In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts
Identifieur interne : 000250 ( Istex/Corpus ); précédent : 000249; suivant : 000251In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts
Auteurs : F. Le Peltier ; P. Chaumette ; J. Saussey ; M. M. Bettahar ; J. C. LavalleySource :
- Journal of Molecular Catalysis A: Chemical [ 1381-1169 ] ; 1997.
Abstract
The kinetics of the CO2/H2 reaction over ZnAl2O4 and Cu–ZnAl2O4 catalysts at 250°C up to 0.3 MPa have been followed by in situ FT-IR spectroscopy. Both methanol and carbon monoxide formation were enhanced in presence of copper. They were also produced by independent routes through different adsorbed species. Formate (type I, I′ and II), methoxy and carbonate species were identified on the support and, in addition, copper formate and copper carbonyl species when copper was present. The hydrogenation of carbonate species to copper formate species was found rate determining in methanol synthesis over the Cu–ZnAl2O4 catalyst whereas type I formate species were shown to be the active intermediate for this reaction over the ZnAl2O4 support. Carbon monoxide resulted from the water gas shift reaction probably through the same species as methanol formed over the Cu–ZnAl2O4 catalyst whereas it seemed to stem from formate species of type II in the case of the ZnAl2O4 support. Type II formate species were shown inactive in presence of copper whereas the methoxy species adsorbed on the support were found inactive in presence and in absence of copper. The comparison of these results with those previously obtained with the CO/H2 mixture showed that the nature and the role of the detected species strongly depended on the reactive atmosphere and on the presence or not of copper in the catalyst composition.
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DOI: 10.1016/S1381-1169(97)00235-5
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts</title><author><name sortKey="Le Peltier, F" sort="Le Peltier, F" uniqKey="Le Peltier F" first="F." last="Le Peltier">F. Le Peltier</name><affiliation><mods:affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</mods:affiliation></affiliation></author><author><name sortKey="Chaumette, P" sort="Chaumette, P" uniqKey="Chaumette P" first="P." last="Chaumette">P. Chaumette</name><affiliation><mods:affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</mods:affiliation></affiliation></author><author><name sortKey="Saussey, J" sort="Saussey, J" uniqKey="Saussey J" first="J." last="Saussey">J. Saussey</name><affiliation><mods:affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Bettahar, M M" sort="Bettahar, M M" uniqKey="Bettahar M" first="M. M." last="Bettahar">M. M. Bettahar</name><affiliation><mods:affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</mods:affiliation></affiliation><affiliation><mods:affiliation>Corresponding author. Tel.: +33-3-83912066 ext. 3125; fax: +33-3-8392181; e-mail: bettahar@lcah.u-nancy.fr</mods:affiliation></affiliation><affiliation><mods:affiliation>1 Present address: Laboratoire de Catalyse Hétérogène, Université Henri Poincaré Nancy – I, BP 239, Vandoeuvre-les-Nancy Cedex, France.</mods:affiliation></affiliation></author><author><name sortKey="Lavalley, J C" sort="Lavalley, J C" uniqKey="Lavalley J" first="J. C." last="Lavalley">J. C. Lavalley</name><affiliation><mods:affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:079AC37B86327E725A17F4E24841B02966053B46</idno><date when="1998" year="1998">1998</date><idno type="doi">10.1016/S1381-1169(97)00235-5</idno><idno type="url">https://api.istex.fr/document/079AC37B86327E725A17F4E24841B02966053B46/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000250</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts</title><author><name sortKey="Le Peltier, F" sort="Le Peltier, F" uniqKey="Le Peltier F" first="F." last="Le Peltier">F. Le Peltier</name><affiliation><mods:affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</mods:affiliation></affiliation></author><author><name sortKey="Chaumette, P" sort="Chaumette, P" uniqKey="Chaumette P" first="P." last="Chaumette">P. Chaumette</name><affiliation><mods:affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</mods:affiliation></affiliation></author><author><name sortKey="Saussey, J" sort="Saussey, J" uniqKey="Saussey J" first="J." last="Saussey">J. Saussey</name><affiliation><mods:affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Bettahar, M M" sort="Bettahar, M M" uniqKey="Bettahar M" first="M. M." last="Bettahar">M. M. Bettahar</name><affiliation><mods:affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</mods:affiliation></affiliation><affiliation><mods:affiliation>Corresponding author. Tel.: +33-3-83912066 ext. 3125; fax: +33-3-8392181; e-mail: bettahar@lcah.u-nancy.fr</mods:affiliation></affiliation><affiliation><mods:affiliation>1 Present address: Laboratoire de Catalyse Hétérogène, Université Henri Poincaré Nancy – I, BP 239, Vandoeuvre-les-Nancy Cedex, France.</mods:affiliation></affiliation></author><author><name sortKey="Lavalley, J C" sort="Lavalley, J C" uniqKey="Lavalley J" first="J. C." last="Lavalley">J. C. Lavalley</name><affiliation><mods:affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Journal of Molecular Catalysis A: Chemical</title><title level="j" type="abbrev">MOLCAA</title><idno type="ISSN">1381-1169</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1997">1997</date><biblScope unit="volume">132</biblScope><biblScope unit="issue">1</biblScope><biblScope unit="page" from="91">91</biblScope><biblScope unit="page" to="100">100</biblScope></imprint><idno type="ISSN">1381-1169</idno></series><idno type="istex">079AC37B86327E725A17F4E24841B02966053B46</idno><idno type="DOI">10.1016/S1381-1169(97)00235-5</idno><idno type="PII">S1381-1169(97)00235-5</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1381-1169</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The kinetics of the CO2/H2 reaction over ZnAl2O4 and Cu–ZnAl2O4 catalysts at 250°C up to 0.3 MPa have been followed by in situ FT-IR spectroscopy. Both methanol and carbon monoxide formation were enhanced in presence of copper. They were also produced by independent routes through different adsorbed species. Formate (type I, I′ and II), methoxy and carbonate species were identified on the support and, in addition, copper formate and copper carbonyl species when copper was present. The hydrogenation of carbonate species to copper formate species was found rate determining in methanol synthesis over the Cu–ZnAl2O4 catalyst whereas type I formate species were shown to be the active intermediate for this reaction over the ZnAl2O4 support. Carbon monoxide resulted from the water gas shift reaction probably through the same species as methanol formed over the Cu–ZnAl2O4 catalyst whereas it seemed to stem from formate species of type II in the case of the ZnAl2O4 support. Type II formate species were shown inactive in presence of copper whereas the methoxy species adsorbed on the support were found inactive in presence and in absence of copper. The comparison of these results with those previously obtained with the CO/H2 mixture showed that the nature and the role of the detected species strongly depended on the reactive atmosphere and on the presence or not of copper in the catalyst composition.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>F. Le Peltier</name><affiliations><json:string>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</json:string></affiliations></json:item><json:item><name>P. Chaumette</name><affiliations><json:string>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</json:string></affiliations></json:item><json:item><name>J. Saussey</name><affiliations><json:string>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</json:string></affiliations></json:item><json:item><name>M.M. Bettahar</name><affiliations><json:string>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</json:string><json:string>Corresponding author. Tel.: +33-3-83912066 ext. 3125; fax: +33-3-8392181; e-mail: bettahar@lcah.u-nancy.fr</json:string><json:string>1 Present address: Laboratoire de Catalyse Hétérogène, Université Henri Poincaré Nancy – I, BP 239, Vandoeuvre-les-Nancy Cedex, France.</json:string></affiliations></json:item><json:item><name>J.C. Lavalley</name><affiliations><json:string>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><abstract>The kinetics of the CO2/H2 reaction over ZnAl2O4 and Cu–ZnAl2O4 catalysts at 250°C up to 0.3 MPa have been followed by in situ FT-IR spectroscopy. Both methanol and carbon monoxide formation were enhanced in presence of copper. They were also produced by independent routes through different adsorbed species. Formate (type I, I′ and II), methoxy and carbonate species were identified on the support and, in addition, copper formate and copper carbonyl species when copper was present. The hydrogenation of carbonate species to copper formate species was found rate determining in methanol synthesis over the Cu–ZnAl2O4 catalyst whereas type I formate species were shown to be the active intermediate for this reaction over the ZnAl2O4 support. Carbon monoxide resulted from the water gas shift reaction probably through the same species as methanol formed over the Cu–ZnAl2O4 catalyst whereas it seemed to stem from formate species of type II in the case of the ZnAl2O4 support. Type II formate species were shown inactive in presence of copper whereas the methoxy species adsorbed on the support were found inactive in presence and in absence of copper. The comparison of these results with those previously obtained with the CO/H2 mixture showed that the nature and the role of the detected species strongly depended on the reactive atmosphere and on the presence or not of copper in the catalyst composition.</abstract><qualityIndicators><score>6.881</score><pdfVersion>1.2</pdfVersion><pdfPageSize>540 x 712 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>0</keywordCount><abstractCharCount>1412</abstractCharCount><pdfWordCount>4181</pdfWordCount><pdfCharCount>22331</pdfCharCount><pdfPageCount>10</pdfPageCount><abstractWordCount>225</abstractWordCount></qualityIndicators><title>In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts</title><pii><json:string>S1381-1169(97)00235-5</json:string></pii><genre><json:string>research-article</json:string></genre><host><volume>132</volume><pii><json:string>S1381-1169(00)X0091-X</json:string></pii><pages><last>100</last><first>91</first></pages><issn><json:string>1381-1169</json:string></issn><issue>1</issue><genre></genre><language><json:string>unknown</json:string></language><title>Journal of Molecular Catalysis. A, Chemical</title><publicationDate>1998</publicationDate></host><categories><wos><json:string>CHEMISTRY, PHYSICAL</json:string></wos></categories><publicationDate>1997</publicationDate><copyrightDate>1998</copyrightDate><doi><json:string>10.1016/S1381-1169(97)00235-5</json:string></doi><id>079AC37B86327E725A17F4E24841B02966053B46</id><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/079AC37B86327E725A17F4E24841B02966053B46/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/079AC37B86327E725A17F4E24841B02966053B46/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/079AC37B86327E725A17F4E24841B02966053B46/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>1998</date></publicationStmt><notesStmt><note type="content">Fig. 1: Variations of the wavenumber of the surface carbonyl species as a function of the partial pressure of CO2 in the case of the Cu–ZnAl2O4 catalyst. PH2=0.7 MPa, T=250°C.</note><note type="content">Fig. 2: Variation as a function of the partial pressure of CO2 in the case of the ZnAl2O4 catalyst (PH2=0.7 MPa, T=250°C) of: (A) the intensity of the characteristic bands of the adsorbed species formed; (B) the relative amount of products formed.</note><note type="content">Fig. 3: Variation of the intensity of the characteristic bands of the adsorbed species formed with time on stream under H2 atmosphere in the case of the ZnAl2O4 catalyst after switching off the flow of CO2. T=250°C.</note><note type="content">Fig. 4: Spectrum of the Cu–ZnAl2O4 catalyst under CO2/H2 flow at 250°C.</note><note type="content">Fig. 5: Variation as a function of the partial pressure of CO2 in the case of the Cu–ZnAl2O4 catalyst (PH2=0.7 MPa, T=250°C) of: (A) the intensity of the characteristic bands of the adsorbed species formed; (B) the relative amount of products formed.</note><note type="content">Fig. 6: Variation as a function of the partial pressure of H2 in the case of the Cu–ZnAl2O4 catalyst (PCO2=0.1 MPa, T=250°C) of: (A) the intensity of the characteristic bands of the adsorbed species formed; (B) the relative amount of formed products.</note><note type="content">Fig. 7: Variation of 1/rCH3OH as a function of 1/PCO2 in the case of the Cu–ZnAl2O4 catalyst. PCO2=0.1 MPa, T=250°C.</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts</title><author><persName><forename type="first">F.</forename><surname>Le Peltier</surname></persName><affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</affiliation></author><author><persName><forename type="first">P.</forename><surname>Chaumette</surname></persName><affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</affiliation></author><author><persName><forename type="first">J.</forename><surname>Saussey</surname></persName><affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</affiliation></author><author><persName><forename type="first">M.M.</forename><surname>Bettahar</surname></persName><affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</affiliation><affiliation>Corresponding author. Tel.: +33-3-83912066 ext. 3125; fax: +33-3-8392181; e-mail: bettahar@lcah.u-nancy.fr</affiliation><affiliation>1 Present address: Laboratoire de Catalyse Hétérogène, Université Henri Poincaré Nancy – I, BP 239, Vandoeuvre-les-Nancy Cedex, France.</affiliation></author><author><persName><forename type="first">J.C.</forename><surname>Lavalley</surname></persName><affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</affiliation></author></analytic><monogr><title level="j">Journal of Molecular Catalysis A: Chemical</title><title level="j" type="abbrev">MOLCAA</title><idno type="pISSN">1381-1169</idno><idno type="PII">S1381-1169(00)X0091-X</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1997"></date><biblScope unit="volume">132</biblScope><biblScope unit="issue">1</biblScope><biblScope unit="page" from="91">91</biblScope><biblScope unit="page" to="100">100</biblScope></imprint></monogr><idno type="istex">079AC37B86327E725A17F4E24841B02966053B46</idno><idno type="DOI">10.1016/S1381-1169(97)00235-5</idno><idno type="PII">S1381-1169(97)00235-5</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1998</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The kinetics of the CO2/H2 reaction over ZnAl2O4 and Cu–ZnAl2O4 catalysts at 250°C up to 0.3 MPa have been followed by in situ FT-IR spectroscopy. Both methanol and carbon monoxide formation were enhanced in presence of copper. They were also produced by independent routes through different adsorbed species. Formate (type I, I′ and II), methoxy and carbonate species were identified on the support and, in addition, copper formate and copper carbonyl species when copper was present. The hydrogenation of carbonate species to copper formate species was found rate determining in methanol synthesis over the Cu–ZnAl2O4 catalyst whereas type I formate species were shown to be the active intermediate for this reaction over the ZnAl2O4 support. Carbon monoxide resulted from the water gas shift reaction probably through the same species as methanol formed over the Cu–ZnAl2O4 catalyst whereas it seemed to stem from formate species of type II in the case of the ZnAl2O4 support. Type II formate species were shown inactive in presence of copper whereas the methoxy species adsorbed on the support were found inactive in presence and in absence of copper. The comparison of these results with those previously obtained with the CO/H2 mixture showed that the nature and the role of the detected species strongly depended on the reactive atmosphere and on the presence or not of copper in the catalyst composition.</p></abstract></profileDesc><revisionDesc><change when="1997-10-16">Registration</change><change when="1997">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/079AC37B86327E725A17F4E24841B02966053B46/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="gr1" NDATA="IMAGE" name="gr1"></istex:entity><istex:entity SYSTEM="gr2" NDATA="IMAGE" name="gr2"></istex:entity><istex:entity SYSTEM="gr3" NDATA="IMAGE" name="gr3"></istex:entity><istex:entity SYSTEM="gr4" NDATA="IMAGE" name="gr4"></istex:entity><istex:entity SYSTEM="gr5" NDATA="IMAGE" name="gr5"></istex:entity><istex:entity SYSTEM="gr6" NDATA="IMAGE" name="gr6"></istex:entity><istex:entity SYSTEM="gr7" NDATA="IMAGE" name="gr7"></istex:entity><istex:entity SYSTEM="fx2" NDATA="IMAGE" name="fx2"></istex:entity><istex:entity SYSTEM="fx1" NDATA="IMAGE" name="fx1"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>MOLCAA</jid><aid>1702</aid><ce:pii>S1381-1169(97)00235-5</ce:pii><ce:doi>10.1016/S1381-1169(97)00235-5</ce:doi><ce:copyright year="1998" type="full-transfer">Elsevier Science B.V.</ce:copyright></item-info><head><ce:title>In situ FT-IR and kinetic study of methanol synthesis from CO<ce:inf>2</ce:inf>/H<ce:inf>2</ce:inf> over ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> and Cu–ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> catalysts</ce:title><ce:author-group><ce:author><ce:given-name>F.</ce:given-name><ce:surname>Le Peltier</ce:surname><ce:cross-ref refid="AFF1">a</ce:cross-ref></ce:author><ce:author><ce:given-name>P.</ce:given-name><ce:surname>Chaumette</ce:surname><ce:cross-ref refid="AFF1">a</ce:cross-ref></ce:author><ce:author><ce:given-name>J.</ce:given-name><ce:surname>Saussey</ce:surname><ce:cross-ref refid="AFF2">b</ce:cross-ref></ce:author><ce:author><ce:given-name>M.M.</ce:given-name><ce:surname>Bettahar</ce:surname><ce:cross-ref refid="AFF2">b</ce:cross-ref><ce:cross-ref refid="FN1"><ce:sup>1</ce:sup></ce:cross-ref><ce:cross-ref refid="CORR1">*</ce:cross-ref><ce:cross-ref refid="FN1"><ce:sup>1</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>J.C.</ce:given-name><ce:surname>Lavalley</ce:surname><ce:cross-ref refid="AFF2">b</ce:cross-ref></ce:author><ce:affiliation id="AFF1"><ce:label>a</ce:label><ce:textfn>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</ce:textfn></ce:affiliation><ce:affiliation id="AFF2"><ce:label>b</ce:label><ce:textfn>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</ce:textfn></ce:affiliation><ce:correspondence id="CORR1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +33-3-83912066 ext. 3125; fax: +33-3-8392181; e-mail: bettahar@lcah.u-nancy.fr</ce:text></ce:correspondence><ce:footnote id="FN1"><ce:label>1</ce:label><ce:note-para>Present address: Laboratoire de Catalyse Hétérogène, Université Henri Poincaré Nancy – I, BP 239, Vandoeuvre-les-Nancy Cedex, France.</ce:note-para></ce:footnote></ce:author-group><ce:date-received day="18" month="7" year="1997"></ce:date-received><ce:date-accepted day="16" month="10" year="1997"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The kinetics of the CO<ce:inf>2</ce:inf>/H<ce:inf>2</ce:inf> reaction over ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> and Cu–ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> catalysts at 250°C up to 0.3 MPa have been followed by in situ FT-IR spectroscopy. Both methanol and carbon monoxide formation were enhanced in presence of copper. They were also produced by independent routes through different adsorbed species. Formate (type I, I′ and II), methoxy and carbonate species were identified on the support and, in addition, copper formate and copper carbonyl species when copper was present. The hydrogenation of carbonate species to copper formate species was found rate determining in methanol synthesis over the Cu–ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> catalyst whereas type I formate species were shown to be the active intermediate for this reaction over the ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> support. Carbon monoxide resulted from the water gas shift reaction probably through the same species as methanol formed over the Cu–ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> catalyst whereas it seemed to stem from formate species of type II in the case of the ZnAl<ce:inf>2</ce:inf>O<ce:inf>4</ce:inf> support. Type II formate species were shown inactive in presence of copper whereas the methoxy species adsorbed on the support were found inactive in presence and in absence of copper. The comparison of these results with those previously obtained with the CO/H<ce:inf>2</ce:inf> mixture showed that the nature and the role of the detected species strongly depended on the reactive atmosphere and on the presence or not of copper in the catalyst composition.</ce:simple-para></ce:abstract-sec></ce:abstract></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>In situ FT-IR and kinetic study of methanol synthesis from CO2/H2 over ZnAl2O4 and Cu–ZnAl2O4 catalysts</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>In situ FT-IR and kinetic study of methanol synthesis from CO</title></titleInfo><name type="personal"><namePart type="given">F.</namePart><namePart type="family">Le Peltier</namePart><affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">P.</namePart><namePart type="family">Chaumette</namePart><affiliation>Institut Français du Pétrole, 1, Rue du Bois-Préau, BP 311, 92506 Rueil-Malmaison, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">J.</namePart><namePart type="family">Saussey</namePart><affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">M.M.</namePart><namePart type="family">Bettahar</namePart><affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</affiliation><affiliation>Corresponding author. Tel.: +33-3-83912066 ext. 3125; fax: +33-3-8392181; e-mail: bettahar@lcah.u-nancy.fr</affiliation><affiliation>1 Present address: Laboratoire de Catalyse Hétérogène, Université Henri Poincaré Nancy – I, BP 239, Vandoeuvre-les-Nancy Cedex, France.</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">J.C.</namePart><namePart type="family">Lavalley</namePart><affiliation>Laboratoire de Catalyse et Spectrochimie, UMR CNRS 6605, ISMRA, 6, Boulevard du Maréchal Juin, 14050 Caen Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1997</dateIssued><dateValid encoding="w3cdtf">1997-10-16</dateValid><copyrightDate encoding="w3cdtf">1998</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract lang="en">The kinetics of the CO2/H2 reaction over ZnAl2O4 and Cu–ZnAl2O4 catalysts at 250°C up to 0.3 MPa have been followed by in situ FT-IR spectroscopy. Both methanol and carbon monoxide formation were enhanced in presence of copper. They were also produced by independent routes through different adsorbed species. Formate (type I, I′ and II), methoxy and carbonate species were identified on the support and, in addition, copper formate and copper carbonyl species when copper was present. The hydrogenation of carbonate species to copper formate species was found rate determining in methanol synthesis over the Cu–ZnAl2O4 catalyst whereas type I formate species were shown to be the active intermediate for this reaction over the ZnAl2O4 support. Carbon monoxide resulted from the water gas shift reaction probably through the same species as methanol formed over the Cu–ZnAl2O4 catalyst whereas it seemed to stem from formate species of type II in the case of the ZnAl2O4 support. Type II formate species were shown inactive in presence of copper whereas the methoxy species adsorbed on the support were found inactive in presence and in absence of copper. The comparison of these results with those previously obtained with the CO/H2 mixture showed that the nature and the role of the detected species strongly depended on the reactive atmosphere and on the presence or not of copper in the catalyst composition.</abstract><note type="content">Fig. 1: Variations of the wavenumber of the surface carbonyl species as a function of the partial pressure of CO2 in the case of the Cu–ZnAl2O4 catalyst. PH2=0.7 MPa, T=250°C.</note><note type="content">Fig. 2: Variation as a function of the partial pressure of CO2 in the case of the ZnAl2O4 catalyst (PH2=0.7 MPa, T=250°C) of: (A) the intensity of the characteristic bands of the adsorbed species formed; (B) the relative amount of products formed.</note><note type="content">Fig. 3: Variation of the intensity of the characteristic bands of the adsorbed species formed with time on stream under H2 atmosphere in the case of the ZnAl2O4 catalyst after switching off the flow of CO2. T=250°C.</note><note type="content">Fig. 4: Spectrum of the Cu–ZnAl2O4 catalyst under CO2/H2 flow at 250°C.</note><note type="content">Fig. 5: Variation as a function of the partial pressure of CO2 in the case of the Cu–ZnAl2O4 catalyst (PH2=0.7 MPa, T=250°C) of: (A) the intensity of the characteristic bands of the adsorbed species formed; (B) the relative amount of products formed.</note><note type="content">Fig. 6: Variation as a function of the partial pressure of H2 in the case of the Cu–ZnAl2O4 catalyst (PCO2=0.1 MPa, T=250°C) of: (A) the intensity of the characteristic bands of the adsorbed species formed; (B) the relative amount of formed products.</note><note type="content">Fig. 7: Variation of 1/rCH3OH as a function of 1/PCO2 in the case of the Cu–ZnAl2O4 catalyst. PCO2=0.1 MPa, T=250°C.</note><relatedItem type="host"><titleInfo><title>Journal of Molecular Catalysis A: Chemical</title></titleInfo><titleInfo type="abbreviated"><title>MOLCAA</title></titleInfo><genre type="Journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">19980528</dateIssued></originInfo><identifier type="ISSN">1381-1169</identifier><identifier type="PII">S1381-1169(00)X0091-X</identifier><part><date>19980528</date><detail type="volume"><number>132</number><caption>vol.</caption></detail><detail type="issue"><number>1</number><caption>no.</caption></detail><extent unit="issue pages"><start>L1</start><end>L4</end></extent><extent unit="issue pages"><start>5</start><end>144</end></extent><extent unit="pages"><start>91</start><end>100</end></extent></part></relatedItem><identifier type="istex">079AC37B86327E725A17F4E24841B02966053B46</identifier><identifier type="DOI">10.1016/S1381-1169(97)00235-5</identifier><identifier type="PII">S1381-1169(97)00235-5</identifier><accessCondition type="use and reproduction" contentType="">© 1998Elsevier Science B.V.</accessCondition><recordInfo><recordContentSource>ELSEVIER</recordContentSource><recordOrigin>Elsevier Science B.V., ©1998</recordOrigin></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/079AC37B86327E725A17F4E24841B02966053B46/enrichments/catWos"><teiHeader><profileDesc><textClass><classCode scheme="WOS">CHEMISTRY, PHYSICAL</classCode></textClass></profileDesc></teiHeader></istex:catWosTEI></enrichments><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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