In Situ 3D Structural Determination of Soft Biomaterials by Computationally Assisted Polarized Raman Spectroscopy.

Soft biomaterials, characterized by structural disorder and weak interactions, pose significant challenges for structural characterization by conventional methods, which typically rely on long-range crystalline order or strong electron scattering. Here, we report a computationally assisted polarized Raman spectroscopy strategy that enables direct, in situ determination of three-dimensional (3D) molecular structures and their intermolecular interactions, correlating molecular-scale orientations with macroscopic morphologies. We validated our approach using the well-characterized α-glycine crystal, achieving structural precision comparable to that of single-crystal X-ray diffraction (RMSD = 0.

Trimerization of 1,2-Diaminocyclohexane Catalyzed by a Metal-Organic Cage Tandem Catalyst with Dual Biomimetic Active Sites.

Cascade reactions that form multiple chemical bonds in one synthetic step are important for the synthesis of complex molecules. Molecular catalysts for cascade reactions generally require two or more catalytic centers, yet anchoring distinct catalytic centers onto a single molecular catalyst remains extremely challenging. Here a metal-organic cage (MOC) [(ClO)@Zn(L)(HCO)(OH)(HO)] (Zn-MOC) (HL = tris(2-benzimidazolylmethyl)amine) carrying dual biomimetic active sites is reported, i.

Microdroplet Cascade Catalysis for Highly Selective Production of Propylene Glycol under Ambient Conditions.

Conventional propylene glycol (PG) production relies on an energy-intensive two-step thermocatalytic process, contributing significantly to CO emissions. A sustainable alternative under ambient conditions remains elusive, hindered by challenges in selectivity and energy efficiency. Here, we present a cascade catalysis strategy for efficient and selective PG production within water microdroplets under ambient conditions.

Efficient synthesis of Au(SR) nanoclusters the cluster-from-cluster approach.

Monodisperse gold nanoclusters constitute a new branch of nanomaterials with atomically precise molecular structures. Recently, we developed a "cluster-from-cluster" approach to assemble gold nanoclusters [Au(SR)] (Au25) atomically precise Au13 precursors. Herein we demonstrated that efficient synthesis of Au(SR) (Au36) nanoclusters can be realized this facile approach.

Catalyst-Free Nitrogen Fixation by Microdroplets through a Radical-Mediated Disproportionation Mechanism under Ambient Conditions.

Nitrogen fixation is essential for the sustainable development of both human society and the environment. Due to the chemical inertness of the N≡N bond, the traditional Haber-Bosch process operates under extreme conditions, making nitrogen fixation under ambient conditions highly desirable but challenging. In this study, we present an ultrasonic atomizing microdroplet method that achieves nitrogen fixation using water and air under ambient conditions in a rationally designed sealed device, without the need for any catalyst.

Formation Dynamics of Thermally Stable 1D/3D Perovskite Interfaces for High-Performance Photovoltaics.

Direct understanding of the formation and crystallization of low-dimensional (LD) perovskites with varying dimensionalities employing the same bulky cations can offer insights into LD perovskites and their heterostructures with 3D perovskites. In this study, the secondary amine cation of N-methyl-1-(naphthalen-1-yl)methylammonium (M-NMA) and the formation dynamics of its corresponding LD perovskite are investigated. The intermolecular π-π stacking of M-NMA and their connection with inorganic PbI octahedrons within the product structures control the formation of LD perovskite.

Triphenylamine-Functionalized Metal Nanoclusters for Efficient and Stable Perovskite Solar Cells.

Reported herein is a ligand engineering strategy to develop photoelectric active metal nanoclusters (NCs) with atomic precision. Triphenylamine (TPA), a typical organic molecule in the photoelectric field, is introduced for the first time to prepare atomically precise metal NCs that prove effective in the fabrication of perovskite solar cells (PSCs). The scalable synthetic prototype, unique electronic strucuture, and atomically precise structure of the cluster ([(AgCu)(PPh)(TPA-C≡C)]) are illustrated in this work.

Enhancing Optoelectronic Performance of All-Inorganic Double Perovskites via Halogen Doping: Synergistic Screening Strategies and Multiscale Simulations.

Designing all-inorganic double perovskites through element mixing is a promising strategy to enhance their optoelectronic performance and structural stability. The complex interplay between multilevel structures and optoelectronic properties in element-mixed double perovskites necessitates further in-depth theoretical exploration. In this study, we employ screening strategies and multiscale simulations combining first-principles methods and device-scale continuum models to identify two novel element-mixed compounds, RbAgInClI and CsAgInClI, as promising candidates for photovoltaic applications.

'Passivated Precursor' Approach to All-Alkynyl-Protected Gold Nanoclusters and Total Structure Determination of Au.

A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all-alkynyl-protected gold nanoclusters. Direct reduction of dpa-passivated precursor Au-dpa (Hdpa=2,2'-dipyridylamine) in one-pot under ambient conditions gives a series of clusters including Au(C≡CR) (R=-CH-2-F), Au(C≡CR), Au(C≡CR), Au(C≡CR), and Au(C≡CR). These clusters can be well separated via column chromatography.

What Elements Really Intercalate into Pd Lattice When Heated in Dimethylformamide?

Palladium hydrides (PdH) are pivotal in both fundamental research and practical applications across a wide spectrum. PdH nanocrystals, synthesized by heating in dimethylformamide (DMF), exhibit remarkable stability, granting them widespread applications in the field of electrocatalysis. However, this stability appears inconsistent with their metastable nature.

Soaking the Rare-Earth Carbonates for a Change: An Alternative Approach to Explore Carbonate Nonlinear Optical Crystals.

Alkali-metal rare-earth carbonates (ARECs) find great potential in nonlinear optical applications. As the most common method, the hydrothermal reaction is widely used in synthesizing ARECs. The black-box nature of the hydrothermal reaction makes it difficult for understanding the formation processes and therefore may slow down the pace of structural discovery.

Temperature-Dependent Separation of CO from Light Hydrocarbons in a Porous Self-Assembly of Vertexes Sharing Octahedra.

Design of flexible porous materials where the diffusion of guest molecules is regulated by the dynamics of contracted pore aperture is challenging. Here, a flexible porous self-assembly consisting of 1D channels with dynamic bottleneck gates is reported. The dynamic pendant naphthimidazolylmethyl moieties at the channel necks provide kinetic gate function, that enables unusual adsorption for light hydrocarbons.

Utilization of charged microdroplets for the controlled rapid synthesis of hollow sodium chloride single crystals.

Charged microdroplets are favored in microfluidic control, biomedicine, chemistry and materials processing due to their unique physicochemical environment, including interface double layers, high electric fields, surface concentration enrichment, and more. Herein, we investigated the crystallization of charged sodium chloride microdroplets and achieved the formation of hollow single crystals in a single-step process lasting only a few seconds, without the use of templates. Additionally, we discussed the plausible crystal growth mechanism, which appears to be an unconventional outward-inward growth process.

Efficient Tin-Based Perovskite Solar Cells Enabled by Precisely Synthesized Single-Isomer Fullerene Bisadducts with Regulated Molecular Packing.

Designing and synthesizing fullerene bisadducts with a higher-lying conduction band minimum is promising to further improve the device performance of tin-based perovskite solar cells (TPSCs). However, the commonly obtained fullerene bisadduct products are isomeric mixtures and require complicated separation. Moreover, the isomeric mixtures are prone to resulting in energy alignment disorders, interfacial charge loss, and limited device performance improvement.

Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds.

Ester hydrates, as the intermediates of the esterification between acid and alcohol, are very short-lived and challenging to be trapped. Therefore, the crystal structures of ester hydrates have rarely been characterized. Herein, we present that the mono-deprotonated ester hydrates [CHOSO(OH)], serving as the template for the self-assembly of a π-stacked boat-shaped macrocycle (CHOSO(OH))(CHOSO)@{[ClLCo]}·Cl·13CHOH·9HO () (L = tris(2-benzimidazolylmethyl) amine), can be trapped in the host by multiple NH···O hydrogen bonds.

Metalation of a Hierarchical Self-Assembly Consisting of -Stacked Cubes through Single-Crystal-to-Single-Crystal Transformation.

Single-crystal-to-single-crystal metalation of organic ligands represents a novel method to prepare metal-organic complexes, but remains challenging. Herein, a hierarchical self-assembly {(HL)·([N(CH)])·(ClO)·(HO)} () (L = tris(2-benzimidazolylmethyl) amine) consisting of -stacked cubes which are assembled from eight partially protonated L ligands is obtained. By soaking the crystals of compound in the aqueous solution of Co(SCN), the ligands coordinate with Co ions stoichiometrically and ClO exchange with SCN via single-crystal-to-single-crystal transformation, leading to {([CoSCNL])·([NCH])·(SCN)·(HO)} ().

Improving the Hydrogen Oxidation Reaction Rate of Ru by Active Hydrogen in the Ultrathin Pd Interlayer.

Enhancing the catalytic activity of Ru metal in the hydrogen oxidation reaction (HOR) potential range, improving the insufficient activity of Ru caused by its oxophilicity, is of great significance for reducing the cost of anion exchange membrane fuel cells (AEMFCs). Here, we use Ru grown on Au@Pd as a model system to understand the underlying mechanism for activity improvement by combining direct in situ surface-enhanced Raman spectroscopy (SERS) evidence of the catalytic reaction intermediate (OH) with in situ X-ray diffraction (XRD), electrochemical characterization, as well as DFT calculations. The results showed that the Au@Pd@Ru nanocatalyst utilizes the hydrogen storage capacity of the Pd interlayer to "temporarily" store the activated hydrogen enriched at the interface, which spontaneously overflows at the "hydrogen-deficient interface" to react with OH adsorbed on Ru.

Modulating the electronic structure of atomically dispersed Fe-Pt dual-site catalysts for efficient oxygen reduction reactions.

Atomically dispersed catalysts, with a high atomic dispersion of active sites, are efficient electrocatalysts. However, their unique catalytic sites make it challenging to improve their catalytic activity further. In this study, an atomically dispersed Fe-Pt dual-site catalyst (FePtNC) has been designed as a high-activity catalyst by modulating the electronic structure between adjacent metal sites.

High Chemical Potential Driven Amorphization of Pd-based Nanoalloys.

Amorphous metals and alloys are promising candidates for superior catalysts in many catalytic and electrocatalytic reactions. It is of great urgency to develop a general method to construct amorphous alloys and further clarify the growth mechanism in a wet-chemical system. Herein, inspired by the conservation of energy during the crystallization process, amorphous PdCu nanoalloys have been successfully synthesized by promoting the chemical potential of the building blocks in solution.

An alkynyl-protected AgCu nanocluster for catalytic hydrogenation.

A novel alkynyl-stabilized silver-copper alloy nanocluster with the composition of [AgCu(BuCHCC)(PPh)](SbF) was prepared by the (PPh)CuBH-mediated reduction approach. The nanocluster features a centred disordered-octahedral AgCu kernel, which is protected by hybrid alkynyl and triphenylphosphine ligands. Structural comparison of this two-electron nanocluster with other alkynyl-capped Ag/Cu ones suggested that the structure of alkynyl ligands played an important role in dictating the structures of the resulting nanoclusters.

A general method for rapid synthesis of refractory carbides by low-pressure carbothermal shock reduction.

Refractory carbides are attractive candidates for support materials in heterogeneous catalysis because of their high thermal, chemical, and mechanical stability. However, the industrial applications of refractory carbides, especially silicon carbide (SiC), are greatly hampered by their low surface area and harsh synthetic conditions, typically have a very limited surface area (<200 m g), and are prepared in a high-temperature environment (>1,400 °C) that lasts for several or even tens of hours. Based on Le Chatelier's principle, we theoretically proposed and experimentally verified that a low-pressure carbothermal reduction (CR) strategy was capable of synthesizing high-surface area SiC (569.

Defect Passivation by a Multifunctional Phosphate Additive toward Improvements of Efficiency and Stability of Perovskite Solar Cells.

The quality of perovskite films plays a crucial role in the performance of the corresponding devices. However, the commonly employed perovskite polycrystalline films often contain a high density of defects created during film production and cell operation, including unsaturated coordinated Pb and Pb, which can act as nonradiative recombination centers, thus reducing open-circuit voltage. Effectively eliminating both kinds of defects is an important subject of research to improve the power conversion efficiency (PCE).