Energy Maps of Complex Catalyst Surfaces

Chemical reactions that are crucial for energy conversion require catalysts with intricate functional interfaces characterized by high structural and compositional complexity. Computational catalysis offers predictive insights through the simulation of surface structures and elementary processes, bu...

Full description

Saved in:
Bibliographic Details
Published inACS catalysis Vol. 14; no. 16; pp. 12581 - 12591
Main Authors Tarasov, Andrey V., Wrabetz, Sabine, Kröhnert, Jutta, Rosowski, Frank, Schlögl, Robert, Trunschke, Annette
Format Journal Article
LanguageEnglish
Published American Chemical Society 16.08.2024
Subjects
microcalorimetry
adsorption sites
propene adsorption
alkane oxidation
propane adsorption
Online AccessGet full text

Cover

Abstract Chemical reactions that are crucial for energy conversion require catalysts with intricate functional interfaces characterized by high structural and compositional complexity. Computational catalysis offers predictive insights through the simulation of surface structures and elementary processes, but reliable experimental benchmarks are essential for validation. In this study, we provide such experimental data by determining the energetic distribution of adsorption sites of short-chain alkanes (ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) on the surface of the polycrystalline oxides V2O5, MnWO4, SmMnO3, and MoVO x , and on the benchmark catalyst vanadyl pyrophosphate (VO)2P2O7 (VPP) using microcalorimetry. From the measurement of the heat of adsorption as a function of the degree of coverage, energy distribution spectra were derived, which represent a quantitative energetic fingerprint of the functional interface. Using the adsorption data, turnover frequencies were determined for the oxidation of propane, which served as a complex probe reaction. The integral heat of adsorption of the reactant propane normalized to the number of adsorption sites was thus determined as a descriptor for activity. Correlation diagrams of propane and propene adsorption allow to predict the selectivity. The maximum turnover frequency of the formation of valuable oxygenates is found at moderate adsorption strength of the intermediate propene. The presented method provides a reference data set for systems where detailed atomistic information about the structure of active sites is difficult to obtain due to their inherent complexity.
AbstractList Chemical reactions that are crucial for energy conversion require catalysts with intricate functional interfaces characterized by high structural and compositional complexity. Computational catalysis offers predictive insights through the simulation of surface structures and elementary processes, but reliable experimental benchmarks are essential for validation. In this study, we provide such experimental data by determining the energetic distribution of adsorption sites of short-chain alkanes (ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) on the surface of the polycrystalline oxides V2O5, MnWO4, SmMnO3, and MoVO x , and on the benchmark catalyst vanadyl pyrophosphate (VO)2P2O7 (VPP) using microcalorimetry. From the measurement of the heat of adsorption as a function of the degree of coverage, energy distribution spectra were derived, which represent a quantitative energetic fingerprint of the functional interface. Using the adsorption data, turnover frequencies were determined for the oxidation of propane, which served as a complex probe reaction. The integral heat of adsorption of the reactant propane normalized to the number of adsorption sites was thus determined as a descriptor for activity. Correlation diagrams of propane and propene adsorption allow to predict the selectivity. The maximum turnover frequency of the formation of valuable oxygenates is found at moderate adsorption strength of the intermediate propene. The presented method provides a reference data set for systems where detailed atomistic information about the structure of active sites is difficult to obtain due to their inherent complexity.
Author Schlögl, Robert
Kröhnert, Jutta
Wrabetz, Sabine
Tarasov, Andrey V.
Trunschke, Annette
Rosowski, Frank
AuthorAffiliation Department of Inorganic Chemistry
BasCatUniCat BASF JointLab
AuthorAffiliation_xml – name: Department of Inorganic Chemistry
– name: BasCatUniCat BASF JointLab
Author_xml – sequence: 1
  givenname: Andrey V.
  surname: Tarasov
  fullname: Tarasov, Andrey V.
  organization: Department of Inorganic Chemistry
– sequence: 2
  givenname: Sabine
  surname: Wrabetz
  fullname: Wrabetz, Sabine
  organization: Department of Inorganic Chemistry
– sequence: 3
  givenname: Jutta
  surname: Kröhnert
  fullname: Kröhnert, Jutta
  organization: Department of Inorganic Chemistry
– sequence: 4
  givenname: Frank
  surname: Rosowski
  fullname: Rosowski, Frank
  organization: BasCatUniCat BASF JointLab
– sequence: 5
  givenname: Robert
  surname: Schlögl
  fullname: Schlögl, Robert
  organization: Department of Inorganic Chemistry
– sequence: 6
  givenname: Annette
  orcidid: 0000-0003-2869-0181
  surname: Trunschke
  fullname: Trunschke, Annette
  email: trunschke@fhi-berlin.mpg.de
  organization: Department of Inorganic Chemistry
BookMark eNp1j71PwzAQxS1UJErpzpiRgZTzV2KPKCofUhEDMFu2YyOqNI7sVCL_Pa5aJBZuudO7e0_3u0SzPvQOoWsMKwwE32mbrB51t2IWMAVxhuYEc15yRvnsz3yBliltIRfjlahhjm7WvYufU_Gih1QEXzRhN3Tuu2gOcVMai7d99Nq6dIXOve6SW576An08rN-bp3Lz-vjc3G9KjSs6lsbyljhrQBha1UK32nFpjJSeYcqA-QoIJYJAlgVxrQBRGyYZ5rI1AI4uEBxzbQwpRefVEL92Ok4KgzrAql9YdYLNltujJW_UNuxjnx_8__wHIB5YZA
Cites_doi 10.1246/bcsj.52.2849
10.1002/cssc.201802248
10.1002/cctc.202301242
10.1002/cctc.201601194
10.1038/s41929-022-00906-z
10.1021/acs.chemrev.0c01060
10.1016/j.jcat.2009.11.018
10.1021/acscatal.0c01289
10.1021/acs.jpcc.1c10401
10.1021/cr00035a009
10.1021/jacs.2c11117
10.1038/s41570-021-00340-y
10.1038/s43588-022-00280-7
10.1002/anie.201201866
10.1021/acscatal.7b00130
10.1098/rspa.1925.0061
10.3389/fchem.2021.746229
10.1007/978-3-642-11954-5
10.1021/acscatal.7b01648
10.1039/a908988h
10.1021/j100084a023
10.1021/acs.jpcc.6b09949
10.1021/ja0611745
10.1016/j.cattod.2018.06.003
10.1557/s43577-021-00165-6
10.1016/j.jcat.2011.09.012
10.1103/PhysRevB.100.035439
10.1021/acs.jpcc.0c04777
10.1006/jcat.2002.3615
10.1038/s41467-022-28042-z
10.1016/j.jcat.2017.08.020
10.1021/cr300329s
10.1002/cctc.202201276
10.1021/acs.jpcc.8b07417
10.1021/acs.accounts.8b00579
10.1021/acs.chemrev.0c00394
10.1016/j.cattod.2014.05.036
10.1039/C8SC04641G
10.1002/9783527810253.ch3
10.1016/j.susc.2015.03.023
10.1021/acs.chemrev.7b00236
10.1039/C3CY00705G
10.1021/acs.jctc.2c01005
10.1021/ja02242a004
10.1016/j.jcat.2014.12.033
10.1038/s41929-019-0376-6
10.1002/anie.201510201
10.1016/j.jcat.2014.06.003
10.1016/S1381-1169(00)00333-2
10.1016/j.jcat.2012.08.010
10.1016/0926-860X(95)00322-3
10.1063/1.4974931
10.1016/0040-6031(85)80075-7
10.1021/acs.jpcc.9b01273
10.1038/s41929-017-0016-y
10.1039/D0CP03732J
10.1002/anie.201410738
10.1002/cctc.201700847
10.1016/S0079-6816(00)00019-8
10.1016/j.coelec.2017.01.004
10.1021/acs.jpcb.7b06314
10.1021/jp961816i
10.1016/s0360-0564(08)60007-3
10.1038/s41467-019-12858-3
10.1021/jp074452a
10.1002/anie.202302971
ContentType Journal Article
Copyright 2024 The Authors. Published by American Chemical Society
Copyright_xml – notice: 2024 The Authors. Published by American Chemical Society
DBID AAYXX
CITATION
DOI 10.1021/acscatal.4c01308
DatabaseName CrossRef
DatabaseTitle CrossRef
DatabaseTitleList
DeliveryMethod fulltext_linktorsrc
Discipline Chemistry
EISSN 2155-5435
EndPage 12591
ExternalDocumentID 10_1021_acscatal_4c01308
d204064226
GroupedDBID .K2
55A
7~N
AABXI
AAHBH
ABJNI
ABMVS
ABQRX
ABUCX
ACGFO
ACGFS
ACS
ADHLV
AEESW
AENEX
AFEFF
AHGAQ
ALMA_UNASSIGNED_HOLDINGS
AQSVZ
BAANH
CUPRZ
EBS
ED~
GGK
GNL
IH9
JG~
RNS
ROL
UI2
VF5
VG9
W1F
AAYXX
CITATION
ID FETCH-LOGICAL-a163t-bc5d2ecb08b3678adae59bb99f413404f60232820e5982ed8087b494159db00e3
IEDL.DBID ACS
ISSN 2155-5435
IngestDate Wed Aug 28 12:34:27 EDT 2024
Mon Aug 19 05:43:27 EDT 2024
IsPeerReviewed true
IsScholarly true
Issue 16
Keywords microcalorimetry
adsorption sites
propene adsorption
alkane oxidation
propane adsorption
Language English
LinkModel DirectLink
MergedId FETCHMERGED-LOGICAL-a163t-bc5d2ecb08b3678adae59bb99f413404f60232820e5982ed8087b494159db00e3
ORCID 0000-0003-2869-0181
PageCount 11
ParticipantIDs crossref_primary_10_1021_acscatal_4c01308
acs_journals_10_1021_acscatal_4c01308
PublicationCentury 2000
PublicationDate 2024-08-16
PublicationDateYYYYMMDD 2024-08-16
PublicationDate_xml – month: 08
  year: 2024
  text: 2024-08-16
  day: 16
PublicationDecade 2020
PublicationTitle ACS catalysis
PublicationTitleAlternate ACS Catal
PublicationYear 2024
Publisher American Chemical Society
Publisher_xml – name: American Chemical Society
References ref9/cit9
ref45/cit45
ref3/cit3
ref27/cit27
ref63/cit63
Dummer N. F. (ref40/cit40) 2011; 54
ref56/cit56
Rumble J. R. (ref59/cit59) 2022
ref16/cit16
Bennici S. (ref6/cit6) 2009
ref52/cit52
ref23/cit23
ref8/cit8
ref31/cit31
ref2/cit2
ref34/cit34
ref71/cit71
ref37/cit37
ref20/cit20
ref48/cit48
ref60/cit60
ref17/cit17
ref10/cit10
Klyachko A. L. (ref12/cit12) 1978; 19
ref35/cit35
ref53/cit53
ref19/cit19
ref21/cit21
ref42/cit42
ref46/cit46
ref49/cit49
ref13/cit13
ref67/cit67
ref24/cit24
ref38/cit38
ref50/cit50
ref64/cit64
ref54/cit54
ref36/cit36
ref18/cit18
van Santen R. A. (ref61/cit61) 2017
Calvet E. (ref4/cit4) 1958
ref65/cit65
ref25/cit25
ref29/cit29
ref72/cit72
ref32/cit32
ref39/cit39
ref14/cit14
ref57/cit57
ref5/cit5
ref51/cit51
ref43/cit43
ref28/cit28
ref68/cit68
ref26/cit26
ref55/cit55
ref69/cit69
Auroux A. (ref11/cit11) 1982; 10
ref15/cit15
ref62/cit62
ref66/cit66
ref41/cit41
ref58/cit58
ref22/cit22
ref33/cit33
ref30/cit30
ref47/cit47
ref1/cit1
Auroux A. (ref44/cit44) 2013
ref70/cit70
ref7/cit7
References_xml – ident: ref10/cit10
  doi: 10.1246/bcsj.52.2849
– ident: ref39/cit39
  doi: 10.1002/cssc.201802248
– ident: ref68/cit68
  doi: 10.1002/cctc.202301242
– ident: ref47/cit47
  doi: 10.1002/cctc.201601194
– ident: ref50/cit50
  doi: 10.1038/s41929-022-00906-z
– ident: ref18/cit18
  doi: 10.1021/acs.chemrev.0c01060
– ident: ref43/cit43
  doi: 10.1016/j.jcat.2009.11.018
– ident: ref33/cit33
  doi: 10.1021/acscatal.0c01289
– ident: ref48/cit48
  doi: 10.1021/acs.jpcc.1c10401
– ident: ref17/cit17
  doi: 10.1021/cr00035a009
– volume: 54
  start-page: 189
  volume-title: Advances in Catalysis
  year: 2011
  ident: ref40/cit40
  contributor:
    fullname: Dummer N. F.
– ident: ref37/cit37
  doi: 10.1021/jacs.2c11117
– ident: ref60/cit60
  doi: 10.1038/s41570-021-00340-y
– ident: ref21/cit21
  doi: 10.1038/s43588-022-00280-7
– ident: ref31/cit31
  doi: 10.1002/anie.201201866
– ident: ref34/cit34
  doi: 10.1021/acscatal.7b00130
– ident: ref13/cit13
  doi: 10.1098/rspa.1925.0061
– ident: ref32/cit32
  doi: 10.3389/fchem.2021.746229
– volume-title: Calorimetry and Thermal Methods in Catalysis
  year: 2013
  ident: ref44/cit44
  doi: 10.1007/978-3-642-11954-5
  contributor:
    fullname: Auroux A.
– ident: ref20/cit20
  doi: 10.1021/acscatal.7b01648
– ident: ref51/cit51
  doi: 10.1039/a908988h
– ident: ref42/cit42
  doi: 10.1021/j100084a023
– volume: 19
  start-page: 1218
  issue: 5
  year: 1978
  ident: ref12/cit12
  publication-title: Kinet. Katal.
  contributor:
    fullname: Klyachko A. L.
– ident: ref54/cit54
  doi: 10.1021/acs.jpcc.6b09949
– volume: 10
  start-page: 305
  volume-title: Studies in Surface Science and Catalysis
  year: 1982
  ident: ref11/cit11
  contributor:
    fullname: Auroux A.
– ident: ref53/cit53
  doi: 10.1021/ja0611745
– ident: ref56/cit56
  doi: 10.1016/j.cattod.2018.06.003
– ident: ref36/cit36
  doi: 10.1557/s43577-021-00165-6
– volume-title: CRC Handbook of Chemistry and Physics
  year: 2022
  ident: ref59/cit59
  contributor:
    fullname: Rumble J. R.
– ident: ref46/cit46
  doi: 10.1016/j.jcat.2011.09.012
– ident: ref23/cit23
  doi: 10.1103/PhysRevB.100.035439
– ident: ref41/cit41
  doi: 10.1021/acs.jpcc.0c04777
– ident: ref62/cit62
  doi: 10.1006/jcat.2002.3615
– ident: ref22/cit22
  doi: 10.1038/s41467-022-28042-z
– ident: ref67/cit67
  doi: 10.1016/j.jcat.2017.08.020
– ident: ref9/cit9
  doi: 10.1021/cr300329s
– ident: ref71/cit71
  doi: 10.1002/cctc.202201276
– ident: ref28/cit28
  doi: 10.1021/acs.jpcc.8b07417
– ident: ref27/cit27
  doi: 10.1021/acs.accounts.8b00579
– ident: ref2/cit2
  doi: 10.1021/acs.chemrev.0c00394
– ident: ref14/cit14
  doi: 10.1016/j.cattod.2014.05.036
– ident: ref30/cit30
  doi: 10.1039/C8SC04641G
– start-page: 59
  volume-title: Modern Heterogeneous Catalysis
  year: 2017
  ident: ref61/cit61
  doi: 10.1002/9783527810253.ch3
  contributor:
    fullname: van Santen R. A.
– ident: ref8/cit8
  doi: 10.1016/j.susc.2015.03.023
– ident: ref38/cit38
  doi: 10.1021/acs.chemrev.7b00236
– ident: ref66/cit66
  doi: 10.1039/C3CY00705G
– ident: ref24/cit24
  doi: 10.1021/acs.jctc.2c01005
– ident: ref1/cit1
  doi: 10.1021/ja02242a004
– ident: ref19/cit19
  doi: 10.1016/j.jcat.2014.12.033
– ident: ref26/cit26
  doi: 10.1038/s41929-019-0376-6
– ident: ref29/cit29
  doi: 10.1002/anie.201510201
– ident: ref64/cit64
  doi: 10.1016/j.jcat.2014.06.003
– ident: ref57/cit57
  doi: 10.1016/S1381-1169(00)00333-2
– ident: ref52/cit52
  doi: 10.1016/j.jcat.2012.08.010
– ident: ref58/cit58
  doi: 10.1016/0926-860X(95)00322-3
– ident: ref25/cit25
  doi: 10.1063/1.4974931
– ident: ref5/cit5
  doi: 10.1016/0040-6031(85)80075-7
– ident: ref35/cit35
  doi: 10.1021/acs.jpcc.9b01273
– ident: ref70/cit70
  doi: 10.1038/s41929-017-0016-y
– ident: ref63/cit63
  doi: 10.1039/D0CP03732J
– ident: ref15/cit15
  doi: 10.1002/anie.201410738
– ident: ref45/cit45
  doi: 10.1002/cctc.201700847
– ident: ref3/cit3
  doi: 10.1016/S0079-6816(00)00019-8
– ident: ref16/cit16
  doi: 10.1016/j.coelec.2017.01.004
– ident: ref65/cit65
  doi: 10.1021/acs.jpcb.7b06314
– ident: ref49/cit49
  doi: 10.1021/jp961816i
– ident: ref7/cit7
  doi: 10.1016/s0360-0564(08)60007-3
– start-page: 391
  volume-title: Metal Oxide Catalysis
  year: 2009
  ident: ref6/cit6
  contributor:
    fullname: Bennici S.
– ident: ref69/cit69
  doi: 10.1038/s41467-019-12858-3
– ident: ref55/cit55
  doi: 10.1021/jp074452a
– volume-title: Récents Progrès en Microcalorimétrie
  year: 1958
  ident: ref4/cit4
  contributor:
    fullname: Calvet E.
– ident: ref72/cit72
  doi: 10.1002/anie.202302971
SSID ssj0000456870
Score 2.4670372
Snippet Chemical reactions that are crucial for energy conversion require catalysts with intricate functional interfaces characterized by high structural and...
SourceID crossref
acs
SourceType Aggregation Database
Publisher
StartPage 12581
Title Energy Maps of Complex Catalyst Surfaces
URI http://dx.doi.org/10.1021/acscatal.4c01308
Volume 14
hasFullText 1
inHoldings 1
isFullTextHit
isPrint
link http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwjV1LS8NAEB60HvTiW1pf7EFBD6lJ9pHNsYSWItRLLfQWdjebi9KWJgX11zubplp8QK9hGXbC7H7fzuzOB3AjKOVGYfBmVEl3QAm9mGpcV5GwSlKhrHaPkwdPoj9ij2M-_m6T87OCHwYPyhRVJqPNjKuyyW3YCSM_djINnWT4lU9x1ERW2nAIYtzjSAPqquRfRhwWmWINi9ZApXewVCcqql6E7i7JS3tR6rb5-N2pcYP5HsJ-zS1JZxkMR7BlJ8ewm6wk3U7grlu99CMDNSvINCduM3i1byRxlt6LkgwX89zd0TqFUa_7nPS9WirBU0ioSk8bnoXWaF9qivCjMmV5rHUc5whSzGe5QGzG05VvXcM-m0lfRprFiN5xhgvP0jNoTKYT2wQijI2kDnhOmWKBiZQRClmDiAIt8DNrwS26mNahXqRVFTsM0pXfae13C-5XPzedLTtn_Dv2fEObF7AXIqlwOd1AXEKjnC_sFZKCUl9X0fAJjjmvcg
link.rule.ids 315,783,787,2774,27090,27938,27939,57072,57122
linkProvider American Chemical Society
linkToHtml http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwlV1LT8MwDLbGOIwLb8R49gASHDraNUnT41RtGrDtwDZptypJ0wtom9ZOAn49TtfChECCa1RZduXk-2LHNsAV8zyqBDpv7AluLihNO_Ak7iufacE9JrQ0xcn9AeuOycOETirglrUwqESKktI8if_VXcC9w7U8oNEgyiTb-AZsUt_xzdCCVjj8DKsYhsLzEXGIZdSmyAaK5ORPQgwkqXQNktawpbMDT59a5U9KnhvLTDbU-7eGjf9Sexe2C6ZptVausQcVPd2HWlgOeDuAm3Ze92f1xTy1ZolljoYX_WqFRtJbmlnD5SIxL7YOYdxpj8KuXQxOsAXSq8yWisZNraTDpYdgJGKhaSBlECQIWcQhCUOkxruWo037Ph1zh_uSBIjlQYzbUHtHUJ3OpvoYLKa0z6VLE48I4ipfKCaQQzDflQyXSR2u0cSocPw0ynPaTTcq7Y4Ku-twW_7jaL7qo_Hrtyd_lHkJte6o34t694PHU9hqIt0w0V6XnUE1Wyz1OdKFTF7kDvIB10C32w
linkToPdf http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwlV1LS8NAEB5qBfXiW6zPHBT0kJrH7mZzLLWlPlqEWukt7G42F6UtTQrqr3c2TUoRBb0uYZgJO_t9O7MzA3DBfJ8qgZs39gU3FxTPDn2JfhUwLbjPhJamOLnbY50BuR_SYQVoWQuDSqQoKc2T-MarJ3FSdBhwb3A9D2rUiTIJN74CqzRwPTO4oNHsL0IrhqXwfEwc4hm1KTKCIkH5kxADSypdgqUlfGlvwctCs_xZyWt9lsm6-vzWtPHfqm_DZsE4rcZ8i-xARY92Yb1ZDnrbg6tWXv9ndcUktcaJZY6IN_1uNY2kjzSz-rNpYl5u7cOg3XpuduxigIItkGZltlQ09rSSDpc-gpKIhaahlGGYIHQRhyQMERvvXI42bfx0zB0eSBIipocxuqP2D6A6Go_0IVhM6YBLlyY-EcRVgVBMIJdggSsZLpMaXKKJUeEAaZTntj03Ku2OCrtrcF3-52gy76fx67dHf5R5DmtPt-3o8a73cAwbHrIOE_R12QlUs-lMnyJryORZvke-AAD1ulU
openUrl ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Energy+Maps+of+Complex+Catalyst+Surfaces&rft.jtitle=ACS+catalysis&rft.au=Tarasov%2C+Andrey+V.&rft.au=Wrabetz%2C+Sabine&rft.au=Kro%CC%88hnert%2C+Jutta&rft.au=Rosowski%2C+Frank&rft.date=2024-08-16&rft.pub=American+Chemical+Society&rft.issn=2155-5435&rft.eissn=2155-5435&rft.volume=14&rft.issue=16&rft.spage=12581&rft.epage=12591&rft_id=info:doi/10.1021%2Facscatal.4c01308&rft.externalDocID=d204064226
thumbnail_l http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=2155-5435&client=summon
thumbnail_m http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=2155-5435&client=summon
thumbnail_s http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=2155-5435&client=summon