Design of Pd–Zn Bimetal MOF Nanosheets and MOF-Derived Pd3.9Zn6.1/CNS Catalyst for Selective Hydrogenation of Acetylene under Simulated Front-End Conditions

Abstract

Novel zinc–palladium–porphyrin bimetal metal–organic framework (MOF) nanosheets were directly synthesized by coordination chelation between Zn(II) and Pd(II) tetra(4-carboxyphenyl)porphin (TCPP(Pd)) using a solvothermal method. Furthermore, a serial of carbon nanosheets supported Pd–Zn intermetallics (Pd–Zn-ins/CNS) with different Pd: Zn atomic ratios were obtained by one-step carbonization under different temperature using the prepared Zn-TCPP(Pd) MOF nanosheets as precursor. In the carbonization process, Pd–Zn-ins went through the transformation from PdZn (650 °C) to Pd3.9Zn6.1 (~950 °C) then to Pd3.9Zn6.1/Pd (1000 °C) with the temperature increasing. The synthesized Pd–Zn-ins/CNS were further employed as catalysts for selective hydrogenation of acetylene. Pd3.9Zn6.1 showed the best catalytic performance compared with other Pd–Zn intermetallic forms.

Cu-Metalated Porphyrin-Based MOFs Coupled with Anatase as Photocatalysts for CO2 Reduction: The Effect of Metalation Proportion

“…Interestingly, the peak centered at ca. 1683 cm −1 that corresponds to the C O stretching vibration from the carboxyl functional groups greatly weakened in the MOF spectra when compared with the H2TCPP, suggesting the successful coordination of the porphyrin's -COOH groups with Zr to form the MOF crystal [41,42]. Most importantly, the peak centered at ca.…”

Synthetic Strategies of Supported Pd-Based Bimetallic Catalysts for Selective Semi-Hydrogenation of Acetylene: A Review and Perspectives

“…The keys to success in preparing samples by this method are that the screened support precursors generally need to contain N, S, P, etc., in easy coordination with metal atoms, so as to anchor and immobilize the metal particles formed during the thermal pyrolysis process, and avoid aggregation, as well as possess a specific surface area and appropriate pore structure after pyrolysis. Since the discovery of metal–organic frameworks (MOFs) and covalent organic framework (COFs) materials, the fabrication of MOFs- [ 150 , 151 , 152 , 153 ] and COF- [ 63 , 154 , 155 ] derived carbon supported metal nanoparticles has received more and more attention, due to their abundant intrinsic molecular metal sites, ordered pore structures, large surface areas, as well as chemical tunability. MOF- and COF-derived carbon materials have a porous structure and a high surface area, as well as abundant nitrogen atoms, which can anchor metal atoms.…”

“…MOF- and COF-derived carbon materials have a porous structure and a high surface area, as well as abundant nitrogen atoms, which can anchor metal atoms. Our group [ 153 ] reported a series of carbon nanosheet-supported Pd–Zn inter-metallics (Pd–Zn-ins/CNS) prepared by a one-step thermal pyrolysis method with new palladium–zinc MOFs for selective hydrogenation of acetylene under simulated front-end conditions. Sarkar et al [ 156 ] impregnated a methanol solution of palladium nitrate into Cu-BTC-MOFs (HKUST-1) as the catalyst precursor, and then carbonized it at 450 °C under N 2 atmosphere for 3 h to obtain the targeted catalyst.…”