Gao Jinsen

Engineering metal–organic frameworks immobilize gold catalysts for highly efficient one-pot synthesis of propargylamines

Engineering metal–organic frameworks (MOF) for heterogeneous catalysts have been of extreme interest since they could bridge the gap between homogeneous and heterogeneous catalysis. We have designed and synthesized gold functionalized IRMOF-3 catalysts by post-covalent modification (PM) and one-pot (OP) synthesis methods. The gold functionalized IRMOF-3 catalysts provide an efficient, economic, and novel route for the one-pot synthesis of structurally divergent propargylamines via three component coupling of alkyne, amine, and aldehyde (A3) without any additives or an inert atmosphere. The catalysts were characterized in depth to understand their structure–property relationship. It was shown that the 4.6%Au/IRMOF-3 catalyst, prepared by the PM method, contains a fraction of cationic gold (Au3+/Au0 = 0.2), which shows much higher catalytic activity than that of 3.2% or 0.6%Au/IRMOF-3 prepared by OP method, although the former exhibits much lower crystallinity than the latter two catalysts. Notably, the catalytic activity of the Au/IRMOF-3 catalysts could be significantly enhanced at a moderate reaction temperature (150 °C). All the Au/IRMOF-3 catalysts can be easily recycled and used repetitively at least 5 times, especially the catalysts prepared by the OP method, which showed no drop in activity for the successive 5 uses. These features render the catalysts particularly attractive in the practice of propargylamines synthesis in an environmentally friendly manner.

Catalysis by metal–organic frameworks: proline and gold functionalized MOFs for the aldol and three-component coupling reactions

Translation of homogeneous catalysis into heterogeneous catalysis is a promising solution to green and sustainable development in the chemical industry. Recent research has shown that metal–organic frameworks (MOFs) could bridge the gap between homogeneous and heterogeneous catalysis. We successfully prepared for the first time a novel homochiral Zn-containing MOF referred to as CUP-1 based on the mixed linkers of 2-aminoterephthalic acid and L-lactic acid in a one-pot synthesis. The free NH2 group in the homochiral framework of CUP-1, similar to the well known achiral IRMOF-3, is potentially available for undergoing a variety of organic transformations, as demonstrated by choosing the auxiliary chiral L-proline and nano gold to functionalize MOFs with postsynthetic modification and one-pot synthesis strategies. IRMOF-3, CUP-1 and their functionalized samples were in-depth characterized by X-ray diffraction, N2 adsorption–desorption, optical and transmission electron microscopy, infrared spectroscopy, solid state nuclear magnetic resonance, thermogravimetric and differential thermal analysis, and temperature-programmed reduction. L-Proline functionalized IRMOF-3 shows fair to excellent enantioselectivity (up to 98%) in asymmetrical aldol reactions of aldehydes and acetone with higher turnover numbers and catalytic stabilities than the homogeneous counterpart. The gold functionalized CUP-1 catalysts are found to be highly active, stable and reusable for the three-component coupling reactions of aldehydes, alkynes and amines. This work provides general methods to functionalize MOFs with the active ligand and metal nanoparticles for fabrication of highly efficient MOF-based heterogeneous catalysts.

Development of solvent extraction separation process for clean oil production

Solvent extraction separation process is widely used in art of petrochemical engineering which provides a method for clean oil production. In this paper, the development of solvent extraction separation process has been described, such as aromatics extraction process, solvent extraction desulfurization process, and critical components oriented separation process. The advantage of solvent extraction separation in the process of oil refining was carefully discussed. Finally, a prospect about the development of solvent extraction separation process was introduced, considering the social problem of the conversion of olefin in the production of China standard VI gasoline and the adjustment of product mix of gasoline.

Molecular-refining oriented strategy of catalytic cracking for processing heavy oil

With the upgrading and transformation of Chinese refining industry, the cognition of oil fractions should be transformed from mixture level to molecular level and maximizing the value of any petroleum molecule entirely. Based on molecular composition, building block and structural characteristic, and revealing fluid catalytic cracking and hydrogenation reaction behaviors of “tractable” and “refractory” building blocks in the heavy oil molecule, the relationship between conversion of above two blocks and structure-performance of catalyst, molecular refining-oriented strategy for catalytic cracking is presented in this work. Aimed at breaking through the limitation of improving heavy oil conversion efficiently, synergistic process of fluid catalytic cracking and hydrogenation is established to realize “molecular reforming” of polyaromatics, and then “shape-selective cracking” of the naphthenic and alkyl-chain structure in heavy oil molecule will be achieved with feedstocks zoning-cracking and special catalyst. Moreover, the proper use of specific catalyst according to molecular composition in feedstock, aim of production, operating conditions is necessary. Under the guidance of molecular refining, which will provide a new technological approach for China to shift processing mode from deep conversion to high selectivity.

The application of UNIFAC group-contribution model in vapor-liquid equilibrium of heavy oil

A normal alkylane model molecular-UNIFAC model for prediction of the vapor-liquid equilibrium of heavy oil is introduced in this paper. There is only one sort of main group in this model, and the types and numbers of subgroups in the narrow fractions can be determined only according to one property factor. The errors of vapor-liquid equilibrium of Daqing crude oil between experimental values and the ones calculated by this model are satisfactorily within engineering accuracy. The application field of this model in vapor-liquid equilibrium of heavy oil is expected for expansion in the future.