To develop new OER catalysts to improve efficiency for renewable energy storage, observing oxygen intermediates is essential yet challenging. Herein, based on the electronic structure and chemical property of oxygen intermediates, we design a chemical method to probe oxygen intermediates at operating conditions of OER. Alcohols are demonstrated to be excellent probing molecules to detect oxygen intermediates over various types of catalysts at different reaction media. The general and feasible method could be widely used in every electrochemical laboratory.
The key step for rational catalyst design in heterogeneous electrocatalysis is to reveal the distinctive energy profile of redox reactions of a catalyst that give rise to specific activity. However, it is challenging to experimentally obtain the energetics of oxygen redox in oxygen electrocatalysis because of the liquid reaction environment. Here we develop a kinetic model that constructs a quantitative relation between the energy profile of oxygen redox and electrochemical kinetic fingerprints. The detailed study here demonstrates that the kinetic fingerprints observed from experiments can be well described by different energetics of oxygen redox. On the basis of the model, a feasible methodology is demonstrated to derive binding energies of the oxygen intermediates from electrochemical data. The surface property of different catalysts derived from our model well rationalizes the experimental trends and predicts potential directions for catalyst design.
Very few experimental data on the mechanical behaviour of unsaturated soils exists, particularly on the collapse behaviour under general stress states, because of the technical difficulties and time-consuming nature of measuring suction and deformation. This paper presents the results of a series of controlled-suction triaxial tests on the collapse behaviour of an unsaturated compacted clay with different initial dry densities and suctions. The collapse behaviour here includes deformation characteristics, such as volume changes, and hydraulic characteristics, such as saturation changes. It is found that the wetting-caused collapse mainly depends on the mean net stress and the initial density, and that the volume decrease reaches a maximum when the specimen is under the initial yielding mean net stress. It is also found that the soil-water characteristic curve in terms of suction and degree of saturation shifts upwards with increasing specimen density. The soil-water characteristic curve of a compacted soil mainly depends upon the current density, not directly upon the stress state. In addition, experimental data show that the collapse occurs mainly in an intermediate range of suction levels, which are neither very high nor very low, and that the wetting-caused volume decrease is accompanied by an increase in the degree of saturation.Key words: unsaturated soil, density, triaxial test, suction, collapse, degree of saturation.
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