Multiscale Manipulation of Functional Imperfection Atomic Interfaces

ConspectusThe imperfect atomic interfaces (IAIs) refer to the interface area with incomplete crystal structure formed by precise atomic-scale structure modulation. Unlike the traditional perfectly crystalline interfaces, IAIs show structural defects and symmetry breaking in their atomic arrangement and coordination environment. These characteristics can be achieved by accurately adjusting the spin state, orbital electron configuration, or charge distribution of the interface atom. Therefore, IAIs have become a promising strategy to overcome the inherent activity limitations of traditional catalysts. However, the inherent instability of IAIs in energy conversion and storage systems poses major challenges. Therefore, the precise construction and stability of IAIs with customized defect configurations are crucial for fundamental research and large-scale industrial catalysis.The construction of IAIs depends on multiscale structural regulation, mainly including strategies such as interface space limitation, template-guided assembly, and competitive chemical bond modulation. Among them, the spatial limitation effect aims to take advantage of the local constraints of the defect carriers, while the template-guided assembly aims to induce uneven charge distribution in the polymetallic system so as to regulate the electronic structure and surface energy state and promote the formation of IAIs. In particular, competitive chemical bond modulation through heteroatomic coordination will destroy the symmetry of metal centers, fine-tune the d-band center, and promote electron transfer, thus promoting the functional evolution of the interface. Collectively, these multiscale operations expose highly active unsaturated sites and optimize electron transfer pathways. At the same time, the combination of theoretical calculation and in situ characterization provides important guidance for accurate construction of the catalytic interface. In addition, it can also comprehensively analyze the intrinsic relationship between the catalyst structure and catalytic performance. Therefore, it is of great significance to promote future development to systematically summarize the research results in this field and deeply explore the application of high-efficiency industrial catalysts with an optimal interface atomic arrangement.Building on our 2016 discovery of symmetry breaking in wurtzite ZnSe nanocrystals, we realized that imperfections underlie the functional characteristics. In this Account, we systematically summarize the design and functionalization strategies of IAIs developed by our team around electronic degrees of freedom over the past decade and elucidate their unique roles in the synthesis of high-value chemicals and the catalytic transformation of small molecules. Through rational interfacial manipulation and performance design, IAIs provide a theoretical framework and feasible methods for the development of high-performance catalysts.