Using the combination of Concentrated solar power (CSP) and calcium looping (CaL) technology is an effective way to solve the problems of intermittent solar energy, but calcium-based materials are prone to sintering due to the densification of the surface structure during high-temperature cycling. In this study, the enhancement mechanism of Co and Cr doping in terms of the adsorption properties of CaO was investigated by Density Functional Theory (DFT) calculations. The results indicate that Co and Cr doping shortens the bond length between metal and oxygen atoms, enhances covalent bonding interactions, and reduces the oxygen vacancy formation energy. Meanwhile, the O²⁻ diffusion energy barrier decreased from 4.606 eV for CaO to 3.648 eV for Co-CaO and 2.854 eV for Cr-CaO, which promoted CO₂ adsorption kinetics. The CO₂ adsorption energy was significantly increased in terms of the absolute value, and a partial density of states (PDOS) analysis indicated that doping enhanced the C-O orbital hybridization strength. In addition, Ca₄O₄ cluster adsorption calculations indicated that the formation of stronger metal–oxygen bonds on the doped surface effectively inhibited particle migration and sintering. This work reveals the mechanisms of transition metal doping in optimizing the electronic structure of CaO and enhancing CO₂ adsorption performance and sintering resistance, which provides a theoretical basis for the design of efficient calcium-based sorbents.

In this paper, the enhancement of thermochemical energy storage by alkali metal chloride salts-doped Ca-based sorbents is revealed by experiments and DFT calculations. The results indicate that NaCl and KCl doping increases the reaction rate and cycle stability. Compared to CaO, the conversion of NaCl-CaO and KCl-CaO after one cycle is increased by 59.1% and 61.9%, respectively. This enhancement originates from the oxygen vacancies generated by Na₂O and K₂O and the significantly increased surface area by CaCl₂ as well as the sintering delay. The synergistic effect between Na₂O, K₂O, and CaCl₂ increases the reaction rate of calcium-based materials. Meanwhile, the penetration of low-viscosity molten NaCl and KCl into the calcium-based materials successfully segregates the CaO grains and allows the calcium-based material to maintain the porous structure after 80 cycles, thus exhibiting a high effective conversion rate. In addition, the KCl-CaO composites show the best combined performance in terms of effective conversion and averaged thermal energy density. This work paves the way for the application of chloride salts-doped calcium-based materials.

The Ni/Al₂O₃ interface bears the load transfer and energy dissipation, which determines the service performance of the composite materials. In this study, three distinct vacancy-defect-modified interface models (D₁, D₂, and D₃, corresponding to vacancies in the first, second, and third layers of the Ni substrate surface, respectively) were constructed to systematically investigate the regulatory mechanism of vacancies on interfacial stability. The underlying mechanism of vacancy-enhanced interfacial stability was elucidated from both atomic-scale structural and electronic property perspectives. The results demonstrate that the D₁, D₂, and D₃ structures increase the adhesion work of the interface by 2.0%, 6.7%, and 0.3%, respectively. This enhancement effect mainly stems from vacancy-induced atomic relaxation at the interface, which optimizes the equilibrium interfacial spacing and effectively releases residual strain energy. Further electronic structure analysis reveals a notable increase in charge density at the vacancy-modified interface (particularly in the D₂ structure), indicating that vacancy defects promote charge transfer and redistribution by altering local electron distribution. More importantly, the bonding strength of the interface exhibits a positive correlation with electron orbital hybridization intensity, where stronger s-, p-, and d-orbit hybridization directly leads to a more stable interface. These findings provide atomic- and electronic-scale insights into the mechanistic role of vacancy defects in governing bonding at the Ni/Al₂O₃ interface.

Although concentrated solar power (CSP) coupled with calcium looping (CaL) offers a promising avenue for efficient thermal chemical energy storage, calcium-based sorbents suffer from accelerated structural degradation and decreased CO₂ capture capacity during multiple cycles. This study used Density Functional Theory (DFT) calculations to investigate the mechanism by which Mg and Ni doping improves the adsorption/desorption performance of CaO. The DFT results indicate that Mg and Ni doping can effectively reduce the formation energy of oxygen vacancies on the CaO surface. Mg–Ni co-doping exhibits a significant synergistic effect, with the formation energy of oxygen vacancies reduced to 5.072 eV. Meanwhile, the O²⁻ diffusion energy barrier in the co-doped system was reduced to 2.692 eV, significantly improving the ion transport efficiency. In terms of CO₂ adsorption, Mg and Ni co-doping enhances the interaction between surface O atoms and CO₂, increasing the adsorption energy to −1.703 eV and forming a more stable CO₃²⁻ structure. For the desorption process, Mg and Ni co-doping restructured the CaCO₃ surface structure, reducing the CO₂ desorption energy barrier to 3.922 eV and significantly promoting carbonate decomposition. This work reveals, at the molecular level, how Mg and Ni doping optimizes adsorption–desorption in calcium-based materials, providing theoretical guidance for designing high-performance sorbents.

The metal-based/ceramic interface structure is a key research focus in science, and addressing the stability of the interface has significant scientific importance as well as economic value. In this project, the work of adhesion, heat of segregation, electronic structure, charge density, and density of states for doped-M (M = Ti, Mg, Cu, Zn, Si, Mn, or Al) Ni (111)/Al₂O₃ (0001) interface structures are studied using first-principle calculation methods. The calculation results demonstrate that doping Ti and Mg can increase the bonding strength of the Ni–Al₂O₃ interface by factors of 3.4 and 1.5, respectively. However, other dopants, such as Si, Mn, and Al, have a negative effect on the bonding of the Ni–Al₂O₃ interface. As a result, the alloying elements may be beneficial to the bonding of the Ni–Al₂O₃ interface, but they may also play an opposite role. Moreover, the Ti and Mg dopants segregate from the matrix and move to the middle position of the Ni–Al₂O₃ interface during relaxation, while other dopants exhibit a slight segregation and solid solution in the matrix. Most remarkably, the segregation behavior of Ti and Mg induced electron transfer to the middle of the interface, thereby increasing the charge density of the Ni–Al₂O₃ interface. For the optimal doped-Ti Ni–Al₂O₃ interface, bonds of Ti–O and Ti–Ni are found, which indicates that the dopant Ti generates stable compounds in the interface region, acting as a stabilizer for the interface. Consequently, selecting Ti as an additive in the fabrication of metal-based ceramic Ni–Al₂O₃ composites will contribute to prolonging the service lifetime of the composite.

Here, the effects of Fe vacancy defects on the bonding properties of γ-Fe (111)/α-Al₂O₃ (0001) interfaces are studied in depth at the atomic and electronic levels using first-principles calculations. The first (V₁), second (V₂), third (V₃), and fourth (V₄) layers of vacancy structures within the Fe substrate, as well as the ideal Fe/Al₂O₃ interface structure, are proposed and contrasted, including their thermodynamic parameters and atomic/electronic properties. The results demonstrate that the presence of vacancies in the first atomic layer of Fe deteriorates the interfacial bonding strength, whereas vacancies situated in the third layer enhance the interfacial bonding strength. The effect of vacancy beyond the third layer becomes negligible. This occurs mainly because vacancy defects at different positions induce the relaxation behavior of atoms, resulting in bond-breaking and bond-forming reactions at the interface. Following that, the formation process of vacancies can cause the transfer and rearrangement of the electrons at the interface. This process leads to significant changes in the charge concentration of the interfaces, where V₃ is the largest and V₁ is the smallest, indicating that the greater the charge concentration, the stronger the bonding strength of the interface. Furthermore, it is discovered that vacancy defects can induce new electronic orbital hybridization between Fe and O at the interface, which is the fundamental reason for changes in the properties of the interface. Interestingly, it is also found that more electronic orbital hybridization will strengthen the bonding performance of the interface. It seems, then, that the existence of vacancy defects not only changes the electronic environment of the Fe/Al₂O₃ interface but also directly affects the bonding properties of the interface.