Self-Matching Assembly of Chiral Gold Nanoparticles Leads to High Optical Asymmetry and Sensitive Detection of Adenosine Triphosphate.

To achieve chiral amplification, life uses small chiral molecules as building blocks to construct hierarchical chiral architectures that can realize advanced physiological functions. Inspired by the chiral amplification strategy of nature, we herein demonstrate that the chiral assembly of chiral gold nanorods (GNRs) leads to enhanced optical asymmetry factors (g-factors), up to 0.24. The assembly of chiral GNRs, dictated by structural self-matching, leads to g-factors with over 100-fold higher values than those of individual chiral GNRs, as confirmed by numerical simulations. Moreover, the efficient optical asymmetry of chiral GNR assemblies enables their application as highly sensitive sensors of adenosine triphosphate (ATP detection limit of 1.0 µM), with selectivity against adenosine diphosphate and adenosine monophosphate.

Tuneable mesoporous silica material for hydrogen storage application via nano-confined clathrate hydrate construction.

Safe storage and utilisation of hydrogen is an ongoing area of research, showing potential to enable hydrogen becoming an effective fuel, substituting current carbon-based sources. Hydrogen storage is associated with a high energy cost due to its low density and boiling point, which drives a high price. Clathrates (gas hydrates) are water-based (ice-like) structures incorporating small non-polar compounds such as H2 in cages formed by hydrogen bonded water molecules. Since only water is required to construct the cages, clathrates have been identified as a potential solution for safe storage of hydrogen. In bulk, pure hydrogen clathrate (H2O-H2) only forms in harsh conditions, but confined in nanospaces the properties of water are altered and hydrogen storage at mild pressure and temperature could become possible. Here, specifically a hydrophobic mesoporous silica is proposed as a host material, providing a suitable nano-confinement for ice-like clathrate hydrate. The hybrid silica material shows an important decrease of the pressure required for clathrate formation (approx. 20%) compared to the pure H2O-H2 system. In-situ inelastic neutron scattering (INS) and neutron diffraction (ND) provided unique insights into the interaction of hydrogen with the complex surface of the hybrid material and demonstrated the stability of nano-confined hydrogen clathrate hydrate.

Seed-Mediated Growth and Advanced Characterization of Chiral Gold Nanorods.

The controlled growth of gold nanostructures with complex shapes and reduced symmetry, exemplified by chiral gold nanorods and nanoparticles, is one of the most dynamic fields of nanochemistry. A timely summary of underlying concepts, including growth mechanisms and redefined chirality measures, would further promote this research area. In this perspective, we aim to establish qualitative connections between the chiral shapes and growth conditions, specifically for the seed-mediated synthesis of chiral gold nanorods as a convenient case of chiral morphogenesis. The crystallographic and morphological features of achiral nanorods used as seeds, the experimental conditions during chiral growth, and the symmetry of the chiral inducers, can all be exploited to obtain nanorods with intricate chiral shapes. Chirality characterization (such as electron tomography techniques) and quantification (including chirality measures) emerge as critical aspects to comprehensively explore and understand such structures, enabling optimization of their geometric and optical features. We conclude by discussing relevant challenges to be addressed toward a better controlled synthesis of chiral plasmonic nanostructures.

Pentatwinned AuAg Nanorattles with Tailored Plasmonic Properties for Near-Infrared Applications.

Noble metal nanoparticles, particularly gold and silver nanoparticles, have garnered significant attention due to their ability to manipulate light at the nanoscale through their localized surface plasmon resonance (LSPR). While their LSPRs below 1100 nm were extensively exploited in a wide range of applications, their potential in the near-infrared (NIR) region, crucial for optical communication and sensing, remains relatively underexplored. One primary reason is likely the limited strategies available to obtain highly stable plasmonic nanoparticles with tailored optical properties in the NIR region. Herein, we synthesized AuAg nanorattles (NRTs) with tailored and narrow plasmonic responses ranging from 1000 to 3000 nm. Additionally, we performed comprehensive characterization, employing advanced electron microscopy and various spectroscopic techniques, coupled with finite difference time domain (FDTD) simulations, to elucidate their optical properties. Notably, we unveiled the main external and internal LSPR modes by combining electron energy-loss spectroscopy (EELS) with surface-enhanced Raman scattering (SERS). Furthermore, we demonstrated through surface-enhanced infrared absorption spectroscopy (SEIRA) that the NRTs can significantly enhance the infrared signals of a model molecule. This study not only reports the synthesis of plasmonic NRTs with tunable LSPRs over the entire NIR range but also demonstrates their potential for NIR sensing and optical communication.

Investigation of the Octahedral Network Structure in Formamidinium Lead Bromide Nanocrystals by Low-Dose Scanning Transmission Electron Microscopy.

Metal halide perovskites (MHP) are highly promising semiconductors. In this study, we focus on FAPbBr3 nanocrystals, which are of great interest for green light-emitting diodes. Structural parameters significantly impact the properties of MHPs and are linked to phase instability, which hampers long-term applications. Clearly, there is a need for local and precise characterization techniques at the atomic scale, such as transmission electron microscopy. Because of the high electron beam sensitivity of MHPs, these investigations are extremely challenging. Here, we applied a low-dose method based on four-dimensional scanning transmission electron microscopy. We quantified the observed elongation of the projections of the Br atomic columns, suggesting an alternation in the position of the Br atoms perpendicular to the Pb-Br-Pb bonds. Together with molecular dynamics simulations, these results remarkably reveal local distortions in an on-average cubic structure. Additionally, this study provides an approach to prospectively investigating the fundamental degradation mechanisms of MHPs.

Functionalization of three-dimensional epitaxial graphene with metal nanoparticles.

We demonstrate the first successful functionalization of epitaxial three-dimensional graphene with metal nanoparticles. The functionalization is obtained by immersing three-dimensional graphene in a nanoparticle colloidal solution. This method is versatile and demonstrated here for gold and palladium, but can be extended to other types of nanoparticles. We have measured the nanoparticle density on the top surface and in the porous layer volume by scanning electron microscopy and scanning transmission electron microscopy. The samples exhibit a wide coverage of nanoparticles with minimal clustering. We demonstrate that high-quality graphene promotes the functionalization, leading to higher nanoparticle density both on the surface and in the pores. X-ray photoelectron spectroscopy shows the absence of contamination after the functionalization process. Moreover, it confirms the thermal stability of the Au- and Pd-functionalized three-dimensional graphene up to 530 °C. Our approach opens new avenues for utilizing three-dimensional graphene as a versatile platform for catalytic applications, sensors, and energy storage and conversion.

Rashba-Type Band Splitting Effect in 2D (PEA)2PbI4 Perovskites and Its Impact on Exciton-Phonon Coupling.

Despite a few recent reports on Rashba effects in two-dimensional (2D) Ruddlesden-Popper (RP) hybrid perovskites, the precise role of organic spacer cations in influencing Rashba band splitting remains unclear. Here, using a combination of temperature-dependent two-photon photoluminescence (2PPL) and time-resolved photoluminescence spectroscopy, alongside density functional theory (DFT) calculations, we contribute to significant insights into the Rashba band splitting found for 2D RP hybrid perovskites. The results demonstrate that the polarity of the organic spacer cation is crucial in inducing structural distortions that lead to Rashba-type band splitting. Our investigations show that the intricate details of the Rashba band splitting occur for organic cations with low polarity but not for more polar ones. Furthermore, we have observed stronger exciton-phonon interactions due to the Rashba-type band splitting effect. These findings clarify the importance of selecting appropriate organic spacer cations to manipulate the electronic properties of 2D perovskites.

Organic Molecular Glues to Design Three-Dimensional Cubic Nano-assemblies of Magnetic Nanoparticles.

Self-assembled magnetic nanoparticles offer next-generation materials that allow harnessing of their physicochemical properties for many applications. However, how three-dimensional nanoassemblies of magnetic nanoparticles can be synthesized in one-pot synthesis without excessive postsynthesis processes is still a bottleneck. Here, we propose a panel of small organic molecules that glue nanoparticle crystallites during the growth of particles to form large nanoassembled nanoparticles (NANs). We find that both carbonyl and carboxyl functional groups, presenting in benzaldehyde and benzoic acid, respectively, are needed to anchor with metal ions, while aromatic rings are needed to create NANs through π-π stacking. When benzyl alcohol, lacking carbonyl and carboxyl groups, is employed, no NANs are formed. NANs formed by benzoic acid reveal a unique combination of high magnetization and coercivity, whereas NANs formed by benzaldehyde show the largest exchange bias reported in nanoparticles. Surprisingly, our NANs show unconventional colloidal stability due to their unique nanoporous architectures.

Defect Engineering of MoTe2 via Thiol Treatment for Type III van der Waals Heterojunction Phototransistor.

Molybdenum ditelluride (MoTe2) nanosheets have displayed intriguing physicochemical properties and opto-electric characteristics as a result of their tunable and small band gap (Eg ∼ 1 eV), facilitating concurrent electron and hole transport. Despite the numerous efforts devoted to the development of p-type MoTe2 field-effect transistors (FETs), the presence of tellurium (Te) point vacancies has caused serious reliability issues. Here, we overcome this major limitation by treating the MoTe2 surface with thiolated molecules to heal Te vacancies. Comprehensive materials and electrical characterizations provided unambiguous evidence for the efficient chemisorption of butanethiol. Our thiol-treated MoTe2 FET exhibited a 10-fold increase in hole current and a positive threshold voltage shift of 25 V, indicative of efficient hole carrier doping. We demonstrated that our powerful molecular engineering strategy can be extended to the controlled formation of van der Waals heterostructures by developing an n-SnS2/thiol-MoTe2 junction FET (thiol-JFET). Notably, the thiol-JFET exhibited a significant negative photoresponse with a responsivity of 50 A W-1 and a fast response time of 80 ms based on band-to-band tunneling. More interestingly, the thiol-JFET displayed a gate tunable trimodal photodetection comprising two photoactive modes (positive and negative photoresponse) and one photoinactive mode. These findings underscore the potential of molecular engineering approaches in enhancing the performance and functionality of MoTe2-based nanodevices as key components in advanced 2D-based optoelectronics.

Quantitative 3D structural analysis of small colloidal assemblies under native conditions by liquid-cell fast electron tomography.

Electron tomography has become a commonly used tool to investigate the three-dimensional (3D) structure of nanomaterials, including colloidal nanoparticle assemblies. However, electron microscopy is typically done under high-vacuum conditions, requiring sample preparation for assemblies obtained by wet colloid chemistry methods. This involves solvent evaporation and deposition on a solid support, which consistently alters the nanoparticle organization. Here, we suggest using electron tomography to study nanoparticle assemblies in their original colloidal liquid environment. To address the challenges related to electron tomography in liquid, we devise a method that combines fast data acquisition in a commercial liquid-cell with a dedicated alignment and reconstruction workflow. We present the advantages of this methodology in accurately characterizing two different systems. 3D reconstructions of assemblies comprising polystyrene-capped Au nanoparticles encapsulated in polymeric shells reveal less compact and more distorted configurations for experiments performed in a liquid medium compared to their dried counterparts. A similar expansion can be observed in quantitative analysis of the surface-to-surface distances of self-assembled Au nanorods in water rather than in a vacuum, in agreement with bulk measurements. This study, therefore, emphasizes the importance of developing high-resolution characterization tools that preserve the native environment of colloidal nanostructures.

A robust Fe-based heterogeneous photocatalyst for the visible-light-mediated selective reduction of an impure CO2 stream.

The transformation of CO2 into value-added products from an impure CO2 stream, such as flue gas or exhaust gas, directly contributes to the principle of carbon capture and utilization (CCU). Thus, we have developed a robust iron-based heterogeneous photocatalyst that can convert the exhaust gas from the car into CO with an exceptional production rate of 145 µmol g-1 h-1. We characterized this photocatalyst by PXRD, XPS, ssNMR, EXAFS, XANES, HR-TEM, and further provided mechanistic experiments, and multi-scale/level computational studies. We have reached a clear understanding of its properties and performance that indicates that this highly robust photocatalyst could be used to design an efficient visible-light-mediated reduction strategy for the transformation of impure CO2 streams into value-added products.

Direct visualization of ligands on gold nanoparticles in a liquid environment.

The interactions between gold nanoparticles, their surface ligands and the solvent critically influence the properties of these nanoparticles. Although spectroscopic and scattering techniques have been used to investigate their ensemble structure, a comprehensive understanding of these processes at the nanoscale remains challenging. Electron microscopy makes it possible to characterize the local structure and composition but is limited by insufficient contrast, electron beam sensitivity and the requirement for ultrahigh-vacuum conditions, which prevent the investigation of dynamic aspects. Here we show that, by exploiting high-quality graphene liquid cells, we can overcome these limitations and investigate the structure of the ligand shell around gold nanoparticles and at the ligand-gold interface in a liquid environment. Using this graphene liquid cell, we visualize the anisotropy, composition and dynamics of ligand distribution on gold nanorod surfaces. Our results indicate a micellar model for surfactant organization. This work provides a reliable and direct visualization of ligand distribution around colloidal nanoparticles.

Cs3Bi2Br9 nanoparticles decorated C3N4 nanotubes composite photocatalyst for highly selective oxidation of benzylic alcohol.

Solar-light driven oxidation of benzylic alcohols over photocatalysts endows significant prospects in value-added organics evolution owing to its facile, inexpensive and sustainable process. However, the unsatisfactory performance of actual photocatalysts due to the inefficient charge separation, low photoredox potential and sluggish surface reaction impedes the practical application of this process. Herein, we developed an innovative Z-Scheme Cs3BiBr9 nanoparticles@porous C3N4 tubes (CBB-NP@P-tube-CN) heterojunction photocatalyst for highly selective benzyl alcohol oxidation. Such composite combining increased photo-oxidation potential, Z-Scheme charge migration route as well as the structural advantages of porous tubular C3N4 ensures the accelerated mass and ions diffusion kinetics, the fast photoinduced carriers dissociation and sufficient photoredox potentials. The CBB-NP@P-tube-CN photocatalyst demonstrates an exceptional performance for selective photo-oxidation of benzylic alcohol into benzaldehyde with 19, 14 and 3 times higher benzylic alcohols conversion rate than those of C3N4 nanotubes, Cs3Bi2Br9 and Cs3Bi2Br9@bulk C3N4 photocatalysts, respectively. This work offers a sustainable photocatalytic system based on lead-free halide perovskite toward large scale solar-light driven value-added chemicals production.

Decoding Excimer Formation in Covalent-Organic Frameworks Induced by Morphology and Ring Torsion.

A thorough and quantitative understanding of the fate of excitons in covalent-organic frameworks (COFs) after photoexcitation is essential for their augmented optoelectronic and photocatalytic applications via precise structure tuning. The synthesis of a library of COFs having identical chemical backbone with impeded conjugation, but varied morphology and surface topography to study the effect of these physical properties on the photophysics of the materials is herein reported. The variation of crystallite size and surface topography substantified different aggregation pattern in the COFs, which leads to disparities in their photoexcitation and relaxation properties. Depending on aggregation, an inverse correlation between bulk luminescence decay time and exciton binding energy of the materials is perceived. Further transient absorption spectroscopic analysis confirms the presence of highly localized, immobile, Frenkel excitons (of diameter 0.3-0.5 nm) via an absence of annihilation at high density, most likely induced by structural torsion of the COF skeletons, which in turn preferentially relaxes via long-lived (nanosecond to microsecond) excimer formation (in femtosecond scale) over direct emission. These insights underpin the importance of structural and topological design of COFs for their targeted use in photocatalysis.

Single Crystal and Pentatwinned Gold Nanorods Result in Chiral Nanocrystals with Reverse Handedness.

Handedness is an essential attribute of chiral nanocrystals, having a major influence on their properties. During chemical growth, the handedness of nanocrystals is usually tuned by selecting the corresponding enantiomer of chiral molecules involved in asymmetric growth, often known as chiral inducers. We report that, even using the same chiral inducer enantiomer, the handedness of chiral gold nanocrystals can be reversed by using Au nanorod seeds with either single crystalline or pentatwinned structure. This effect holds for chiral growth induced both by amino acids and by chiral micelles. Although it was challenging to discern the morphological handedness for L-cystine-directed particles, even using electron tomography, both cases showed circular dichroism bands of opposite sign, with nearly mirrored chiroptical signatures for chiral micelle-directed growth, along with quasi-helical wrinkles of inverted handedness. These results expand the chiral growth toolbox with an effect that might be exploited to yield a host of interesting morphologies with tunable optical properties.

High-Throughput Morphological Chirality Quantification of Twisted and Wrinkled Gold Nanorods.

Chirality in gold nanostructures offers an exciting opportunity to tune their differential optical response to left- and right-handed circularly polarized light, as well as their interactions with biomolecules and living matter. However, tuning and understanding such interactions demands quantification of the structural features that are responsible for the chiral behavior. Electron tomography (ET) enables structural characterization at the single-particle level and has been used to quantify the helicity of complex chiral nanorods. However, the technique is time-consuming and consequently lacks statistical value. To address this issue, we introduce herein a high-throughput methodology that combines images acquired by secondary electron-based electron beam-induced current (SEEBIC) with quantitative image analysis. As a result, the geometric chirality of hundreds of nanoparticles can be quantified in less than 1 h. When combining the drastic gain in data collection efficiency of SEEBIC with a limited number of ET data sets, a better understanding of how the chiral structure of individual chiral nanoparticles translates into the ensemble chiroptical response can be reached.

Scaling-Up Microwave-Assisted Synthesis of Highly Defective Pd@UiO-66-NH2 Catalysts for Selective Olefin Hydrogenation under Ambient Conditions.

The need to develop green and cost-effective industrial catalytic processes has led to growing interest in preparing more robust, efficient, and selective heterogeneous catalysts at a large scale. In this regard, microwave-assisted synthesis is a fast method for fabricating heterogeneous catalysts (including metal oxides, zeolites, metal-organic frameworks, and supported metal nanoparticles) with enhanced catalytic properties, enabling synthesis scale-up. Herein, the synthesis of nanosized UiO-66-NH2 was optimized via a microwave-assisted hydrothermal method to obtain defective matrices essential for the stabilization of metal nanoparticles, promoting catalytically active sites for hydrogenation reactions (760 kg·m-3·day-1 space time yield, STY). Then, this protocol was scaled up in a multimodal microwave reactor, reaching 86% yield (ca. 1 g, 1450 kg·m-3·day-1 STY) in only 30 min. Afterward, Pd nanoparticles were formed in situ decorating the nanoMOF by an effective and fast microwave-assisted hydrothermal method, resulting in the formation of Pd@UiO-66-NH2 composites. Both the localization and oxidation states of Pd nanoparticles (NPs) in the MOF were achieved using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), respectively. The optimal composite, loaded with 1.7 wt % Pd, exhibited an extraordinary catalytic activity (>95% yield, 100% selectivity) under mild conditions (1 bar H2, 25 °C, 1 h reaction time), not only in the selective hydrogenation of a variety of single alkenes (1-hexene, 1-octene, 1-tridecene, cyclohexene, and tetraphenyl ethylene) but also in the conversion of a complex mixture of alkenes (i.e., 1-hexene, 1-tridecene, and anethole). The results showed a powerful interaction and synergy between the active phase (Pd NPs) and the catalytic porous scaffold (UiO-66-NH2), which are essential for the selectivity and recyclability.

Sampling Real-Time Atomic Dynamics in Metal Nanoparticles by Combining Experiments, Simulations, and Machine Learning.

Even at low temperatures, metal nanoparticles (NPs) possess atomic dynamics that are key for their properties but challenging to elucidate. Recent experimental advances allow obtaining atomic-resolution snapshots of the NPs in realistic regimes, but data acquisition limitations hinder the experimental reconstruction of the atomic dynamics present within them. Molecular simulations have the advantage that these allow directly tracking the motion of atoms over time. However, these typically start from ideal/perfect NP structures and, suffering from sampling limits, provide results that are often dependent on the initial/putative structure and remain purely indicative. Here, by combining state-of-the-art experimental and computational approaches, how it is possible to tackle the limitations of both approaches and resolve the atomistic dynamics present in metal NPs in realistic conditions is demonstrated. Annular dark-field scanning transmission electron microscopy enables the acquisition of ten high-resolution images of an Au NP at intervals of 0.6 s. These are used to reconstruct atomistic 3D models of the real NP used to run ten independent molecular dynamics simulations. Machine learning analyses of the simulation trajectories allow resolving the real-time atomic dynamics present within the NP. This provides a robust combined experimental/computational approach to characterize the structural dynamics of metal NPs in realistic conditions.

AuNP/MIL-88B-NH2 Nanocomposite for the Valorization of Nitroarene by Green Catalytic Hydrogenation.

The efficiency of a catalytic process is assessed based on conversion, yield, and time effectiveness. However, these parameters are insufficient for evaluating environmentally sustainable research. As the world is urged to shift towards green catalysis, additional factors such as reaction media, raw material availability, sustainability, waste minimization and catalyst biosafety, need to be considered to accurately determine the efficacy and sustainability of the process. By combining the high porosity and versatility of metal organic frameworks (MOFs) and the activity of gold nanoparticles (AuNPs), efficient, cyclable and biosafe composite catalysts can be achieved. Thus, a composite based on AuNPs and the nanometric flexible porous iron(III) aminoterephthalate MIL-88B-NH2 was successfully synthesized and fully characterized. This nanocomposite was tested as catalyst in the reduction of nitroarenes, which were identified as anthropogenic water pollutants, reaching cyclable high conversion rates at short times for different nitroarenes. Both synthesis and catalytic reactions were performed using green conditions, and even further tested in a time-optimizing one-pot synthesis and catalysis experiment. The sustainability and environmental impact of the catalytic conditions were assessed by green metrics. Thus, this study provides an easily implementable synthesis, and efficient catalysis, while minimizing the environmental and health impact of the process.