New material facilitates the production of key industrial supplies
Manuel A. Ortuño
Zhanyong Li

Hollow channels of a sponge-like metal-organic framework material. Image courtesy of Manuel A. Ortuño, Inorganometallic Catalyst Design Center

Just look around: bottles, cups, furniture. We use plastics every day. Researchers at the Inorganometallic Catalyst Design Center have discovered a new material that can efficiently transform propane into propylene, a key component of the common plastics around you.

Propylene has a broad variety of applications in industry. In 2013, the United States alone used more than 14 million tons of it! However, the typical industrial methods to obtain propylene are not very energy efficient. First, propylene is produced along with many other products with very low yield; second, the process requires temperatures as high as 650 °C or 1,200 °F. As an alternative, the addition of oxygen in the propane feed helps decrease the temperature needed for synthesis, but the reaction still requires a material to make the system more efficient. Here is where metal-organic frameworks, a.k.a. MOFs, make their entrance.

Versatile sponges. MOFs are a family of materials in which metallic centers are connected by organic molecules forming a 3D network. They contain large pores resembling those of a sponge. The MOFs can absorb and carry several times their own weight, so they can be used for gas storage and separation, detection of chemicals, and chemical reaction catalysis.

MOF catalysts coming to the rescue. One major application of MOFs is catalysis. A catalyst is a material that boosts the rates of chemical reactions, thereby making them more efficient and sustainable. Some reactions are not practical unless a catalyst is present. The activity of a solid catalyst usually depends on the amount of its surface that can be seen by the chemical reactants, such as propane. The use of highly porous MOFs tremendously increases the contact surface, such that each and every “hot spot” (catalytic site) can cause a chemical transformation.

There are a few known catalysts that, in the presence of oxygen, transform propane (an inert gas) into propylene (a valuable chemical). For example, some cobalt oxides can achieve this, but their catalytic activity is low because they are large particles. In other words, they have a small contact surface with the propane.

However, by using a porous MOF to support cobalt oxides, scientists can prepare very small particles. Just like a hundred marbles have more surface than one bowling ball, smaller cobalt oxides have larger contact surfaces. The particles are well separated in the MOF network, and that preserves the activity and lifetime of the catalyst. As a result, this new material can operate efficiently at low temperatures (for example, 230 °C or 446 °F) while maintaining a high and constant reaction rate for about 20 hours. Computational modeling has confirmed the experimental results showing that propylene is produced faster than other non-desirable products.

The first step of a long walk. This study provides a first step towards obtaining MOF-supported catalysts that are effective for low-temperature, more efficient, propylene production. Further optimization of these materials could ultimately affect the manufacture and pricing of everyday plastics. The impact of MOFs in daily life may soon be felt, with cheaper furniture, cups, and bottles possibly just around the corner!

More Information

Li Z, AW Peters, V Bernales, MA Ortuño, NM Schweitzer, MR DeStefano, LC Gallington, AE Platero-Prats, KW Chapman, CJ Cramer, L Gagliardi, JT Hupp, and OK Farha. 2017. “Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature.” ACS Central Science 3(1):31-38. DOI: 10.1021/acscentsci.6b00290


Sponsors: This work was supported by the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. A.W.P. and M.R.D. were supported by the Department of Defense through the National Defense Science and Engineering Fellowship program. A.E.P.P. acknowledges a Beatriu de Pinós fellowship from the Ministry of Economy and Knowledge from the Catalan Government.

User facilities: This work made use of the J.B. Cohen X-ray Diffraction Facility supported by the Materials Research Science and Engineering Centers program of the National Science Foundation at the Materials Research Center of Northwestern University. This work made use of the Electron Probe Instrumentation Center and Keck-II facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource; the Materials Research Science and Engineering Centers program at the Materials Research Center; the International Institute for Nanotechnology; the Keck Foundation; and the State of Illinois, through the International Institute for Nanotechnology.

Use of the Advanced Photon Source is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Materials Research Collaborative Access Team (MRCAT, Sector 10-ID-B) operations are supported by the U.S. Department of Energy and the MRCAT's institutions. The authors acknowledge the Minnesota Supercomputing Institute at the University of Minnesota for providing computational resources.

About the author(s):

Manuel A. Ortuño is a postdoctoral researcher in computational chemistry at the University of Minnesota in the Cramer group. He is also a member of the Inorganometallic Catalyst Design Center (ICDC). His research focuses on understanding reaction mechanisms to design new catalysts, from the molecular level (homogeneous catalysis) to material science (metal-organic frameworks).

Zhanyong Li is a postdoctoral researcher from the Hupp and Farha group in the chemistry department at Northwestern University and a member of the Inorganometallic Catalyst Design Center (ICDC). His research projects involve the development of new metal-organic framework derived materials for gas-phase catalysis.

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