Monitoring the Activation of Open Metal Sites in [Fe x M 3– x (μ 3 -O)] Cluster-Based Metal–Organic Frameworks by Single-Crystal X-ray Diffraction
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- State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China, Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States
- School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, P. R. China
- Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States
- Department of Materials Science & Engineering, University of Texas at Dallas, Richardson, Texas 75080, United States
- Chemical Sciences & Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
- State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China
- Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States, Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77842, United States
While trinuclear [FexM3–x(μ3-O)] cluster-based metal–organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [FexM3–x(μ3-O)]-based MOFs (PCN-250, M = Ni2+, Co2+, Zn2+, Mg2+) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe3+ sites was observed along with the transformation of Fe3+ coordination geometries from octahedron to square pyramid. Furthermore, the effect of divalent metals in heterometallic PCN-250 was studied for the purpose of reducing the activation temperature and increasing the number of open metal sites. The metal site structures were corroborated by X-ray absorption and infrared spectroscopy. These results will not only guide the pretreatment of [FexM3–x(μ3-O)]-based MOFs but also corroborate spectral and computational studies on these materials.
- Research Organization:
- Univ. of North Texas, Denton, TX (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- Grant/Contract Number:
- SC0019902; AC02-06CH11357
- OSTI ID:
- 2287711
- Alternate ID(s):
- OSTI ID: 2307856; OSTI ID: 2310903
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 145 Journal Issue: 8; ISSN 0002-7863
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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