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The exploration of 1D magnetism, frequently portrayed as spin chains, constitutes an actively pursued research field that illuminates fundamental principles in many-body problems and applications in magnonics and spintronics. The inherent reduction in dimensionality often leads to robust spin fluctuations, impacting magnetic ordering and resulting in novel magnetic phenomena. Here, structural, magnetic, and optical properties of highly anisotropic 2D van der Waals antiferromagnets that uniquely host spin chains are explored. First-principle calculations reveal that the weakest interaction is interchain, leading to essentially 1D magnetic behavior in each layer. With the additional degree of freedom arising from its anisotropic structure, the structure is engineered by alloying, varying the 1D spin chain lengths using electron beam irradiation, or twisting for localized patterning, and spin textures are calculated, predicting robust stability of the antiferromagnetic ordering. Comparing with other spin chain magnets, these materials are anticipated to bring fresh perspectives on harvesting low-dimensional magnetism.

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition, and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts─in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity─are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag, and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. The integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

Rational catalyst design is crucial toward achieving more energy-efficient and sustainable catalytic processes. Understanding and modeling catalytic reaction pathways and kinetics require atomic level knowledge of the active sites. These structures often change dynamically during reactions and are difficult to decipher. A prototypical example is the hydrogen-deuterium exchange reaction catalyzed by dilute Pd-in-Au alloy nanoparticles. From a combination of catalytic activity measurements, machine learning-enabled spectroscopic analysis, and first-principles based kinetic modeling, we demonstrate that the active species are surface Pd ensembles containing only a few (from 1 to 3) Pd atoms. These species simultaneously explain the observed X-ray spectra and equate the experimental and theoretical values of the apparent activation energy. Remarkably, we find that the catalytic activity can be tuned on demand by controlling the size of the Pd ensembles through catalyst pretreatment. Our data-driven multimodal approach enables decoding of reactive structures in complex and dynamic alloy catalysts.

HfSe2 and ZrSe2 transition metal dichalcogenide (TMD) films are of interest for their potential applications in field-effect transistors. To implement the use of these materials in devices, the formation of an oxide/TMD interface with well-defined dielectric/semiconductor properties is essential. The method by which the oxide is created, as well as any structural changes in the TMD under the conditions used for oxide formation, will affect the performance of both the dielectric and the semiconductor. In this work, we describe the structure of the oxide and the morphological changes occurring in HfSe2 and ZrSe2 under several oxidation conditions. Using in situ transmission electron microscopy, we show that room temperature oxidation in air causes segregation of Se and uneven surface oxidation. Exposure to O2 at high temperatures readily forms a crystalline oxide layer, although defects and cavities are also detectable. Finally, plasma oxidation forms a smoother and more uniform oxide layer than that formed by thermal oxidation. These results can guide the rational design of oxide/TMD interfaces for field-effect transistors and other electronic devices that incorporate HfSe2 and ZrSe2. [ABSTRACT FROM AUTHOR]

Supported Au–Pd nanoparticles with low Pd content (between 2% and 25%) are excellent catalysts for the selective hydrogenation of alkynes into alkenes, a crucial step for elimination of alkynes from the reactants for olefin polymerization. They have better selectivity at high conversions for the hydrogenation of 1-hexyne to 1-hexene compared to that of pure Pd. However, the role of Pd concentration in Au–Pd particles in maximizing the activity per gram of Pd remains elusive. This work combines scanning transmission electron microscopy (STEM) and density functional theory (DFT) to determine how Pd concentration in the dilute limit affects the activity and selectivity of Au–Pd particles for the hydrogenation of acetylene. Atomic resolution microscopy shows increased Pd segregation to the surface with increasing Pd concentration (above 9%), and DFT analysis shows that isolated Pd atoms on the Au–Pd surface are highly active for acetylene hydrogenation compared to Pd atoms adjacent to other Pd atoms. A high concentration of isolated and active Pd atoms combined with increased segregation of Pd toward the surface explains the existence of an optimum for catalytic properties. It explains the high performance of Au0.96Pd0.04 compared to Au–Pd particles with lower or higher Pd concentrations. [ABSTRACT FROM AUTHOR]

The use of nanoporous metals as catalysts has attracted significant interest in recent years. Their high‐curvature, nanoscale ligaments provide not only high surface area but also a high density of undercoordinated step edge and kink sites. However, their long‐term stability, especially at higher temperatures, is often limited by thermal coarsening and the associated loss of surface area. Herein, it is demonstrated that the nanoscale morphology of nanoporous Cu can be regenerated by applying oxidation/reduction cycles at 250 °C. Specifically, the morphological evolution and H2 dissociation activity of hierarchical nanoporous Cu catalysts doped with Ti during structural rearrangement triggered by oxidative and reductive atmospheres at elevated temperatures are studied. In addition to coarsening of the structure at elevated temperatures, oxidation at 400 °C causes an expansion of the ligaments. Subsequent reduction at 400 °C leads to the formation of particles and a drop in the H2 dissociation activity compared the fresh catalyst. However, performing the redox cycle at 250 °C reverses coarsening and boosts the H2 dissociation activity for the hydrogen–deuterium (H2–D2) reaction. Herein, the possibility to reverse coarsening is demonstrated, thereby mitigating the loss of activity frequently observed in nanoporous catalysts. [ABSTRACT FROM AUTHOR]