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Adsorption and Deactivation Characteristics of Cu/ZnO-Based Catalysts for Methanol Synthesis from Carbon Dioxide

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Abstract

The adsorption and deactivation characteristics of coprecipitated Cu/ZnO-based catalysts were examined and correlated to their performance in methanol synthesis from CO2 hydrogenation. The addition of Ga2O3 and Y2O3 promoters is shown to increase the Cu surface area and CO2/H2 adsorption capacities of the catalysts and enhance methanol synthesis activity. Infrared studies showed that CO2 adsorbs spontaneously on these catalysts at room temperature as both mono- and bi-dentate carbonate species. These weakly bound species desorb completely from the catalyst surface by 200 °C while other carbonate species persist up to 500 °C. Characterization using N2O decomposition, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy with energy-dispersive X-ray spectroscopy analysis clearly indicated that Cu sintering is the main cause of catalyst deactivation. Ga and Y promotion improves the catalyst stability by suppressing the agglomeration of Cu and ZnO particles under pretreatment and reaction conditions.

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Acknowledgments

As part of the National Energy Technology Laboratory’s Regional University Alliance (NETL-RUA), a collaborative initiative of the NETL, this technical effort was performed under the RES contract DE-FE-0004000. This project was funded by the Department of Energy, National Energy Technology Laboratory, an agency of the United States Government, through a support contract with URS Energy & Construction, Inc. Neither the United States Government nor any agency thereof, nor any of their employees, nor URS Energy & Construction, Inc., nor any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

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Authors and Affiliations

  1. United States Department of Energy, National Energy Technology Laboratory, P.O. Box 10940, Pittsburgh, PA, 15236, USA

    Sittichai Natesakhawat, Paul R. Ohodnicki Jr., Bret H. Howard, Jonathan W. Lekse, John P. Baltrus & Christopher Matranga

  2. Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA, 15261, USA

    Sittichai Natesakhawat

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  1. Sittichai Natesakhawat
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  2. Paul R. Ohodnicki Jr.
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  3. Bret H. Howard
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  6. Christopher Matranga
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Correspondence to Sittichai Natesakhawat.

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Natesakhawat, S., Ohodnicki, P.R., Howard, B.H. et al. Adsorption and Deactivation Characteristics of Cu/ZnO-Based Catalysts for Methanol Synthesis from Carbon Dioxide. Top Catal 56, 1752–1763 (2013). https://doi.org/10.1007/s11244-013-0111-5

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