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At least 361 records · Page 20

Highly Active and Stable Palladium Catalysts on Novel Ceria–Alumina Supports for Efficient Oxidation of Carbon Monoxide and Hydrocarbons

Precious metal catalysts with superior low-temperature activity and excellent thermal stability are highly needed in environmental catalysis field. In this study, a novel two-step incipient wetness impregnation (T-IWI) method was developed for the fabrication of a unique and highly stable CeO 2 /Al 2 O 3 support (CA-T). Pd anchored on CA-T exhibited a much higher low-temperature catalytic activity and superior thermal stability in carbon monoxide (CO) and hydrocarbon (HC) oxidations, compared to Pd anchored on conventional CeO 2 /Al 2 O 3 (CA), which was prepared by a one-step IWI method. After aging treatment at 800 °C, the CO oxidation rate on Pd/CA-T (1.69 mmol/(g Pd s)) at 120 °C was 4.1 and 84.5 times of those on Pd/CA (0.41 mmol/(g Pd s)) and Pd/Al 2 O 3 (0.02 mmol/(g Pd s)), respectively. It was revealed that the CA-T support with well-controlled small CeO 2 particles (ca. 12 nm) possessed abundant defects for Pd anchoring, which created rich Pd-CeO 2 interfaces with strengthened interaction between Pd and CeO 2 where oxygen could be efficiently activated. This resulted in the significantly improved oxidation activity and thermal stability of Pd/CA-T catalysts. The T-IWI method developed herein can be applied as a universal approach to prepare highly stable metal oxide-alumina-based supports, which have broad application in environmental catalyst design, especially for automobile exhaust aftertreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustainable Conversion of Carbon Dioxide and Shale Gas to Green Acetic Acid via a Thermochemical Cyclic Redox Scheme (Final Report)

The large-scale production of commodity chemicals relies heavily on the combustion of fossil fuels. As a result, enormous amounts of carbon dioxide (CO 2 ) are emitted which severely affects the global climate. The challenges for CO 2 utilization reside in the high stability of CO 2 molecules relative to the products, which requires the addition of significant external energy and overcoming slow and/or unfavorable reaction kinetics/thermodynamics. Chemical looping dry reforming of methane (CLDRM), also known as a hybrid redox process (HRP), is a promising alternative that allows the utilization of CO 2 and domestic shale gas resources to produce commodity chemicals. HRP works in two steps: In the first step, a redox catalyst reacts with methane to yield synthesis gas with a H 2 /CO ratio near 2:1, which is suitable for methanol and Fischer–Tropsch synthesis. The reduced redox catalyst then reacts with an oxidizing agent, such as CO 2 , to yield CO. In comparison to conventional thermochemical CO 2 splitting approaches, the use of methane as the reducing agent in HRP can significantly lower the operating temperature for CO 2 splitting.

03 NATURAL GAS↗

Utilizing biochars to stabilize mercury in contaminated floodplain sediment: Implications on mercury remediation

Major weather events contribute to the mobility and remobilization of legacy mercury (Hg) contamination and sequestration within sediments. Remediation using biochar as a soil amendment is a useful technique to immobilize and decrease Hg toxicity. This study explored whether biochar application is effective at stabilizing labile mercury (LaHg) from floodplain sediment. Controlled mesocosms simulating contamination events and flooding conditions were conducted. Floodplain sediment, which experiences annual periodic flooding, was collected. Sediment was spiked with inorganic Hg, applied with different types of biochar, and experienced simulated flooding events. Four types of biochar, pure rice husk (RH), pure peanut hull (PH), sulfur-modified rice husk (SMRH), and sulfur-modified peanut hull (SMPH), were applied at 10 and 40 g/kg rates (i.e., RH 10, RH 40; PH 10, PH 40, SMRH 10, SMRH 40, SMPH 10, SMPH 40). Total Hg, methylmercury, and LaHg concentrations were analyzed by coupling with redox potential measurements. Results indicate that SMRH 10, PH 10, PH 40, SMPH 10, and SMPH 40 successfully remediate Hg by stabilizing and reducing LaHg species from floodplain sediment. However, a high Hg methylation potential was observed with unsulfated and sulfated peanut hulls (PH 10, PH 40, SMPH 10, and SMPH 40), as they tend to create a reducing microenvironment that favors sulfate reduction reactions. Additionally, sulfur-modified biochar tends to promote Hg methylation potential at high application rates (i.e., 40 g/kg). We thus recommend using SMRH at a relatively low application rate (SMRH 10) for the remediation of Hg from floodplain sediment.

54 ENVIRONMENTAL SCIENCES↗

Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions

Polyoxometalates (POMs) featuring 7, 12, 18, or more redox-accessible transition metal ions are ubiquitous as selective catalysts, especially for oxidation reactions. The corresponding synthetic and catalytic chemistry of stable, discrete, capping-ligand-free polythiometalates (PTMs), which could be especially attractive for reduction reactions, is much less well developed. Among the challenges are the propensity of PTMs to agglomerate and the tendency for agglomeration to block reactant access of catalyst active sites. Nevertheless, the pervasive presence of transition metal sulfur clusters metalloenzymes or cofactors that catalyze reduction reactions and the justifiable proliferation of studies of two-dimensional (2D) metal-chalcogenides as reduction catalysts point to the promise of well-defined and controllable PTMs as reduction catalysts. Here, we report the fabrication of agglomeration-immune, reactant-accessible, capping-ligand-free Co II Mo 6 IV S 24 n– clusters as periodic arrays in a water-stable, hierarchically porous Zr-metal–organic framework (MOF; NU1K) by first installing a disk-like Anderson polyoxometalate, Co III Mo 6 VI O 24 m– , in size-matched micropores where the siting is established via difference electron density (DED) X-ray diffraction (XRD) experiments. Flowing H 2 S, while heating, reduces molybdenum(VI) ions to Mo(IV) and quantitatively replaces oxygen anions with sulfur anions (S 2– , HS – , S 2 2– ). DED maps show that MOF-templated POM-to-PTM conversion leaves clusters individually isolated in open-channel-connected micropores. Importantly, the structure of the immobilized cluster as determined, in part, by X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analysis, and pair distribution function (PDF) analysis of total X-ray scattering agrees well with the theoretically simulated structure. PTM@MOF displays both electrocatalytic and photocatalytic competency for hydrogen evolution. Nevertheless, the initially installed PTM appears to be a precatalyst, gaining competency only after the loss of ~3 to 6 sulfurs and exposure to hydride-forming metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rejuvenating dead lithium supply in lithium metal anodes by iodine redox

Inactive lithium (more frequently called dead lithium) in the forms of solid-electrolyte interphase and electrically isolated metallic lithium is principally responsible for the performance decay commonly observed in lithium metal batteries. A fundamental solution of recovering dead lithium is urgently needed to stabilize lithium metal batteries. In this paper, we quantify the solid-electrolyte interphase components, and determine their relation with the formation of electrically isolated dead lithium metal. We present a lithium restoration method based on a series of iodine redox reactions mainly involving I 3 - /I - . Using a biochar capsule host for iodine, we show that the I 3 - /I - redox takes place spontaneously, effectively rejuvenating dead lithium to compensate the lithium loss. Through this design, a full-cell using a very limited lithium metal anode exhibits an excellent lifespan of 1,000 cycles with a high Coulombic efficiency of 99.9%. We also demonstrate the design with a commercial cathode in pouch cells. Cycling lithium batteries often results in inactive lithium that no longer participates in redox reactions, leading to performance deterioration. Here the authors use an iodic species to react with inactive lithium, bringing it back to life and thus making batteries last longer.

25 ENERGY STORAGE↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

Computer-aided design of stability enhanced nicotinamide cofactor biomimetics for cell-free biocatalysis

Cell-free biocatalysis (CFB) is an efficient and environmentally friendly method to synthesize molecules such as pharmaceuticals, biochemicals, and biofuels through the in vitro use of enzyme cascades. These enzymes often require redox cofactors to drive chemical reactions. Natural redox cofactors (NAD(P)H) are expensive to isolate, motivating synthetic nicotinamide cofactor biomimetics (NCBs) as a cost-effective solution. A select handful of NCBs have been identified as potential NAD(P)H alternatives with comparable or improved redox capabilities, however, they display a tendency to degrade in common buffers. In this study, a library of 132 NCB candidates is systematically generated, over 85% of which have not been characterized in the literature, to expand the diversity of currently explored NCBs. The decomposition mechanism of NCBs in phosphate is evaluated using density functional theory (DFT), revealing protonation at the nicotinamide C5 position as a reporter of cofactor stability. Based on this result, we trained a linear regression model on DFT calculated descriptors to predict NCB stability in phosphate buffer, achieving mean absolute error (MAE) and root mean squared error (RMSE) values within computational accuracy. Analysis of key atomic descriptors and qualitative trends in our dataset informed the design of novel NCB candidates we propose with optimized stability. This work enables researchers to predict the relative stability of NCBs before synthesis, thereby streamlining the process to make CFB more affordable and viable at industry scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantification of the Electrostatic Effect on Redox Potential by Positive Charges in a Catalyst Microenvironment

Charged functional groups in the secondary coordination sphere (SCS) of a heterogeneous nanoparticle or homogeneous electrocatalyst are of growing interest due to enhancements in reactivity that derive from specific interactions that stabilize substrate binding or charged intermediates. At the same time, accurate benchmarking of electrocatalyst systems most often depends on the development of linear free-energy scaling relationships. Furthermore, the thermodynamic axis in those kinetic–thermodynamic correlations is most often obtained by a direct electrochemical measurement of the catalyst redox potential and might be influenced by electrostatic effects of a charged SCS. In this report, we systematically probe positive charges in a SCS and their electrostatic contributions to the electrocatalyst redox potential. A series of 11 iron carbonyl clusters modified with charged and uncharged ligands was probed, and a linear correlation between the ν CO absorption band energy and electrochemical redox potentials is observed except where the SCS is positively charged.

14 SOLAR ENERGY↗

Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions

Platinum is the primary catalyst for many chemical reactions in the field of heterogeneous catalysis. However, platinum is both expensive and rare. Therefore, it is advantageous to combine Pt with another metal to reduce cost while also enhancing stability. To that end, Pt is often combined with Co to form Co-Pt nanocrystals. However, dynamical restructuring effects that occur during reaction in Co-Pt ensembles can impact catalytic properties. In this study, model Co 2 Pt 3 nanoparticles supported on carbon were characterized during a redox cycle with two in situ approaches, namely X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy (STEM) using a multimodal microreactor. The sample was exposed to temperatures up to 500 °C under H 2 , and then to O 2 at 300 °C. Irreversible segregation of Co in the Co-Pt particles was seen during redox cycling and substantial changes of the oxidation state of Co were observed. After the H 2 treatment, a fraction of Co could not be fully reduced and incorporated into a mixed Co-Pt phase. Re-oxidation of the sample increased Co segregation, and the segregated material had a different valence state than in the fresh, oxidized sample. Furthermore, this in situ study describes dynamical restructuring effects in CoPt nano-catalysts at the atomic scale that are crucial to understand to improve the design of catalysts used in major chemical processes.

36 MATERIALS SCIENCE↗

Electrode Blocking Due to Redox Reactions in Aluminum Chloride-Sodium Iodide Molten Salts

Iodide redox reactions in molten NaI/AlCl 3 are shown to generate surface-blocking films, which may limit the useful cycling rates and energy densities of molten sodium batteries below 150 °C. An experimental investigation of electrode interfacial stability at 110 °C reveals the source of the reaction rate limitations. Electrochemical experiments in a 3-electrode configuration confirm an increase of resistance on the electrode surface after oxidation or reduction current is passed. Using chronopotentiometry, chronoamperometry, cyclic voltammetry, and electrochemical impedance spectroscopy, the film formation is shown to depend on the electrode material (W, Mo, Ta, or glassy carbon), as well as the Lewis acidity and molar ratio of I − /I 3 − in the molten salt electrolytes. These factors impact the amount of charge that can be passed at a given current density prior to developing excessive overpotential due to film formation that blocks the electrode surface. The results presented here guide the design and use of iodide-based molten salt electrolytes and electrode materials for grid scale battery applications.

25 ENERGY STORAGE↗

Operational stability of mixed Sn–Pb perovskite solar cells: Mechanisms, mitigation strategies, and perspectives

Mixed Sn–Pb perovskites provide the 1.2–1.3 eV narrow-bandgap absorber needed for high efficiency of all perovskite tandems, but their deployment is limited by operational instability under light. This review synthesizes mechanistic origins and recent mitigation strategies for mixed Sn–Pb perovskite solar cells. The oxidation of Sn 2+ to Sn 4+ , often driven by iodine formation under light and bias, is the primary failure pathway; it creates Sn vacancies, self-doping, and nonradiative loss. Surface/grain-boundary defects, halide migration, reactive oxygen species, and interfacial redox at charge-transport layers, along with hole accumulation from poor band alignment, further accelerate Sn–Pb perovskite degradation. Here we survey recent stability advances across additive chemistry, surface and grain-boundary passivation, buried-interface redesign with modified or alternative hole transport layers, and solvent systems that preserve Sn 2+ and correct Sn–Pb speciation for scalable coating. Together, these recent advances have enabled devices to retain 80%–90% output for hundreds to over a thousand hours. Lastly, we provide our perspectives on further improving the operational stability of Sn–Pb perovskite and solar cells.

14 SOLAR ENERGY↗

Template‐Directed Growth of Palladium Nanoparticles in Holey Single‐Layer Graphene for High‐Performance Room‐Temperature Hydrogen Sensing

Holey graphene (HG), formed by introducing nanoscale perforations into graphene sheets, combines the structural advantages of continuous sp 2 conjugation with the beneficial effects of high surface area and enhanced chemical reactivity associated with nanoscopic holes. Conventional HG fabrication methods often rely on harsh oxidative treatments that compromise graphene's intrinsic electronic properties by disrupting its sp 2 conjugation. A new approach is introduced to fabricate HG directly from single-layer graphene (SLG), using two-dimensional covalent organic frameworks (COFs) as a template followed by controlled oxygen plasma etching. This method preserves the integrity of the SLG's sp 2 network while producing well-defined holes with an average diameter of 2.7 nm. These hole edges act as reactive sites that facilitate the confined, autoreductive growth of palladium nanoparticles (PdNPs) without external reducing agents. The confined hole geometry prevents NP agglomeration and ensures a uniform size distribution. The resulting Pd@HG hybrid exhibits exceptional chemiresistive hydrogen sensing characteristics, including ultrahigh sensitivity, low detection limits, rapid response and recovery, and long-term stability under both dry and humid conditions. Mechanistic investigations reveal a two-step sensing process involving surface redox interactions and hydrogen absorption into the PdNP lattices. This strategy presents a scalable platform for integrating metal NPs within conductive carbon frameworks for advanced sensing applications.

chemical vapor deposition↗

Complexions at the iron-magnetite interface

Synthesizing distinct phases and controlling crystalline defects are key concepts in materials design. These approaches are often decoupled, with the former grounded in equilibrium thermodynamics and the latter in nonequilibrium kinetics. By unifying them through defect phase diagrams, we can apply phase equilibrium models to thermodynamically evaluate defects—including dislocations, grain boundaries, and phase boundaries—establishing a theoretical framework linking material imperfections to properties. Using scanning transmission electron microscopy (STEM) with differential phase contrast (DPC) imaging, we achieve the simultaneous imaging of heavy Fe and light O atoms, precisely mapping the atomic structure and chemical composition at the iron-magnetite (Fe/Fe 3 O 4 ) interface. We identify a well-ordered two-layer interface-stabilized phase state (referred to as complexion) at the Fe[001]/Fe 3 O 4 [001] interface. Using density-functional theory (DFT), we explain the observed complexion and map out various interface-stabilized phases as a function of the O chemical potential. The formation of complexions increases interface adhesion by 20% and alters charge transfer between adjacent materials, impacting transport properties. Our findings highlight the potential of tunable defect-stabilized phase states as a degree of freedom in materials design, enabling optimized corrosion protection, catalysis, and redox-driven phase transitions, with applications in materials sustainability, efficient energy conversion, and green steel production.

36 MATERIALS SCIENCE↗

Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries

Sodium-ion batteries are among the most promising alternatives to lithium-based technologies for grid and other energy storage applications due to their cost benefits and sustainable resource supply. For the cathode—the component that largely determines the energy density of a sodium-ion battery cell—one major category of materials is P2-type layered oxides. Unfortunately, at high state-of-charge, such materials tend to undergo a phase transition with a very large volume change and consequent structural degradation during long-term cycling. Here we address this issue by introducing vacancies into the transition metal layer of P2-Na$_{0.7}$Fe$_{0.1}$Mn$_{0.75\square}$$_{0.15}$O2 (‘$_{\square}$’ represents a vacancy). The transition metal vacancy serves to suppress migration of neighbouring Na ions and therefore maintain structural and thermal stability in Na-depleted states. Moreover, the specific Na-O-$_{\square}$ configuration triggers a reversible anionic redox reaction and boosts the energy density. As a result, the cathode design here enables pouch cells with energy densities of 170 Wh kg -1 and 120 Wh kg -1 that can operate for over 600 and 1,000 cycles, respectively. In conclusion, our work not only suggests a feasible strategy for cathode design but also confirms the possibility of developing a battery chemistry that features a reduced need for critical raw materials.

25 ENERGY STORAGE↗

Stabilized Co-Free Li-Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Li-rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g –1 . However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well-known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full-cell performance degradation. In this study, an artificial surface prereconstruction (ASR) for Li 1.2 Mn 0.6 Ni 0.2 O 2 particles with a molten-molybdate leaching is conducted, which creates a crystal-dense anion-redox-free LiMn 1.5 Ni 0.5 O 4 shell that completely encloses the LXMO lattice (ASR-LXMO). Differential electrochemical mass spectroscopy and soft X-ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR-LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR-LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g –1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full-cell matched with a commercial graphite anode and lean (2 g A –1 h –1 ) electrolyte, ASR-LXMO shows high capacity retention of 76% after 125 cycles in full-cell cycling.

25 ENERGY STORAGE↗

Composite Membrane for Sodium Polysulfide Hybrid Redox Flow Batteries

Non-aqueous redox flow batteries (NARFBs) using earth-abundant materials, such as sodium and sulfur, are promising long-duration energy storage technologies. NARFBs utilize organic solvents, which enable higher operating voltages and potentially higher energy densities compared with their aqueous counterparts. Despite exciting progress throughout the past decade, the lack of low-cost membranes with adequate ionic conductivity and selectivity remains as one of the major bottlenecks of NARFBs. Here, we developed a composite membrane composed of a thin (<25 µm) Na+-Nafion coating on a porous polypropylene scaffold. The composite membrane significantly improves the electrochemical stability of Na + -Nafion against sodium metal, exhibiting stable Na symmetric cell performance for over 2300 h, while Na + -Nafion shorted by 445 h. Additionally, the composite membrane demonstrates a higher room temperature storage modulus than the porous polypropylene scaffold and Na + -Nafion separately while maintaining high Na + conductivity (0.24 mS/cm at 20 °C). Our method shows that a composite membrane utilizing Na + -Nafion is a promising approach for sodium-based hybrid redox flow batteries.

25 ENERGY STORAGE↗

Inter-cofactor protein remodeling rewires short-circuited transmembrane electron transfer

Intraprotein electron transfer (ET) requires explicit local control of the environment of cofactors to influence their intermolecular distances, relative orientations, and redox properties. Efficient, longer-range ET often utilizes molecular orbitals of aromatic residues present in the intervening space. Here, revitalization of a vestigial ET pathway in the bacterial photosynthetic reaction center is achieved by scanning with tryptophans to uncover markedly improved routes of electron conduction in a key stabilizing step spanning 15 Å between tetrapyrrole and quinone cofactors. This ET event is maximally enhanced by pairing one or more tryptophans with a threonine to influence quinone binding and/or redox potential. Synergistic effects of these substitutions increase the yield of that ET step to ~95%. Joining these substitutions with mutant residues that improve initial ET steps dramatically enhances transmembrane charge separation via this redesigned version of a pathway that is quantitatively inactive in the native protein-cofactor complex.

Biophysical chemistry↗