Construction of a Unique Structure of Ru Sites in the RuP Structure for Propane Dehydrogenation

Abstract

It is an important task to develop low-cost and anticoking catalysts for the propane dehydrogenation (PDH) reaction. In this work, the P element is introduced to the Ru-based catalyst to obtain Ru sites with a unique structure and the obtained Ru x P y (x/y = 2:1, 1:1, 1:2) catalysts are then employed in PDH. Density functional theory (DFT) results show that the addition of P leads to the formation of separated Ru sites and the adjustment of the valance band state of Ru. The upward shift of the d-band center leads to a reduction of the reaction energy barrier for dehydrogenation of propane and an enhancement of catalytic activity. The analysis of the competition between propylene deep dehydrogenation and propylene desorption for each catalyst shows that desorption of propylene is preferred on the RuP(112) surface. Considering both catalytic activity and propylene selectivity, the RuP catalyst is potential for the propane dehydrogenation reaction. On the RuP surface, the PDH reaction proceeds by the dehydrogenation of the H atom on the methylene group (isopropyl pathway), thus restraining the deep dehydrogenation of propylene. The Ru x P y catalysts are also synthesized in experiments, and PDH evaluation shows that the RuP structure is a remarkable PDH catalyst with a stable structure, anticoking ability, and low cost.

Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook

“…The promotion of Ru catalyst with phosphorous led to the formation of the separate Ru clusters and lower energy barrier for propane DDH: the synthesis of RuP active sites supported on silica sharply increased the catalyst stability. 72…”

“…The promotion of Ru catalyst with phosphorous led to the formation of the separate Ru clusters and lower energy barrier for propane DDH: the synthesis of RuP active sites supported on silica sharply increased the catalyst stability. 72 Second, there is an increasing focus on propane DDH catalysts without precious metals. The most popular systems are Mo, Ti, Cr, V, Zn, Ga, Sn or Co, which are used without or with promoters.…”

Transition Metal Phosphide Nanoarchitectonics for Versatile Organic Catalysis

“…In another report, Yang et al. [ 331 ] also prepared RuP‐based catalyst for propane dehydrogenation with different ratios of Ru x P y ( x / y = 2:1, 1:1, 1:2). The reaction was carried out in the presence of catalyst and mixture of gasses (1.25% hydrogen, 1.25% propane, and balanced nitrogen) under atmosphere pressure at 600 °C.…”

Advanced design and development of catalysts in propane dehydrogenation

“…In addition, a wide variety of non-noble metal materials such as Fe, Co, Ru, Rh, Zn, V, Ga, W, and Zr-based dehydrogenation catalysts also have been intensively explored, which exhibit excellent performance serving as promising candidates as catalysts for PDH, but still many problems are unsolved. 13–21…”

“…In addition, a wide variety of nonnoble metal materials such as Fe, Co, Ru, Rh, Zn, V, Ga, W, and Zr-based dehydrogenation catalysts also have been intensively explored, which exhibit excellent performance serving as promising candidates as catalysts for PDH, but still many problems are unsolved. [13][14][15][16][17][18][19][20][21] In this review, a comprehensive overview of the research progress and future prospects for PDH catalysts will be given. Firstly, the recent advances in Pt-based, CrO x -based and other non-noble metal based PDH catalysis are summarized in categories.…”