Unlike homogeneous catalysts, heterogeneous catalysts that have been optimized through decades are typically so complex and hard to characterize that the nature of the catalytically active site is not known. This is one of the main stumbling blocks in developing rational catalyst design strategies in heterogeneous catalysis. We show here how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst. Using a combination of experimental evidence from bulk-, surface-sensitive and imaging methods collected on real high-performance catalytic systems in combination with DFT calculations. We show that the active site consists of Cu steps peppered with Zn atoms, all stabilized by a series of well defined bulk defects and surface species that need jointly to be present for the system to work.

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The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts

CO2 conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO2 utilization as a measure for global CO2 mitigation. Whereas the latter focuses on reducing the end-of-pipe problem “CO2 emissions” from todays’ industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO2-based chemistry does...

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al2O3) catalysts for carbon dioxide (CO2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. We report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO and allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. Our results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.

http://science.sciencemag.org/content/sci/355/6331/1296.full.pdf

Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts

Starting with coal, followed by petroleum oil and natural gas, the utilization of fossil fuels has allowed the fast and unprecedented development of human society. However, the burning of these resources in ever increasing pace is accompanied by large amounts of anthropogenic CO2 emissions, which are outpacing the natural carbon cycle, causing adverse global environmental changes, the full extent of which is still unclear. Even through fossil fuels are still abundant, they are nevertheless limited and will, in time, be depleted. Chemical recycling of CO2 to renewable fuels and materials, primarily methanol, offers a powerful alternative to tackle both issues, that is, global climate change and fossil fuel depletion. The energy needed for the reduction of CO2 can come from any renewable energy source such as solar and wind. Methanol, the simplest C1 liquid product that can be easily obtained from any carbon source, including biomass and CO2, has been proposed as a key component of such an anthropogenic carbon cycle in the framework of a “Methanol Economy”. Methanol itself is an excellent fuel for internal combustion engines, fuel cells, stoves, etc. It's dehydration product, dimethyl ether, is a diesel fuel and liquefied petroleum gas (LPG) substitute. Furthermore, methanol can be transformed to ethylene, propylene and most of the petrochemical products currently obtained from fossil fuels. The conversion of CO2 to methanol is discussed in detail in this review.

Recycling of carbon dioxide to methanol and derived products – closing the loop

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

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Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes.

A significant effect of the support on the catalytic activity of palladium-based catalysts for methanol synthesis from carbon dioxide and hydrogen was observed, where Pd/Ga 2 O 3 was more active than Cu/ZnO by a factor of 2 in yield and 20 in turnover frequency

Development of an active Ga2O3 supported palladium catalyst for the synthesis of methanol from carbon dioxide and hydrogen

The coverage of oxygen formed on the surface of catalysts during methanol synthesis from CO2 has been measured for copper-based catalysts including various metal oxides using a method called reactive frontal chromatography (RFC). An excellent correlation between the specific activity for methanol synthesis and the oxygen coverage (θ) was obtained, where the activity increased linearly with oxygen coverage atθ 0.18. The results strongly indicate that the support effect or addition of metal oxides revealed in methanol synthesis over copper catalysts is ascribed to the ratio of Cu+ to Cu0 on the surface of copper particles.

The role of metal oxides in promoting a copper catalyst for methanol synthesis

The hydrogenation of CO2 over physically-mixed Cu/SiO2 and ZnO/SiO2 was carried out to clarify the synergetic effect between Cu and ZnO in Cu/ZnO methanol synthesis catalysts The activity of the physical mixtures significantly increased with increasing reduction temperature in the range of 573–723 K TEM-EDX results definitely showed that ZnOx moieties migrated from ZnO/SiO2 particles onto the surface of Cu particles when the physical mixtures were reduced at high temperatures above 573 K Upon the migration of the ZnOx species, the oxygen coverage on the surface of Cu, measured after the hydrogenation of CO2, increased with the reduction temperature The results clearly showed that the synergetic effect of ZnO in the physical mixtures can be ascribed to the creation of active sites such as Cu+ which the ZnOx moieties stabilize on the Cu surface Further, XRD results showed that the migrated ZnOx species partly dissolved into the Cu particles to form a Cu—Zn alloy

Y. Kanai

Papers

Development of an active Ga2O3 supported palladium catalyst for the synthesis of methanol from carbon dioxide and hydrogen

The role of metal oxides in promoting a copper catalyst for methanol synthesis

The synergy between Cu and ZnO in methanol synthesis catalysts

The role of ZnO in Cu/ZnO methanol synthesis catalysts

A Surface Science Investigation of Methanol Synthesis over a Zn-Deposited Polycrystalline Cu Surface