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At least 1,243 records · Page 69

Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% and 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.

Choi, Jae-Soon↗

Thermal Barrier Coatings Overview: Design, Manufacturing, and Applications in High-Temperature Industries

Today’s competitive world economy is creating an indispensable demand for increased efficiency of engineering components that operate in harsh environments (i.e., very high-temperature, corrosive, or neutron irradiation environments), for applications in the energy, automotive, aerospace, electronics, and power industries. Increased research is being done on thermal barrier coatings (TBCs) for protecting such components, since the versatility of manufacturing techniques and the scale of deployment result in increased life, economics, performance, and durability. This review focuses on the advances that led to using TBCs for component life extension and, more recently, as an integral part of advanced component design for high-temperature and other types of harsh environments, such as those found in nuclear-related applications. Furthermore, factors that led to state-of-the-art advanced coating-fabrication techniques [e.g., electron-beam physical vapor deposition (EB-PVD), plasma spray deposition, and electrophoretically deposited TBCs, as well as functionally graded material (FGM) manufacturing] have also been emphasized in current coating R&D. This review explores the current state of TBCs, i.e., the latest advances regarding their fabrication and performance, associated challenges, and recommendations for their future use in aerospace, nuclear, high-temperature, or otherwise harsh environments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals

In this study, complexes of 3-amino-6-(3,5-dimethylpyrazole)tetrazine) (NH 2 TzDMP, 1) and 3-(3,3'-dinitroazetidine)-6-(3,5-dimethylpyrazole)tetrazine) (DNAZTzDMP, 2) with first row transition metal centers were synthesized. Reactions of Fe II (H 2 O) 6 (BF 4 ) 2 and Fe(NO 3 ) 3 ·9H 2 O with 1 and 2 both led to complexes of the form [(RTzDMP) 3 Fe]X 2 (X = BF 4 , R = NH 2 (3), DNAZ (4); X = NO 3 , R = NH 2 (5), DNAZ (6)), which showed intense MLCT bands in the visible region of the spectrum. Ligands 1 and 2 also reacted with Cu II (NO 3 ) 2 ·5/2H 2 O to form [(RTzDMP) 2 Cu(NO 3 )][NO 3 ] (R = NH 2 (7), DNAZ (8)) in addition to reacting with Cu I (CH 3 CN) 4 (PF 6 ) to form [(RTzDMP) 2 Cu][PF 6 ] (R = NH 2 (9), DNAZ (10)). Finally, reactions of 1 and 2 with Co(NO 3 ) 2 ·6H 2 O and Ni(NO 3 ) 2 ·6H 2 O led to [(NH 2 TzDMP) 2 Co(H 2 O) (NO 3 )][NO 3 ] (11), [(DNAZTzDMP) 2 Co(H 2 O) 2 ][NO 3 ] 2 (12), [(NH 2 TzDMP) 3 Ni][NO 3 ] 2 (13), and [(DNAZTzDMP) 2 Ni(H 2 O) 2 ][NO 3 ] 2 (14). The complexes display rich electrochemical and photophysical properties that are unaffected by derivation with explosive groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactions of U(DMSO) 8 (ClO 4 ) 4 with Terpyridine Yield Dimeric Hydrolysis Products and Induce C–C Coupling

Reactions have been carried out using UIV(DMSO) 8 (ClO 4 ) 4 with 2,2′:6′,2″-terpyridine (terpy) under nonaqueous conditions. At room temperature in acetonitrile, the combination of the U(IV) starting material with terpy resulted in a mixture containing [UO 2 (DMSO) 2 terpy][ClO 4 ] 2 ·MeCN, while increasing the water content led to the hydrolysis products [(UO 2 (DMSO)terpy) 2 (μ 2 –O)][ClO 4 ] 2 and [(UO 2 terpy) 2 (μ 2 –OH) 2 ][ClO 4 ] 2 ·MeCN·H 2 O. Performing the reaction at slightly elevated temperature with no added water led to the formation of [UO 2 sexipyridine][ClO 4 ] 2 ·MeCN. This new uranyl complex contains the hexadentate ligand 2,2′:6′,2″:6″,2″:6‴,2⁗:6⁗,2⁗′-sexipyridine, which formed in situ from the tetravalent uranium starting material, where photoexcited uranyl or in situ generated peroxide could have induced C–C coupling. Analysis of bonding in the dimeric uranyl species via quantum chemical methods revealed a small increase in covalency of the bridging oxo unit and a slightly greater stability compared to the bridging hydroxo compound, which causes a significant shift in the uranyl symmetric stretch in the Raman spectrum. Structural, spectroscopic, and computational comparisons are made across the series of compounds, providing insight into the bonding and reactivity of uranium in nonaqueous media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design, Synthesis, and Biological Evaluation of 4-Quinoline Carboxylic Acids as Inhibitors of Dihydroorotate Dehydrogenase

In this work, we pursued a structure-guided approach toward the development of improved dihydroorotate dehydrogenase (DHODH) inhibitors with the goal of forming new interactions between DHODH and the brequinar class of inhibitors. Two potential residues, T63 and Y356, suitable for novel H-bonding interactions, were identified in the brequinarbinding pocket. Analogues were designed to maintain the essential pharmacophore and form new electrostatic interactions through strategically positioned H-bond accepting groups. This effort led to the discovery of potent quinolinebased analogues 41 (DHODH IC 50 = 9.71 ± 1.4 nM) and 43 (DHODH IC 50 = 26.2 ± 1.8 nM). A cocrystal structure between 43 and DHODH depicts a novel water mediated H-bond interaction with T63. Additional optimization led to the 1,7- naphthyridine 46 (DHODH IC 50 = 28.3 ± 3.3 nM) that forms a novel H-bond with Y356. Importantly, compound 41 possesses significant oral bioavailability ($F$ = 56%) and an elimination $t_{1/2}$ = 2.78 h (PO dosing). In conclusion, the data supports further preclinical studies of our lead compounds toward selection of a candidate for early-stage clinical development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and Theoretical Study of Oxolan-3-one Thermal Decomposition

The thermal decomposition of oxolan-3-one, a common component of the bio-oil formed during biomass pyrolysis, has been studied using ab initio calculations and experiments employing pulsed gas-phase pyrolysis with matrix isolation FTIR product detection. Four pathways for unimolecular decomposition were predicted using computational methods. The dominant reaction channel led to carbon monoxide, formaldehyde, and ethylene, all of which were observed experimentally. Here, the other channels led to an assortment of products including ketene, water, propyne, and acetylene, which were all confirmed in the matrix-isolation FTIR spectra. There is also evidence for the production of substituted ketenes in pyrolysis, most likely hydroxyketene and methylketene.

09 BIOMASS FUELS↗

Machine Learning Classical Interatomic Potentials for Molecular Dynamics from First-Principles Training Data

The ever-increasing power of modern super-computers, along with the availability of highly scalable atomistic simulation codes, has begun to revolutionize predictive modeling of materials. In particular, molecular dynamics (MD) has led to breakthrough advances in diverse fields, including tribology, catalysis, sensing, and nanoparticle self-assembly. Furthermore, recent integration of MD simulations with X-ray characterization has demonstrated promise in real-time 3-D characterization of materials on the atomic scale. The popularity of MD is driven by its applicability at disparate length/time scales, ranging from ab initio MD (hundreds of atoms and tens of picoseconds) to all-atom classical MD (millions of atoms over microseconds), and coarse-grained (CG) models (micrometers and tens of microseconds). Nevertheless, a substantial gap persists between AIMD, which is highly accurate but restricted to extremely small sizes, and those based on classical force fields (atomistic and CG) with limited accuracy but access to larger length/time scales. The accuracy and predictive power of classical MD simulations is dictated by the empirical force fields, and their capability to capture the relevant physics. Here, we discuss some of our recent work on the use of machine learning (ML) to combine the accuracy and flexibility of electronic structure calculations with the speed of classical potentials. Our ML framework attempts to bridge the significant gulf that exists between the handful of research groups that develop new interatomic potential models (often requiring several years of effort), and the increasingly large user community from academia and industry that applies these models. Our data-driven approach represents significant departure from the status quo and involves several steps including generation and manipulation of extensive training data sets through electronic structure calculations, defining novel potential functional forms, employing state-of-the-art ML algorithms to formulate highly optimized training procedures, and subsequently developing user-friendly workflow tools integrating these algorithms on high-performance computers (HPCs). Our ML approach shows marked success in developing force fields for a wide range of materials from metals, oxides, nitrides, and heterointerfaces to two-dimensional (2D) materials.

Chan, Henry↗

Structural Investigation of Cesium Lead Halide Perovskites for High-Efficiency Quantum Dot Light-Emitting Diodes

We have investigated the effect of reaction temperature of hot-injection method on the structural properties of CsPbX3 (X: Br, I, Cl) perovskite nanocrystals (NCs) using the small- and wide-angle X-ray scattering. It is confirmed that the size of the NCs decreased as the reaction temperature decreased, resulting stronger quantum confinement. The cubic-phase perovskite NCs were formed despite the reaction temperatures increased from 140 to 180 °C. However, monodispersive NC cubes which are required for densely packing self-assembly film were only formed at lower temperatures. From the X-ray scattering measurements, the spin-coated film from more monodispersive perovskite nanocubes synthesized at lower temperatures resulted in more preferred orientation. This dense-packing perovskite film with preferred orientation yielded efficient light-emitting diode (LED) performance. Thus, the dense-packing structure of NC assemblies formed after spin-coating should be considered for high-efficient LEDs based on perovskite quantum dots in addition to quantum confinement effect of the quantum dots.

Le, Quyet Van↗

Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes

Multivalent counterion-induced bridging interactions have been identified as the key mechanism of drastic collapse of the height of polyelectrolyte (PE) brushes. In this article, we employ all-atom molecular dynamics (MD) simulations to quantify the bridging interactions in PE brushes for counterions of different sizes and valences. We identify that unlike the current notion, bridging interactions are not the sole function of the counterion valence. Rather the bridging interactions depend on the fraction of counterions (of a given type) that get physically condensed on the PE backbone as well as the size of the counterion solvation shell. These mechanisms ensure that certain monovalent counterions demonstrate much stronger bridging interactions than that witnessed for certain divalent and trivalent counterions, while certain counterions of identical valences show drastically different bridging. Here, we argue that these counterion-specific bridging interactions eventually enable not only the significant reduction of the PE brush height in presence of certain multivalent screening counterions, but may also give rise to scenarios where the brush height reduction for certain monovalent counterions is larger than certain divalent and trivalent counterions. This latter observation contradicts the experimental findings where the multivalent counterions invariably led to a larger decrease in the height of the PE brushes: we argue that this discrepancy stems from the fact that in our simulations we only consider densely grafted and short (and hence less flexible) PE brushes that hinder the formation of different laterally inhomogeneous structures (like pinned micelles and cylindrical bundles) that would have led to a larger brush height reduction (in experiments, which invariably consider longer and less densely grafted brushes, the formation of such inhomogeneous structures are primarily responsible for larger brush height reduction in presence of multivalent counterions). Finally, we also probe the dynamic properties of the counterions (i.e., their time-dependent displacements) and their bridging interactions (i.e., lifetime of bridging interactions).

42 ENGINEERING↗

Growth and Anion Exchange Conversion of CH 3 NH 3 PbX 3 Nanorod Arrays for Light-Emitting Diodes

The nanowire and nanorod morphology offers great advantages for application in a range of optoelectronic devices, but these high-quality nanorod arrays are typically based on high temperature growth techniques. Here, we demonstrate the successful room temperature growth of a hybrid perovskite (CH 3 NH 3 PbBr 3 ) nanorod array, and we also introduce a new low temperature anion exchange technique to convert the CH 3 NH 3 PbBr 3 nanorod array into a CH 3 NH 3 PbI 3 nanorod array while preserving morphology. We demonstrate the application of both these hybrid perovskite nanorod arrays for LEDs. This work highlights the potential utility of postsynthetic interconversion of hybrid perovskites for nanostructured optoelectronic devices such as LEDs, which enables new strategies for the application of hybrid perovskites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Record surface state mobility and quantum Hall effect in topological insulator thin films via interface engineering

Material defects remain as the main bottleneck to the progress of topological insulators (TIs). In particular, efforts to achieve thin TI samples with dominant surface transport have always led to increased defects and degraded mobilities, thus making it difficult to probe the quantum regime of the topological surface states. Here, by utilizing a novel buffer layer scheme composed of an In 2 Se 3 /(Bi 0.5 In 0.5 ) 2 Se 3 heterostructure, we introduce a quantum generation of Bi 2 Se 3 films with an order of magnitude enhanced mobilities than before. Furthermore, this scheme has led to the first observation of the quantum Hall effect in Bi 2 Se 3 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Heterogeneous Organochromium Catalysts for Stereoselective Isoprene Polymerization

In this study, heterogeneous organochromium catalysts have been developed via surface lithiation of traditional surface organometallic complexes to mediate stereoselective isoprene polymerization. Chemisorption of the molecular complex Cr(CH 2 SiMe 3 ) 4 on high surface area anatase titania nanoparticles as well as on a silica support led to the bipodal complexes Cr/TiO 2 and Cr/SiO 2 , respectively. Subsequent reductive lithium intercalation with n-butyllithium led to the formation of lower valent Cr 2+ species Cr/LTO and Cr/Li/SiO 2 . Alternatively, Cr(CH 2 SiMe 3 ) 4 was allowed to react with nBuLi-reduced anatase titania (LTO) to provide Cr/LTO Inv . Cr/LTO and Cr/Li/SiO 2 both polymerize isoprene with very high activities (154 and 174 kg molCr –1 h –1 , respectively) to provide polyisoprene with cis-1,4 selectivity up to 82% in toluene at 50 °C. On the other hand, Cr/SiO 2 provides polyisoprene with excellent trans-1,4 selectivity up to 98% (16 kg molCr –1 h –1 ), and Cr/TiO 2 was catalytically inactive. Cr/LTO Inv is less active and selective, and X-ray absorption spectroscopy (XAS) measurements of the precatalyst revealed the presence of a mixture of metallic Cr 0 , Cr 4+ , and only minor Cr 2+ species. Thus, surface lithiation can promote the formation of lower valent metal centers which enable stereocontrol in isoprene polymerizations and may be extended as a general protocol to other catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the Long-Term Stability of Anion Exchange Membranes for Electrochemical CO 2 Reduction

Materials and cell components used in CO 2 electrolysis have largely been adapted from technologies initially developed for water electrolysis and fuel cells. However, electrochemical CO 2 reduction introduces distinct material challenges due to the unique chemical environment in this process. Here, in this study, we conducted ex-situ 1000 h stability tests on commonly used anion exchange membranes, exposing them exclusively to electrolytes and organic molecules used or produced during CO 2 electrolysis, at concentrations relevant to and compatible with postseparation processes. Notably, 15% w/w n-propanol and 5 M acetic acid caused complete dissolution or partial disintegration of the membranes unless cross-linking was present and remained stable throughout the test. When the membranes stayed physically intact, most of them exhibited excellent chemical stability in alkaline medium containing alcohols or formic acid, which was confirmed by vibrational spectroscopy and ion exchange capacity measurements. However, exposure to alcohol-and acid-containing solutions led to a substantial increase in swelling and water uptake, with potential implications for mechanical stability, ion/product crossover, and compression management of adjacent components. The potential effects of CO 2 electroreduction products on membrane stability, their subsequent impact on electrolyzer performance, and mitigation strategies are discussed.

CO2RR↗

Performance of Spherical Quantum Well Down Converters in Solid State Lighting

We report the color conversion performance of amber and red emitting quantum dots (QDs) on InGaN solid-state lighting (SSL) light emitting diode (LED) packages. Spherical quantum well (SQW) architectures (CdS/CdSe 1- x S x /CdS) were prepared using a library of thio- and selenourea synthesis reagents and high throughput synthesis robotics. CdS/CdSe 1- x S x QDs with narrow luminescence bands were coated with thick CdS shells (thickness = 1.6-7.5 nm) to achieve photoluminescence quantum yields (PLQY) up to 88% at amber and red emission wavelengths (λ max = 600-642 nm, FWHM < 45 nm). The photoluminescence from SQWs encapsulated in silicone and deposited on LED packages was monitored under accelerated aging conditions (oven temperature = 85 °C, relative humidity = 5-85%, blue optical power density = 3-45 W/cm 2 ) by monitoring the red photon output over several hundred hours of continuous operation. The growth of a ZnS shell on the SQW surface increases the stability under long-term operation but also reduces the PLQY, especially of SQWs with thick CdS shells. The results illustrate that the outer ZnS shell layer is key to optimizing the PLQY and the long-term stability of QDs during operation on SSL packages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Control of Excitonic Energy Transfer in RGB Quantum Dot:Polymer Composites for Tunable White Emission

Tint-controlled white light is crucial for both illumination systems and display applications. Here, in this study, we demonstrate solution-processed quantum-dot light-emitting diodes (QD-LEDs) featuring a red–green–blue (RGB) QD–poly(methyl methacrylate) (PMMA) composite emissive layer (EML) for tunable white electroluminescence (EL). In this composite EML, PMMA functions as a dispersion matrix that modulates the interdot spacing (d), thereby controlling Förster resonance energy transfer (FRET) between QDs. By adjustment of the PMMA content, the balance of R, G, and B emissions is controlled, enabling systematic and continuous tuning of the EL color from greenish to reddish white at a fixed RGB ratio and constant driving bias. Time-resolved photoluminescence measurements confirm that the variation in the exciton lifetime with the PMMA fraction is the primary factor for tuning the EL color. Notably, nearly pure white EL with CIE coordinates close to (0.33, 0.33) is achieved using a diluted PMMA matrix without significant degradation of the electrical properties. Our results demonstrate d as an independent design parameter for decoupling color tuning from RGB composition and electrical operation, providing a versatile design framework for high-quality white- or tint-controlled QD-LEDs toward advanced solid-state lighting and display technologies.

36 MATERIALS SCIENCE↗

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

We investigate the effect of the poly(acrylic acid) (PAA) carrier polymer concentration on the microstructure and rheological properties of catalyst inks for electrospun polymer–electrolyte membrane fuel-cell catalyst layers. Characterization of an ink microstructure using oscillatory shear rheology showed that the catalyst particles (platinum on carbon) are significantly agglomerated in the absence of PAA or an ionomer. Both the ionomer and PAA promoted the stability of the particles against agglomeration via electrosteric stabilization by adsorbing onto the particle surface. Increasing the PAA concentration increased the stability of the particles (or reduced the agglomerated structure) due to increasing PAA coverage onto the free surface area of the particles. However, beyond a certain increase in concentration, PAA was found to predominantly remain as an excess free polymer in the ink due to an insufficient free/available surface area on the particles for further PAA coverage. Extensional rheology measurements demonstrated that PAA enhances the extensional viscosities of the inks. Consequently, increasing the PAA concentration in the ink promoted the evolution of uniform nanofibers. However, beyond a certain concentration, a significant increase in the shear viscosities of the inks led to defective fiber morphologies because of the onset of flow instabilities. Electrochemical performance comparisons between catalyst layers with different PAA concentrations showed maximum performance at the PAA concentration that led to the least agglomerated structure of the catalyst, most uniform fiber morphologies, and low concentrations of free (non-adsorbing) PAA in the electrode. These results provide a rationale for optimization of electrospun catalyst nanofibers for both spinnability and electrochemical performance.

25 ENERGY STORAGE↗

Alcohol-Induced Low-Temperature Blockage of Supported-Metal Catalysts for Enhanced Catalysis

The partial or complete blockage of active sites of metal nanoparticles (NPs) on supported-metal catalysts has been of interest for tuning the stability, selectivity, and rate of reactions. In this study, we show that Au-sites in Au/TiO 2 surprisingly become blocked upon treatment in common alcohols (2-propanol and methanol), with 2-propanol causing a greater extent of blockage. Nearly 95% of Au-sites are covered after treatment in 2-propanol at room temperature, followed by desorption at 150 °C. Infrared spectroscopy of CO adsorption unambiguously confirms the occurrence of this phenomenon. Electron energy loss spectroscopy (EELS), temperature-programmed desorption (TPD), Raman spectroscopy, and DFT simulations suggest that the formation of carbon deposits from 2-propanol decomposition and/or the migration of a TiO x layer over the supported NPs may be responsible for the blockage of Au-sites. Nearly full coverage of Au NPs after treatment in 2-propanol led to negligible activity for catalytic CO oxidation, whereas partial retraction of the overlayer led to enhanced activity with time-on-stream, suggesting a self-activating catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roll-to-Roll Printing of Perovskite Solar Cells

High efficiency combined with transformative roll-to-roll (R2R) printability makes metal halide perovskite-based solar cells the most promising solar technology to address the terawatt challenge of the future energy demand. However, translation from lab-scale deposition solution processing techniques to large-scale R2R methods has typically led to reduced photovoltaic performance. Here, we demonstrate large-scale, highly crystalline, uniaxially oriented, smooth perovskite films printed at room temperature and in the ambient environment. Confirmed with high speed in situ X-ray diffraction measurements, the perovskite films reach 98% of relative crystallinity at room temperature and display high texture within 1 s of the coating. We demonstrate an all-blade-coated metal halide perovskite cell with power conversion efficiency (PCE) up to 19.6%, a slot-die coated cell with a PCE of 17.3%, and a partially R2R slot-die coated flexible glass-based cell efficiency of 14.1%. As a result the developed printing method can be applied to diverse perovskite compositions, enabling a variety of bandgaps to pave the way for the future R2R printing of highly efficient perovskite–perovskite tandem cells.

14 SOLAR ENERGY↗