TY - JOUR
T1 - Surface Organometallic Chemistry on Zeolites: Synthesis of Group IV Metal Alkyls and Metal Hydrides on Hierarchical Mesoporous H-ZSM-5
AU - Gangwar, Manoj Kumar
AU - Pandey, Swechchha
AU - Parsapur, Rajesh Kumar
AU - Harb, Moussab
AU - Murugesan, Sathiyamoorthy
AU - Emwas, Abdul-Hamid M.
AU - Koseoglu, Omer Refa
AU - Hodgkins, Robert Peter
AU - Bendjeriou-Sedjerari, Anissa
AU - Rueping, Magnus
AU - Huang, Kuo-Wei
AU - Basset, Jean-Marie
N1 - KAUST Repository Item: Exported on 2022-09-26
Acknowledgements: This research work was supported by the King Abdullah University of Science and Technology (KAUST) in collaboration with the Catalyst Center of Excellence R&D Division, Research and Development Center, Saudi Aramco. The authors acknowledge the KAUST NMR Core Lab and analytical core lab (ACL) and the KAUST Supercomputing Laboratory for providing computational resources using the Supercomputer Shaheen II.
PY - 2022/9/21
Y1 - 2022/9/21
N2 - Surface organometallic chemistry (SOMC) has mainly been devoted to the reaction of organometallics with surfaces comprising highly divided and dehydroxylated oxides. The field has been extended to SOMC on metal nanoparticles. However, to the best of our knowledge, SOMC has not been extended to hierarchical fibrous zeolites, although zeolitic materials are a particular class of oxides. Zeolite catalysis is important in hydrocarbon industrial chemistry. However, having an optimum balance between the activity and selectivity of the zeolitic catalysts remains a major challenge in the field. The main difficultly is the plethora of surface sites, only some of which are catalytically active. Given that the acido–basic properties and porosity of zeolites are especially important to the refining and petrochemical industries, we decided to explore this rather unexplored area. Here, three novel well-defined single-site materials [(Np)3M@ZSM-5, M = Ti, Zr, and Hf] supported on a hierarchical mesoporous H-ZSM-5 material (1) are reported. They are prepared using the concepts and tools of SOMC. They are further converted to their corresponding metal hydride [(H)nM@ZSM-5, M = Ti, Zr, and Hf, (n = 1–2)] materials (5–7) through controlled hydrogenolysis of [(≡Si–O−)M(Np)3, M = Ti, Zr, and Hf] materials (2–4) under H2 (1 atm) at 150 °C for 16 h. All these surface catalysts are characterized by various spectroscopic techniques including Fourier transform infrared spectroscopy, elemental analysis, solid-state NMR spectroscopy, powder X-ray diffraction, Brunauer–Emmett–Teller surface area measurements, and scanning electron microscopy and high-resolution transmission electron microscopy analyses and are supported by density functional theory calculations. The catalytic activity of these well-defined single-site novel materials will be tested for the catalytic applications in petrochemistry for refinery processes such as hydrocracking of distillates from crude oil or intermediate refinery process streams to useful petroleum value-added products for the society.
AB - Surface organometallic chemistry (SOMC) has mainly been devoted to the reaction of organometallics with surfaces comprising highly divided and dehydroxylated oxides. The field has been extended to SOMC on metal nanoparticles. However, to the best of our knowledge, SOMC has not been extended to hierarchical fibrous zeolites, although zeolitic materials are a particular class of oxides. Zeolite catalysis is important in hydrocarbon industrial chemistry. However, having an optimum balance between the activity and selectivity of the zeolitic catalysts remains a major challenge in the field. The main difficultly is the plethora of surface sites, only some of which are catalytically active. Given that the acido–basic properties and porosity of zeolites are especially important to the refining and petrochemical industries, we decided to explore this rather unexplored area. Here, three novel well-defined single-site materials [(Np)3M@ZSM-5, M = Ti, Zr, and Hf] supported on a hierarchical mesoporous H-ZSM-5 material (1) are reported. They are prepared using the concepts and tools of SOMC. They are further converted to their corresponding metal hydride [(H)nM@ZSM-5, M = Ti, Zr, and Hf, (n = 1–2)] materials (5–7) through controlled hydrogenolysis of [(≡Si–O−)M(Np)3, M = Ti, Zr, and Hf] materials (2–4) under H2 (1 atm) at 150 °C for 16 h. All these surface catalysts are characterized by various spectroscopic techniques including Fourier transform infrared spectroscopy, elemental analysis, solid-state NMR spectroscopy, powder X-ray diffraction, Brunauer–Emmett–Teller surface area measurements, and scanning electron microscopy and high-resolution transmission electron microscopy analyses and are supported by density functional theory calculations. The catalytic activity of these well-defined single-site novel materials will be tested for the catalytic applications in petrochemistry for refinery processes such as hydrocracking of distillates from crude oil or intermediate refinery process streams to useful petroleum value-added products for the society.
UR - http://hdl.handle.net/10754/681654
UR - https://pubs.acs.org/doi/10.1021/acs.chemmater.2c02033
U2 - 10.1021/acs.chemmater.2c02033
DO - 10.1021/acs.chemmater.2c02033
M3 - Article
SN - 0897-4756
JO - Chemistry of Materials
JF - Chemistry of Materials
ER -