Controlled Manufacture of Heterogeneous Catalysts for the Hydrogenation of CO₂ via Steam Pyrolysis of Different Metal–Organic Frameworks

Abstract

The use of metal−organic frameworks (MOFs) as precursors for the manufacture of heterogeneous catalysts has gained a great deal of attention over the last decade. By subjecting a given MOF to pyrolysis, electrochemical degradation, or other treatments under a controlled atmosphere, (supported) metal (oxide) nanoparticles with very narrow size distributions can be obtained, opening the door to the design of more efficient catalytic solids. Here, we demonstrate the benefits of steam during the controlled decomposition of two different MOF structures (Basolite F300(Fe) and In@ZIF-67(Co)) and the consequences of treatment under this mildly oxidizing atmosphere on the properties of the resulting catalysts for the direct hydrogenation of CO 2 to hydrocarbons and methanol. In-depth characterization demonstrates that steam addition helps to control the phase composition both before and after catalysis; additionally, it results in the formation of smaller nanoparticles, thus leading to more efficient catalysts in comparison with conventional pyrolysis.

Enabling the Methanol Economy: Opportunities and Challenges for Heterogeneous Catalysis in the Production of Liquid Fuels via Methanol

“…The performance of the catalyst could be further improved by feeding water during the pyrolysis step, which hinders the formation of the support carbidic species. 27…”

“…This structural reorganization accounts for the observed induction period, while the presence of the amorphous mixed cobalt indium oxide shell is responsible for achieving a high methanol yield and selectivity. The performance of the catalyst could be further improved by feeding water during the pyrolysis step, which hinders the formation of the support carbidic species …”

Unlocking the potential of catalysts in thermochemical energy conversion processes

“…A potential method to enhance the catalytic activity of metal–organic frameworks is to subject them to controlled treatments, such as pyrolysis, which can yield supported metal or metal oxide nanoparticles with highly uniform size distributions. 91 The complete transformation of relevant precursor into the required product can be achieved by passing through a selectivity-determining intermediate by adjusting the reactive site composition and pore sizes. 92 In impregnation-pyrolysis method, coupling nitrogen doped carbonaceous materials with transition metal elements is found to be a successful strategy to expose more active sites while avoiding metal corrosion and immersion, which can improve catalytic capacity even further.…”

Simple Synthesis of Novel Cr-EDTA-MOF: A Green, Reusable, and Versatile Catalyst for the Production of Biodiesel Fuel from Oleic Acid and Palmitic Acid

“…Furthermore, it is still of extraordinary problem to explore facile techniques for the synthesis of novel MOF materials bearing unique structures and properties, as well as to widen and deepen the utility of MOF-based totally hybrid materials in the chemical industry . The capability of designing and modification after preparation has led these solids to be suitable as heterogeneous catalysts for organic transformations. , Notwithstanding the wide-spreading use of these catalysts, the leaching of costly or toxic metals into favorable products is one of the negative aspects of the employing of heterogeneous metal-based catalysts in sustainable nanocatalysis phenomena. , To overcome this problem, MOFs as a catalyst for organic reactions seem to be a suitable solution …”

“… 13 The capability of designing and modification after preparation has led these solids to be suitable as heterogeneous catalysts for organic transformations. 14 , 15 Notwithstanding the wide-spreading use of these catalysts, the leaching of costly or toxic metals into favorable products is one of the negative aspects of the employing of heterogeneous metal-based catalysts in sustainable nanocatalysis phenomena. 16 , 17 To overcome this problem, MOFs as a catalyst for organic reactions seem to be a suitable solution.…”