TY - JOUR
T1 - Sinter-Resistant Platinum Catalyst Supported by Metal–Organic Framework
AU - Kim, In Soo
AU - Li, Zhanyong
AU - Zheng, Jian
AU - Platero-Prats, Ana E.
AU - Mavrandonakis, Andreas
AU - Pellizzeri, Steven
AU - Ferrandon, Magali
AU - Vjunov, Aleksei
AU - Gallington, Leighanne C.
AU - Webber, Thomas E.
AU - Vermeulen, Nicolaas A.
AU - Penn, R. Lee
AU - Getman, Rachel B.
AU - Cramer, Christopher J.
AU - Chapman, Karena W.
AU - Camaioni, Donald M.
AU - Fulton, John L.
AU - Lercher, Johannes A.
AU - Farha, Omar K.
AU - Hupp, Joseph T.
AU - Martinson, Alex B.F.
N1 - Funding Information:
Sinter-Resistant Platinum Catalyst Supported by Metal–Organic Framework
Funding Information:
In conclusion, the nodes of NU-1000 were post-synthetically modified via ALD derived Pt in order to understand the nature of Pt on this promising high surface area support. Pt-AIM samples consist of both single atoms and few-atom clusters, where the single atoms are prone to catalyst poisoning with CO. While as-synthesized Pt-AIM samples consist of both Pt0 and Pt4+, the fraction of Pt0 increases under reducing atmosphere even at elevated temperatures. While there is evidence for some consolidation of Pt to clusters in the small pores, we find no evidence for sintering to larger particles. Furthermore, oper-ando EXAFS analysis reveals a coordination funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award no. DESC0012702. This work made use of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no. DE-AC02-06CH11357. XAS measurements at Sector 20-BM and Sector 9-BM were further supported by the Canadian Light Source. We thank Dr. Mahalingam Balasubramanian and Dr. Tianpin Wu (APS X-Ray Science Division) for assisting in the XAFS experiments. The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper.
PY - 2018/1/22
Y1 - 2018/1/22
N2 - Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.
AB - Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.
KW - atomic layer deposition (ALD)
KW - heterogeneous catalysis
KW - metal–organic frameworks (MOFs)
KW - platinum
KW - sinter-resistance
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U2 - 10.1002/anie.201708092
DO - 10.1002/anie.201708092
M3 - Article
C2 - 29205697
AN - SCOPUS:85039761733
VL - 57
SP - 909
EP - 913
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 4
ER -