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Catalysis for CO2 Conversion, 2nd Edition
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Catalysis for CO2 Conversion, 2nd Edition

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Environmental Catalysis".

Deadline for manuscript submissions: 20 December 2024 | Viewed by 1508

Special Issue Editor

Prof. Dr. Zhixin Yu

E-Mail Website
Guest Editor
Department of Energy and Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway
Interests: nanomaterials design and synthesis; hydrogen and syngas production; biogas upgrading; CO2 conversion and utilization; batteries and supercapacitors; nanocatalysis; energy conversion and storage
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

CO2, a cheap, nontoxic, and abundant carbon feedstock, has garnered significant interest from academia and industry for its conversion into valuable products. The potential to transform CO2 into fuels, chemicals, polymers, and building materials has opened up new avenues for sustainable development. Although some industrial processes utilizing CO2, such as urea synthesis, are well established, the chemical conversion of CO2 remains challenging due to its thermodynamic nature.

To address these challenges and showcase the latest advancements in CO2 conversion technologies, we are pleased to announce the second edition of our Special Issue on “Catalysis for CO2 Conversion”. This edition aims to bring together leading scientists to present their cutting-edge research in catalyst development, process design, system analysis, and multidisciplinary approaches.

We invite researchers to contribute original research papers, review articles, and short communications that delve into various aspects of CO2 conversion. Topics of interest include, but are not limited to:

  • Catalyst synthesis and characterization;
  • Reactor design and optimization;
  • Process engineering and scale-up;
  • Mechanistic investigations;
  • Numerical simulations and modelling.

Prof. Dr. Zhixin Yu
Guest Editor

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • CO2 conversion
  • thermocatalysis
  • electrocatalysis
  • photocatalysis
  • enzymatic
  • copolymerization

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24 pages, 8451 KiB  
Article
Seeding as a Decisive Tool for Increasing Space-Time-Yields in the Preparation of High-Quality Cu/ZnO/ZrO2 Catalysts
by David Guse, Lucas Warmuth, Moritz Herfet, Katharina Adolf, Thomas A. Zevaco, Stephan Pitter and Matthias Kind
Catalysts 2024, 14(8), 517; https://doi.org/10.3390/catal14080517 - 9 Aug 2024
Viewed by 666
Abstract
Aging is one of the key steps in the preparation of highly active Cu/ZnO-based catalysts for use in the production of methanol. If certain pH and temperature specifications are met, an initially amorphous precipitate transforms into the crystalline precursor phase of zincian malachite, [...] Read more.
Aging is one of the key steps in the preparation of highly active Cu/ZnO-based catalysts for use in the production of methanol. If certain pH and temperature specifications are met, an initially amorphous precipitate transforms into the crystalline precursor phase of zincian malachite, which is characterized by a periodic arrangement of Cu and Zn atoms and has proven advantageous for the quality of the final catalyst. However, aging generally takes between 30 min and multiple hours until the desired phase transformation is completed. With our study, we show that aging can be significantly accelerated by seeding the freshly precipitated suspension with already aged zincian malachite crystals: the necessary aging time was reduced by 41% for seeding mass fractions as low as 3 wt.% and from 83 min to less than 2 min for 30 wt.% seeds. No negative influence of seeding on the phase composition, specific surface area, molar metal ratios, or the morphology of the aged precursor could be identified. Consequently, the catalyst performance in the synthesis of methanol from CO2, as well as from a CO/CO2 mixture, was identical to a catalyst from an unseeded preparation and showed small advantages compared to a commercial sample. Thus, we conclude that seeding is a vital tool to accelerate the preparation of all Cu/Zn-based catalysts while maintaining product quality, presumably also on an industrial scale. Full article
(This article belongs to the Special Issue Catalysis for CO2 Conversion, 2nd Edition)
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Graphical abstract

Graphical abstract
Full article ">Figure 1
<p>Evolution of pH as a function of the aging time <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> </mrow> </semantics></math> from Guse et al. [<a href="#B46-catalysts-14-00517" class="html-bibr">46</a>]: (<b>a</b>) seven independent unseeded reference experiments; (<b>b</b>) two seeded experiments with <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>8</mn> <mo> </mo> <mi>wt</mi> <mo>.</mo> <mo>%</mo> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>42</mn> <mo> </mo> <mi>wt</mi> <mo>.</mo> <mo>%</mo> </mrow> </semantics></math>, respectively.</p> Full article ">Figure 1 Cont.
<p>Evolution of pH as a function of the aging time <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> </mrow> </semantics></math> from Guse et al. [<a href="#B46-catalysts-14-00517" class="html-bibr">46</a>]: (<b>a</b>) seven independent unseeded reference experiments; (<b>b</b>) two seeded experiments with <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>8</mn> <mo> </mo> <mi>wt</mi> <mo>.</mo> <mo>%</mo> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>42</mn> <mo> </mo> <mi>wt</mi> <mo>.</mo> <mo>%</mo> </mrow> </semantics></math>, respectively.</p> Full article ">Figure 2
<p>X-ray diffractograms of dried and washed samples as a function of aging time for: (<b>a</b>) the standard aging process without seeding (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi>wt</mi> <mo>.</mo> <mo>%</mo> </mrow> </semantics></math>) and (<b>b</b>) a preparation where seeds were added after co-precipitation was completed at <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi>min</mi> </mrow> </semantics></math> (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>10</mn> <mo> </mo> <mi>wt</mi> <mo>.</mo> <mo>%</mo> </mrow> </semantics></math>). The phase composition was evaluated by Rietveld refinement.</p> Full article ">Figure 3
<p>Evolution of the molar fraction of Zn in the metals of the solids samples (<span class="html-fig-inline" id="catalysts-14-00517-i001"><img alt="Catalysts 14 00517 i001" src="/catalysts/catalysts-14-00517/article_deploy/html/images/catalysts-14-00517-i001.png"/></span>) and in zincian malachite (<span class="html-fig-inline" id="catalysts-14-00517-i002"><img alt="Catalysts 14 00517 i002" src="/catalysts/catalysts-14-00517/article_deploy/html/images/catalysts-14-00517-i002.png"/></span>) as a function of the aging time <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> </mrow> </semantics></math>: (<b>a</b>) a standard aging process without seeding (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>), based on the work of Guse et al. [<a href="#B46-catalysts-14-00517" class="html-bibr">46</a>]; (<b>b</b>) a preparation where seeds were added after co-precipitation is completed at <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math> (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>10</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>).</p> Full article ">Figure 4
<p>Necessary aging time until the phase change is completed (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>c</mi> <mi>h</mi> <mi>a</mi> <mi>n</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> </mrow> </semantics></math>) as a function of the seed mass fraction <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> </mrow> </semantics></math> for two different seeding methods.</p> Full article ">Figure 5
<p>Necessary aging time until the phase change is completed (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>c</mi> <mi>h</mi> <mi>a</mi> <mi>n</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> </mrow> </semantics></math>) as a function of the seed mass fraction <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> </mrow> </semantics></math> at high reactant concentrations (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>b</mi> </mrow> <mrow> <mi>M</mi> <mo>,</mo> <mi>F</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mn>2</mn> </mrow> </msub> <mo>=</mo> <mn>0.86</mn> <mo> </mo> <mi>mol</mi> <mo>·</mo> <msubsup> <mrow> <mi>kg</mi> </mrow> <mrow> <msub> <mrow> <mi mathvariant="normal">H</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mo>−</mo> <mn>1</mn> </mrow> </msubsup> </mrow> </semantics></math>) when seeding is carried out once and, respectively, repeatedly.</p> Full article ">Figure 6
<p>Space-time-yield of the aging process as a function of the seed mass fraction <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>S</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> </mrow> </semantics></math> for the different seeding methods.</p> Full article ">Figure 7
<p>Correlation between the particle size distribution of seed particles and the impact on the necessary aging time: (<b>a</b>) mean particle size distribution of freshly prepared seed suspensions and of resuspended dried seeds with three different sieving fractions; (<b>b</b>) influence of the seed particle size on the necessary aging time in relation to the aging time without seeding.</p> Full article ">Figure 8
<p>Solid phase composition of (<b>a</b>) the aged precursor and (<b>b</b>) the precatalyst as a function of the seeding mass fraction, as determined by XRD and Rietveld refinement.</p> Full article ">Figure 9
<p>TEM and TEM-EDXS images of the calcined precatalysts. (<b>a</b>,<b>b</b>): unseeded preparation (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>s</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>122</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>); (<b>c</b>,<b>d</b>): unseeded preparation with a shortened aging (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>s</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>60</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>); (<b>e</b>,<b>f</b>): seeded preparation (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>s</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>30</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>55</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>). Cu is marked in red and Zn is marked in green.</p> Full article ">Figure 9 Cont.
<p>TEM and TEM-EDXS images of the calcined precatalysts. (<b>a</b>,<b>b</b>): unseeded preparation (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>s</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>122</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>); (<b>c</b>,<b>d</b>): unseeded preparation with a shortened aging (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>s</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>0</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>60</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>); (<b>e</b>,<b>f</b>): seeded preparation (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>x</mi> </mrow> <mrow> <mi>s</mi> <mi>e</mi> <mi>e</mi> <mi>d</mi> <mi>s</mi> </mrow> </msub> <mo>=</mo> <mn>30</mn> <mo> </mo> <mi mathvariant="normal">w</mi> <mi mathvariant="normal">t</mi> <mo>.</mo> <mi mathvariant="normal">%</mi> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>t</mi> </mrow> <mrow> <mi>a</mi> <mi>g</mi> <mi>e</mi> </mrow> </msub> <mo>=</mo> <mn>55</mn> <mo> </mo> <mi mathvariant="normal">m</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> </mrow> </semantics></math>). Cu is marked in red and Zn is marked in green.</p> Full article ">Figure 10
<p>Influence of seeding and a reduced aging time on the mean methanol productivity over 50 h on stream and in comparison with a commercially available catalyst for two CO<sub>2</sub>/CO inlet ratios at 30 bar and GHSV: 4.41 s<sup>−1</sup>. <math display="inline"><semantics> <mrow> <mi>T</mi> <mo>=</mo> <mn>230</mn> <mo> </mo> <mo>°</mo> <mi mathvariant="normal">C</mi> <mo> </mo> <mi>f</mi> <mi>o</mi> <mi>r</mi> <mo> </mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> </mrow> </semantics></math>/<math display="inline"><semantics> <mrow> <mo>(</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <mi>O</mi> </mrow> </msub> <mo>)</mo> <mo>=</mo> <mn>0.5</mn> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <mi>T</mi> <mo>=</mo> <mn>250</mn> <mo> </mo> <mo>°</mo> <mi mathvariant="normal">C</mi> <mo> </mo> <mi>f</mi> <mi>o</mi> <mi>r</mi> <mo> </mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> </mrow> </semantics></math>/<math display="inline"><semantics> <mrow> <mo>(</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <mi>O</mi> </mrow> </msub> <mo>)</mo> <mo>=</mo> <mn>1.0</mn> </mrow> </semantics></math>.</p> Full article ">Figure 11
<p>Influence of seeding and a reduced aging time on CO<sub>x</sub> conversion and methanol selectivity, in comparison with one commercially available catalyst for two CO<sub>2</sub>/CO inlet ratios at 30 bar and GHSV: 4.41 s<sup>−1</sup>. <math display="inline"><semantics> <mrow> <mi>T</mi> <mo>=</mo> <mn>230</mn> <mo> </mo> <mo>°</mo> <mi mathvariant="normal">C</mi> <mo> </mo> <mi>f</mi> <mi>o</mi> <mi>r</mi> <mo> </mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> </mrow> </semantics></math>/<math display="inline"><semantics> <mrow> <mo>(</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <mi>O</mi> </mrow> </msub> <mo>)</mo> <mo>=</mo> <mn>0.5</mn> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <mi>T</mi> <mo>=</mo> <mn>250</mn> <mo> </mo> <mo>°</mo> <mi mathvariant="normal">C</mi> <mo> </mo> <mi>f</mi> <mi>o</mi> <mi>r</mi> <mo> </mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> </mrow> </semantics></math>/<math display="inline"><semantics> <mrow> <mo>(</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <msub> <mrow> <mi>O</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msub> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mover accent="true"> <mrow> <mi>V</mi> </mrow> <mo>˙</mo> </mover> </mrow> <mrow> <mi>C</mi> <mi>O</mi> </mrow> </msub> <mo>)</mo> <mo>=</mo> <mn>1.0</mn> </mrow> </semantics></math>.</p> Full article ">Figure 12
<p>Experimental setup. M: motor, TCR: temperature control and recording, QR: pH recording. Dimensions are shown in mm. From Guse et al. [<a href="#B35-catalysts-14-00517" class="html-bibr">35</a>,<a href="#B46-catalysts-14-00517" class="html-bibr">46</a>].</p> Full article ">
13 pages, 3785 KiB  
Article
N-Formylation of Carbon Dioxide and Amines with EDTA as a Recyclable Catalyst under Ambient Conditions
by Qiqi Zhou, Yu Chen, Xuexin Yuan, Hai-Jian Yang, Qingqing Jiang, Juncheng Hu and Cun-Yue Guo
Catalysts 2024, 14(8), 492; https://doi.org/10.3390/catal14080492 - 31 Jul 2024
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Abstract
The reduction of CO2 is an important method to produce chemicals such as methanol, formic acid, formaldehyde, etc. In general, the reduction of CO2 is carried out at high temperatures and pressures with precious metals as catalysts, which is not favorable [...] Read more.
The reduction of CO2 is an important method to produce chemicals such as methanol, formic acid, formaldehyde, etc. In general, the reduction of CO2 is carried out at high temperatures and pressures with precious metals as catalysts, which is not favorable for industrial procedures. Thus, it will be very useful if researchers can find cost-effective catalysts for industrial application in CO2 reduction. In this work, commercially available ethylenediaminetetraacetic acid (EDTA) was tested as a cheap, non-toxic, and recyclable catalyst to initiate the N-carbonylation reaction of CO2 with amines. After screening various reaction parameters, including temperature, pressure, time, solvent, and reducing agent, the optimal reaction conditions were obtained: 80 °C, 2 MPa, 6 h, 50 mmol% catalyst dosage, 1 mL DMSO, and 1:1 molar ratio of amine to reducing agent. Notably, further studies confirmed that EDTA could also be effective for N-formylation even under ambient conditions (0.1 MPa and room temperature). The suitability of the catalyst for 26 kinds of substrates (including aliphatic amines, aromatic amines, and alicyclic amines) and its reusability were also investigated, with satisfactory results. Scale-up research has been performed effectively with a high conversion of amine (83%) to obtain the mono-formylated product selectively. Finally, the mechanism of the reaction between amine and CO2 has been proposed via control experiments and compared with results in the literature. Full article
(This article belongs to the Special Issue Catalysis for CO2 Conversion, 2nd Edition)
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Figure 1

Figure 1
<p>Effects of reaction conditions on the conversion of N-methylaniline: (<b>a</b>) amount of EDTA; (<b>b</b>) effect of reaction time; (<b>c</b>) effect of temperature; (<b>d</b>) effect of CO<sub>2</sub> pressure.</p> Full article ">Figure 2
<p>(<b>a</b>) Effect of different solvents on the conversion of N-methylaniline; (<b>b</b>) effect of DMSO dosage on the conversion of N-methylaniline.</p> Full article ">Figure 3
<p>Experiment on the recyclability of EDTA as a catalyst.</p> Full article ">Figure 4
<p>Comparison of IR spectra of EDTA before and after 5 repeated catalytic cycles: (<b>a</b>) fresh EDTA; (<b>b</b>) EDTA after 5 times of reuse.</p> Full article ">Figure 5
<p>EDTA-catalyzed formylation reactions of CO<sub>2</sub> with various amines under high pressure <sup>a</sup>. <sup>a</sup> Reaction conditions: Substrate, 5 mmol; CO<sub>2</sub>, 2 MPa; PhSiH<sub>3</sub>, 5 mmol; EDTA, 50 mmol%; DMSO, 1 mL; temperature, 80 °C; time, 6 h. <sup>b</sup> Reaction conditions: Substrate, 5 mmol; CO<sub>2</sub>, 2 MPa; PhSiH<sub>3</sub>, 5 mmol; EDTA, 50 mmol%; DMSO, 1 mL; temperature, 80 °C; time, 24 h. <sup>c</sup> Reaction conditions: Substrate, 5 mmol; CO<sub>2</sub>, 2 MPa; PhSiH<sub>3</sub>, 5 mmol; EDTA, 50 mmol%; DMSO, 1 mL; temperature, 80 °C; time, 1 h. <sup>d</sup> The conversion and selectivity of the products were detected by <sup>1</sup>H NMR (CDCl<sub>3</sub>, 400 MHz).</p> Full article ">Figure 6
<p>EDTA-catalyzed formylation reactions of CO<sub>2</sub> with various amines at atmospheric pressure <sup>a,b</sup>. <sup>a</sup> Reaction conditions: Substrate, 2.5 mmol; CO<sub>2</sub>, 0.1 MPa; PhSiH<sub>3</sub>, 2.5 mmol; EDTA, 50 mmol%; DMSO, 2 mL; temperature, 25 °C; time, 12 h. <sup>b</sup> The conversion and selectivity of the products were detected by <sup>1</sup>H NMR (CDCl<sub>3</sub>, 400 MHz).</p> Full article ">Figure 7
<p>Possible mechanism of EDTA-catalyzed N-carbonylation reaction of CO<sub>2</sub> with amines.</p> Full article ">Figure 8
<p>Calculations for the conversion, yield, and selectivity of products.</p> Full article ">Scheme 1
<p>Gram-scale study on the formylation of N-methylaniline with CO<sub>2</sub>.</p> Full article ">
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