Simultaneous removal of trace amounts of propyne and propadiene from propylene is an important but challenging industrial process. We report herein a class of microporous metal-organic frameworks (NKMOF-1-M) with exceptional water stability and remarkably high uptakes for both propyne and propadiene at low pressures. NKMOF-1-M separated a ternary propyne/propadiene/propylene (0.5 : 0.5 : 99.0) mixture with the highest reported selectivity for the production of polymer-grade propylene (99.996 %) at ambient temperature, as attributed to its strong binding affinity for propyne and propadiene over propylene. Moreover, we were able to visualize propyne and propadiene molecules in the single-crystal structure of NKMOF-1-M through a convenient approach under ambient conditions, which helped to precisely understand the binding sites and affinity for propyne and propadiene. These results provide important guidance on using ultramicroporous MOFs as physisorbent materials.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.201904312 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Specific Propyne Trapping Sites within a Robust MOF for Efficient Propyne/Propadiene Separation with Record Propadiene Productivity.
Adv Mater
March 2024
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua, 321004, China.
Separating propyne/propadiene to produce pure propadiene is extremely challenging in industry due to their similar properties. Herein, a novel ZrF anion pillared cage-like metal-organic framework (termed as CuZrF -TPA) for highly efficient propyne/propadiene separation is reported. It exhibits high propyne capacity (177.
View Article and Find Full Text PDFEfficient propyne/propadiene separation by microporous crystalline physiadsorbents.
Nat Commun
October 2021
College of Chemistry, Nankai University, Tianjin, 300071, People's Republic of China.
Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.
View Article and Find Full Text PDFIsomerization and Selective Hydrogenation of Propyne: Screening of Metal-Organic Frameworks Modified by Atomic Layer Deposition.
J Am Chem Soc
November 2020
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
Various metal oxide clusters upward of 8 atoms (Cu, Cd, Co, Fe, Ga, Mn, Mo, Ni, Sn, W, Zn, In, and Al) were incorporated into the pores of the metal-organic framework (MOF) NU-1000 via atomic layer deposition (ALD) and tested via high-throughput screening for catalytic isomerization and selective hydrogenation of propyne. Cu and Co were found to be the most active for propyne hydrogenation to propylene, and synergistic bimetallic combinations of Co and Zn, along with standalone Zn and Cd, were established as the most active for conversion to the isomerized product, propadiene. The combination of Co and Zn in NU-1000 diminished the propensity for full hydrogenation to propane as well as coking compared to its individual components.
View Article and Find Full Text PDFCalcium-Based Metal-Organic Framework for Simultaneous Capture of Trace Propyne and Propadiene from Propylene.
ACS Appl Mater Interfaces
April 2020
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China.
The simultaneous capture of trace propyne and propadiene from propylene is one of the important but energy demanding industrial processes because of their similar physicochemical properties as well as the ultralow concentration in the mixtures. Herein, a highly stable Ca-based MOF, constructed from an inexpensive precursor (CaCO) and rigid squaric acid, is capable of preferentially capturing trace propyne and propadiene with record-high uptake capacities of 2.44 and 2.
View Article and Find Full Text PDFDesign of a Highly Active Pd Catalyst with P,N Hemilabile Ligands for Alkoxycarbonylation of Alkynes and Allenes: A Density Functional Theory Study.
Chemistry
September 2019
EastCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST, United Kingdom.
In the palladium-catalysed methoxycarbonylation of technical propyne, the presence of propadiene poisons the hemilabile Pd(P,N) catalyst. According to density functional theory calculations (B3PW91-D3/PCM level), a highly stable π-allyl intermediate is the reason for this catalyst poisoning. Predicted regioselectivities suggest that at least 11 % of propadiene should yield this allyl intermediate, in which the reaction gets stalled under the turnover conditions due to an insurmountable methanolysis barrier of 25.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!