Surface Charge Effects for the Hydrogen Evolution Reaction on Pt(111) Using a Modified Grand-Canonical Potential Kinetics Method

Surface charges of catalysts have important influences on the thermodynamics and kinetics of electrochemical reactions. Herein, we develop a modified version of the grand-canonical potential kinetics (GCP-K) method based on density functional theory (DFT) calculations to explore the effect of surface charges on reaction thermodynamics and kinetics. Using the hydrogen evolution reaction (HER) on the Pt(111) surface as an example, we show how to track the change of surface charge in a reaction and how to analyze its influence on the kinetics. Grand-canonical calculations demonstrate that the optimum hydrogen adsorption energy on Pt under the standard hydrogen electrode condition (SHE) is around -0.2 eV, rather than 0 eV established under the canonical ensemble, due to the high density of surface negative charges. By separating the surface charges that can freely exchange with the external electron reservoir, we obtain a Tafel barrier that is in good agreement with the experimental result. During the Tafel reaction, the net electron inflow into the catalyst leads to a stabilization of canonical energy and a destabilization of the charge-dependent grand-canonical component. This study provides a practical method for obtaining accurate grand-canonical reaction energetics and analyzing the surface charge induced changes

An embeddable spherical smart aggregate for monitoring concrete hydration in very early age based on electromechanical impedance method

In this paper, a new embeddable spherical smart aggregate (SSA) was utilized to monitor concrete curing in very early age. Overcoming the limitation of the existing PZT-patch-based transducers, the SSA provides vital changing information in all directions of host structure. To verify the advantage of SSA in structural health monitoring (SHM), the sensitivities of SSA and smart aggregate (SA) in monitoring concrete cube deformation and stiffness variation were analyzed and compared by numerical simulation. The feasibility of SSA in monitoring the concrete hydration process was studied by experiments utilizing electromechanical impedance (EMI) technique. At last, four SSAs were embedded in a concrete column to study the practicality of SSA in monitoring the concrete curing process in very early age. The EMI signatures and the root mean square deviation (RMSD) values of the collected information from SSAs were analyzed. The results illustrate that the SSA is more sensitive than SA in monitoring the concrete deformation and stiffness variation. The data measured by SSA in monitoring the concrete hydration process fluctuates more obviously than the data recorded by SA. The new spherical transducer can effectively and reliably monitor the concrete hydration process

Damage evaluation of concrete column under impact load using a piezoelectric-based EMI technique

One of the major causes of damage to column-supported concrete structures, such as bridges and highways, are collisions from moving vehicles, such as cars and ships. It is essential to quantify the collision damage of the column so that appropriate actions can be taken to prevent catastrophic events. A widely used method to assess structural damage is through the root-mean-square deviation (RMSD) damage index established by the collected data; however, the RMSD index does not truly provide quantitative information about the structure. Conversely, the damage volume ratio that can only be obtained via simulation provides better detail about the level of damage in a structure. Furthermore, as simulation can also provide the RMSD index relating to that particular damage volume ratio, the empirically obtained RMSD index can thus be related to the structural damage degree through comparison of the empirically obtained RMSD index to numerically-obtained RMSD. Thus, this paper presents a novel method in which the impact-induced damage to a structure is simulated in order to obtain the relationship between the damage volume ratio to the RMSD index, and the relationship can be used to predict the true damage degree by comparison to the empirical RMSD index. In this paper, the collision damage of a bridge column by moving vehicles was simulated by using a concrete beam model subjected to continuous impact loadings by a freefalling steel ball. The variation in admittance signals measured by the surface attached lead zirconate titanate (PZT) patches was used to establish the RMSD index. The results demonstrate that the RMSD index and the damage ratio of concrete have a linear relationship for the particular simulation model

Surface Charge Effects for the Hydrogen Evolution Reaction on Pt(111) Using a Modified Grand-Canonical Potential Kinetics Method

Surface charges of catalysts have important influences on the thermodynamics and kinetics of electrochemical reactions. Herein, we develop a modified version of the grand-canonical potential kinetics (GCP-K) method based on density functional theory (DFT) calculations to explore the effect of surface charges on reaction thermodynamics and kinetics. Using the hydrogen evolution reaction (HER) on the Pt(111) surface as an example, we show how to track the change of surface charge in a reaction and how to analyze its influence on the kinetics. Grand-canonical calculations demonstrate that the optimum hydrogen adsorption energy on Pt under the standard hydrogen electrode condition (SHE) is around −0.2 eV, rather than 0 eV established under the canonical ensemble, due to the high density of surface negative charges. By separating the surface charges that can freely exchange with the external electron reservoir, we obtain a Tafel barrier that is in good agreement with the experimental result. During the Tafel reaction, the net electron inflow into the catalyst leads to a stabilization of canonical energy and a destabilization of the charge-dependent grand-canonical component. This study provides a practical method for obtaining accurate grand-canonical reaction energetics and analyzing the surface charge induced changes