TY - JOUR
T1 - Electronic and catalytic engineering in two-dimensional vdW metal-organic frameworks through alloying
AU - Shen, Yuxia
AU - Shan, Bohan
AU - Muhich, Christopher
AU - Gupta, Srishti
AU - Li, Han
AU - Hays, Patrick
AU - Qin, Ying
AU - Vijay, Shiljashree
AU - Winarta, Joseph
AU - Mu, Bin
AU - Tongay, Sefaattin
N1 - Funding Information:
S.T. acknowledges support from Grant No. DOE-SC0020653, NSF DMR Grant No. 1552220, DMR Grant Nos. 1904716 and 1955889, and NSF CMMI Grant Nos. 1825594 and 1933214. S.T. also acknowledges support from Applied Materials Inc. C.L.M. and S.G. acknowledge support from the National Science Foundation Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (NEWT; Grant No. ERC-1449500). Calculations were conducted in part on the Extreme Science and Engineering Discovery Environment (XSEDE), supported by NSF (Grant No. ACI-1548562), through the Bridges high-performance computer at the Pittsburgh Supercomputing Center (allocation ECD190001). S.T also acknowledges NSF ECCS 2052527 and DMR 2111812 for spectroscopy and electrical characterizations.
Publisher Copyright:
© 2021 Author(s).
PY - 2021/9/1
Y1 - 2021/9/1
N2 - Bimetallic metal-organic framework (MOFs) alloys, in which heterogeneous metal clusters are incorporated into their backbone, are capable of highly selective separations and catalysis. Due to limitations in our fundamental understanding of their alloying, however, established methods result in phase-separated or amorphous two-dimensional (2D) MOFs or lack precise control over alloy ratios. Here, our results demonstrate 2D MOF alloys where metal cation ratios (M1 and M2) in M1xM21-xBDC (M1 or M2= Zn, Cu, Ni, Co, Fe, Mn) can be engineered on demand by controlling the metal salt dissociation constants. Resulting MOF alloys exhibit a highly 2D nature with excellent crystallinity and minute control over metal cation ratios. Our experimental and theoretical results show that their electronic bandgaps and photoexcited carrier lifetimes can be engineered by metal cation alloying. Interestingly, 2D alloyed MOFs enable high-efficiency photo-catalytic water reduction performance in Co/Ni MOF alloys owing to the spatially separated metal clusters in 2D MOF alloys.
AB - Bimetallic metal-organic framework (MOFs) alloys, in which heterogeneous metal clusters are incorporated into their backbone, are capable of highly selective separations and catalysis. Due to limitations in our fundamental understanding of their alloying, however, established methods result in phase-separated or amorphous two-dimensional (2D) MOFs or lack precise control over alloy ratios. Here, our results demonstrate 2D MOF alloys where metal cation ratios (M1 and M2) in M1xM21-xBDC (M1 or M2= Zn, Cu, Ni, Co, Fe, Mn) can be engineered on demand by controlling the metal salt dissociation constants. Resulting MOF alloys exhibit a highly 2D nature with excellent crystallinity and minute control over metal cation ratios. Our experimental and theoretical results show that their electronic bandgaps and photoexcited carrier lifetimes can be engineered by metal cation alloying. Interestingly, 2D alloyed MOFs enable high-efficiency photo-catalytic water reduction performance in Co/Ni MOF alloys owing to the spatially separated metal clusters in 2D MOF alloys.
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U2 - 10.1063/5.0051219
DO - 10.1063/5.0051219
M3 - Article
AN - SCOPUS:85113379014
SN - 1931-9401
VL - 8
JO - Applied Physics Reviews
JF - Applied Physics Reviews
IS - 3
M1 - 031411
ER -