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At least 937 records · Page 52

Utilizing the unique charge extraction properties of antimony tin oxide nanoparticles for efficient and stable organic photovoltaics

Simultaneously enhancing device performance and longevity, as well as balancing the requirements on cost, scalability, and simplification of processing, is the goal of interface engineering of organic solar cells (OSCs). In our work, we strategically introduce antimony (Sb 3+ ) cations into an efficient and generic n-type SnO 2 nanoparticles (NPs) host during the scalable flame spray pyrolysis synthesis. Accordingly, a significant switch of conduction property from an n-type character to a p-type character is observed, with a corresponding shift in the work function (WF) from 4.01 ± 0.02 eV for pristine SnO 2 NPs to 5.28 ± 0.02 eV for SnO 2 NPs with 20 mol. % Sb content (ATO). Both pristine SnO 2 and ATO NPs with fine-tuned optoelectronic properties exhibit remarkable charge carrier extraction properties, excellent UV resistance and photo-stability being compatible with various state-of-the-art OSCs systems. The reliable and scalable pristine SnO 2 and ATO NPs processed by doctor-blading in air demand no complex post-treatment. Our work offers a simple but unique approach to accelerate the development of advanced interfacial materials, which could circumvent the major existing interfacial problems in solution-processed OSCs.

14 SOLAR ENERGY↗

Chemistry-mediated Ostwald ripening in carbon-rich C/O systems at extreme conditions

Abstract There is significant interest in establishing a capability for tailored synthesis of next-generation carbon-based nanomaterials due to their broad range of applications and high degree of tunability. High pressure (e.g., shockwave-driven) synthesis holds promise as an effective discovery method, but experimental challenges preclude elucidating the processes governing nanocarbon production from carbon-rich precursors that could otherwise guide efforts through the prohibitively expansive design space. Here we report findings from large scale atomistically-resolved simulations of carbon condensation from C/O mixtures subjected to extreme pressures and temperatures, made possible by machine-learned reactive interatomic potentials. We find that liquid nanocarbon formation follows classical growth kinetics driven by Ostwald ripening (i.e., growth of large clusters at the expense of shrinking small ones) and obeys dynamical scaling in a process mediated by carbon chemistry in the surrounding reactive fluid. The results provide direct insight into carbon condensation in a representative system and pave the way for its exploration in higher complexity organic materials. They also suggest that simulations using machine-learned interatomic potentials could eventually be employed as in-silico design tools for new nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave synthesis of single-phase nanoparticles made of multi-principal element alloys

In this work, metal nanoparticles of multi-principal element alloys (MPEA) with a single crystalline phase have been synthesized by flash heating/cooling of nanosized metals encapsulated in micelle vesicles dispersed in an oil phase (e.g., cyclohexane). Flash heating is realized by selective absorption of a microwave pulse in metals to rapidly heat metals into uniform melts. The oil phase barely absorbs microwave and maintains the low temperature, which can rapidly quench the high-temperature metal melts to enable the flash cooling process. The precursor ions of four metals, including Au, Pt, Pd, and Cu, can be simultaneously reduced by hydrazine in the aqueous solution encapsulated in the micelle vesicles. The resulting metals efficiently absorb microwave energy to locally reach a temperature high enough to melt themselves into a uniform mixture. The duration of microwave pulse is crucial to ensure the reduced metals mix uniformly, while the temperature of oil phase is still low to rapidly quench the metals and freeze the single-phase crystalline lattices in alloy nanoparticles. The microwave-enabled flash heating/cooling provides a new method to synthesize single-phase MPEA nanoparticles of many metal combinations when the appropriate water-in-oil micelle systems and the appropriate reduction reactions of metal precursors are available.

36 MATERIALS SCIENCE↗

Causal discovery from data assisted by large language models

Knowledge-driven discovery of novel materials necessitates the development of causal models for property emergence. While in the classical physical paradigm, the causal relationships are deduced based on physical principles or via experiment, the rapid accumulation of observational data necessitates learning causal relationships between dissimilar aspects of material structure and functionalities based on observations. For this, it is essential to integrate experimental data with prior domain knowledge. Here, we demonstrate this approach by combining high-resolution scanning transmission electron microscopy data with insights derived from large language models (LLMs). By applying ChatGPT to domain-specific literature, such as arXiv papers on ferroelectrics, and combining the obtained information with data-driven causal discovery, we construct adjacency matrices for directed acyclic graphs that map the causal relationships between structural, chemical, and polarization degrees of freedom in Sm-doped BiFeO 3 . This approach enables us to hypothesize how synthesis conditions influence material properties and guides experimental validation. Furthermore, the ultimate objective of this work is to develop a unified framework that integrates LLM-driven literature analysis with data-driven discovery, facilitating the precise engineering of ferroelectric materials by establishing clear connections between synthesis conditions and their resulting material properties.

Causal inference↗

Divergent Responses of Carbon Nitride Dot‐Based Amorphous Species and Small Molecule Hybrids to Trace Level Analytes

Bottom-up synthesis of carbon nitride dots (CNDs) offers a versatile platform for the creation of diverse nanomaterials with tunable properties. Here, we report a facile hydrothermal approach using citric acid (CA) and urea (U) as precursors to synthesize CNDs with varying degrees of condensation and crystallinity. By carefully controlling reaction conditions and post-synthetic treatments, we obtained two distinct fractions: a polycrystalline fraction composed of small-molecule hybrids and an amorphous fraction containing CNDs. We then sought to understand how the dominant species in these fractions impact sensing abilities using trace-level explosive exemplars. In conclusion, the results have important implications for sensing and related applications where understanding the complex interplay between synthetic conditions and post-synthetic processing play vital roles in determining the final properties of CND materials.

carbon nitride dots↗

Towards Low-Temperature CVD Synthesis and Characterization of Mono- or Few-Layer Molybdenum Disulfide

Molybdenum disulfide (MoS 2 ) transistors are a promising alternative for the semiconductor industry due to their large on/off current ratio (>10 10 ), immunity to short-channel effects, and unique switching characteristics. MoS 2 has drawn considerable interest due to its intriguing electrical, optical, sensing, and catalytic properties. Monolayer MoS 2 is a semiconducting material with a direct band gap of ~1.9 eV, which can be tuned. Commercially, the aim of synthesizing a novel material is to grow high-quality samples over a large area and at a low cost. Although chemical vapor deposition (CVD) growth techniques are associated with a low-cost pathway and large-area material growth, a drawback concerns meeting the high crystalline quality required for nanoelectronic and optoelectronic applications. This research presents a lower-temperature CVD for the repeatable synthesis of large-size mono- or few-layer MoS 2 using the direct vapor phase sulfurization of MoO 3 . The samples grown on Si/SiO 2 substrates demonstrate a uniform single-crystalline quality in Raman spectroscopy, photoluminescence (PL), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy. These characterization techniques were targeted to confirm the uniform thickness, stoichiometry, and lattice spacing of the MoS 2 layers. The MoS 2 crystals were deposited over the entire surface of the sample substrate. With a detailed discussion of the CVD setup and an explanation of the process parameters that influence nucleation and growth, this work opens a new platform for the repeatable synthesis of highly crystalline mono- or few-layer MoS 2 suitable for optoelectronic application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗

Ni-catalysed dicarbofunctionalization for the synthesis of sequence-encoded cyclooctene monomers

The properties of polymeric materials can be modulated by factors such as sequence control or functional group modifications. However, the synthesis of new macromolecular scaffolds is limited by the accessibility of structurally diverse monomers. This work describes a one-step, nickel-catalysed synthesis of 5,6-diaryl cyclooctene monomers from the feedstock chemical 1,5-cyclooctadiene. The reaction proceeds in a modular, regio- and diastereoselective fashion, granting access to both homo- and hetero-diaryl cyclooctene monomers that smoothly undergo ring-opening metathesis polymerization (ROMP). The resulting 1,2-diaryl-substituted polymers possess sequences with head-to-head styrene dyads that have not been previously explored, giving rise to unique and tunable properties. Density functional theory calculations highlight mechanistic aspects of the nickel-catalysed diarylation reaction and the ruthenium-catalysed ROMP process, revealing a previously unappreciated role of the boronic ester in promoting migratory insertion, which was leveraged to provide enantioinduction.

Catalytic mechanisms↗

Nanostructured, Targeted Layered Metal Oxides as Active and Selective Heterogeneous Electrocatalysts for Oxygen Evolution

Oxygen evolution reaction (OER) is an important chemical transformation that governs the performance of technologically relevant energy conversion and storage processes, such as electrochemical water splitting in electrolyzers and metal-air batteries. This reaction involves the evolution of oxygen gas from (i) oxygen ions formed from water splitting at high temperatures, (ii) oxygen containing species (i.e., OH, OOH) formed from water splitting at low temperatures, and (iii) metal-oxide discharge products (M x O 2 ) in metal-air batteries. One of the main challenges with OER is that it is catalyzed at low temperatures by noble metal-based electrocatalysts, which are expensive (making this process economically unviable), or at high temperatures by metal-oxide based electrocatalysts that are inefficient and lead to high overpotential losses. Our preliminary results, as well as other results in the literature, show that non-noble metal-based oxide electrocatalysts with layered structures, known as nickelate oxides, exhibit promising OER activity. Nickelate oxides (A 2 MO 4+δ ) belong to the Ruddlesden-Popper series composed of alternating perovskite-like and rocksalt-like layers. They are promising OER electrocatalysts due to their high oxygen transport/exchange properties compared to the state-of-the-art perovskite-type oxides. Unfortunately, these materials are fairly unexplored and little is known about the properties that govern their OER activity. Our preliminary studies, where we combine density functional theory (DFT) calculations, selective synthesis and characterization, show that engineering their nanocrystalline structure can significantly impact their catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced PGM-free Cathode Engineering for High Power Density and Durability

Polymer electrolyte fuel cells (PEFCs) are among the most promising technologies for future electric vehicles by using clean H2 with much-improved energy conversion efficiency, longer range, and rapid refueling. However, due to a large amount of platinum group metal (PGM) catalyst used in their electrodes, their prohibitively high cost hinders broad commercialization of PEFCs for transportation. Therefore, there is a critical need to develop low-cost, high-performance PGM-free cathode catalysts that have the potential to dramatically transform the economics of PEFC commercialization by reducing catalyst costs by one to two orders of magnitude. However, before PGM-free cathodes become viable, several technical challenges associated with PGM-free cathodes must be addressed, including insufficient activity and stability of the catalysts, as well as severe water flooding and large transport losses in the electrodes. Overcoming those barriers and ultimately meeting the challenging automotive PEFC performance targets was the focus of this comprehensive research and development effort on new PGM-free cathodes. To this end, we assembled a team including leading researchers from universities and industry with different but complementary expertise and capabilities. The project combined three novel and promising approaches: Advanced metal-organic framework (MOF)-derived M-N-C catalysts with a high activity and impressive durability, Novel PGM-free specific cathode architectures and fabrication strategies capable of addressing the substantial flooding and transport resistances in thicker cathodes by introducing engineered hydrophobicity through additives and support layers, and Advanced electrode ionomers with high proton conductivity for low ohmic losses across the electrode and more uniform catalyst utilization. The implementation of these new materials and electrode designs was supported by a suite of advanced experimental and simulation tools that allows us to identify performance and durability bottlenecks, devise solutions, and establish rational material design and synthesis targets. These methods include advanced electrochemical characterization, high-resolution imaging, and multi-scale modeling. In addition, the project team leveraged a broad cross-section of the ElectroCat consortium’s national laboratory facilities and expertise in advancing these materials and design strategies. Finally, the industry partners on the project facilitated the evaluation of scaled-up synthesis and manufacturing in the United States. Over its four-year period, the project made significant year-over-year advances in PGM-free cathode performance and viability. A combination of high activity and highly durable catalysts were developed through novel catalyst synthesis strategies, which met several performance and durability targets. More specifically, a catalyst prepared from MOFs and Fe2O3 nanoparticles with ammonium chloride and chemical vapor deposition treatments yielded a significant advancement in PGM-free cathode durability. Several novel strategies for fabricating cathodes were demonstrated, including those designed to reduce flooding and thickness of the cells for significantly increased volumetric power density. An optimized cathode with high conductivity ionomer and tuned ink processing for hydrophobicity yielded high fuel cell performance with new levels power density and maximum current. The scientific studies and modeling assessment also provided an outlook for future efforts, including a focus on catalysts with an increased density of the highly stable active sites developed in this project.

08 HYDROGEN↗

Bio-Based Polyurethane Materials: Technical, Environmental, and Economic Insights

Polyurethane (PU) is widely used due to its attractive properties, but the shift to a low-carbon economy necessitates alternative, renewable feedstocks for its production. This review examines the synthesis, properties, and sustainability of bio-based PU materials, focusing on renewable resources such as lignin, vegetable oils, and polysaccharides. It discusses recent advances in bio-based polyols, their incorporation into PU formulations, and the use of bio-fillers like chitin and nanocellulose to improve mechanical, thermal, and biocompatibility properties. Despite promising material performance, challenges related to large-scale production, economic feasibility, and recycling technologies are highlighted. The paper also reviews life cycle assessment (LCA) studies, revealing the complex and context-dependent environmental benefits of bio-based PU materials. These studies indicate that while bio-based PU materials generally reduce greenhouse gas emissions and non-renewable energy use, their environmental performance varies depending on feedstock and formulation. The paper identifies key areas for future research, including improving biorefinery processes, optimizing crosslinker performance, and advancing recycling methods to unlock the full environmental and economic potential of bio-based PU in commercial applications.

Jayalath, Piumi↗

Kinetic and Mechanistic Understanding of Boron-Containing Catalysts for the Production of Light Olefins through Selective Oxidation

In recent years, an abundance of natural gas obtained from shale deposits has created opportunities for the US chemical industry to establish new and more efficient processes for the production of chemical intermediates and polymers. For example, the replacement of petroleum-derived naphtha as a to shale-derived ethane as feedstocks has made the production of ethylene/polyethylene less costly. However, this shift in feedstock has led to lower production of propylene from steam crackers, and new “on-purpose” light olefin production technologies have been implemented to bridge the gap between propylene supply and demand. The most important of these processes is direct propane dehydrogenation (PDH), but catalyst deactivation and high temperatures lead to high capital and operating costs. Oxidative dehydrogenation of propane (ODHP) is an efficient alternative to PDH, but high selectivity to CO2 from previous metal oxide catalyst prevents implementation. Hexagonal boron nitride (hBN) and other boron-containing materials have been recently developed as highly selective catalysts for both ODHP and oxidative cracking, surpassing previous systems. Much is still unknown in regard to the mechanism and the dynamic surface changes that occur under reaction conditions. This research project aims to combine in situ/operando spectroscopic investigation and kinetic studies to elucidate the interplay between the proposed gas-phase mechanism and the surface structures on the working catalyst. These insights will be leveraged to create a framework for optimizing reaction conditions and material synthesis for the next generation of boron-containing selective oxidation catalysts.

02 PETROLEUM↗

I – /I 3 – Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives

Here, we report a set of three new mixed-valent Au I Au III iodides: (ClPy) 3 [AuI 2 ] 2 [AuI 4 ] [1], (BrPy) 3 [AuI 2 ] 2 [AuI 4 ] [2], and (ClPy) 2 [AuI 2 ][AuI 4 ] [3], as well as three new monovalent Au III iodides: (XPy) 2 [AuI 4 ][I 3 ] (Py = 4-X-pyridinium X = Cl, Br, and I) [4–6]. Two of these mixed-valent compounds (1 and 2) incorporate both monovalent Au I ···Au I (aurophilic bonding) and mixed-valent Au I I···Au III I couples (Au–I halogen bonding), to the best of our knowledge an unprecedented structural feature. These same two mixed-valent compounds also exhibit a rare low-dimensional molecular architecture with respect to second sphere Au···I interactions, namely, 1D chains of Au···I interactions, extending along a single crystallographic axis. All compounds were synthesized with the assistance of the I – /I 3 – redox couple and tacit manipulation of the polyiodide content during synthesis. Air-free synthesis was used to influence the redox process of I – /I 3 – , resulting in better selection for mixed-valent products. Compounds 1–2 and 4–5 exhibit a characteristically narrow bandgap (1.04–1.25 eV), as measured via diffuse reflectance spectroscopy (DRS). Computational analyses were used to rationalize the specific assembly modes of [AuI 2 ] – and [AuI 4 ] – species, and they show that the Au I ···I interaction type is favored over the Au III ···I.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Influence of Disorder in the Synthesis, Characterization and Applications of a Modifiable Two-Dimensional Covalent Organic Framework

Two-dimensional covalent organic frameworks (2D-COFs) have been of increasing interest in the past decade due to their porous structures that ideally can be highly ordered. One of the most common routes to these polymers relies on Schiff-base chemistry, i.e., the condensation reaction between a carbonyl and an amine. In this report, we elaborate on the condensation of 3,6-dibromobenzene-1,2,4,5-tetraamine with hexaketocyclohexane (HKH) and the subsequent carbonylation of the resulting COF, along with the possibility that the condensation reaction on HKH can result in a trans configuration resulting in the formation of a disordered 2D-COF. This strategy enables modification of COFs via bromine substitution reactions to place functional groups within the pores of the materials. Ion-sieving measurements using membranes from this COF, reaction of small molecules with unreacted keto groups along with modeling studies indicate disorder in the COF polymerization process. We also present a Monte Carlo simulation that demonstrates the influence of even small amounts of disorder upon both the 2D and 3D structure of the resulting COF.

carboxylated pores↗

The Synthesis of Manganese Hydroxide Nanowire Arrays for a High-Performance Zinc-Ion Battery

The morphology, microstructure as well as the orientation of cathodic materials are the key issues when preparing high-performance aqueous zinc-ion batteries (ZIBs). In this paper, binder-free electrode Mn(OH)2 nanowire arrays were facilely synthesized via electrodeposition. The nanowires were aligned vertically on a carbon cloth. The as-prepared Mn(OH)2 nanowire arrays were used as cathode to fabricate rechargeable ZIBs. The vertically aligned configuration is beneficial to electron transport and the free space between the nanowires can provide more ion-diffusion pathways. As a result, Mn(OH)2 nanowire arrays yield a high specific capacitance of 146.3 Ma h g−1 at a current density of 0.5 A g−1. They also demonstrates ultra-high diffusion coefficients of 4.5 × 10−8~1.0 × 10−9 cm2 s−1 during charging and 1.0 × 10−9~2.7 × 10−11 cm−2 s−1 during discharging processes, which are one or two orders of magnitude higher than what is reported in the studies. Furthermore, the rechargeable Zn//Mn(OH)2 battery presents a good capacity retention of 61.1% of the initial value after 400 cycles. This study opens a new avenue to boost the electrochemical kinetics for high-performance aqueous ZIBs.

25 ENERGY STORAGE↗

Shape Control of Colloidal Semiconductor Nanocrystals through Thermodynamically Driven Aggregative Growth

The optoelectronic properties of colloidal semiconductor nanocrystals (NCs) can be manipulated by changing their geometric shapes. The precise synthetic control over particle morphologies, however, has remained elusive. Conventional growth techniques rely on the kinetic assembly of atomic units, where supersaturation and precipitation processes can lead to a broad distribution of particle shapes. In this paper, we demonstrate that replacing atomic precursors with small-size nanocrystals as building blocks for larger colloids offers an easier, more predictive control over nanoparticle shape evolution. The reported growth strategy is illustrated via shape-selective syntheses of CdSe and CdS NC cubes, spheres, rods, as well as unprecedented “donut” and ring-like structures. Growth of desired particle morphologies was achieved by choosing an appropriate reaction solvent that minimizes the surface free energy through a unique shape formation. This so-called "aggregative growth mechanism" is explained using a thermodynamic model for interacting viscous colloids. We expect that this novel growth strategy will offer a viable platform for shape–selective synthesis of many inorganic colloids, providing pathways to optimizable optoelectronic materials.

36 MATERIALS SCIENCE↗

Trends in Carbon, Oxygen, and Nitrogen Core in the X-ray Absorption Spectroscopy of Carbon Nanomaterials: A Guide for the Perplexed

Successful deployment of carbon nanomaterials in many applications, such as sensing, energy storage, and catalysis, relies on the selection, synthesis, and tailoring of the surface properties. Predictive analysis of the behavior is difficult without detailed knowledge of the differences between various carbon nanomaterials and their surface functionalization, thus leaving the selection process to traditional trial-and-error work. The present characterization fills this knowledge gap for carbon nanomaterial surface properties with respect to chemical states and functionalization. We present an overview of the chemical trends that can be extracted from soft X-ray absorption spectroscopy (XAS) spectra on an extended set of nonideal carbon nanomaterials as a function of sp 2 bonded carbon and bond ordering. In particular, the surface chemical state, the presence of long-range order in the carbon matrix, and a qualitative estimation of the amount of oxygen and nitrogen and their respective functional group formation on the material surface, together with the detailed material fabrication parameters, are reported. The results expand our understanding of carbon nanomaterial functionalization, which can support material selection in practice, provided that the specifications of the application are known.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of antiferromagnetic Weyl semimetal Mn 3 Ge on insulating substrates by electron beam assisted molecular beam epitaxy

The antiferromagnetic kagome semimetals Mn 3 X (X = Ge, Sn, Ga) are of great interest due to properties arising from their Berry curvature, such as large anomalous Nernst and anomalous Hall coefficients, and spin to charge conversion efficiencies at ambient temperatures. However, the synthesis of epitaxial thin films of Mn 3 Ge in the desired hexagonal phase has been challenging because they do not wet insulating substrates, necessitating the use of a metallic buffer layer. Furthermore, a ferrimagnetic tetragonal phase also forms readily under typical growth conditions, interfering with hexagonal phase properties. We have synthesized atomically smooth and continuous epitaxial thin films of hexagonal Mn 3 Ge directly on insulating LaAlO 3 (111) substrates using electron beam assisted molecular beam epitaxy, using a three-step process that mitigates the formation of the tetragonal phase. The anomalous Nernst coefficient is found to be more than six times larger in our films than in sputtered thin films of Mn 3 Ge and significantly larger than that of Fe. Our approach can be used to grow thin layers of kagome materials, without interference from a buffer layer in transport properties, and may be applicable to a broader range of materials with large surface energies that do not grow readily on insulating substrates.

36 MATERIALS SCIENCE↗