Electrically Tunable Reactivity of Substrate-Supported Cobalt Oxide Nanocrystals.

First-row transition metal oxides are promising materials for catalyzing the oxygen evolution reaction. Surface sensitive techniques provide a unique perspective allowing the study of the structure, adsorption sites, and reactivity of catalysts at the atomic scale, which furnishes rationalization and improves the design of highly efficient catalytic materials. Here, a scanning probe microscopy study complemented by density functional theory on the structural and electronic properties of CoO nanoislands grown on Au(111) is reported. Two distinct phases are observed: The most extended displays a Moiré pattern (α-region), while the less abundant is 1Co:1Au coincidental (ß-region). As a result of the surface registry, in the ß-region the oxide adlayer is compressed by 9%, increasing the unoccupied local density of states and enhancing the selective water adsorption at low temperature through a cobalt inversion mechanism. Tip-induced voltage pulses irreversibly transform α- into ß-regions, thus opening avenues to modify the structure and reactivity of transition metal oxides by external stimuli like electric fields.

CO2 Conversion on N-Doped Carbon Catalysts via Thermo- and Electrocatalysis: Role of C-NO x Moieties.

N-doped carbon (N-C) materials are increasingly popular in different electrochemical and catalytic applications. Due to the structural and stoichiometric diversity of these materials, however, the role of different functional moieties is still controversial. We have synthesized a set of N-C catalysts, with identical morphologies (∼27 nm pore size). By systematically changing the precursors, we have varied the amount and chemical nature of N-functions on the catalyst surface. The CO2 reduction (CO2R) properties of these catalysts were tested in both electrochemical (EC) and thermal catalytic (TC) experiments (i.e., CO2 + H2 reaction). CO was the major CO2R product in all cases, while CH4 appeared as a minor product. Importantly, the CO2R activity changed with the chemical composition, and the activity trend was similar in the EC and TC scenarios. The activity was correlated with the amount of different N-functions, and a correlation was found for the -NO x species. Interestingly, the amount of this species decreased radically during EC CO2R, which was coupled with the performance decrease. The observations were rationalized by the adsorption/desorption properties of the samples, while theoretical insights indicated a similarity between the EC and TC paths.

Non-redox doping boosts oxygen evolution electrocatalysis on hematite.

The oxygen evolution reaction (OER) is the major bottleneck to develop viable and cost-effective water electrolysis, a key process in the production of renewable fuels. Hematite, all iron α-Fe2O3, would be an ideal OER catalyst in alkaline media due to its abundance and easy processing. Despite its promising theoretical potential, it has demonstrated very poor OER activity under multiple experimental conditions, significantly worse than that of Co or Ni-based oxides. In the search for improving hematite performance, we have analysed the effect of doping with redox vs. non-redox active species (Ni or Zn). Our results indicate that Zn doping clearly outperforms Ni, commonly accepted as a preferred dopant. Zn-doped hematite exhibits catalytic performances close to the state-of-the-art for alkaline water splitting: reaching 10 mA cm-2 at just 350 mV overpotential (η) at pH 13, thus twenty times that of hematite. Such a catalytic enhancement can be traced back to a dramatic change in the reaction pathway. Incorporation of Ni, as previously suggested, decreases the energetic barrier for the OER on the available centres. In contrast, Zn facilitates the appearance of a dominant and faster alternative via a two-site reaction, where the four electron oxidation reaction starts on Fe, but is completed on Zn after thermodynamically favoured proton coupled electron transfer between adjacent metal centres. This unique behaviour is prompted by the non-redox character of Zn centres, which maintain the same charge during OER. Our results open an alternative role for dopants on oxide surfaces and provide a powerful approach for catalytic optimisation of oxides, including but not limited to highly preferred all-iron oxides.

Au/Pb Interface Allows the Methane Formation Pathway in Carbon Dioxide Electroreduction.

The electrochemical conversion of carbon dioxide (CO2) to high-value chemicals is an attractive approach to create an artificial carbon cycle. Tuning the activity and product selectivity while maintaining long-term stability, however, remains a significant challenge. Here, we study a series of Au-Pb bimetallic electrocatalysts with different Au/Pb interfaces, generating carbon monoxide (CO), formic acid (HCOOH), and methane (CH4) as CO2 reduction products. The formation of CH4 is significant because it has only been observed on very few Cu-free electrodes. The maximum CH4 formation rate of 0.33 mA cm-2 was achieved when the most Au/Pb interfaces were present. In situ Raman spectroelectrochemical studies confirmed the stability of the Pb native substoichiometric oxide under the reduction conditions on the Au-Pb catalyst, which seems to be a major contributor to CH4 formation. Density functional theory simulations showed that without Au, the reaction would get stuck on the COOH intermediate, and without O, the reaction would not evolve further than the CHOH intermediate. In addition, they confirmed that the Au/Pb bimetallic interface (together with the subsurface oxygen in the model) possesses a moderate binding strength for the key intermediates, which is indeed necessary for the CH4 pathway. Overall, this study demonstrates how bimetallic nanoparticles can be employed to overcome scaling relations in the CO2 reduction reaction.

Conformation-dependent conductance through a molecular break junction.

Ab initio molecular dynamics simulations have been performed of a gold-1,4-benzenedithiol (BDT)-gold nanojunction under mechanical stress. For three different pulling rates between 10 and 40 m s(-1), it is found that the nanowire always ruptures between the second and third Au atom from the thiol sulfur. Larger rupture forces and longer extensions are required at higher pulling rates and vice versa. The electrical conductance was calculated along a pulling trajectory using the DFT-NEGF method to study the effect of thermal and stress-induced structural changes on the electrical transport properties. While the mechanically induced stretching of the junction is seen to lower the time-averaged conductance, thermal conformational changes are capable of altering the conductance by one order of magnitude. No single geometric quantity could be identified as the main contributor to the conductance fluctuations. Small modulations, however, can be explained in terms of C=C double bond vibrations in the BDT molecule. The dependence of the conductance on different geometric variables has further been investigated systematically by performing constrained geometry optimizations along a number of angle and dihedral coordinates. The largest changes in the conductance are observed when the Au-S-C angle and the Au-S-C-C dihedral are simultaneously constrained.