Hydride-doped coinage metal superatoms and their catalytic applications.

Superatomic constructs have been identified as a critical component of future technologies. The isolation of coinage metal superatoms relies on partially reducing metallic frameworks to accommodate the mixed valent state required to generate a superatom. Controlling this reduction requires careful consideration in reducing the agent, temperature, and the ligand that directs the self-assembly process. Hydride-based reducing agents dominate the synthetic wet chemical routes to coinage metal clusters. However, within this category, a unique subset of superatoms that retain a hydride/s within the nanocluster post-reduction have emerged. These stable constructs have only recently been characterized in the solid state and have highly unique structural features and properties. The difficulty in identifying the position of hydrides in electron-rich metallic constructs requires the combination and correlation of several analytical methods, including ESI-MS, NMR, SCXRD, and DFT. This text highlights the importance of NMR in detecting hydride environments in these superatomic systems. Added to the complexity of these systems is the dual nature of the hydride, which can act as metallic hydrogen in some cases, resulting in entirely different physical properties. This review includes all hydride-doped superatomic nanoclusters emphasizing synthesis, structure, and catalytic potential.

Diselenophosphate Ligands as a Surface Engineering Tool in PdH-Doped Silver Superatomic Nanoclusters.

The first hydride-doped Pd/Ag superatoms stabilized by selenolates are reported: [PdHAg19(dsep)12] [dsep = Se2P(OiPr)2] 1 and [PdHAg20(dsep)12]+ 2. 1 was derived from the targeted transformation of [PdHAg19(dtp)12] [dtp = S2P(OiPr)2] by ligand exchange, whereas 2 was obtained from the addition of trifluoroacetic acid to 1, resulting in a symmetric redistribution of the capping silver atoms. The transformations are all achieved while retaining an 8-electron superatomic configuration. VT-NMR attests to the good stability of the NCs in solution, and single-crystal X-ray diffraction reveals the crucial role that the interstitial hydride plays in directing the position of the capping silver atoms. The total structures are reported alongside their electronic and optical properties. 1 and 2 are phosphorescent with a lifetime of 73 and 84 µs at 77 K, respectively. The first antibacterial activity data for superatomic bimetallic Pd/Ag nanoclusters are also reported.

The mineral manaksite, KNaMnSi4O10, as a supercapattery-type electrochemical energy storage material.

The manaksite mineral KNaMnSi4O10 was synthesized and used to fabricate electrodes, which were investigated for electrochemical energy storage (EES) application using cyclic voltammetry (CV), galvanostatic charge and discharge (GCD), and electrochemical impedance spectroscopy (EIS). Optimum weight percentages (wt%) of electrode components were established as 10 wt% polytetrafluoroethylene (PTFE) binder, 15 wt% RuO2 and 5 wt% carbon black. RuO2 was added to improve electrical conductivity. A ratio of 13 : 3 for KNaMnSi4O10 : RuO2 was used in the fabrication of the electrode. A study of the suitable electrolyte and corresponding concentration to use was done using NaOH and KOH, both at concentrations of 1 M, 3 M and 6 M, with 3 M NaOH as the optimum electrolyte and concentration. The KNaMnSi4O10 yielded a specific capacity of 106 mA h g-1. An investigation into the energy storage mechanism from a plot of log I(ν) vs. log ν, where I is current and ν is the scan rate gave a b value parameter of 0.8; that is, in-between 0.5 obtained for a pure battery material and 1.0 for a pure capacitor material. Accordingly, KNaMnSi4O10 exhibited a battery-supercapacitor duality phenomenon consistent with supercapattery materials. The KNaMnSi4O10 electrochemical system involved both capacitive and diffusion-controlled processes and was found to have good cyclic stability. It is concluded that KNaMnSi4O10 is a potential electrochemical energy storage material.

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters.

The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19 (dtp)12 ] (dtp=S2 P(Oi Pr)2 - ) 1 and [PdHAg20 (dtp)12 ]+ 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg21 (dtp)12 ]+ 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s1 electron to the superatomic electron count and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 µs (λex =448; λem =842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.

Heptanuclear Silver Hydride Clusters as Catalytic Precursors for the Reduction of 4-Nitrophenol.

We report on the design, synthesis, and characterization of the first silver hydride clusters solely protected and stabilized by dithiophosphonate ligands and their application for the in situ generation of silver nanoparticles towards the catalytic reduction of 4-nitrophenol in an aqueous system. The synthesis of the silver monohydride cluster involves the incorporation of an interstitial hydride using sodium borohydride. Poly-nuclear magnetic resonance and mass spectrometry were used to establish the structural properties. The structural properties were then confirmed with a single-crystal X-ray diffraction analysis, which showed a distorted tetracapped tetrahedron core with one hydride ion encapsulated within the core of the silver framework. Additionally, the synthesized heptanuclear silver hydride was utilized as a precursor for the in situ generation of silver nanoparticles, which simultaneously catalyzed the reduction of 4-nitrophenol. The mechanism of the catalytic activity was investigated by first synthesizing AgNPs, which was subsequently used as a catalyst. The kinetic study showed that the pseudo-first constant obtained using the cluster (2.43 × 10-2 s-1) was higher than that obtained using the synthesized AgNPs (2.43 × 10-2 s-1). This indicated that the silver monohydride cluster was more active owing to the release of the encapsulated hydride ion and greater reaction surface prior to aggregation.

A construction guide for high-nuclearity (≥50 metal atoms) coinage metal clusters at the nanoscale: bridging molecular precise constructs with the bulk material phase.

Synthesis remains a major strength in chemistry and materials science and relies on the formation of new molecules and diverse forms of matter. The construction and identification of large molecules poses specific challenges and has historically lain in the realm of biological (organic)-type molecules with evolved synthesis methods to support such endeavours. But with the development of analytical tools such as X-ray crystallography, new synthesis methods toward large metal-based (inorganic) molecules and clusters have come to the fore, making it possible to accurately determine the precise distribution of hundreds of atoms in large clusters. In this review, we focus on different synthesis protocols used to form new metal clusters such as templating, alloying and size-focusing strategies. A specific focus is on group 11 metals (Cu, Ag, Au) as they currently predominate large metal cluster investigations and related Au and Ag bulk surface phenomena. This review focuses on metal clusters that have very high-nuclearity, i.e. with 50 or more metal centers within the isolated cluster. This size domain, it is believed, will become increasingly important for a variety of applications as these metal clusters are positioned at the interface between the molecular and bulk phases, whilst remaining a classic nanomaterial and retaining unique nano-sized properties.

Formation of dialysis-free Kombucha-based bacterial nanocellulose embedded in a polypyrrole/PVA composite for bulk conductivity measurements.

The preparation of dialysis-free bacterial nanocrystalline cellulose (BNCC) combined with a suitable polymer to form a robust conducting material remains a challenge. In this work, we developed a polypyrrole@BNCC/PVA nanocomposite that avoids the time-consuming dialysis step and which exhibits bulk electrical conductivity. The nanocellulose (NC) was derived from bacterial cellulose (BC) that was grown from a symbiotic colony of bacteria and yeast (SCOBY) starting from Kombucha tea, and then subjected to sulfuric acid hydrolysis that led to isolable bacterial nanocrystalline cellulose (BNCC) product and subsequently utilized as a stabilizer and support. Pyrrole monomer was reacted with FeCl3·6H2O as a polymerization initiator to form polypyrrole (PPy) and combined with BNCC it produced PPy@BNCC nanocomposite. We found PPy to BNCC in a 1 : 1 ratio provided the best suspension of the components and formed a well dispersed homogeneous network. The PPy@BNCC nanocomposite was then suspended in polyvinyl alcohol (PVA), that facilitated the construction of a continuous PPy@BNCC/PVA conductive network in the matrix. We designed an in-house electrical measurement apparatus and developed a method that recorded bulk resistance. The results obtained from the measurements of the electrical properties of the PPy@BNCC/PVA composite prepared dialysis-free were then compared with (i) a dialyzed sample of similar composition, and (ii) a traditional four-point probe measurement. The PPy@BNCC/PVA dialysis-free sample showed a higher conductivity compared to the dialyzed composite at 4.27 × 10-1 and 3.41 × 10-1 S m-1, respectively, and both values closely matched the traditional four-point probe measurement.

Aqueous Route to Stable Luminescent Tetranuclear Copper(I) Dithiophosphonate Clusters.

A series of seven luminescent copper(I) dithiophosphonate (dtp) clusters of the type Cu4L4 (L = S2PR(OR')-) were formed from CuCl2·2H2O precursor in aqueous medium under ambient conditions. The dtp ligand serves the dual function of acting as a sacrificial reducing agent and cluster core stabilizer. The new clusters were characterized by 1H and 31P NMR and ESI-MS, and the single-crystal X-ray structures for two representative clusters [Cu4{(S2P(1,4-C6H4OMe)(OR')}4] (R' = OCH(CH3)2; CH2C6H5) were determined. The redox reaction yielded clusters in satisfactory yield, and all exhibited luminescence with λemmax in the range 519-534 nm and half-lives in the range 10-14 µs.