanism of extracellular enzyme inactivation, which have pivotal implications for predicting the active enzyme pool in redox-oscillating environments.

58 GEOSCIENCES↗

Revealing High Na-Content P2-Type Layered Oxides as Advanced Sodium-Ion Cathodes

Layered Na-based oxides with the general composition of Na x TMO 2 (TM: transition metal) have attracted significant attention for their high compositional diversity that provides tunable electrochemical performance for electrodes in sodium-ion batteries. The various compositions bring forward complex structural chemistry that is decisive for the layered stacking structure, Na-ion conductivity, and the redox activity, potentially promising new avenues in functional material properties. In this work, we have explored the maximum Na content in P2-type layered oxides and discovered that the high-content Na in the host enhances the structural stability; moreover, it promotes the oxidation of low-valent cations to their high oxidation states (in this case Ni 2+ ). This can be rationalized by the increased hybridization of the O(2p)-TM(3d-e g *) states, affecting both the local TM environment as well as the interactions between the NaO 2 and TMO 2 layers. These properties are highly beneficial for the Na storage capabilities as required for cathode materials in sodium-ion batteries. It leads to excellent Na-ion mobility, a large storage capacity (>100 mAh g –1 between 2.0-4.0 V), yet preventing the detrimental sliding of the TMO 2 layers (P2–O2 structural transition), as reflected by the ultralong cycle life (3000 (dis)charge cycles demonstrated). These findings expand the horizons of high Na-content P2-type materials, providing new insights of the electronic and structural chemistry for advanced cathode materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen

Producing liquid fuels such as ethanol from CO 2 , H 2 O, and renewable electricity offers a route to store sustainable energy. The search for efficient electrocatalysts for the CO 2 reduction reaction relies on tuning the adsorption strength of carbonaceous intermediates. Here, we report a complementary approach in which we utilize hydroxide and oxide doping of a catalyst surface to tune the adsorbed hydrogen on Cu. Density functional theory studies indicate that this doping accelerates water dissociation and changes the hydrogen adsorption energy on Cu. We synthesize and investigate a suite of metal-hydroxide-interface-doped-Cu catalysts, and find that the most efficient, Ce(OH) x -doped-Cu, exhibits an ethanol Faradaic efficiency of 43% and a partial current density of 128 mA cm -2 . Mechanistic studies, wherein we combine investigation of hydrogen evolution performance with the results of operando Raman spectroscopy, show that adsorbed hydrogen hydrogenates surface *HCCOH, a key intermediate whose fate determines branching to ethanol versus ethylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing delamination of an electron-transporting polymer from a metal oxide for electrochemical applications

Delamination of the electron-transporting polymer N2200 from indium tin oxide (ITO) in aqueous electrolytes is mitigated by modifying ITO with an azide-functionalized phosphonic acid (PA) which, upon UV irradiation, reacts with the polymer. Here, the optical, electrochemical, and spectroelectrochemical properties of N2200 thin films are retained in aqueous and non-aqueous media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer

The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗