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.

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.

Partial Hydrolysis of Diphosphonate Ester During the Formation of Hybrid TiO2 Nanoparticles: Role of Acid Concentration.

The hydrolysis of the phosphonate ester linker during the synthesis of hybrid (organic-inorganic) TiO2 nanoparticles is important when forming porous hybrid organic-inorganic metal phosphonates. In the present work, a method was utilized to control the in-situ partial hydrolysis of diphosphonate ester in the presence of a titania precursor as a function of acid content, and its impact on the hybrid nanoparticles was assessed. Organodiphosphonate esters, and more specific, their hydrolysis degree during the formation of hybrid organic-inorganic metal oxide nanoparticles, are relatively under explored as linkers. Here, a detailed analysis on the hydrolysis of tetraethyl propylene diphosphonate ester (TEPD) as diphosphonate linker to produce hybrid TiO2 nanoparticles is discussed as a function of acid content. Quantitative solution NMR spectroscopy revealed that during the synthesis of TiO2 nanoparticles, an increase in acid concentration introduces a higher degree of partial hydrolysis of the TEPD linker into diverse acid/ester derivatives of TEPD. Increasing the HCl/Ti ratio from 1 to 3, resulted in an increase in degree of partial hydrolysis of the TEPD linker in solution from 4 % to 18.8 % under the applied conditions. As a result of the difference in partial hydrolysis, the linker-TiO2 bonding was altered. Upon subsequent drying of the colloidal TiO2 solution, different textures, at nanoscale and macroscopic scale, were obtained dependent on the HCl/Ti ratio and thus the degree of hydrolysis of TEPD. Understanding such linker-TiO2 nanoparticle surface dynamics is crucial for making hybrid organic-inorganic materials (i. e. (porous) metal phosphonates) employed in applications such as electronic/photonic devices, separation technology and heterogeneous catalysis.

Electrochemical Stability of Rhodium-Platinum Core-Shell Nanoparticles: An Identical Location Scanning Transmission Electron Microscopy Study.

Rhodium-platinum core-shell nanoparticles on a carbon support (Rh@Pt/C NPs) are promising candidates as anode catalysts for polymer electrolyte membrane fuel cells. However, their electrochemical stability needs to be further explored for successful application in commercial fuel cells. Here we employ identical location scanning transmission electron microscopy to track the morphological and compositional changes of Rh@Pt/C NPs during potential cycling (10 000 cycles, 0.06-0.8 VRHE, 0.5 H2SO4) down to the atomic level, which are then used for understanding the current evolution occurring during the potential cycles. Our results reveal a high stability of the Rh@Pt/C system and point toward particle detachment from the carbon support as the main degradation mechanism.

Enabling hydrate-based methane storage under mild operating conditions by periodic mesoporous organosilica nanotubes.

Biomethane is a renewable natural gas substitute produced from biogas. Storage of this sustainable energy vector in confined clathrate hydrates, encapsulated in the pores of a host material, is a highly promising avenue to improve storage capacity and energy efficiency. Herein, a new type of periodic mesoporous organosilica (PMO) nanotubes, referred to as hollow ring PMO (HR-PMO), capable of promoting methane clathrate hydrate formation under mild working conditions (273 K, 3.5 MPa) and at high water loading (5.1 g water/g HR-PMO) is reported. Gravimetric uptake measurements reveal a steep single-stepped isotherm and a noticeably high methane storage capacity (0.55 g methane/g HR-PMO; 0.11 g methane/g water at 3.5 MPa). The large working capacity throughout consecutive pressure-induced clathrate hydrate formation-dissociation cycles demonstrates the material's excellent recyclability (97% preservation of capacity). Supported by ex situ cryo-electron tomography and x-ray diffraction, HR-PMO nanotubes are hypothesized to promote clathrate hydrate nucleation and growth by distribution and confinement of water in the mesopores of their outer wall, along the central channels of the nanotubes and on the external nanotube surface. These findings showcase the potential for application of organosilica materials with hierarchical and interconnected pore systems for pressure-based storage of biomethane in confined clathrate hydrates.

Study of the Mechanism and Increasing Crystallinity in the Self-Templated Growth of Ultrathin PbS Nanosheets.

Colloidal 2D semiconductor nanocrystals, the analogue of solid-state quantum wells, have attracted strong interest in material science and physics. Molar quantities of suspended quantum objects with spectrally pure absorption and emission can be synthesized. For the visible region, CdSe nanoplatelets with atomically precise thickness and tailorable emission have been (almost) perfected. For the near-infrared region, PbS nanosheets (NSs) hold strong promise, but the photoluminescence quantum yield is low and many questions on the crystallinity, atomic structure, intriguing rectangular shape, and formation mechanism remain to be answered. Here, we report on a detailed investigation of the PbS NSs prepared with a lead thiocyanate single source precursor. Atomically resolved HAADF-STEM imaging reveals the presence of defects and small cubic domains in the deformed orthorhombic PbS crystal lattice. Moreover, variations in thickness are observed in the NSs, but only in steps of 2 PbS monolayers. To study the reaction mechanism, a synthesis at a lower temperature allowed for the study of reaction intermediates. Specifically, we studied the evolution of pseudo-crystalline templates toward mature, crystalline PbS NSs. We propose a self-induced templating mechanism based on an oleylamine-lead-thiocyanate (OLAM-Pb-SCN) complex with two Pb-SCN units as a building block; the interactions between the long-chain ligands regulate the crystal structure and possibly the lateral dimensions.

Investigating Reaction Intermediates during the Seedless Growth of Gold Nanostars Using Electron Tomography.

Good's buffers can act both as nucleating and shape-directing agents during the synthesis of anisotropic gold nanostars (AuNS). Although different Good's buffers can produce AuNS shapes with branches that are oriented along specific crystallographic directions, the mechanism is not fully understood. This paper reports how an analysis of the intermediate structures during AuNS synthesis from HEPES, EPPS, and MOPS Good's buffers can provide insight into the formation of seedless AuNS. Electron tomography of AuNS structures quenched at early times (minutes) was used to characterize the morphology of the incipient seeds, and later times were used to construct the growth maps. Through this approach, we identified how the crystallinity and shape of the first structures synthesized with different Good's buffers determine the final AuNS morphologies.

Two-Dimensional CdSe-PbSe Heterostructures and PbSe Nanoplatelets: Formation, Atomic Structure, and Optical Properties.

Cation exchange enables the preparation of nanocrystals (NCs), which are not reachable by direct synthesis methods. In this work, we applied Pb2+-for-Cd2+ cation exchange on CdSe nanoplatelets (NPLs) to prepare two-dimensional CdSe-PbSe heterostructures and PbSe NPLs. Lowering the reaction temperature slowed down the rate of cation exchange, making it possible to characterize the intermediary NCs ex situ with atomically resolved high-angle annular dark-field scanning transmission electron microscopy and optical spectroscopy. We observe that the Pb2+-for-Cd2+ cation exchange starts from the vertices of the NPLs and grows into the zinc blende CdSe (zb-CdSe) lattice as a rock salt PbSe phase (rs-PbSe), while the anion (selenium) sublattice is being preserved. In agreement with previous works on CdTe-PbTe films, the interfaces between zb-CdSe and rs-PbSe consist of shared {001} and {011} planes. The final PbSe NPLs are highly crystalline and contain protrusions at the edges, which are slightly rotated, indicating an atomic reconfiguration of material. The growth of PbSe domains into CdSe NPLs could also be monitored by the emission peak shift as a function of the exchange time. Temperature-dependent emission measurements confirm a size-dependent change of the band gap energy with temperature and reveal a strong influence of the anisotropic shape. Time-resolved photoluminescence measurements between 4 and 30 K show a dark-bright exciton-state splitting different from PbSe QDs with three-dimensional quantum confinement.

Creation of Exclusive Artificial Cluster Defects by Selective Metal Removal in the (Zn, Zr) Mixed-Metal UiO-66.

The differentiation between missing linker defects and missing cluster defects in MOFs is difficult, thereby limiting the ability to correlate materials properties to a specific type of defects. Herein, we present a novel and easy synthesis strategy for the creation of solely "missing cluster defects" by preparing mixed-metal (Zn, Zr)-UiO-66 followed by a gentle acid wash to remove the Zn nodes. The resulting material has the reo UiO-66 structure, typical for well-defined missing cluster defects. The missing clusters are thoroughly characterized, including low-pressure Ar-sorption, iDPC-STEM at a low dose (1.5 pA), and XANES/EXAFS analysis. We show that the missing cluster UiO-66 has a negligible number of missing linkers. We show the performance of the missing cluster UiO-66 in CO2 sorption and heterogeneous catalysis.

Layer-by-Layer-Stabilized Plasmonic Gold-Silver Nanoparticles on TiO2: Towards Stable Solar Active Photocatalysts.

To broaden the activity window of TiO2, a broadband plasmonic photocatalyst has been designed and optimized. This plasmonic 'rainbow' photocatalyst consists of TiO2 modified with gold-silver composite nanoparticles of various sizes and compositions, thus inducing a broadband interaction with polychromatic solar light. However, these nanoparticles are inherently unstable, especially due to the use of silver. Hence, in this study the application of the layer-by-layer technique is introduced to create a protective polymer shell around the metal cores with a very high degree of control. Various TiO2 species (pure anatase, PC500, and P25) were loaded with different plasmonic metal loadings (0-2 wt %) in order to identify the most solar active composite materials. The prepared plasmonic photocatalysts were tested towards stearic acid degradation under simulated sunlight. From all materials tested, P25 + 2 wt % of plasmonic 'rainbow' nanoparticles proved to be the most promising (56% more efficient compared to pristine P25) and was also identified as the most cost-effective. Further, 2 wt % of layer-by-layer-stabilized 'rainbow' nanoparticles were loaded on P25. These layer-by-layer-stabilized metals showed superior stability under a heated oxidative atmosphere, as well as in a salt solution. Finally, the activity of the composite was almost completely retained after 1 month of aging, while the nonstabilized equivalent lost 34% of its initial activity. This work shows for the first time the synergetic application of a plasmonic 'rainbow' concept and the layer-by-layer stabilization technique, resulting in a promising solar active, and long-term stable photocatalyst.

The design of magneto-plasmonic nanostructures formed by magnetic Prussian Blue-type nanocrystals decorated with Au nanoparticles.

We have developed a general protocol for the preparation of hybrid nanostructures formed by nanoparticles (NPs) of molecule-based magnets based on Prussian Blue Analogues (PBAs) decorated with plasmonic Au NPs of different shapes. By adjusting the pH, Au NPs can be attached preferentially along the edges of the PBA or randomly on the surface. The protocol allows tuning the plasmonic properties of the hybrids in the whole visible spectrum.

Organometallic-Derived Carbon (ODC)-Metal Nano-Oxide Composites as Improved Electrode Materials for Supercapacitors.

In the search for the new generation of electrochemical energy storage materials, a novel and straightforward synthetic route for porous carbons and metal oxide nanoparticle composites based on the chlorination of the organometallic compounds Ni(C5H5)2 and Mn(C5H7O2)2 at moderate temperatures, followed by hydrothermal treatment, has been developed. Electrochemical measurements in a three-electrode configuration show that, in both composites NiO@ODC and Mn3O4@ODC, a synergistic effect between the capacitive and pseudocapacitive energy storage mechanisms is observed, thereby improving their electrochemical performance vs pure carbon materials. Electrochemical evaluation of symmetric cells gave gravimetric capacitances of 124 and 130 F g-1 for NiO@ODC and Mn3O4@ODC, respectively. However, the porous structure of the carbon matrix and the higher conductivity of Mn3O4, together, were found to be responsible for the superior electrochemical performance of Mn3O4@ODC.