One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

Seok Jhin Kim; Shuai Tan; Micaela Taborga Claure; Laura Briones Gil; Karren L. More; Yujun Liu; Jason S. Moore; Ravindra S. Dixit; John G. Pendergast; David S. Sholl; Christopher W. Jones; Sankar Nair

doi:10.1021/acsami.6b06576

One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

Seok Jhin Kim, Shuai Tan, Micaela Taborga Claure, Laura Briones Gil, Karren L. More, Yujun Liu, Jason S. Moore, Ravindra S. Dixit, John G. Pendergast, David S. Sholl, Christopher W. Jones, Sankar Nair

Center for Nanophase Matls Sciences

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H₂ removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

Original language	English
Pages (from-to)	24671-24681
Number of pages	11
Journal	ACS Applied Materials and Interfaces
Volume	8
Issue number	37
DOIs	https://doi.org/10.1021/acsami.6b06576
State	Published - Sep 21 2016

Funding

This work was supported by the Dow Chemical Company. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. The authors wish to express special thanks to the assistance received from X-18B beamline personnel at BNL, Dr. Syed Khalid and Dr. Nebojsa Marinkovic. Microscopy research was conducted at ORNL's Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility, and was supported in part by ORNL's ShaRE User Facility. We also acknowledge Yolande Berta (Georgia Tech) for assistance in SEM imaging and Kimberly Reeves (ORNL) for assistance in TEM sample preparation.

Keywords

MFI
membrane reactor
metal cluster
propane dehydrogenation
zeolite membrane

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10.1021/acsami.6b06576

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@article{0317c915ffe04275a5bd89893b92f551,

title = "One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters",

abstract = "Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.",

keywords = "MFI, membrane reactor, metal cluster, propane dehydrogenation, zeolite membrane",

author = "Kim, {Seok Jhin} and Shuai Tan and {Taborga Claure}, Micaela and {Briones Gil}, Laura and More, {Karren L.} and Yujun Liu and Moore, {Jason S.} and Dixit, {Ravindra S.} and Pendergast, {John G.} and Sholl, {David S.} and Jones, {Christopher W.} and Sankar Nair",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

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doi = "10.1021/acsami.6b06576",

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T1 - One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

AU - Kim, Seok Jhin

AU - Tan, Shuai

AU - Taborga Claure, Micaela

AU - Briones Gil, Laura

AU - More, Karren L.

AU - Liu, Yujun

AU - Moore, Jason S.

AU - Dixit, Ravindra S.

AU - Pendergast, John G.

AU - Sholl, David S.

AU - Jones, Christopher W.

AU - Nair, Sankar

PY - 2016/9/21

Y1 - 2016/9/21

N2 - Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

AB - Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

KW - MFI

KW - membrane reactor

KW - metal cluster

KW - propane dehydrogenation

KW - zeolite membrane

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U2 - 10.1021/acsami.6b06576

DO - 10.1021/acsami.6b06576

M3 - Article

AN - SCOPUS:84988462547

SN - 1944-8244

VL - 8

SP - 24671

EP - 24681

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 37

ER -

One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

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Keywords

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