Structure Design and Performance Tuning of Nanomaterials for Electrochemical Energy Conversion and Storage.

The performance of nanomaterials in electrochemical energy conversion (fuel cells) and storage (secondary batteries) strongly depends on the nature of their surfaces. Designing the structure of electrode materials is the key approach to achieving better performance. Metal or metal oxide nanocrystals (NCs) with high-energy surfaces and open surface structures have attained significant attention in the past decade since such features possess intrinsically exceptional properties. However, they are thermodynamically metastable, resulting in a huge challenge in their shape-controlled synthesis. The tuning of material structure, design, and performance on the nanoscale for electrochemical energy conversion and storage has attracted extended attention over the past few years. In this Account, recent progress made in shape-controlled synthesis of nanomaterials with high-energy surfaces and open surface structures using both electrochemical methods and surfactant-based wet chemical route are reviewed. In fuel cells, the most important catalytic materials are Pt and Pd and their NCs with high-energy surfaces of convex or concave morphology. These exhibit remarkable activity toward electrooxidation of small organic molecules, such as formic acid, methanol, and ethanol and so on. In practical applications, the successful synthesis of Pt NCs with high-energy surfaces of small sizes (sub-10 nm) realized a superior high mass activity. The electrocatalytic performances have been further boosted by synergetic effects in bimetallic systems, either through surface decoration using foreign metal atoms or by alloying in which the high-index facet structure is preserved and the electronic structure of the NCs is altered. The intrinsic relationship of high electrocatalytic performance dependent on open structure and high-energy surface is also valid for (metal) oxide nanomaterials used in Li ion batteries (LIB). It is essential for the anode nanomaterials to have optimized structures to keep them more stable during the charge/discharge processes for reducing damaging volume expansion via intercalation and subsequent reduced battery lifetime. In the case of cathodes, tuning the surface structure of nanomaterials should be one of the most beneficial strategies to enhance the capacity and rate performance. In addition, metal oxides with unique defective structure of high catalytic activity and carbon materials of porous structure for facilitating fast Li+ diffusion paths and efficiently trapping polysulfide are most important approached and employed in Li-O2 battery and Li-S battery, respectively. In summary, significant progress has already been made in the electrocatalytic field, and likely emerging techniques based on NCs enclosed with high-energy surfaces and high-index facets could provide a promising platform to investigate the surface structure-catalytic functionality at nanoscale, thus shedding light on the rational design of practical catalysts with high activity, selectivity, and durability for energy conversion and storage.

In-situ infrared spectroscopic studies of electrochemical energy conversion and storage.

With their ability to convert chemical energy of fuels directly into electrical power or reversibly store electrical energy, systems such as fuel cells and lithium ion batteries are of great importance in managing energy use. In these electrochemical energy conversion and storage (EECS) systems, controlled electrochemical redox reactions generate or store the electrical energy, ideally under conditions that avoid or kinetically suppress side reactions. A comprehensive understanding of electrode reactions is critical for the exploration and optimization of electrode materials and is therefore the key issue for developing advanced EECS systems. Based on its fingerprint and surface selection rules, electrochemical in-situ FTIR spectroscopy (in-situ FTIRS) can provide real-time information about the chemical nature of adsorbates and solution species as well as intermediate/product species involved in the electrochemical reactions. These unique features make this technique well-suited for insitu studies of EECS. In this Account, we review the characterization of electrode materials and the investigation of interfacial reaction processes involved in EECS systems by using state-of-the-art in-situ FTIR reflection technologies, primarily with an external configuration. We introduce the application of in-situ FTIRS to EECS systems and describe relevant technologies including in-situ microscope FTIRS, in-situ time-resolved FTIRS, and the combinatorial FTIRS approach. We focus first on the in-situ steady-state and time-resolved FTIRS studies on the electrooxidation of small organic molecules. Next, we review the characterization of electrocatalysts through the IR properties of nanomaterials, such as abnormal IR effects (AIREs) and surface enhanced infrared absorption (SEIRA). Finally, we introduce the application of in-situ FTIRS to demonstrate the decomposition of electrolyte and (de)lithiation processes involved in lithium ion batteries. The body of work summarized here has substantially advanced the knowledge of electrode processes and represents the forefront in studies of EECS at the molecular level.

Nanomaterials of high surface energy with exceptional properties in catalysis and energy storage.

The properties of nanomaterials for use in catalytic and energy storage applications strongly depends on the nature of their surfaces. Nanocrystals with high surface energy have an open surface structure and possess a high density of low-coordinated step and kink atoms. Possession of such features can lead to exceptional catalytic properties. The current barrier for widespread industrial use is found in the difficulty to synthesise nanocrystals with high-energy surfaces. In this critical review we present a review of the progress made for producing shape-controlled synthesis of nanomaterials of high surface energy using electrochemical and wet chemistry techniques. Important nanomaterials such as nanocrystal catalysts based on Pt, Pd, Au and Fe, metal oxides TiO(2) and SnO(2), as well as lithium Mn-rich metal oxides are covered. Emphasis of current applications in electrocatalysis, photocatalysis, gas sensor and lithium ion batteries are extensively discussed. Finally, a future synopsis about emerging applications is given (139 references).

A density functional theory approach to mushroom-like platinum clusters on palladium-shell over Au core nanoparticles for high electrocatalytic activity.

Recently, it was found that Pt clusters deposited on Pd shell over Au core nanoparticles (Au@Pd@Pt NPs) exhibit unusually high electrocatalytic activity for the electro-oxidation of formic acid (P. P. Fang, S. Duan, et al., Chem. Sci., 2011, 2, 531-539). In an attempt to offer an explanation, we used here carbon monoxide (CO) as probed molecules, and applied density functional theory (DFT) to simulate the surface Raman spectra of CO at this core-shell-cluster NPs with a two monolayer thickness of Pd shell and various Pt cluster coverage. Our DFT results show that the calculated Pt coverage dependent spectra fit the experimental ones well only if the Pt clusters adopt a mushroom-like structure, while currently the island-like structure is the widely accepted model, which follows the Volmer-Weber growth mode. This result infers that there should be a new growth mode, i.e., the mushroom growth mode as proposed in the present work, for Au@Pd@Pt NPs. We suggest that such a mushroom-like structure may offer novel active sites, which accounts for the observed high electrocatalytic activity of Au@Pd@Pt NPs.