Abstract <p>Reduction of <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> to <InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation><InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq3.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="14" /> </InlineMediaObject> <EquationSource Format="TEX">$^-$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mo>-</mo> </mmultiscripts> </math></EquationSource> </InlineEquation> is a bottleneck in the conversion of <InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> into various value-added chemicals. Here, based on quantum chemical calculations, we propose that the complexation of <InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> with a carbene drastically reduces the electron affinity of <InlineEquation ID="IEq6"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> and thus makes the reduction of <InlineEquation ID="IEq7"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> spontaneous. Using various carbenes of different nucleophilicity, we have shown that the facile reduction of <InlineEquation ID="IEq8"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> in the presence of a carbene can be achieved for a variety of carbenes, and hence, offers an attractive route for converting <InlineEquation ID="IEq9"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="32" /> </InlineMediaObject> <EquationSource Format="TEX">$\hbox {CO}_2$</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mtext>CO</mtext> <mn>2</mn> </msub> </math></EquationSource> </InlineEquation> into various useful chemicals.</p> Graphical abstract <p> the reduction of CO<InlineEquation ID="IEq10"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> to CO<InlineEquation ID="IEq11"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> <InlineEquation ID="IEq12"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq3.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="14" /> </InlineMediaObject> <EquationSource Format="TEX">$^-$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mo>-</mo> </mmultiscripts> </math></EquationSource> </InlineEquation> is a bottleneck in the conversion of CO<InlineEquation ID="IEq13"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> into various value-added chemicals. There are two main challenges in converting CO<InlineEquation ID="IEq14"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> to CO<InlineEquation ID="IEq15"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> <InlineEquation ID="IEq16"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq3.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="14" /> </InlineMediaObject> <EquationSource Format="TEX">$^-$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mo>-</mo> </mmultiscripts> </math></EquationSource> </InlineEquation>. First, the high energy barrier associated with CO<InlineEquation ID="IEq17"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> to CO<InlineEquation ID="IEq18"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq18.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="14" /> </InlineMediaObject> <EquationSource Format="TEX">$_2^-$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mo>-</mo> </mmultiscripts> </math></EquationSource> </InlineEquation> reduction, and a low solubility of CO<InlineEquation ID="IEq19"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> in water. We have shown that by using a carbene-CO<InlineEquation ID="IEq20"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> complex rather a bare CO<InlineEquation ID="IEq21"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="12039_2025_2378_Article_IEq10.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="8" /> </InlineMediaObject> <EquationSource Format="TEX">$_2$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mn>2</mn> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation>, both of these limitations can be circumvented. </p>

Can carbene be used for a metal free reduction of carbon dioxide?

期刊论文
发表日期：

2025年8月20日

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Priyanka Yadav,
Pradeep Kumar

摘要

Abstract

Reduction of $\hbox {CO}_2$ ${CO}_{2}$ to $\hbox {CO}_2$ ${CO}_{2}$ $^-$ $^{-}$ is a bottleneck in the conversion of $\hbox {CO}_2$ ${CO}_{2}$ into various value-added chemicals. Here, based on quantum chemical calculations, we propose that the complexation of $\hbox {CO}_2$ ${CO}_{2}$ with a carbene drastically reduces the electron affinity of $\hbox {CO}_2$ ${CO}_{2}$ and thus makes the reduction of $\hbox {CO}_2$ ${CO}_{2}$ spontaneous. Using various carbenes of different nucleophilicity, we have shown that the facile reduction of $\hbox {CO}_2$ ${CO}_{2}$ in the presence of a carbene can be achieved for a variety of carbenes, and hence, offers an attractive route for converting $\hbox {CO}_2$ ${CO}_{2}$ into various useful chemicals.

Graphical abstract

the reduction of CO $_2$ $_{2}$ to CO $_2$ $_{2}$ $^-$ $^{-}$ is a bottleneck in the conversion of CO $_2$ $_{2}$ into various value-added chemicals. There are two main challenges in converting CO $_2$ $_{2}$ to CO $_2$ $_{2}$ $^-$ $^{-}$ . First, the high energy barrier associated with CO $_2$ $_{2}$ to CO $_2^-$ $_{2}^{-}$ reduction, and a low solubility of CO $_2$ $_{2}$ in water. We have shown that by using a carbene-CO $_2$ $_{2}$ complex rather a bare CO $_2$ $_{2}$ , both of these limitations can be circumvented.