A transition from metal-like double-layer capacitive charging to redox-like charging was observed in electrochemical ensemble Coulomb staircase experiments on solutions of gold nanoparticles of varied core size. The monodisperse gold nanoparticles are stabilized by short-chain alkanethiolate monolayers and have 8 to 38 kilodaltons core mass (1.1 to 1.9 nanometers in diameter). Larger cores display Coulomb staircase responses consistent with double-layer charging of metal-electrolyte interfaces, whereas smaller core nanoparticles exhibit redox chemical character, including a large central gap. The change in behavior is consistent with new near-infrared spectroscopic data showing an emerging gap between the highest occupied and lowest unoccupied orbitals of 0.4 to 0.9 electron volt.

Isolable, water-soluble gold clusters protected by monolayers of tiopronin (tiopronin−MPCs) or coenzyme A (CoA−MPCs) were synthesized by a procedure of comparable simplicity to the Brust synthesis for alkanethiolate monolayer-protected gold clusters. High-resolution transmission electron microscopy shows that, like their alkanethiolate−MPC counterparts, the average core diameters of tiopronin−MPCs can be systematically controlled by varying the tiopronin:Au mole ratio employed in the reaction. The UV−vis spectra of tiopronin−MPCs exhibit pH and core size dependency of the surface plasmon band position and intensity, respectively. Thermogravimetric analysis of the tiopronin−MPCs gave average numbers of tiopronin ligands per cluster; for example, tiopronin−MPCs with an average core size of 1.8 nm (∼Au201) are protected with an average of 85 tiopronin ligands. 1H NMR reveals a size-dependent evolution of spectral features interpreted as reflecting differences in attachment sites (terrace, defects) and/or restriction in ligand mobility. Infrared spectroscopy reveals strong hydrogen bonding in the monolayer and provides evidence for intercluster association, and acid/base titrations produce pK A values similar to the free ligand in the presence of a charge-screening supporting electrolyte, but higher in its absence. The same analytical methods were also applied to CoA-MPCs.

Carbon nanoparticles were prepared by refluxing the combustion soot of natural gas in nitric acid. Transmission Electron Microscopy measurements showed that the resulting particles exhibited an average diameter of 4.8 ± 0.6 nm, and the crystalline lattices were consistent with graphitic carbons. 13C NMR and FTIR spectroscopic measurements further confirmed the presence of sp2 carbons in the form of aryl and carboxylic/carbonyl moieties. The resulting carbon nanoparticles were found to emit photoluminescence with a quantum yield of approximately 0.43%. Additionally, the emission band energy of the carbon nanoparticle was very similar to that of much smaller carbon nanoparticles obtained from candle soot, suggesting that the photoluminescence might arise from particle surface states, analogous to the behaviors of semiconductor quantum dots with an indirect bandgap. In electrochemical measurements, two pairs of well-defined voltammetric waves were observed, which might be ascribed to the peripheral functional moieties that were analogous to phenanthrenequinone derivatives. Interestingly, the carbon nanoparticles might also be exploited as nanoscale structural scaffolds for the deposition of nanostructures of varied transition metals, leading to the formation of metal−carbon functional nanocomposites.

Electrocatalysts with single metal atoms as active sites have received increasing attention owing to their high atomic utilization efficiency and exotic catalytic activity and selectivity. This review aims to provide a comprehensive summary on the recent development of such single-atom electrocatalysts (SAECs) for various energy-conversion reactions. The discussion starts with an introduction of the different types of SAECs, followed by an overview of the synthetic methodologies to control the atomic dispersion of metal sites and atomically resolved characterization using state-of-the-art microscopic and spectroscopic techniques. In recognition of the extensive applications of SAECs, the electrocatalytic studies are dissected in terms of various important electrochemical reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), and nitrogen reduction reaction (NRR). Examples of SAECs are deliberated in each case in terms of their catalytic performance, structure−property relationships, and catalytic enhancement mechanisms. A perspective is provided at the end of each section about remaining challenges and opportunities for the development of SAECs for the targeted reaction.