I. The Period of Germination and Exploration (1960s - 1991)
In 1967, when Akira Fujishima was a graduate student at the University of Tokyo, he discovered the "Honda - Fujishima Effect," which means that a single - crystal titanium dioxide electrode can electrolyze water under light irradiation. This discovery laid the foundation for photocatalytic technology and inspired the development of mesoporous titanium dioxide photocatalytic materials. In the following decades, he continued to conduct in - depth research on photocatalytic materials, revealing the role of the mesoporous structure in enhancing photocatalytic performance. From the end of the 20th century to the beginning of the 21st century, he published a series of related achievements, promoting the development of mesoporous photocatalytic materials.
Akira Fujishima
In 1990, Japanese scientists Yanagisawa et al. mixed the layered silicate material Kanemite with long - chain alkyltrimethylamine (ATMA) under alkaline conditions. Through ion - exchange, a three - dimensional mesoporous silica material with a narrow pore - size distribution was obtained. This strategy could produce pores with a maximum diameter of 4 nm, but it was limited to the Kanemite material. This was the earliest discovered mesoporous silica material.
Yanagisawa
During this period, scientists had already started to pay attention to some materials with mesoporous structural characteristics, but a systematic concept of mesoporous materials had not yet been formed. The research mainly focused on some naturally occurring substances or those with irregular mesoporous structures prepared by simple methods. The understanding of the relationship between the mesoporous structure and properties was relatively limited. Although the synthesis methods were simple and not very precise, these early attempts laid the foundation for the in - depth research on mesoporous materials.
2. The Rapid Development Period (1992 - the End of the 20th Century)
German scientist Thomas E. Müller attempted to prepare mesoporous materials using the sol - gel method. Although there were still some limitations in pore - size control, it provided an important reference method for subsequent research. He found that by adjusting the acidity and alkalinity of the sol and the reaction temperature, the initial formation of mesopores could be influenced to a certain extent.
Thomas E. Müller
Since the 1980s, German scientist Karl Klinkenberg has used adsorption isotherm measurement technology and molecular dynamics simulation to study the adsorption and diffusion properties of mesoporous materials. It was found that the mesoporous pore size, pore - channel shape, and surface properties significantly affect the adsorption and diffusion of gas molecules. Mesoporous materials with regular pore channels have a higher adsorption selectivity for small - molecule gases, providing a theoretical basis for the application of mesoporous materials in gas separation and storage.
Karl Klinkenberg
1Around 1990, the research team led by Zhao Dongyuan began to explore mesoporous materials. They deeply studied the principles of traditional synthesis methods and tried to prepare mesoporous silica materials with different pore - size distributions by changing the raw material ratios and reaction conditions. Their achievements provided basic data for the improvement of subsequent mesoporous material synthesis methods and preliminarily explored the influence laws of various factors in the synthesis process of mesoporous materials.
During this period, Li Can focused on the basic research on the application of mesoporous materials in the catalytic field. Through the analysis of the surface active sites of mesoporous materials, he proposed an assumption about the relationship between the distribution of surface active centers of mesoporous materials and catalytic activity, pointing out the direction for the subsequent research on the application of mesoporous materials in catalytic reactions and opening up in - depth exploration of mesoporous materials in the catalytic field.
In 1992, a research team from Mobil Corporation in the United States, including C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, etc., successfully synthesized new silicon - based molecular sieve materials such as MCM - 41 with regular pore - channel structures and pore sizes in the mesoporous range (2 - 50 nm) by using liquid - crystal templates formed by surfactants. They also formally proposed the concept of mesoporous materials. This achievement opened a new era in the research of mesoporous materials. This discovery broke through the limitations of the pore sizes of traditional microporous molecular sieves, opened up a brand - new research field of mesoporous materials, attracted great attention in academia and industry, and promoted the development of many fields such as materials science.
1In 1994, American scientist Stucky proposed the idea that inorganic and organic molecular - level species cooperate to form a three - dimensionally ordered structure. He believed that the interaction between poly - silicate anions and surfactant anions, with charge matching controlling the arrangement of surfactants. In the same year, he used double - chain - structured surfactants to synthesize a series of mesoporous materials containing cage structures at room temperature or lower temperatures in a short time under acidic conditions, further enriching the types and synthesis methods of mesoporous materials.
Stucky
Around 1995, the research team led by Yang Qihua innovatively introduced microwave radiation technology into the synthesis of mesoporous materials. When synthesizing mesoporous silica, by using the characteristics of rapid and uniform heating of microwaves, the synthesis cycle was shortened, and the prepared mesoporous materials had more regular pore channels and larger specific surface areas. This method improved the synthesis efficiency and quality of mesoporous materials and promoted the development of mesoporous material synthesis technology.
Yang Qihua
Japanese scientist Masakazu Anpo: Since the 1990s, he has been committed to the interdisciplinary research of photocatalysis and mesoporous materials. Around 1995, through a unique preparation process, he highly dispersed active metal nanoparticles in mesoporous titanium dioxide materials, significantly improving the photocatalytic reaction efficiency. For example, under visible - light driving, the degradation rate of organic pollutants by mesoporous titanium dioxide loaded with platinum nanoparticles was several times higher than that of ordinary titanium dioxide catalysts, providing new ideas for the development of photocatalytic technology in the field of environmental purification. At the same time, he continued to conduct in - depth research on the photogenerated carrier transport mechanism of mesoporous materials and published a series of theoretical research results in the following years, laying a theoretical foundation for optimizing photocatalytic performance.
Masakazu Anpo
In 1997, American scientist Brinker used an acidic alcohol solution as the reaction medium and the evaporation - induced self - assembly (EISA) process to successfully synthesize high - quality silica mesoporous films. This achievement opened up new paths for the application of mesoporous materials in membrane separation and catalysis, microelectronics, sensors, optoelectronic functional devices, and other fields, expanding the application scope of mesoporous materials.
In 1998, the team of Gallen D. Stucky at the University of California, Santa Barbara, brought another milestone breakthrough in porous materials. American scientist Zhao first synthesized large - pore SBA - 15 mesoporous materials using non - ionic triblock copolymers. SBA - 15 not only has a larger pore size (5 - 30 nm), but also a thicker pore wall (3.1 - 6.4 nm), a higher pore volume, and better hydrothermal stability, becoming one of the classic materials in mesoporous materials.
During the period from 1997 to 1999, the research team led by Tian He was committed to the functionalization of mesoporous materials. They modified organic molecules with fluorescence - emitting properties onto the surface of mesoporous materials by chemical grafting, preparing mesoporous composite materials with fluorescence - sensing functions. This material can be used to detect specific metal ions and biomolecules, expanding the application scope of mesoporous materials in the sensing field.
Tian He
