Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalystsElectronic supplementary information (ESI) available: Nitrogen physisorption isotherms and textural parameters of prepared catalysts; Cu 2p XPS spectrum of 5-Cu; glycerol conversions at varying temperatures, oxygen pressures and NaOH : glycerol molar ratios; glycerol conversion after adding additional NaOH during the reaction; selectivity-time profiles in water/ethanol mixtures; selectivities and carbon mass bala

Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by sel...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Hauptverfasser: Schünemann, Stefan, Schüth, Ferdi, Tüysüz, Harun
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 5624
container_issue 23
container_start_page 5614
container_title
container_volume 7
creator Schünemann, Stefan
Schüth, Ferdi
Tüysüz, Harun
description Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by selective oxidation. Usually, the selective oxidation of glycerol utilizes expensive noble metal catalysts, such as Au, Pt, and Pd. Here we report the selective oxidation of glycerol in basic media, using ordered mesoporous Cu-Al 2 O 3 catalysts with various Cu loadings prepared by a facile soft-templating method. The materials were characterized in detail by nitrogen physisorption, vis-NIR spectroscopy, EDX, low- and wide-angle XRD, XPS, and TEM. Subsequently the reaction conditions for glycerol oxidation were optimized. The catalytic oxidation of glycerol yields C 3 products, such as glyceric acid and tartronic acid, and also C 2 and C 1 products, such as glycolic acid, oxalic acid, and formic acid. Moreover, the role of the solvent on the catalytic reaction was investigated, and the addition of various co-solvents to the aqueous reaction mixture was found to increase the initial reaction rate up to a factor of three. The trends of the initial reaction rates correlate well with the polarity of the water/co-solvent mixtures. The prepared Cu-Al 2 O 3 catalysts are a more cost-efficient and environmentally viable alternative to the reported noble metal catalysts. Ordered mesoporous Cu-Al 2 O 3 catalysts were employed for the selective oxidation of glycerol into value-added products. Co-solvents such as ethanol, 1-propanol, and tert -butanol strongly improve the reaction kinetics.
doi_str_mv 10.1039/c7cy01451a
format Article
fullrecord <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_c7cy01451a</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>c7cy01451a</sourcerecordid><originalsourceid>FETCH-rsc_primary_c7cy01451a3</originalsourceid><addsrcrecordid>eNqFkj2P00AQhg0CiRNcQ480dCARzs4Hx13KKOhoDqRQ0EUTe5ws2i_NrEPc0fI3-RWUzJooR4HA0mo_xvO-z7t2UTytytdVObm6qC_rvqymswrvF2fjcjodTS_fVA9O69nkUXEu8qXUZ3pVlW_HZ_d-rshSncyeYGv7mjhYCAfTYDLBQ9gTQ-CGmBpwJCEGDp1AHWLUCtrOGd-5oYOgxoS2lyTLLMnBmxqki9GSI5-QezC-Dex-a79Yrt6_BNyjsbixdA23Rnu25CHuejESOA7v6SrtiJ0A-gYSHVLHaCEio6NELBBaiEx6oJAnhjksOhhH-PxxBRIzT-ZsYTZadPO7rHXwmlHUSPUT7JXS-K3aOA2IakXySuP1A5duJJ8MJLf44ebHt-_XOk5qLlhk4BxQ_moC2KZ8cU2TXfKUM2qcrAZNx4P5joAJ61yagxw_kEn9KBlHihFaY5XCePiKKndBaYc-25vDQPxnkzni1sgb9XcoAhu0-KR42KIVOj_Oj4tn75afFjcjlnod2Ti9ifXdHzX5f_35v-rr2LSTXzL-73g</addsrcrecordid><sourcetype>Enrichment Source</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalystsElectronic supplementary information (ESI) available: Nitrogen physisorption isotherms and textural parameters of prepared catalysts; Cu 2p XPS spectrum of 5-Cu; glycerol conversions at varying temperatures, oxygen pressures and NaOH : glycerol molar ratios; glycerol conversion after adding additional NaOH during the reaction; selectivity-time profiles in water/ethanol mixtures; selectivities and carbon mass bala</title><source>Royal Society Of Chemistry Journals 2008-</source><creator>Schünemann, Stefan ; Schüth, Ferdi ; Tüysüz, Harun</creator><creatorcontrib>Schünemann, Stefan ; Schüth, Ferdi ; Tüysüz, Harun</creatorcontrib><description>Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by selective oxidation. Usually, the selective oxidation of glycerol utilizes expensive noble metal catalysts, such as Au, Pt, and Pd. Here we report the selective oxidation of glycerol in basic media, using ordered mesoporous Cu-Al 2 O 3 catalysts with various Cu loadings prepared by a facile soft-templating method. The materials were characterized in detail by nitrogen physisorption, vis-NIR spectroscopy, EDX, low- and wide-angle XRD, XPS, and TEM. Subsequently the reaction conditions for glycerol oxidation were optimized. The catalytic oxidation of glycerol yields C 3 products, such as glyceric acid and tartronic acid, and also C 2 and C 1 products, such as glycolic acid, oxalic acid, and formic acid. Moreover, the role of the solvent on the catalytic reaction was investigated, and the addition of various co-solvents to the aqueous reaction mixture was found to increase the initial reaction rate up to a factor of three. The trends of the initial reaction rates correlate well with the polarity of the water/co-solvent mixtures. The prepared Cu-Al 2 O 3 catalysts are a more cost-efficient and environmentally viable alternative to the reported noble metal catalysts. Ordered mesoporous Cu-Al 2 O 3 catalysts were employed for the selective oxidation of glycerol into value-added products. Co-solvents such as ethanol, 1-propanol, and tert -butanol strongly improve the reaction kinetics.</description><identifier>ISSN: 2044-4753</identifier><identifier>EISSN: 2044-4761</identifier><identifier>DOI: 10.1039/c7cy01451a</identifier><language>eng</language><creationdate>2017-11</creationdate><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids></links><search><creatorcontrib>Schünemann, Stefan</creatorcontrib><creatorcontrib>Schüth, Ferdi</creatorcontrib><creatorcontrib>Tüysüz, Harun</creatorcontrib><title>Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalystsElectronic supplementary information (ESI) available: Nitrogen physisorption isotherms and textural parameters of prepared catalysts; Cu 2p XPS spectrum of 5-Cu; glycerol conversions at varying temperatures, oxygen pressures and NaOH : glycerol molar ratios; glycerol conversion after adding additional NaOH during the reaction; selectivity-time profiles in water/ethanol mixtures; selectivities and carbon mass bala</title><description>Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by selective oxidation. Usually, the selective oxidation of glycerol utilizes expensive noble metal catalysts, such as Au, Pt, and Pd. Here we report the selective oxidation of glycerol in basic media, using ordered mesoporous Cu-Al 2 O 3 catalysts with various Cu loadings prepared by a facile soft-templating method. The materials were characterized in detail by nitrogen physisorption, vis-NIR spectroscopy, EDX, low- and wide-angle XRD, XPS, and TEM. Subsequently the reaction conditions for glycerol oxidation were optimized. The catalytic oxidation of glycerol yields C 3 products, such as glyceric acid and tartronic acid, and also C 2 and C 1 products, such as glycolic acid, oxalic acid, and formic acid. Moreover, the role of the solvent on the catalytic reaction was investigated, and the addition of various co-solvents to the aqueous reaction mixture was found to increase the initial reaction rate up to a factor of three. The trends of the initial reaction rates correlate well with the polarity of the water/co-solvent mixtures. The prepared Cu-Al 2 O 3 catalysts are a more cost-efficient and environmentally viable alternative to the reported noble metal catalysts. Ordered mesoporous Cu-Al 2 O 3 catalysts were employed for the selective oxidation of glycerol into value-added products. Co-solvents such as ethanol, 1-propanol, and tert -butanol strongly improve the reaction kinetics.</description><issn>2044-4753</issn><issn>2044-4761</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFkj2P00AQhg0CiRNcQ480dCARzs4Hx13KKOhoDqRQ0EUTe5ws2i_NrEPc0fI3-RWUzJooR4HA0mo_xvO-z7t2UTytytdVObm6qC_rvqymswrvF2fjcjodTS_fVA9O69nkUXEu8qXUZ3pVlW_HZ_d-rshSncyeYGv7mjhYCAfTYDLBQ9gTQ-CGmBpwJCEGDp1AHWLUCtrOGd-5oYOgxoS2lyTLLMnBmxqki9GSI5-QezC-Dex-a79Yrt6_BNyjsbixdA23Rnu25CHuejESOA7v6SrtiJ0A-gYSHVLHaCEio6NELBBaiEx6oJAnhjksOhhH-PxxBRIzT-ZsYTZadPO7rHXwmlHUSPUT7JXS-K3aOA2IakXySuP1A5duJJ8MJLf44ebHt-_XOk5qLlhk4BxQ_moC2KZ8cU2TXfKUM2qcrAZNx4P5joAJ61yagxw_kEn9KBlHihFaY5XCePiKKndBaYc-25vDQPxnkzni1sgb9XcoAhu0-KR42KIVOj_Oj4tn75afFjcjlnod2Ti9ifXdHzX5f_35v-rr2LSTXzL-73g</recordid><startdate>20171127</startdate><enddate>20171127</enddate><creator>Schünemann, Stefan</creator><creator>Schüth, Ferdi</creator><creator>Tüysüz, Harun</creator><scope/></search><sort><creationdate>20171127</creationdate><title>Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalystsElectronic supplementary information (ESI) available: Nitrogen physisorption isotherms and textural parameters of prepared catalysts; Cu 2p XPS spectrum of 5-Cu; glycerol conversions at varying temperatures, oxygen pressures and NaOH : glycerol molar ratios; glycerol conversion after adding additional NaOH during the reaction; selectivity-time profiles in water/ethanol mixtures; selectivities and carbon mass bala</title><author>Schünemann, Stefan ; Schüth, Ferdi ; Tüysüz, Harun</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c7cy01451a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>online_resources</toplevel><creatorcontrib>Schünemann, Stefan</creatorcontrib><creatorcontrib>Schüth, Ferdi</creatorcontrib><creatorcontrib>Tüysüz, Harun</creatorcontrib></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Schünemann, Stefan</au><au>Schüth, Ferdi</au><au>Tüysüz, Harun</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalystsElectronic supplementary information (ESI) available: Nitrogen physisorption isotherms and textural parameters of prepared catalysts; Cu 2p XPS spectrum of 5-Cu; glycerol conversions at varying temperatures, oxygen pressures and NaOH : glycerol molar ratios; glycerol conversion after adding additional NaOH during the reaction; selectivity-time profiles in water/ethanol mixtures; selectivities and carbon mass bala</atitle><date>2017-11-27</date><risdate>2017</risdate><volume>7</volume><issue>23</issue><spage>5614</spage><epage>5624</epage><pages>5614-5624</pages><issn>2044-4753</issn><eissn>2044-4761</eissn><abstract>Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by selective oxidation. Usually, the selective oxidation of glycerol utilizes expensive noble metal catalysts, such as Au, Pt, and Pd. Here we report the selective oxidation of glycerol in basic media, using ordered mesoporous Cu-Al 2 O 3 catalysts with various Cu loadings prepared by a facile soft-templating method. The materials were characterized in detail by nitrogen physisorption, vis-NIR spectroscopy, EDX, low- and wide-angle XRD, XPS, and TEM. Subsequently the reaction conditions for glycerol oxidation were optimized. The catalytic oxidation of glycerol yields C 3 products, such as glyceric acid and tartronic acid, and also C 2 and C 1 products, such as glycolic acid, oxalic acid, and formic acid. Moreover, the role of the solvent on the catalytic reaction was investigated, and the addition of various co-solvents to the aqueous reaction mixture was found to increase the initial reaction rate up to a factor of three. The trends of the initial reaction rates correlate well with the polarity of the water/co-solvent mixtures. The prepared Cu-Al 2 O 3 catalysts are a more cost-efficient and environmentally viable alternative to the reported noble metal catalysts. Ordered mesoporous Cu-Al 2 O 3 catalysts were employed for the selective oxidation of glycerol into value-added products. Co-solvents such as ethanol, 1-propanol, and tert -butanol strongly improve the reaction kinetics.</abstract><doi>10.1039/c7cy01451a</doi><tpages>11</tpages></addata></record>
fulltext fulltext
identifier ISSN: 2044-4753
ispartof
issn 2044-4753
2044-4761
language eng
recordid cdi_rsc_primary_c7cy01451a
source Royal Society Of Chemistry Journals 2008-
title Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalystsElectronic supplementary information (ESI) available: Nitrogen physisorption isotherms and textural parameters of prepared catalysts; Cu 2p XPS spectrum of 5-Cu; glycerol conversions at varying temperatures, oxygen pressures and NaOH : glycerol molar ratios; glycerol conversion after adding additional NaOH during the reaction; selectivity-time profiles in water/ethanol mixtures; selectivities and carbon mass bala
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-26T21%3A30%3A23IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-rsc&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Selective%20glycerol%20oxidation%20over%20ordered%20mesoporous%20copper%20aluminum%20oxide%20catalystsElectronic%20supplementary%20information%20(ESI)%20available:%20Nitrogen%20physisorption%20isotherms%20and%20textural%20parameters%20of%20prepared%20catalysts;%20Cu%202p%20XPS%20spectrum%20of%205-Cu;%20glycerol%20conversions%20at%20varying%20temperatures,%20oxygen%20pressures%20and%20NaOH%E2%80%89:%E2%80%89glycerol%20molar%20ratios;%20glycerol%20conversion%20after%20adding%20additional%20NaOH%20during%20the%20reaction;%20selectivity-time%20profiles%20in%20water/ethanol%20mixtures;%20selectivities%20and%20carbon%20mass%20bala&rft.au=Sch%C3%BCnemann,%20Stefan&rft.date=2017-11-27&rft.volume=7&rft.issue=23&rft.spage=5614&rft.epage=5624&rft.pages=5614-5624&rft.issn=2044-4753&rft.eissn=2044-4761&rft_id=info:doi/10.1039/c7cy01451a&rft_dat=%3Crsc%3Ec7cy01451a%3C/rsc%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true