Dalian Dye Institute realizes high selectivity hydrogenation of carbon dioxide to synthesize methanol catalyst technology

Recently, Li Can, a researcher of the State Key Laboratory of Catalysis of Dalian Institute of Chemical Physics, Chinese Academy of Sciences, and a member of the Chinese Academy of Sciences, Li Can, have developed a bimetallic solid solution oxide catalyst to achieve high selectivity, high stability, and hydrogenation to methanol synthesis. Related research results Posted in Science Advances.

The emission reduction of CO2 has aroused widespread concern in the international community. The use of renewable energies such as solar energy to produce CO2 and other fuels and chemicals through photocatalysis, photoelectrocatalysis or electrolysis of water to produce CO2 and reduce emissions The most viable strategy for the sustainable use of resources. From the perspective of scientific understanding of natural photosynthesis, the hydrogenation of CO2 to methanol, which mimics the efficacy of dark reactions in photosynthesis, is an important approach for making liquid fuels from solar energy. Professor Olah of the University of Southern California, USA, has forwardly proposed the concept of "methanol economy" for converting CO2. The Li Can team emphasized the use of renewable energy to achieve the carbon resource utilization of CO2. Methanol is an important platform chemical molecule. Methanol can be used to produce olefins, aromatics and other bulk chemicals as well as gasoline, diesel, and can also be directly used as fuel or fuel additives. At present, the bottleneck of realizing the industrialization of CO2 hydrogenation and methanol production is the development of efficient solar energy and renewable energy hydrogen generation technologies and the catalytic technology of highly selective and highly active CO2 hydrogenation to methanol production.

Li Can's team is dedicated to the research of solar photocatalysis, photoelectrocatalysis and hydrogen production from electrolyzed water. At the same time, research on CO2+H2 has been carried out to realize the artificial light synthesis of solar fuel strategy. In the process of CO2+H2, increasing the methanol selectivity is the biggest challenge for hydroconversion of CO2. For example, when Cu-based catalysts used for syngas to methanol are used in CO2 hydrogenation to produce methanol, the outstanding problem is low methanol selectivity (50 ~ 60%). In addition, water generated by the reaction accelerates the deactivation of the Cu-based catalyst. This work has developed a bimetallic solid solution oxide catalyst, ZnO-ZrO2, which is different from the traditional metal catalysts. When the CO2 conversion per pass is more than 10%, the methanol selectivity remains at about 90%, which is the most comprehensive level in the current research of similar type. good result. Studies have shown that the solid solution structure characteristic of the catalyst provides a dual active center reaction site—Zn and Zr, in which H2 and CO2 are activated at the Zn position and at the adjacent Zr position of the atom, respectively, and show the CO2 hydrogenation process. Synergistically, methanol can be produced with high selectivity. In situ infrared-mass spectrometry isotope experiments and DFT theoretical calculations show that surface HCOO* and H3CO* are the main reactive intermediate species in the reaction. This work has opened up new ways for hydrogenation of CO2 to methanol.

In addition, the catalyst has been continuously operated for 500 hours without deactivation, has excellent sintering stability and a certain ability to resist sulfur, and shows a promising industrial application prospect. Traditional methanol synthesis of Cu-based catalysts requires the feed gas to contain less than 0.5 ppm of sulfur, and the catalyst's ability to resist sulfur reduces the cost of raw gas purification and represents a potential advantage in industrial applications. The above related achievements have declared 4 Chinese invention patents and 1 international PCT patent.

The research work was supported by the Chinese Academy of Sciences' strategic pilot technology project, the National Natural Science Foundation of China, the Dalian Institute of Chemical Subsidiary and the Fundamental Research Fund for the new technology of coal conversion and coal oil generation, and the postdoctoral fund.

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