Advanced Catalyst for CO2 Photo-Reduction: From Controllable Product Selectivity by Architecture Engineering to Improving Charge Transfer Using Stabilized Au Clusters.

Despite enormous progress and improvement in photocatalytic CO2 reduction reaction (CO2 RR), the development of photocatalysts that suppress H2 evolution reaction (HER), during CO2 RR, remains still a challenge. Here, new insight is presented for controllable CO2 RR selectivity by tuning the architecture of the photocatalyst. Au/carbon nitride with planar structure (p Au/CN) showed high activity for HER with 87% selectivity. In contrast, the same composition with a yolk@shell structure (Y@S Au@CN) exhibited high selectivity of carbon products by suppressing the HER to 26% under visible light irradiation. Further improvement for CO2 RR activity was achieved by a surface decoration of the yolk@shell structure with Au25 (PET)18 clusters as favorable electron acceptors, resulting in longer charge separation in Au@CN/Auc Y@S structure. Finally, by covering the structure with graphene layers, the designed catalyst maintained high photostability during light illumination and showed high photocatalytic efficiency. The optimized Au@CN/Auc /G Y@S structure displays high photocatalytic CO2 RR selectivity of 88%, where the CO and CH4 generations during 8 h are 494 and 198 µmol/gcat., respectively. This approach combining architecture engineering and composition modification provides a new strategy with improved activity and controllable selectivity toward targeting applications in energy conversion catalysis.

Exceptionally Stable Dimers and Trimers of Au25 Clusters Linked with a Bidentate Dithiol: Synthesis, Structure and Chirality Study.

A bidentate chiral dithiol (diBINAS) is utilised to bridge Au25 nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by small-angle X-ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion-ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed self-assembly of metal clusters.

Experimental Confirmation of a Topological Isomer of the Ubiquitous Au25(SR)18 Cluster in the Gas Phase.

High-resolution electrospray ionization ion mobility mass spectrometry has revealed a gas-phase isomer of the ubiquitous, extremely well-studied Au25(SR)18 cluster both in anionic and cationic form. The relative abundance of the isomeric structures can be controlled by in-source activation. The measured collision cross section of the new isomer agrees extremely well with a recent theoretical prediction (Matus, M. F.; et al. Chem. Commun. 2020, 56, 8087) corresponding to a Au25(SR)18- isomer that is energetically close and topologically connected to the known ground-state structure via a simple rotation of the gold core without breaking any Au-S bonds. The results imply that the structural dynamics leading to isomerization of thiolate-protected gold clusters may play an important role in their gas-phase reactions and that isomerization could be controlled by external stimuli.

Raman Spectroscopic Fingerprints of Atomically Precise Ligand Protected Noble Metal Clusters: Au38 (PET)24 and Au38-x Agx (PET)24.

Distinct Raman spectroscopic signatures of the metal core of atomically precise, ligand-protected noble metal nanoclusters are reported using Au38 (PET)24 and Au38-x Agx (PET)24 (PET = 2-phenylethanethiolate, -SC2 H4 C6 H5 ) as model systems. The fingerprint Raman features (occurring <200 cm-1 ) of these clusters arise due to the vibrations involving metal atoms of their Au23 or Au23-x Agx cores. A distinct core breathing vibrational mode of the Au23 core has been observed at 90 cm-1 . Whereas the breathing mode shifts to higher frequencies with increasing Ag content of the cluster, the vibrational signatures due to the outer metal-ligand staple motifs (between 200 and 500 cm-1 ) do not shift significantly. DFT calculations furthermore reveal weak Raman bands at higher frequencies compared to the breathing mode, which are associated mostly with the rattling of two central gold atoms of the bi-icosahedral Au23 core. These vibrations are also observed in the experimental spectrum. The study indicates that low-frequency Raman spectra are a characteristic fingerprint of atomically precise clusters, just as electronic absorption spectroscopy, in contrast to the spectrum associated with the ligand shell, which is observed at higher frequencies.

Downsizing of Nanocrystals While Retaining Bistable Spin Crossover Properties in Three-Dimensional Hofmann-Type {Fe(pz)[Pt(CN)4]}-Iodine Adducts.

Mastering nanostructuration of functional materials into electronic devices is presently an essential task in materials science. This is particularly relevant for spin crossover (SCO) compounds, whose properties are extremely sensitive to size reduction. Indeed, the search for materials displaying strong cooperative hysteretic SCO properties operative at the nanoscale close near room temperature is extremely challenging. In this context, we describe here the synthesis and characterization of 20-30 nm surfactant-free nanocrystals of the FeII Hofmann-type polymer {FeII(pz)[PtII,IVIx(CN)4]} (pz = pyrazine), which affords the first example of a robust three-dimensional coordination polymer, substantially keeping operational thermally induced SCO bistability at such a scale.

On the mechanism of rapid metal exchange between thiolate-protected gold and gold/silver clusters: a time-resolved in situ XAFS study.

The fast metal exchange reaction between Au38 and AgxAu38-x nanoclusters in solution at -20 °C has been studied by in situ X-ray absorption spectroscopy (time resolved quick XAFS) in transmission mode. A cell was designed for this purpose consisting of a cooling system, remote injection and mixing devices. The capability of the set-up is demonstrated for second and minute time scale measurements of the metal exchange reaction upon mixing Au38/toluene and AgxAu38-x/toluene solutions at both Ag K-edge and Au L3-edge. It has been proposed that the exchange of gold and silver atoms between the clusters occurs via the SR(-M-SR)n (n = 1, 2; M = Au, Ag) staple units in the surface of the reacting clusters during their collision. However, at no point during the reaction (before, during, after) evidence is found for cationic silver atoms within the staples. This means that either the exchange occurs directly between the cores of the involved clusters or the residence time of the silver atoms in the staples is very short in a mechanism involving the metal exchange within the staples.

Doping of thiolate protected gold clusters through reaction with metal surfaces.

A new technique is introduced for doping gold nanoclusters by using a metal surface such as Ag, Cu and Cd as a source of heteroatoms. The importance of the thiol ligand in the doping process is examined by following the reactions with MALDI-TOF mass spectrometry in the presence and the absence of the thiols on the surface. The doping reactions depend greatly on the type of the cluster and the availability of the ligand which is a crucial element for alloying. The thiol acts as a messenger exchanging the metal atoms between the cluster and the metal surface as revealed by the XPS studies performed on the metal surfaces.

Au38Cu1(2-PET)24 nanocluster: synthesis, enantioseparation and luminescence.

A CuAu38 bimetallic nanocluster was synthesized by adding a single copper atom to the Au38(2-PET)24 nanocluster. The absence of CuxAu38-x(2-PET)24 doped species was demonstrated by MALDI-TOF mass spectrometry. A separation of bimetallic clusters was attained for the first time where isomers of the E2 enantiomer of the Au38Cu1(2-PET)24 adduct were successfully isolated from their parent cluster using chiral HPLC. The CD of the isolated isomers revealed a change in their electronic structure upon copper addition. The luminescence of the Au38Cu1 adduct is significantly enhanced in comparison with the parent Au38 nanocluster. The stability of the newly formed adduct is strongly dependent on the coexistence of the Au38 nanoclusters.