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At least 811 records · Page 45

Enhanced alcohol production over binary Mo/Co carbide catalysts in syngas conversion

Recently metal carbide catalysts have attracted attention as alternatives to pure metals for the conversion of syngas to higher oxygenates, a process which could enable the sustainable production of fuels, polymers, and chemicals. Although Mo and Co carbides have both shown promise for higher oxygenate production, they have not achieved the requisite activity and selectivity for practical implementation. In this work we synthesize and characterize a binary Mo and Co carbide catalyst that exhibits improved activity and oxygenate selectivity relative to either pure metal carbide. In this work, we apply a combination of advanced electron microscopy and X-ray diffraction to show that the binary Mo/Co carbide catalyst forms uniformly mixed amorphous nanoparticles. Through in situ X-ray absorption spectroscopy studies, we determine that the structure of the mixed metal carbide catalyst under reaction conditions consists of both carbidic and bimetallic components. By testing the catalytic properties of a series of Mo/Co carbide catalysts prepared by different synthesis methods, we find that the Mo and Co sites must be in close contact to achieve improved syngas conversion to higher alcohols. Through in situ DRIFTS measurements, both Mo and Co atoms at the surface of the catalyst are identified as adsorption sites for reactive species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evading strength and ductility trade-off in an inverse nacre structured magnesium matrix nanocomposite

Mimicking nacre structure is an often-used strategy for developing materials which combine high strength and high toughness. Here, a novel strategy, named inverse nacre structure, is proposed where elongated and curled soft constituents are embedded in a matrix of hard constituent to form an ordered brick-and-mortar arrangement. This strategy is demonstrated in a particle reinforced metal matrix composite, using pure Mg as the soft phase and SiC nanoparticle reinforced Mg as the hard phase. In this work, the resulting nanocomposite yields high strength, and especially high tensile elongation which is five times that of the homogeneous counterpart. The superior comprehensive strengthening-toughening effect originates from the tailored inverse nacre structure which enables a stable microcrack-multiplication process by sufficiently promoting strain hardening so as to avoid any significant decrease in post-ultimate tensile strength. This strategy, while demonstrated here for the specific case of particle reinforced Mg, is not restricted to any particular material system but constitutes a generic pathway for the development of high-performance materials for engineering applications.

36 MATERIALS SCIENCE↗

Directly Embedded Ni3S2/Co9S8@S-Doped Carbon Nanofiber Networks as a Free-Standing Anode for Lithium-Ion Batteries

Transition metal sulfides as electrode materials for lithium-ion batteries have attracted significant research attention due to their high theoretical capacity, excellent redox reversibility, and earth abundance. However, this material family still suffers from poor conductivity and experiences huge volume changes. Here, we demonstrate a facile and scalable electrospinning method to prepare Ni3S2 and Co9S8 nanoparticles embedded in sulfur doped carbon nanofiber networks as a free-standing anode material for lithium ion batteries. Similar to literature findings, the coupling of two different metal sulfides indeed synergistically promoted the electrochemical performance. Embedding them within individual carbon nanofibers not only enhances the intrinsic conductivity, but also provides a highly stable structure, which results in excellent battery performance. Furthermore, the individual carbon nanofibers intertwine with each other to form a free-standing 3D nanofiber network which acts as a freeway network for fast electron transfer and the pores between fibers allow easy penetration of the electrolyte, namely easy lithium ion access to active nanoparticles. When directly applied as the anode in lithium ion batteries, the free-standing nanofiber mat bypassed all slurry making steps and showed excellent cycling stability with a high specific capacity of 528 mA h g-1 after 200 cycles at a current density of 300 mA g-1. Good rate capability was also obtained. Additionally, the charge storage process analysis indicated that the pseudocapacitive behavior of the material is attributed to its good performance. This work introduces a facile strategy to simultaneously and in situ generate Co9S8 and Ni3S2 nanoparticles within a S-doped carbon fiber matrix via facile electrospinning followed by a one-step heating procedure. It is demonstrated that the free-standing transition bimetallic sulfide nanofibers prepared are very promising for light and small battery applications.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗

Decoding α-MoC 1− x Nanoparticle Formation in Continuous Flow via Machine Learning

Molybdenum carbide nanoparticles (α-MoC 1−x NPs) are promising catalysts that offer noble-metal-like performance at lower cost. We report a mild continuous-flow synthesis of α-MoC 1−x NPs from Mo(CO) 6 , coupled with in-line spectroscopic monitoring and machine learning (ML)-based analysis to quantify precursor conversion and product formation in real time. A multilayer perceptron ML model was found to accurately deconvolute complex, nonlinear spectral patterns, enabling identification of a two-step reaction pathway, involving precursor conversion to an amorphous intermediate followed by intraparticle crystallization to α-MoC 1−x NPs, with the first step being rate limiting. Ex situ small angle X-ray scattering (SAXS) and X-ray diffraction (XRD) validation confirm the predicted concentration profiles and crystallization behavior. This integrated approach showcases how ML can empower insights into NP nucleation and growth, paving the way for self-driving, flow-based platforms for NP synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-equilibrium reducing flame aerosol process to create supported high-entropy alloy nanoparticles

High-entropy alloy (HEA) nanomaterials provide opportunities and property combinations for energy and electronic applications, but their practical synthesis faces challenges of elemental immiscibility, metal reducibility, and particle aggregation during their synthesis. Herein, we report a broadly applicable non-equilibrium, scalable, and in-situ reducing flame aerosol process for synthesis of supported HEA nanoparticles. This versatile process can directly load a high concentration of 2 ~ 4 nm HEA nanoparticles on various 1- to 3-dimensional supports. Notably, simultaneous formation of HEA nanoparticles and a mesoporous silica support was successfully realized in a single step. Exploration of this process demonstrates the role of kinetics and entropy on decreasing alloy particle size and altering the reducibility of elements. We propose an entropy-induced reduction mechanism to incorporate oxidizable elements into HEAs, which extends the compositional space of HEA nanoparticles. As a representative catalytic application, we present a RuPdOsIrPt/graphene electrocatalyst with high activity and stability for hydrogen oxidation reaction. Our findings open horizons for high-performance HEA design and applications in diverse fields such as catalysis, electrochemistry, and sensing.

organic↗

Nanosized Zirconium Porphyrinic Metal–Organic Frameworks that Catalyze the Oxygen Reduction Reaction in Acid

Porphyrinic metal–organic frameworks (PMOFs) are very appealing electrocatalytic materials, in part, due to their highly porous backbone, well-defined and dispersed metal active sites, and their long-range order. Herein a series of (Co)PCN222 (PCN: porous coordination network) (nano)particles with different sizes are successfully prepared by coordination modulation synthesis. These particles exhibit stability in 0.1 M HClO 4 electrolyte with no obvious particle size or compositional changes observed after being soaked for 3 days in the electrolyte or during electrocatalysis. This long-term stability enables the in-depth investigation into the electrocatalytic oxygen reduction, and it is further demonstrated that the (Co)PCN222 particle size correlates with its catalytic activity. Of the three particle sizes evaluated (characteristic length scales of 200, 500, and 1000 nm), the smallest size demonstrates the highest mass activity while the largest size has the highest surface area normalized activity. Together these results highlight the importance of determining the structural stability of framework catalysts and provide insights into the important roles of particle size, opening new avenues to investigate and improve the electrocatalytic performance of this class of framework material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantized Grain Boundary States Promote Nanoparticle Alignment During Imperfect Oriented Attachment

Oriented attachment (OA) has become a well-recognized mechanism for the growth of metal, ceramic, and biomineral crystals. While many computational and experimental studies of OA have shown that particles can attach with some misorientation then rotate to remove adjoining grain boundaries, the underlying atomistic pathways for this “Imperfect OA” process remain the subject of debate. In this paper, molecular dynamics and in situ TEM were used to probe the crystallographic evolution of up to 30 gold and copper nanoparticles during aggregation. It was found that Imperfect OA occurs because (1) grain boundaries become quantized when their size is comparable to the separation between constituent dislocations and (2) kinetic barriers associated with the glide of grain boundary dislocations are small. In support of these findings, TEM experiments show the formation of a single crystal aggregate after annealing 9 initially misoriented, agglomerated particles with evidence of dislocation slip and twin formation during particle/grain alignment. These observations motivate future work on assembled nanocrystals with tailored defects and call for a revision of Read-Shockley models for grain boundary energies in nanocrystalline materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diazo coupling for surface attachment of small molecules to TiO 2 nanoparticles

Robust surface attachment of molecular species to metal oxide semiconductors is desirable for many applications. In this work, we report the interfacial diazo coupling of surface-bound amines with aromatics to bind them to the surface of TiO 2 nanoparticles via a robust siloxane anchor and a diazo link. The technique shows potential for the inexpensive, stable, modular and tunable attachment of molecules to metal oxide surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state synthesis of UV-plasmonic Cr2N nanoparticles

Materials that exhibit plasmonic response in the UV region can be advantageous for many applications, such as biological photodegradation, photocatalysis, disinfection, and bioimaging. Transition metal nitrides have recently emerged as chemically and thermally stable alternatives to metal-based plasmonic materials. However, most free-standing nitride nanostructures explored so far have plasmonic responses in the visible and near-IR regions. Herein, we report the synthesis of UV-plasmonic Cr2N nanoparticles using a solid-state nitridation reaction. The nanoparticles had an average diameter of 9 ± 5 nm and a positively charged surface that yields stable colloidal suspension. The particles were composed of a crystalline nitride core and an amorphous oxide/oxynitride shell whose thickness varied between 1 and 7 nm. Calculations performed using the finite element method predicted the localized surface plasmon resonance (LSPR) for these nanoparticles to be in the UV-C region (100–280 nm). While a distinctive LSPR peak could not be observed using absorbance measurements, low-loss electron energy loss spectroscopy showed the presence of surface plasmons between 80 and 250 nm (or ∼5 to 15 eV) and bulk plasmons centered around 50–62 nm (or ∼20 to 25 eV). Plasmonic coupling was also observed between the nanoparticles, resulting in resonances between 250 and 400 nm (or ∼2.5 to 5 eV).

Chemistry↗

Rapid microwave-assisted preparation of high-performance bifunctional Ni3Fe/Co-N-C for rechargeable Zn-air battery

Precious metal-free bifunctional catalysts offer scalable possibilities for achieving oxygen cathodes in rechargeable metal-air batteries. Literature thus far suggests that the oxygen reduction and evolution reactions (i.e ORR and OER) take place at different active sites. However, the design and preparation of oxygen electrocatalysts with high-performance is still a great challenge. This work develops a general approach to introduce a nanoparticle that offers oxygen evolution reaction sites onto an oxygen reduction reaction catalyst via rapid microwave treatment. The metal–organic frameworks (Co, ZIF-8) derived Co-N-C with high ORR performance is employed as a support to homogeneously disperse OER active Ni3Fe nanoparticles. Potentials of 1.54 V and 0.79 V have been achieved at current densities of 10 mA cm -2 for OER and 3 mA cm -2 toward ORR, respectively. The developed rechargeable Zn-air battery assembled with Ni 3 Fe/Co-N-C as an oxygen-electrode exhibits superior efficiency and robust durability, exceeding that of commercial Pt/C + IrO 2 . Furthermore, the satisfactory activity of our fabricated wristband shows the successfully practical application of flexible Zn-air batteries for wearable devices.

25 ENERGY STORAGE↗

Adsorption and activation of CO 2 on Pt/CeOx/TiO 2 (110): Role of the Pt-CeO x interface

The adsorption and dissociation of CO 2 on TiO 2 (110), CeO x /TiO 2 (110) and Pt/CeO x /TiO 2 (110) surfaces has been examined using Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS). The substrates under study exhibited different degrees of complexity which were tested for the binding of the adsorbate and the cleavage of C-O bonds. The surfaces were prepared by depositing CeO x (0.1 ML) onto TiO 2 (110) to form a mixed oxide support, onto which Pt nanoparticles (0.2 ML) were deposited. This configuration yields a complex set of interfaces between metal and oxides and we have systematically titrated the active role of each component (Pt 4f, Ce 3d and Ti 2p regions) and the arising surface intermediates (C 1s and O 1s regions). CO 2 barely bonds to stoichiometric TiO 2 (110). It heals oxygen vacancies of this oxide surface (CO 2,gas → CO gas + O a ) and does not form stable carbonates. A stable carbonate was seen upon adsorption of CO 2 on CeO x /TiO 2 (110) and on this type of substrate the adsorbate also removed O vacancies leading to the oxidation of Ti 3+ and Ce 3+ sites. Pt nanoparticles dispersed on CeO x /TiO 2 (110) were highly effective for the binding and dissociation of CO 2 , with the formation of CO 3 , CO, C and CH x species on the Pt/CeO x /TiO 2 (110) system. The results of theoretical calculations based on density-functional theory (DFT) show that Pt/CeOx/TiO2(110) binds CO2 much stronger than surfaces of bulk platinum {(111), (100), (110)} or other late transition metals. On a Pt-CeO x interface, the molecule adsorbs with a bent configuration (~ 130° O-C-O bond angle) and with a substantial elongation (~ 0.1 Å) of the C-O bonds, facilitating its transformation into high value chemicals.

36 MATERIALS SCIENCE↗

Understanding palladium–tellurium cluster formation on WTe2: From a kinetically hindered distribution to thermodynamically controlled monodispersity

Abstract A fundamental understanding of the transition metal dichalcogenide (TMDC)–metal interface is critical for their utilization in a broad range of applications. We investigate how the deposition of palladium (Pd), as a model metal, on WTe2(001), leads to the assembly of Pd into clusters and nanoparticles. Using X-ray photoemission spectroscopy, scanning tunneling microscopy imaging, and ab initio simulations, we find that Pd nucleation is driven by the interaction with and the availability of mobile excess tellurium (Te) leading to the formation of Pd-Te clusters at room temperature. Surprisingly, the nucleation of Pd-Te clusters is not affected by intrinsic surface defects, even at elevated temperatures. Upon annealing, the Pd-Te nanoclusters adopt an identical nanostructure and are stable up to ∼523 K. Density functional theory calculations provide a foundation for our understanding of the mobility of Pd and Te atoms, preferential nucleation of Pd-Te clusters, and the origin of their annealing-induced monodispersity. These results highlight the role the excess chalcogenide atoms may play in the metal deposition process. More broadly, the discoveries of synthetic pathways yielding thermally robust monodispersed nanostructures on TMDCs are critical to the manufacturing of novel quantum and microelectronics devices and catalytically active nano-alloy centers.

36 MATERIALS SCIENCE↗

Spinel Cu–Mn–Cr Oxide Nanoparticle-Pigmented Solar Selective Coatings Maintaining >94% Efficiency at 750 °C

High-temperature concentrating solar power (CSP) system is capable of harvesting and storing solar energy as heat towards cost-effective dispatchable solar electricity. Solar selective coating is a critical component to boost its efficiency by maximizing solar absorptance and minimizing thermal emittance losses. However, maintaining a high solar-thermal conversion efficiency >90% for long-term operation at ≥750 ºC remains a significant challenge. Herein, we report spray-coated spinel Cu-Mn-Cr oxide nanoparticle-pigmented solar selective coatings on Inconel tube sections maintaining ≥94% efficiency at 750 ºC and ≥92.5% at 800 ºC under 1000x solar concentration after 60 simulated day-night thermal cycles in air, each cycle comprising 12h at 750 ºC/800 ºC and 12h cooling to 25 ºC. The solar spectral selectivity is intrinsic to the band-to-band and d-d transitions of non-stoichiometric spinel Cu-Mn-Cr oxide nanoparticles. Furthermore, this feature offers a large fabrication tolerance in nanoparticle volume fraction and coating thickness, facilitating low-cost and scalable spray-coated high-efficiency solar selective absorbers for high-temperature CSP systems.

14 SOLAR ENERGY↗

Preparation of Nonprecious Metal Electrocatalysts for the Reduction of Oxygen Using a Low-Temperature Sacrificial Metal

Non-platinum group metal (non-PGM) electrocatalysts for the oxygen reduction reaction (ORR) are generally composed of iron, nitrogen, and carbon synthesized through high-temperature pyrolysis. Among the various types of precursors, metal-organic frameworks (MOFs), zeolitic imidazolate framework (ZIF)-8 in particular, have often been used in the synthesis. The pyrolysis of ZIF-8 precursor relies on the use of Zn as a sacrificial metal (SM), and the optimal processing temperatures often exceed 1000 degrees C to generate active non-PGM catalysts. The high pyrolysis temperature tends to result in heterogeneous active moieties ranging from Fe single atoms to nanoparticles. In this study, we present the synthesis of non-PGM catalysts using Cd as the sacrificial metal instead of Zn. By using Cd, we were able to generate active non-PGM electrocatalysts from the MOF precursors at a low pyrolysis temperature of 750 degrees C, which helps preserve the single atomic iron active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MoS 2 -supported Au 31 for CO hydrogenation: A first-principle study

While the basal plane of single-layer molybdenum disulphide (MoS 2 ) is inert, attempts have been made to functionalize it chemically through the creation of defects and/or addition of dopants. With nanoparticles as dopants, the authors present density functional theory-based calculations of the hydrogenation of CO on a 31-atom, bilayer Au cluster supported on single-layer MoS 2 (Au31/MoS 2 ). Not surprisingly, the adsorption and reaction of all species involved in the hydrogenation occur at the edges of the cluster—the regions at which the interaction between MoS 2 and the Au cluster is tracked to be the strongest. The authors find two possible mechanisms that lead to the formation of methanol: (1) CO* → CHO* → CH 2 O* → CH 3 O* → CH 3 OH* and (2) CO* → CHO* → HCOH* → CH2OH* → CH3OH*, where * indicates the adsorbed species. Detailed analysis of the reaction pathways, however, does not result in favoring one mechanism over the other. Rather, both mechanisms are facile. In addition, the rate-limiting step in each mechanism is found to be the formation of the formyl radical group (CO* + H* → CHO*).

2D materials↗