Revealing the interfacial water structure on a -nitrobenzoic acid specifically adsorbed Au(111) surface.

The detailed structure of the water layer in the inner Helmholtz plane of a solid/aqueous solution interface is closely related to the electrochemical and catalytic performances of electrode materials. While the applied potential can have a great impact, specifically adsorbed species can also influence the interfacial water structure. With the specific adsorption of -nitrobenzoic acid on the Au(111) surface, a protruding band above 3600 cm appears in the electrochemical infrared spectra, indicating a distinct interfacial water structure as compared to that on bare metal surfaces, which displays a potential-dependent broad band in the range of 3400-3500 cm.

Mechanism of Cations Suppressing Proton Diffusion Kinetics for Electrocatalysis.

Proton transfer is crucial for electrocatalysis. Accumulating cations at electrochemical interfaces can alter the proton transfer rate and then tune electrocatalytic performance. However, the mechanism for regulating proton transfer remains ambiguous.

Accelerated interfacial proton transfer for promoting electrocatalytic activity.

Interfacial pH is critical to electrocatalytic reactions involving proton-coupled electron transfer (PCET) processes, and maintaining an optimal interfacial pH at the electrochemical interface is required to achieve high activity. However, the interfacial pH varies inevitably during the electrochemical reaction owing to slow proton transfer at the interfacial layer, even in buffer solutions. It is therefore necessary to find an effective and general way to promote proton transfer for regulating the interfacial pH.

Impact of Pore Structure on Two-Electron Oxygen Reduction Reaction in Nitrogen-Doped Carbon Materials: Rotating Ring-Disk Electrode vs. Flow Cell.

The impact of pore structure on the two-electron oxygen reduction reaction (ORR) in nitrogen-doped carbon materials is currently under debate, and previous studies are mainly limited to the rotating ring-disk electrode (RRDE) rather than the practical flow cell (FC) system. In this study, assisted by a group of reliable pore models, the impact of two pore structure parameters, that is, Brunauer-Emmett-Teller surface area (S ) and micropore surface fraction (f ), on ORR activity and selectivity are investigated in both RRDE and FC. The ORR mass activity correlates positively to the S in the RRDE and FC because a higher S can host more active sites.

Interfacial Structure of Water as a New Descriptor of the Hydrogen Evolution Reaction.

Driven by the persisting poor understanding of the sluggish kinetics of the hydrogen evolution reaction (HER) on Pt in alkaline media, a direct correlation of the interfacial water structure and activity is still yet to be established. Herein, using Pt and Pt-Ni nanoparticles we first demonstrate a strong dependence of the proton donor structure on the HER activity and pH. The structure of the first layer changes from the proton acceptors to the donors with increasing pH.

Electrochemical CO reduction on Cu and Au electrodes studied using in situ sum frequency generation spectroscopy.

As an important pathway for energy storage and a key reaction in the carbon cycle, the CO electrochemical reduction reaction has recently gained significant interest. A variety of catalysts have been used to approach this topic experimentally and theoretically; however, the molecular level insight into the reaction mechanism is lacking due to the complexity of the surface processes and the challenges in probing the intermediate species. In this study, CO reduction reactions on polycrystalline Cu and Au electrodes were investigated in 0.

Cooperative Stabilization of the [Pyridinium-CO-Co] Adduct on a Metal-Organic Layer Enhances Electrocatalytic CO Reduction.

Pyridinium has been shown to be a cocatalyst for the electrochemical reduction of CO on metal and semiconductor electrodes, but its exact role has been difficult to elucidate. In this work, we create cooperative cobalt-protoporphyrin (CoPP) and pyridine/pyridinium (py/pyH) catalytic sites on metal-organic layers (MOLs) for an electrocatalytic CO reduction reaction (CORR). Constructed from [Hf(μ-O)(μ-OH)(HCO)] secondary building units (SBUs) and terpyridine-based tricarboxylate ligands, the MOL was postsynthetically functionalized with CoPP via carboxylate exchange with formate capping groups.

Synergy between Plasmonic and Electrocatalytic Activation of Methanol Oxidation on Palladium-Silver Alloy Nanotubes.

Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel-cell-relevant reaction. The electrocatalyst consists of Pd Ag alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible-light plasmonic response of Ag.

The in situ etching assisted synthesis of Pt-Fe-Mn ternary alloys with high-index facets as efficient catalysts for electro-oxidation reactions.

Pt-Based alloys enclosed with high-index facets (HIFs) generally show much higher specific catalytic activities than their counterparts with low-index facets in electro-catalytic reactions. However, the exposure of a certain Pt surface would require a well-defined nanostructure, which usually can only be obtained at larger sizes. Therefore, a low dispersion of Pt atoms in Pt-based alloys with HIFs would affect the atomic utilization of Pt, resulting in most of these Pt-based alloys exhibiting lower mass activity than commercial Pt/C and Pt black catalysts for electro-catalytic reactions.

[Monthly changes in the benthic macro-invertebrate community structure in the habitats of Phragmites australis marsh in the Dongtan wetland of the Yangtze River estuary, China].

Based on the data of the benthic macro-invertebrates community in the Phragmites australis marsh in the Dongtan Wetland of the Yangtze River estuary collected from May 2015 to April 2016, we evaluated the monthly variations in the species composition, biodiversity and community structure of the benthic macro-invertebrates. The results showed that the average height and degree of coverage for P. australis increased monthly from March to August, and then deceased from September.

[Subhabitat selection and differences of diet composition for Acanthogobius ommaturus in the Dongtan wetland of the Yangtze estuary, China].

We examined the temporal and spatial variation in the abundance and diet composition of Acanthogobius ommaturus at three subhabitats (mudflat, salt marsh, and creek) of the Dongtan wetland of Yangtze Estuary with monthly field samplings from July 2015 to June 2016. The results showed that the samples of A. ommaturus were mainly composed of young individuals in the period of June-November, whereas no fish was collected during the other months.

Seeds and Potentials Mediated Synthesis of High-Index Faceted Gold Nanocrystals with Enhanced Electrocatalytic Activities.

Because high-index facets (HIFs) possess high surface energy, the metal nanoparticles enclosed with HIFs are eliminated during their growth in a conventional shape-controlled synthesis due to the thermodynamics that drives the particles minimizing their total surface energy. This study develops a double-step potential method to prepare an unprecedentedly stellated Au nanocrystals (NCs) bounded by high-index {711} and {331} facets in deep eutectic solvent (DES) medium. The formation of Au NCs bounded by HIFs was systematically studied.

An insight into methanol oxidation mechanisms on RuO(100) under an aqueous environment by DFT calculations.

In this work, we have studied methanol oxidation mechanisms on RuO(100) by using density functional theory (DFT) calculations and ab initio molecular dynamics (MD) simulations with some explicit interfacial water molecules. The overall mechanisms are identified as: CHOH* → CHO* → HCHO* → HCH(OH)* → HCHOOH* → HCOOH* → mono-HCOO* → CO*, without CO formation. This study provides a theoretical insight into C1 molecule oxidation mechanisms at atomic levels on metal oxide surfaces under an aqueous environment.

A comparative study of CO adsorption on tetrahexahedral Pt nanocrystals and interrelated Pt single crystal electrodes by using cyclic voltammetry and in situ FTIR spectroscopy.

This study focuses on CO adsorption at tetrahexahedral Pt nanocrystals (THH Pt NCs) by using cyclic voltammetry and in situ FTIR spectroscopy. Since the electrochemically prepared THH Pt NCs in this study are enclosed by {730} facets which could be considered by a subfacet configuration of 2{210} + {310}, we have also studied CO adsorption on the interrelated Pt(310) and Pt(210) single crystal electrodes as a comparison. Cyclic voltammetry results demonstrated that CO adsorbs dominantly on the (100) sites of THH Pt NCs at low CO coverage (θ(CO)≤ 0.

Oxygen reduction reaction activity on Pt{111} surface alloys.

PtM overlayers (where M=Fe, Co or Ni) supported on Pt{111} are prepared via thermal annealing in either a nitrogen/water or hydrogen ambient of dilute aqueous droplets containing M(Z+) cations directly attached to the electrode. Two different PtM phases are detected depending on the nature of the post-annealing cooling environment. The first of these consists of small (<20 nm), closely packed microcrystals comprised of a central metallic core and a shell (several monolayers thick) of mixed metal oxides/hydroxides.