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Electrochemical CO 2 reduction (CO 2 R) in acidic media provides a pathway to curtail CO 2 losses by suppressing the formation of (bi)carbonates. In such systems, a high concentration of alkali metal cations is necessary for mitigating the proton-rich environment and suppressing the competing hydrogen evolution reaction. However, a high cation concentration also promotes salt precipitation within the gas diffusion layer, resulting in poor system durability. Here, we resolve this conundrum by replacing the liquid catholyte with a solid-state proton conductor to regulate H + transport. This is postulated to allow for a locally alkaline environment at the cathode, enabling selective CO 2 R even without alkali metal cations. We show that this strategy is effective over a broad range of catalyst systems. For instance, we achieve an 87% CO faradaic efficiency (FE) at 300 mA/cm 2 using a composite nanoporous Au and single-atom Ni catalyst, with 0.25 M H 2 SO 4 as the anolyte. Stable operation over 110 h and a high single-pass carbon efficiency of 82.8% were also successfully demonstrated. Importantly, we find that this solid-state system is also particularly effective at converting dilute feedstock (5% CO 2 ) with a CO FE of 47.7%, a factor of 16.4 times higher than a conventional system. Our results introduce a simple yet effective design approach for developing efficient acidic CO 2 R electrolyzers.

The pursuit of high-performance thermoelectric materials is of paramount importance in addressing energy sustainability and environmental concerns. Here, we explore the multifaceted impact of sulfur passivation in the matrix of tellurium nanowires (TeNWs), encompassing environmental control, thermoelectric properties, and charge carrier mobility. In this study, we present the facile production of TeNWs using an aqueous solution synthesis approach. The synthesized TeNWs were subsequently subjected to surface modification involving sulfur moieties. Our findings demonstrate that sulfur passivation not only effectively safeguards the nanowires from environmental degradation but also significantly augments their thermoelectric properties. Notably, the highest recorded values were achieved at 560 K for passivated tellurium nanowires, exhibiting a Seebeck coefficient of 246 μV/K, an electrical conductivity of 14.2 S/cm, and power factors of 86.7 μW/m-K 2 . This strategy presents a promising avenue for the development of advanced thermoelectric materials for applications in energy harvesting, waste heat recovery, and sustainable energy conversion technologies.

In this study, magnetic Fe 3 O 4 nanoparticles (NPs) were dispersed uniformly by varying the thickness of the SiO 2 coating, and their electronic and magnetic properties were investigated. X-ray diffraction confirmed the structural configuration of monophase inverse-spinel Fe 3 O 4 NPs in nanometer size. Scanning electron microscopy revealed the formation of proper nonporous crystallite particles with a clear core-shell structure with silica on the surface of Fe 3 O 4 NPs. The absorption mechanism studied through the zeta potential indicates that SiO 2 -coated Fe 3 O 4 nanocomposites (SiO 2 @Fe 3 O 4 NCs) possess electrostatic interactions to control their agglomeration in stabilizing suspensions by providing a protective shield of amorphous SiO 2 on the oxide surface. High-resolution transmission electron microscopy images demonstrate a spherical morphology having an average grain diameter of ∼11-17 nm with increasing thickness of SiO 2 coating with the addition of a quantitative presence and proportion of elements determined through elemental mapping and electron energy loss spectroscopy studies. Synchrotron-based element-specific soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) techniques have been involved in the bulk-sensitive total fluorescence yield mode to understand the origin of magnetization in SiO 2 @Fe 3 O 4 NCs. The magnetization hysteresis of Fe 3 O 4 was determined by XMCD. At room temperature, the magnetic coercivity ( H c ) is as high as 1 T, which is about 2 times more than the value of the thin film and about 5 times more pronounced than that of NPs. For noninteracting single-domain NPs with the H c spread from 1 to 3 T, the Stoner-Wohlfarth model provided an intriguing explanation for the hysteresis curve. These curves determine the different components of Fe oxides present in the samples that derive the remnant magnetization involved in each oxidation state of Fe and clarify which Fe component is responsible for the resultant magnetism and magnetocrystalline anisotropy based on noninteracting single-domain particles.

Platinum-based metal catalysts are considered excellent converters in various catalytic reactions, particularly in fuel cell applications. The atomic structure at the nanocrystal surface and the metal interface both influence the catalytic performance, controlling the efficiency of the electrochemical reactions. Here we report the synthesis of Ag/Pt and Ag/Pd core/shell nanocrystals and insight into the formation mechanism of these bimetallic core/shell nanocrystals when undergoing oxygen plasma treatment. We carefully designed the oxidation treatment that determines the structural and compositional evolution. The accelerated oxidation-triggered diffusion of Ag toward the outer metal shell leads to the Kirkendall effect. After prolonged oxygen plasma treatment, most core/shell nanocrystals evolve into hollow spheres. At the same time, a minor fraction of the metal remains unchanged with a well-protected Ag core and a monocrystalline Pt or Pd shell. We hypothesize that the O 2 plasma disturbs the Pt or Pd shell surface and introduces active O species that react with the diffused Ag from the inside out. Based on EDX elemental mapping, combined with several electron microscopic techniques, we deduced the formation mechanism of the hollow structures to be as follows: (I) the oxidation of Ag within the Pt or Pd lattice causes a disrupted crystal lattice of Pt or Pd; (II) nanochannels arise at the defect locations on the Pt or Pd shell; (III) the remaining Ag atoms pass through these nanochannels and leave a hollow crystal behind. Our findings deepen the understanding of interface dynamics of bimetallic nanostructured catalysts under an oxidative environment and unveil an alternative approach for catalyst pretreatment.

It has been long known that low molecular weight resists can achieve a very high resolution, theoretically close to the probe diameter of the electron beam lithography (EBL) system. Despite technological improvements in EBL systems, the advances in resists have lagged behind. Here we demonstrate that a low-molecular-mass single-source precursor resist (based on cadmium(II) ethylxanthate complexed with pyridine) is capable of a achieving resolution (4 nm) that closely matches the measured probe diameter (∼3.8 nm). Energetic electrons enable the top-down radiolysis of the resist, while they provide the energy to construct the functional material from the bottom-up─unit cell by unit cell. Since this occurs only within the volume of resist exposed to primary electrons, the minimum size of the patterned features is close to the beam diameter. We speculate that angstrom-scale patterning of functional materials is possible with single-source precursor resists using an aberration-corrected electron beam writer with a spot size of ∼1 Å.

Dense arrays of high-aspect-ratio (HAR) vertical nanostructures are essential elements of microelectronic components, photovoltaics, nanoelectromechanical, and energy storage devices. One of the critical challenges in manufacturing the HAR nanostructures is to prevent their capillary-induced aggregation during solution-based nanofabrication processes. Despite the importance of controlling capillary effects, the detailed mechanisms of how a solution interacts with nanostructures are not well understood. Using in situ liquid cell transmission electron microscopy (TEM), we track the dynamics of nanoscale drying process of HAR silicon (Si) nanopillars in real-time and identify a new mechanism responsible for pattern collapse and nanostructure aggregation. During drying, deflection and aggregation of nanopillars are driven by thin-liquid-film instability, which results in much stronger capillary interactions between the nanopillars than the commonly proposed lateral meniscus interaction forces. The importance of thin-film instability in dewetting has been overlooked in prevalent theories on elastocapillary aggregation. The new dynamic mechanism revealed by in situ visualization is essential for the development of robust nanofabrication processes.

Wet chemical etching is a key process in fabricating silicon (Si) nanostructures. Currently, wet etching of Si is proposed to occur through the reaction of surface Si atoms with etchant molecules, forming etch intermediates that dissolve directly into the bulk etchant solution. Here, using in situ transmission electron microscopy (TEM), we follow the nanoscale wet etch dynamics of amorphous Si (a-Si) nanopillars in real-time and show that intermediates generated during alkaline wet etching first aggregate as nanoclusters on the Si surface and then detach from the surface before dissolving in the etchant solution. Molecular dynamics simulations reveal that the molecules of etch intermediates remain weakly bound to the hydroxylated Si surface during the etching and aggregate into nanoclusters via surface diffusion instead of directly diffusing into the etchant solution. We confirmed this model experimentally by suppressing the formation of nanoclusters of etch intermediates on the Si surfaces by shielding the hydroxylated Si sites with large ions. These results suggest that the interaction of etch intermediates with etching surfaces controls the solubility of reaction intermediates and is an important parameter in fabricating densely packed clean 3D nanostructures for future generation microelectronics.

Soft fluidlike nanoscale objects can drive nanoparticle assembly by serving as a scaffold for nanoparticle organization. The intermediate steps in these template-directed nanoscale assemblies are important but remain unresolved. We used real-time in situ transmission electron microscopy to follow the assembly dynamics of platinum nanoparticles into flexible ringlike chains around ethylenediaminetetraacetic acid nanodroplets dispersed in solution. In solution, these nanoring assemblies form via sequential attachment of the nanoparticles to binding sites located along the circumference of the nanodroplets, followed by the rearrangement and reorientation of the attached nanoparticles. Additionally, larger nanoparticle ring assemblies form via the coalescence of smaller ring assemblies. The intermediate steps of assembly reported here reveal how fluidlike nanotemplates drive nanoparticle organization, which can aid the future design of new nanomaterials.

When any two surfaces in a solution come within a distance the size of a few solvent molecules, they experience a solvation force or a hydration force when the solvent is water. Although the range and magnitude of hydration forces are easy to characterize, the effects of these forces on the transient steps of interaction dynamics between nanoscale bodies in solution are poorly understood. Here, using in situ transmission electron microscopy, we show that when two gold nanoparticles in water approach each other at a distance within two water molecules (∼5 Å), which is the combined thickness of the hydration shell of each nanoparticle, they form a sterically stabilized transient nanoparticle dimer. The interacting surfaces of the nanoparticles come in contact and undergo coalescence only after these surfaces are fully dehydrated. Our observations of transient steps in nanoparticle interactions, which reveal the formation of hydration layer mediated metastable nanoparticle pairs in solution, have significant implications for many natural and industrial processes.

Nanoscale defects on a substrate affect the sliding motion of water droplets. Using in situ transmission electron microscopy imaging, we visualized the depinning dynamics of water nanodroplets from gold nanoparticles on a flat SiNx surface. Our observations showed that nanoscale pinning effects of the gold nanoparticle oppose the lateral forces, resulting in stretching, even breakup, of the water nanodroplet. Using continuum long wave theory, we modeled the dynamics of a nanodroplet depinning from a nanoparticle of comparable length scales, and the model results are consistent with experimental findings and show formation of a capillary bridge prior to nanodroplet depinning. Our findings have important implications on surface cleaning at the nanoscale.

Nanocrystal bonding is an important phenomenon in crystal growth and nanoscale welding. Here, we show that for gold nanocrystals bonding in solution can follow two distinct pathways: (1) coherent, defect-free bonding occurs when two nanocrystals attach with their lattices aligned to within a critical angle; and (2) beyond this critical angle, defects form at the interfaces where the nanocrystals merge. The critical misalignment angle for ∼10 nm crystals is ∼15° in both in situ experiments and full-atom molecular dynamics simulations. Understanding the origin of this critical angle during bonding may help us predict and manage strain profiles in nanoscale assemblies and inspire techniques toward reproducible and extensible architectures using only basic crystalline blocks.

We describe the dynamics of 3-10 nm gold nanoparticles encapsulated by ∼30 nm liquid nanodroplets on a flat solid substrate and find that the diffusive motion of these nanoparticles is damped due to strong interactions with the substrate. Such damped dynamics enabled us to obtain time-resolved observations of encapsulated nanoparticles coalescing into larger particles. Techniques described here serve as a platform to study chemical and physical dynamics under highly confined conditions.