Search

The photo-assisted CO2 reduction cell uses a translucent thin film electrode to allow light irradiation onto a photo-responsive catalyst during CO2 electrolysis. Gaseous CO2 turned into CO directly on Au nanoparticles deposited on Ag nanowires.

ConspectusSingle-atom catalysts (SACs), in which surface metal atoms are isolated on the surface of a support, have received a tremendous amount of attention recently because this structure would utilize precious metals fully, without occluding atoms inside nanoparticles, and enable unique surface reactions which typical nanoparticle catalysts cannot induce. Various synthesis methods and characterization techniques have been reported that yield enhanced activity and selectivity. The single-atom structures were realized on various supports such as metal oxide/carbide/nitride, porous materials derived from zeolite or metal-organic frameworks, and carbon-based materials. Additionally, when the metal atoms are isolated on other metal nanoparticles, this material is denoted as a single-atom alloy (SAA). The single-atom structure, however, cannot catalyze the surface reaction that necessitates ensemble sites, where several metal atoms are located nearby. Very recently, ensemble catalysts, in which all of the metal atoms are exposed at the surface with neighboring metal atoms, have been reported, overcoming the limitation of single-atom catalysts. We call all of these materials (SACs, SAAs, and ensemble catalyst) heterogeneous atomic catalysts, indicating that the surface metal atomic structure is intentionally controlled. To use these atomic catalysts for practical applications, high durability should be guaranteed, which has received relatively less attention.In this Account, we discuss recent examples of heterogeneous atomic catalysts with high durability. Structural stability, indicating whether the surface atomic structure is thermodynamically stable, should be carefully considered. Typically, metal atoms are immobilized on a highly defective support, stabilizing both the metal atom and the support. The surface metal atoms might become destabilized upon the adsorption of chemical intermediates. This transient behavior should be carefully monitored; density functional theory (DFT) calculations are particularly useful in estimating this stability. Aside from structural stability, the catalyst performance can be degraded significantly by poisoning with impurities. If the single-atom sites are susceptible to impurities with stronger adsorption, the surface reaction would not occur efficiently, leading to a decrease in activity without structure degradation. A long-term durability test should be performed for target reactions. Heterogeneous atomic catalysts have been used for various electrochemical, photocatalytic, and thermal reactions. Although electricity, light, and heat are just different forms of energy, the specific conditions which the catalyst should satisfy are different. Whereas precious metal atoms are mostly used as surface-active sites, the properties of the support are different depending on the type of reaction. For example, the support should have high conductivity for electrochemical reactions, it should be able to absorb light for photocatalytic reactions, and it should be durable at high temperature in the presence of steam for thermal reactions. Highly durable heterogeneous atomic catalysts are certainly possible with a great potential for practical applications. These new catalysts can accelerate the current paradigm shift toward more sustainable chemical production.

Herein, we introduce a new concept of photo-assisted electrochemical CO

The current chemical industry is encountering an urgent need for CO2 reduction. Producing CO and H2 from CO2 and H2O by using renewable electricity might be a feasible solution to produce “carbon-neutral” chemicals and fuels. Developing easily scalable catalysts is key to this. In this issue of Chem Catalysis, Hahn and co-workers show that Zn–Cu catalysts enable efficient CO2 electro-reduction.

Adsorption behavior of surfactants to rock surfaces is an important issue in oil recovery, especially in the process of surfactant flooding. The surfactant loss through adsorption to rock surfaces makes such process economically less feasible. Here, we investigated the adsorption behavior of anionic surfactants (alcohol alkoxy sulfate, AAS) onto silica with quartz crystal microbalance with dissipation monitoring. The results demonstrated that the surfactant adsorption followed the Langmuir adsorption isotherm. Up to solution pH 10, surfactant adsorption slightly increased with increasing pH. The higher pH leads to more anionic surface sites for binding with an anionic surfactant with the help of a calcium cation bridging. The amount of anionic surfactant binding also increases with increasing calcium ion concentration up to 50 mM. It was found that sodium ions were able to exchange calcium ions near the silica surface, which would reduce the affinity for surfactant adsorption. The effect of the polyanion polystyrene sulfonate (PSS) on the anionic AAS adsorption was investigated to learn the possible competitive adsorptions. Indeed, this was found. Upon addition of 50 ppm PSS to a 0.05 wt% AAS containing solution, the adsorption of AAS was reduced by about 85 %. The obtained results show the interplay of different interacting species affecting the overall degree of anionic surfactant adsorption to silica surfaces. Optimal tuning of the process conditions according to these results will contribute to a more efficient use of anionic surfactants in enhanced oil recovery.

The ability to study the adsorption behavior of surfactant species is of interest in the field of enhanced oil recovery (EOR), especially pertaining to alkaline surfactant flooding. In this work, a calcite model mineral surface was obtained by electrochemically assisted deposition. This was achieved via the nitrate and/or oxygen electroreduction reactions in the presence of bicarbonate and calcium ions, by which controlled deposition of calcium carbonate was effected on a quartz crystal microbalance sensor covered with an electroactive gold layer. In addition, the effect of pH and Ca 2+ concentration on the effective surface charge of the deposited calcite particles was mapped. Calcite-modified sensors were used in conjunction with a quartz crystal microbalance with dissipation monitoring to study the effect of Na + and Ca 2+ concentration on the adsorption behavior of an anionic alcohol alkoxy sulfate (AAS) surfactant. Adsorption of the surfactant remained indifferent to ionic concentrations around the isoelectric point of calcite. Still, electrostatics play an important role in this regard, and it is essential to decrease the Ca 2+ concentration sufficiently to minimize AAS adsorption. The results from this study show that a relatively simple method allows for the controlled deposition of a model rock surface, and there is ample opportunity to extend the work to other metal oxide surface types, including complex mixtures as can be obtained by co-deposition. Furthermore, the findings from these adsorption studies aid in the determination of optimal flooding parameters, with the aim to increase the efficiency and efficacy of EOR.