Revealing the interfacial water structure on a p-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 p-nitrobenzoic acid on the Au(111) surface, a protruding band above 3600 cm-1 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-1. Although three possible structures have been guessed for this protruding infrared band, the band assignment and interfacial water structure remain ambiguous in the past two decades. Herein, by combining surface-enhanced infrared absorption spectroscopy and our newly developed quantitative computational method for electrochemical infrared spectra, the protruding infrared band is clearly assigned to the surface-enhanced stretching mode of water molecules hydrogen-bonded to the adsorbed p-nitrobenzoate ions. Water molecules, meanwhile, are hydrogen-bonded with themselves to form chains of five-membered rings. Based on the reaction free energy diagram, we further demonstrate that both hydrogen-bonding interactions and coverages of specifically adsorbed p-nitrobenzoate play an important role in determining the structure of the water layer in the Au(111)/p-nitrobenzoic acid solution interface. Our work sheds light on structural studies of the inner Helmholtz plane under specific adsorptions, which advances the understanding of structure-property relationships in electrochemical and heterogeneous catalytic systems.

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. Here, we quantify the cation effect on proton diffusion in solution by hydrogen evolution on microelectrodes, revealing the rate can be suppressed by more than 10 times. Different from the prevalent opinions that proton transport is slowed down by modified electric field, we found water structure imposes a more evident effect on kinetics. FTIR test and path integral molecular dynamics simulation indicate that proton prefers to wander within the hydration shell of cations rather than to hop rapidly along water wires. Low connectivity of water networks disrupted by cations corrupts the fast-moving path in bulk water. This study highlights the promising way for regulating proton kinetics via a modified water structure.

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. In this study, we propose that promoting proton transfer at the interfacial layer can be used to regulate the interfacial pH in order to enhance electrocatalytic activity. By adsorbing a bifunctional 4-mercaptopyridine (4MPy) molecule onto the catalyst surface via its thiol group, the pyridyl group can be tethered on the electrochemical interface. The pyridyl group acts as both a good proton acceptor and donor for promoting proton transfer at the interfacial layer. Furthermore, the pK a of 4MPy can be modulated with the applied potentials to accommodate the large variation of interfacial pH under different current densities. By in situ electrochemical surface-enhanced Raman spectroscopy (in situ EC-SERS), we quantitatively demonstrate that proton transfer at the interfacial layer of the Pt catalyst coated with 4MPy (Pt@4MPy) remains ideally thermoneutral during the H+ releasing electrocatalytic oxidation reaction of formic acid (FAOR) at high current densities. Thus, the interfacial pH is controlled effectively. In this way, the FAOR apparent current measured from Pt@4MPy is twice that measured from a pristine Pt catalyst. This work establishes a general strategy for regulating interfacial pH to enhance the electrocatalytic activities.

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 (SBET ) and micropore surface fraction (fmicro ), on ORR activity and selectivity are investigated in both RRDE and FC. The ORR mass activity correlates positively to the SBET in the RRDE and FC because a higher SBET can host more active sites. The H2 O2 selectivity is independent of fmicro in the RRDE but correlates negatively to fmicro in the FC. The inconsistency results from different states of the electrode in the RRDE and the FC. These insights will guide the design of carbon materials for H2 O2 synthesis.

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. In the base, the reactivity of the interfacial water varied its structure, and the activation energies of water dissociation increased in the sequence: the dangling O-H bonds < the trihedrally coordinated water < the tetrahedrally coordinated water. Moreover, optimizing the adsorption of H and OH intermediates can re-orientate the interfacial water molecules with their H atoms pointing towards the electrode surface, thereby enhancing the kinetics of HER. Our results clarified the dynamic role of the water structure at the electrode-electrolyte interface during HER and the design of highly efficient HER catalysts.

Electrochemical CO2 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 CO2 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, CO2 reduction reactions on polycrystalline Cu and Au electrodes were investigated in 0.1 M CO2-saturated NaHCO3 solution. In situ sum frequency generation (SFG) spectroscopy has been adopted to access the intermediates and products on the metal electrodes. On the Au electrode, only linearly adsorbed CO could be detected, and the reduction produced no hydrocarbon species. On the Cu electrode, C-H stretching vibrations corresponding to surface-adsorbed ethoxy species were observed, but no CO vibrations can be detected with SFG. The results revealed that the CO randomly adsorbed on the Cu surface, and the multiple orientations of the adsorbed species may be the reason for the formation of C-C bonding. These results demonstrate direct molecular level evidence for different reaction pathways on the Cu and Au electrodes.

Cooperative Stabilization of the [Pyridinium-CO2-Co] Adduct on a Metal-Organic Layer Enhances Electrocatalytic CO2 Reduction.

Pyridinium has been shown to be a cocatalyst for the electrochemical reduction of CO2 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 CO2 reduction reaction (CO2RR). Constructed from [Hf6(µ3-O)4(µ3-OH)4(HCO2)6] secondary building units (SBUs) and terpyridine-based tricarboxylate ligands, the MOL was postsynthetically functionalized with CoPP via carboxylate exchange with formate capping groups. The CoPP group and the pyridinium (pyH+) moiety on the MOL coactivate CO2 by forming the [pyH+--O2C-CoPP] adduct, which enhances the CO2RR and suppresses hydrogen evolution to afford a high CO/H2 selectivity of 11.8. Cooperative stabilization of the [pyH+--O2C-CoPP] intermediate led to a catalytic current density of 1314 mA/mgCo for CO production at -0.86 VRHE, which corresponds to a turnover frequency of 0.4 s-1.

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 Pdx 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 alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the Pdx Ag NTs.

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. Herein, we address a novel strategy to divide the surface areas of larger sized nanocrystals into small surface area nanocrystals by in situ etching Pt-Fe-Mn concave cubes (CNCs) while maintaining the morphology of the Pt-Fe-Mn alloys to improve the utilization of Pt atoms and thus increase the mass activity. Remarkably, the Pt-Fe-Mn unique concave cube (UCNC) nanocrystals (NCs) showed much higher specific and mass activities toward the methanol oxidation reaction (MOR) than the Pt-Fe-Mn CNCs, commercial Pt black and Pt/C. The kinetic analysis from Tafel plots indicated that UCNC Pt-Fe-Mn NCs had the lowest Tafel slope at whole potentials and the splitting of the first C-H bond of a CH3OH molecule with the first electron transfer was the rate-determining step at high potentials (above 0.45 V). In situ Fourier transform infrared reflection (FTIR) spectroscopic investigation at the molecular level indicated that methanol chemical absorption took place at a low potential of -0.2 V at the UCNC NC electrode. Meanwhile, much higher CO2 productivity was observed at the UCNC NC electrode, indicating the strong anti-poisoning ability of the UCNC Pt-Fe-Mn NCs during methanol electrooxidation. Furthermore, in the formic acid oxidation (FAOR) test, the activity and long-term durability of the Pt-Fe-Mn UCNC NCs were also found to be superior to those of the Pt-Fe-Mn CNCs, commercial Pt black and Pt/C. The enhanced catalytic performance in both the MOR and FAOR is most probably due to the unique HIF structure consisting of small sized particles, enhanced Pt utilization, the richness of crystalline defects and synergetic effects of Pt, Fe, and Mn metals. Our present work provides an insight into the rational design of Pt based alloys with HIFs to improve the catalytic performance of electro-catalytic reactions for fundamental study.

[Subhabitat selection and differences of diet composition for Acanthogobius ommaturus in the Dongtan wetland of the Yangtze estuary, China]. / é•¿æ±Ÿå£ä¸œæ»©æ¹¿åœ°æ–‘å°¾åˆºè™¾è™Žé±¼çš„æ –æ¯äºšç”Ÿå¢ƒé€‰æ‹©å’Œé£Ÿæ€§å·®å¼‚.

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. Most of the samples were collected in July (71) and only three individuals was collected in November. Most of the samples were collected (93) in creek, which was 5.2 and 4.9 times of those in mudflat and salt marsh, respectively. The diet of the A. ommaturus included 10 taxa and 30 prey species, dominated by shrimps. In the taxonomic level, the dominant preys were the Exopalaemon annandalei or other Exopalaemon sp. of shrimps, the Sesarma sp. of crabs and Micromecta quadriseta of insects. Compared with other taxonomic groups, the fish prey had relatively higher mass percentage but lower abundance percentage. The prey composition of A. ommaturus differed among subhabitats. The feeding level of A. ommaturus increased gradually from July to November and reached 3.0 in late autumn. The differences in the abundances of A. ommaturus among subhabitats would be induced by prey composition.

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. It has demonstrated that the shapes of Au NCs are strongly dependent on the size of seeds and the growth potentials as well as the urea adsorbates in the DES. By adjusting the size of seeds and the growth potentials, the stellated Au NCs can be transformed into concave hexoctahedra (HOH) with high-index {421} facets and concave trisoctahedra (TOH) with high-index {991} facets. The electrocatalytic activities of the as-prepared Au NCs are evaluated by glucose oxidation. Thanks to HIFs having high density of atomic steps and kinks, the stellated, TOH, and HOH Au NCs exhibit higher electrocatalytic activity than that of the polycrystalline Au electrode, demonstrating that the steps and kinks serve as the active sites and play an important role in glucose electro-oxidation.

An insight into methanol oxidation mechanisms on RuO2(100) under an aqueous environment by DFT calculations.

In this work, we have studied methanol oxidation mechanisms on RuO2(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: CH3OH* → CH3O* → HCHO* → HCH(OH)2* → HCHOOH* → HCOOH* → mono-HCOO* → CO2*, 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.

[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]. / é•¿æ±Ÿå£ä¸œæ»©æ¹¿åœ°èŠ¦è‹‡ç”Ÿå¢ƒå¤§åž‹åº•æ –æ— è„Šæ¤ŽåŠ¨ç‰©ç¾¤è½ç»“æž„çš„æœˆåŠ¨æ€.

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. The density and aboveground biomass (dry mass, g) of P. australis peaked in July. A total of twenty species (including 2 species only identified to genus level and 2 species identified to family level) were found in the survey periods, including 11 Gastropoda, 5 Malacostraca, 2 Insecta and 2 Polychaeta. Three snail species (Assiminea latericea, Assiminea violacea and Cerithideopsis largillierti) dominated the benthic communities in terms of numerical abundance. The number of epifauna species was the most (11 species), followed by 5 burrowing species and 4 infauna species. There were significant monthly variations in the density and biomass of the macro-invertebrates. The density and biomass of benthic community reached the maximum in August. The Margalef's species richness index (D) and Shannon index (H) showed significant differences monthly, but Pielou's index (J) except in November. Three macro-zoobenthic assemblages were identified with the 42% similarity level. The non-Metric Multidimensional scaling plot indicates that the benthic community in May, October and November was distinct compared to that in the other months. The present study suggested the density of the benthic macro-invertebrates community in the P. australis marshes was somewhat correlated with water temperature, underground biomass and salinity. But those correlation were not significant (P>0.05). Because of the continuous impact of anthropogenic activities, the biodiversity of the benthic macro-invertebrate community has been decreasing for several years. More attention should be paid to the habitat value of the P. australis marshes in the future.

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. The second type of PtM phase is prepared by cooling in a stream of hydrogen gas. Although this second phase also consists of numerous microcrystals covering the Pt{111} electrode surface, these are both flatter than before and moreover are entirely metallic in character. A positive shift in the onset of PtM oxide formation correlates with increased activity towards the oxygen reduction reaction (ORR), which we ascribe to the greater availability of platinum metallic sites under ORR conditions.

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)≤ 0.135), while on both (100) and (110) sites at higher CO coverage. On ordered Pt(310) and Pt(210), i.e. they were flame annealed and then cooled in H(2) + Ar, CO adsorption also illustrates relative priority on (100) sites at low CO coverage; while at high CO coverage or on oxygen-disordered Pt(310) and Pt(210) when they were cooled in air after flame annealing, the adsorption of CO presents a weak preference on (100) sites of Pt(310) and even no preference at all on (100) sites of Pt(210). In situ FTIR spectroscopic studies illustrated that CO adsorption on THH Pt NCs yields anomalous infrared effects (AIREs), which are depicted by the Fano-like IR feature on a dense distribution (60 µm(-2)) and the enhancement of abnormal IR absorption on a sparse distribution (22 µm(-2)) of THH Pt NCs on glassy carbon substrate. Systematic investigation of CO coverage dependence of IR features revealed that, on THH Pt NCs, the IR band center (ν(COL)) of linearly bonded CO (COL) is rapidly shifted to higher wavenumbers along with the increase of CO coverage to 0.184, yielding a fast linear increase rate with a high slope (dν(COL)/dθ(IR)(CO) = 219 cm(-1)); when θ > 0.184, the increase of ν(COL) with θCO slows down and deviates drastically from linearity. In contrast, the ν(COL) on the ordered Pt(310) electrode maintains a linear increase with θ(IR)(CO) for the whole range of θ(IR)(CO) variation, and gives a much smaller increase rate of slope 74.3 cm(-1). The significant differences in CO adsorption behavior on THH Pt NCs and on interrelated Pt single crystal planes demonstrated clearly the unique properties of nanoparticles enclosed by high-index facets.