How Oxygen Vacancies Activate CO2 Dissociation on TiO2 Anatase

Sep 2, 2016 - The introduction of oxygen vacancy defects gives rise to new highly stable adsorption configurations with a stronger activation of the C...
0 downloads 7 Views 637KB Size
Subscriber access provided by CORNELL UNIVERSITY LIBRARY

Article 2

2

How Oxygen Vacancies Activate CO Dissociation on TiO Anatase (001) Stijn Huygh, Annemie Bogaerts, and Erik Cornelis Neyts J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.6b07459 • Publication Date (Web): 02 Sep 2016 Downloaded from http://pubs.acs.org on September 4, 2016

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

The Journal of Physical Chemistry C is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

+RZ2[\JHQ9DFDQFLHV$FWLYDWH&2'LVVRFLDWLRQRQ7L2$QDWDVH    6WLMQ+X\JK$QQHPLH%RJDHUWV(ULN&1H\WV   5HVHDUFK *URXS 3/$60$17 'HSDUWPHQW RI &KHPLVWU\ 8QLYHUVLW\ RI $QWZHUS 8QLYHUVLWHLWVSOHLQ%$QWZHUS%HOJLXP 

&RUUHVSRQGLQJDXWKRU 7HO )D[ HPDLOHULNQH\WV#XDQWZHUSHQEH 



ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

ACS Paragon Plus Environment

Page 2 of 25

Page 3 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

 ,QWURGXFWLRQ 2QH RI WKH PDMRU FRQFHUQV RI WKH FXUUHQW HUD LV WKH JOREDO FOLPDWH FKDQJHV 7KH LQWHUJRYHUQPHQWDOSDQHORQFOLPDWHFKDQJHUHSRUWHGLQWKDWHDFKGHFDGHLQWKHODVW\HDUVKDV EHHQVXFFHVVLYHO\ZDUPHUWKDQDQ\RWKHUVLQFH,WLVJHQHUDOO\DJUHHGXSRQWKDWWKHPDLQFDXVH RI JOREDO ZDUPLQJ LV WKH DQWKURSRJHQLF H[WHQVLRQ RI WKH JUHHQKRXVH HIIHFW E\ HPLVVLRQ RI JUHHQKRXVH JDVVHV OLNH &2±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±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

ACS Paragon Plus Environment

Page 8 of 25

Page 9 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

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ƒ IRUWKHVWRLFKLRPHWULFVXUIDFHDQGEHFRPHVƒXSRQUHGXFWLRQIRUWKH7L2 I 7LPRLHW\ORFDWHG LQWKHVDPH>@URZDVWKHR[\JHQYDFDQF\2QFH&2DGVRUEVWKLVDQJOHLQFUHDVHVWRƒ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

ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

)LJXUH7KHDGVRUSWLRQHQHUJ\RIWKHDGVRUSWLRQFRQILJXUDWLRQVRI&2RQDUHGXFHGDQDWDVH  VXUIDFHZLWKDD 92YDFDQF\E 92YDFDQF\F 92YDFDQF\  $SDUW IURP WKH SRVVLEOH LQIOXHQFH RI WKH UHGXFWLRQ RI WKH 7L2 VXUIDFH RQ WKH RULJLQDO DGVRUSWLRQ FRQILJXUDWLRQV QHZ DGVRUSWLRQ SRVVLELOLWLHV DOVR DULVH RQ WKH UHGXFHG VXUIDFHV $ SLFWRULDO YLHZ RI WKH QHZO\ IRUPHG DGVRUSWLRQ FRQILJXUDWLRQV LV VKRZQ LQ )LJXUH  DQG WKH UHOHYDQW ERQG OHQJWKV ERQGDQJOHVDGVRUSWLRQHQHUJLHVYLEUDWLRQDOIUHTXHQFLHVDQGFKDUJHWUDQVIHULVJLYHQLQ7DEOH  

&2DGVRUSWLRQDWDQR[\JHQYDFDQF\ 



$WWKHVXUIDFHEULGJLQJR[\JHQYDFDQF\92

7KUHH QHZ DGVRUSWLRQ FRQILJXUDWLRQV 'B92 ,  WR 'B92 ,,,  DUH IRXQG RQ WKH UHGXFHG

VXUIDFHFRQWDLQLQJD92YDFDQF\ VHH)LJXUH 'B92 , DQG'B92 ,, DUHFRQILJXUDWLRQVZKLFK

ACS Paragon Plus Environment

Page 10 of 25

Page 11 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

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¶ LQ WKHLU SXEOLFDWLRQ7KH\IRXQGDQDGVRUSWLRQHQHUJ\RINFDOPROIRUWKHLUDGVRUSWLRQFRQILJXUDWLRQ ZKLFKLVPXFKODUJHUWKDQWKHNFDOPROUHSRUWHGLQWKLVZRUN:HVXVSHFWWKDWWKLVVLJQLILFDQW GLIIHUHQFH PLJKW EH FDXVHG E\ WKHLU XVH RI IUR]HQ FOXVWHUV 7KHVH IUR]HQ FOXVWHUV GR QRW DOORZ UHOD[DWLRQ RI WKH VXUIDFH ZKHQ WKH R[\JHQ YDFDQF\ LV FUHDWHG ZKLFK FDXVHV D VWUXFWXUH WKDW LV VLJQLILFDQWO\OHVVVWDEOHDQGWKHUHIRUHLQFUHDVHVWKHDGVRUSWLRQHQHUJ\DVWKHDGVRUSWLRQRI&2ZLOO UHOHDVHDVLJQLILFDQWSDUWRIWKHVWUHVVLQWKHVWUXFWXUH 

7KH'B92 ,, FRQILJXUDWLRQ VHH)LJXUH LVDQDGVRUSWLRQFRQILJXUDWLRQLQZKLFK&2LV

EHQWDQGRQHR[\JHQLVORFDWHGRQWKHSRVLWLRQZKHUHDVXUIDFHR[\JHQDWRPZDVUHPRYHGWRFUHDWH WKH YDFDQF\ 7KH DGVRUSWLRQ HQHUJ\ LV  NFDOPRO VHH 7DEOH   $ VWURQJ FKDUJH WUDQVIHU LV QRWLFHDEOH WR WKH FDUERQ DWRP FDXVHG E\ WKH ZHDNHQHG LQWHUDFWLRQ ZLWK WKH R[\JHQ ORFDWHG DW WKH R[\JHQYDFDQF\VLWHDVWKLVR[\JHQQRZILOOVWKHR[\JHQYDFDQF\7KH&2ERQGOHQJWKLVLQFUHDVHG IURPcLQWKHJDVSKDVHWRcIRUWKHR[\JHQORFDWHGDWWKHR[\JHQYDFDQF\VLWHDQGWR cIRUWKHR[\JHQORFDWHGDERYHWKH7LVLWH7KHWRWDOFKDUJHWUDQVIHUWR&2LVDX ZKLFKLVODUJHUWKDQIRUDQ\SUHYLRXVO\GLVFXVVHGDGVRUSWLRQFRQILJXUDWLRQ0RVWRIWKLVWUDQVIHUUHG FKDUJH LV ORFDWHG RQ WKH FDUERQ DWRP ZLWK D FKDQJH RI  DX FRPSDUHG WR WKH JDV SKDVH VWUXFWXUH,QWKLVFRQILJXUDWLRQDVWURQJUHGVKLIWLVDJDLQIRXQGIURPFPWRFP7KH ORQJHU&2ERQGVVWURQJUHGVKLIWDQGWKHVLJQLILFDQWFKDUJHWUDQVIHULQGLFDWHWKHVWURQJHVWDFWLYDWLRQ RI&2UHGXFWLRQWR&2WKXVIDU

ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60



7KHODVWFRQILJXUDWLRQWKDWZDVIRXQGWREHVWDEOHRQWKHDQDWDVH  VXUIDFHFRQWDLQLQJD

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

:H KDYH WULHG WR UHSURGXFH WKH VWUXFWXUH &2>7L29R@& RI 3LSRUQSRQJ HW DO ,Q WKLV

QRQGLVVRFLDWLYHDGVRUSWLRQFRQILJXUDWLRQWKHR[\JHQYDFDQF\LVILOOHGZLWKRQHRIWKHR[\JHQDWRPV RI &2 DQG &2 LV RULHQWHG LQ D VLPLODU PDQQHU DV 'B92 ,,,  +RZHYHU ZH IRXQG WKDW WKLV FRQILJXUDWLRQ LV QRW VWDEOH DQG VSRQWDQHRXVO\ FRQYHUWV WR 'B92 ,  3RVVLEO\ 3LSRUQSRQJ HW DO IRXQGWKLVVWUXFWXUHWREHVWDEOHDVWKHUHVXOWRIWKHLUIUR]HQFOXVWHUDSSURDFKZKLFKFDQHUURQHRXVO\ FUHDWHDQHQHUJ\EDUULHUEHWZHHQWKHVHWZRFRQILJXUDWLRQV  

$WWKHILUVWVXEVXUIDFHR[\JHQYDFDQF\92

2QHQHZDGVRUSWLRQFRQILJXUDWLRQ'B92 , LVIRXQGRQWKHUHGXFHGVXUIDFHFRQWDLQLQJD

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

$WWKHVHFRQGVXEVXUIDFHR[\JHQYDFDQF\92

:KHQ D 92 R[\JHQ YDFDQF\ LV SUHVHQW ZH ILQG WZR QHZ PRQRGHQWDWHG FDUERQDWH

FRQILJXUDWLRQVRQWKHDQDWDVH  VXUIDFH7KHRQO\GLIIHUHQFHEHWZHHQWKHWZRFRQILJXUDWLRQVLV WKHLURULHQWDWLRQUHODWLYHWRWKHR[\JHQYDFDQF\,QWKH'B92 , FRQILJXUDWLRQWKHR[\JHQDWRPRI &2WKDWLVERQGHGWRWKHVXUIDFHLVORFDWHGDERYHWKHWLWDQLXPDWRPORFDWHGDWWKHR[\JHQYDFDQF\ VLWH ZKLOH LQ WKH 'B92 ,,  FRQILJXUDWLRQ WKLV R[\JHQ LV ORFDWHG DERYH WKH WLWDQLXP DWRP LQ WKH VDPH >@ URZ DQG QHLJKERXULQJ >@ URZ $V PHQWLRQHG EHIRUH ZH KDYH WULHG WR FUHDWH VLPLODU

ACS Paragon Plus Environment

Page 12 of 25

Page 13 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

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

)LJXUH 7KH QHZ DGVRUSWLRQ FRQILJXUDWLRQV RI &2 RQ D UHGXFHG DQDWDVH  VXUIDFHZLWK GLIIHUHQW R[\JHQ YDFDQFLHV LQ VLGH YLHZ DQG WRS YLHZ XSSHU DQG ORZHU SDQHOV UHVSHFWLYHO\  6HHWH[WIRUH[SODQDWLRQ 7L EOXH27L2 UHG2&2 UHGDQG\HOORZSOXVVLJQ& EURZQ   7DEOH$GVRUSWLRQSURSHUWLHVRI&2RQWKHUHGXFHG7L2DQDWDVH  VXUIDFHVZLWK GLIIHUHQWR[\JHQYDFDQFLHV7KHERQGOHQJWKVEHWZHHQ7LDQG2RI&2U 7L2&2 EHWZHHQ WKHVXUIDFH2DQG&U 2V& DQGEHWZHHQ&DQG2RIFDUERQU &2 WKHERQGDQJOHRI&2 Į 2&2 WKHDGVRUSWLRQHQHUJ\YLEUDWLRQDOIUHTXHQFLHVȣ &2 DQGWKHFKDUJHWUDQVIHUIURP WKHVXUIDFHWR&2ǻT &2 _H_ &RQILJXUDWLRQ

U 7L2 

U 2V& 

U &2 

Į 2&2 

(DGV

ȣ &2 

c 

c 

c 

GHJ 

NFDOPRO 

FP 

ǻT &2 _H_

*DVSKDVH





















'B92 , 





















'B92 ,, 





















 'B92 ,,, 





















'B92 , 





















'B92 , 





















'B92 ,, 























&2DGVRUSWLRQDW.RQDQDWDVH   $W QRQ]HUR WHPSHUDWXUH ZH ILQG WKDW WKH &2 DGVRUSWLRQ LV GHVWDELOL]HG UHGXFLQJ WKH DGVRUSWLRQVWUHQJWKRIWKHFKHPLVRUEHGFRQILJXUDWLRQIURPNFDOPRODW.WRNFDOPRODW

ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 25

 . RQ WKH IXOO\ R[LGL]HG VXUIDFH 7KH SK\VLVRUEHG FRQILJXUDWLRQV EHFRPH PHWDVWDEOH DQG WKH DGVRUSWLRQLVHQGRWKHUPLFZLWKDQDGVRUSWLRQHQHUJ\UDQJLQJIURPWRNFDOPROPDLQWDLQLQJ WKH VDPH RUGHU LQ VWDELOLW\ DV DW DEVROXWH ]HUR 7KH GLIIXVLRQ EDUULHUV IURP WKH SK\VLVRUEHG FRQILJXUDWLRQV WR WKH EHQW FDUERQDWH FRQILJXUDWLRQ GHFUHDVH IRU WKH / ,  FRQILJXUDWLRQ IURP  NFDOPRODW.WRNFDOPRODW.DQGLQFUHDVHIRU/ ,, DQG/ ,,, ZLWKDPD[LPDOEDUULHURI  NFDOPRO DW  . IRU / ,,,  7KH UDWH FRQVWDQWV IRU WKH FRQYHUVLRQ RI WKH SK\VLVRUEHG FRQILJXUDWLRQWRWKHFKHPLVRUEHGFRQILJXUDWLRQDUHLQWKHRUGHURI±V+RZHYHUGLIIXVLRQ EHWZHHQDGVRUSWLRQVLWHVIRU% , LVXQOLNHO\WRRFFXUDWWKHVHWHPSHUDWXUHVDVWKHUHDFWLRQUDWHHTXDOV [VDW.7KHLQIOXHQFHRIR[\JHQYDFDQFLHVRQWKHDGVRUSWLRQVWD\VVLPLODUDWHOHYDWHG WHPSHUDWXUHVFRPSDUHGWRWKHLULQIOXHQFHDWDEVROXWH]HUR$OODGVRUSWLRQHQHUJLHVDWDEVROXWH]HUR .DQG.DUHJLYHQLQ7DEOH 7DEOH7KHDGVRUSWLRQHQHUJLHVRQWKHVWRLFKLRPHWULFDQGUHGXFHGVXUIDFHVDWDEVROXWH]HUR .DQG.LQNFDOPRO7KHHQGRWKHUPLFDQGHQGHUJRQLFDGVRUSWLRQFRQILJXUDWLRQVDUH JLYHQLQUHG $EVROXWH]HUR

.

.

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

VLWH

92





























VLWH 

% , 



























/ , 































/ ,, 































/ ,,, 































92



























% , 



















/ , 



















/ ,, 



















/ ,,, 















92































% , 































/ , 































/ ,, 































/ ,,, 































'B92 , 







'B92 ,, 







'B92 ,,, 







'B92 , 







'B92 , 







'B92 ,, 









&2GLVVRFLDWLRQRQDQDWDVH    6WRLFKLRPHWULFDQDWDVH  VXUIDFH

ACS Paragon Plus Environment

Page 15 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

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



)LJXUH7KH&2GLVVRFLDWLRQPLQLPDOHQHUJ\SDWKZD\VWDUWLQJIURP% , RQWKH VWRLFKLRPHWULFDQDWDVH  VXUIDFH1R]HURSRLQWHQHUJ\FRUUHFWLRQVDUHLQFOXGHGLQWKH PLQLPDOHQHUJ\SDWKZD\VKRZQ  5HGXFHGDQDWDVH  VXUIDFH :H KHUH GLVFXVV WKH UHDFWLRQ SRVVLELOLWLHV DQG UDWHV IRU &2 GLVVRFLDWLRQ LQ WKH SUHVHQFH RI WKH GLIIHUHQWR[\JHQYDFDQFLHV:HH[FOXGHWKH92YDFDQF\DVZHIRXQGWKDWWKHGLVVRFLDWLRQUHDFWLRQ ZRXOG EH HQGRWKHUPLF E\ DURXQG  NFDOPRO DQG ZRXOG KHQFH QRW \LHOG D IHDVLEOH GLVVRFLDWLRQ

ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

)LJXUH7KH&2GLVVRFLDWLRQPLQLPDOHQHUJ\SDWKZD\VWDUWLQJIURP'B92 , RQWKH UHGXFHGDQDWDVH  VXUIDFH1R]HURSRLQWHQHUJ\FRUUHFWLRQVDUHLQFOXGHGLQWKHPLQLPDO HQHUJ\SDWKZD\VKRZQ )RU'B92 ,, ZHILQGDEDUULHURINFDOPRO VHH)LJXUH $WWKHWUDQVLWLRQVWDWHWKH&2ERQG OHQJWK KDV LQFUHDVHG IURP  c WR  c DIWHU ZKLFK LW ZLOO FRQYHUW WR DQ DGVRUEHG &2 RQ WKH IXOO\ R[LGL]HG VXUIDFH 7KH UHDFWLRQ LV H[RWKHUPLF ZLWK D UHDFWLRQ HQWKDOS\ RI  NFDOPRO 7KH HTXLOLEULXPFRQVWDQWDW.LVHTXDOWR[ZLWKDGLVVRFLDWLRQUDWHRI[V

ACS Paragon Plus Environment

Page 16 of 25

Page 17 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

)LJXUH7KH&2GLVVRFLDWLRQPLQLPDOHQHUJ\SDWKZD\VWDUWLQJIURP'B92 ,, RQWKH UHGXFHGDQDWDVH  VXUIDFH1R]HURSRLQWHQHUJ\FRUUHFWLRQVDUHLQFOXGHGLQWKHPLQLPDO HQHUJ\SDWKZD\VKRZQ :HDOVRSHUIRUPHGDQXGJHGHODVWLFEDQGFDOFXODWLRQIRUWKHGLVVRFLDWLRQSDWKZD\RIWKH'B92 ,,,  FRQILJXUDWLRQ7KLVFRQILJXUDWLRQKDGDQDGVRUSWLRQHQHUJ\RIRQO\NFDOPRODWDEVROXWH]HURDQG NFDOPRODW.VRLWZLOOQRWVLJQLILFDQWO\FRQWULEXWHWRWKHRYHUDOOGLVVRFLDWLRQRI&27KLV FRQILJXUDWLRQILUVWFRQYHUWVWRWKH/ ,, FRQILJXUDWLRQZLWKQREDUULHUDIWHUZKLFKWKH&2LQWKH/ ,,  FRQILJXUDWLRQ FURVVHV D EDUULHU RI  NFDOPRO 7KH RYHUDOO UHDFWLRQ HQWKDOS\ LV HTXDO WR  NFDOPROVRLIDUHDFWLRQRFFXUVLWLVXQOLNHO\WKDWWKHUHIRUPDWLRQRI'B92 ,,, ZLOORFFXUDVWKH HTXLOLEULXP FRQVWDQW IRU GLVVRFLDWLRQ LV [ 7KLV SDWKZD\ DOVR VKRZV WKDW RQFH &2 LV DGVRUEHG LQ WKH / ,,  FRQILJXUDWLRQ LW RQO\ KDV WR FURVV D EDUULHU RI  NFDOPRO WR GLVVRFLDWH UHVXOWLQJ LQ DGLVVRFLDWLRQ UHDFWLRQ UDWH RI [ V DW  . 7KLV UHDFWLRQ LV FRPSHWLWLYH WR WKH FRQYHUVLRQRI/ ,, WR% , ZKLFKKDGDEDUULHURINFDOPRO

)LJXUH7KH&2GLVVRFLDWLRQPLQLPDOHQHUJ\SDWKZD\VWDUWLQJIURP'B92 ,,, RQWKH UHGXFHGDQDWDVH  VXUIDFH1R]HURSRLQWHQHUJ\FRUUHFWLRQVDUHLQFOXGHGLQWKHPLQLPDO HQHUJ\SDWKZD\VKRZQ $VVWDUWLQJSRLQWVIRUWKHDFWLYDWLRQRIWKHGLVVRFLDWLRQUHDFWLRQRQWKHUHGXFHGDQDWDVH  VXUIDFH ZLWK D 92 R[\JHQ YDFDQF\ ZH XVHG WZR GLIIHUHQW DGVRUSWLRQ FRQILJXUDWLRQV LH 'B92 ,  DQG % ,  DGVRUEHG ZLWK RQH RI WKH R[\JHQ DWRPV RI &2 ERQGHG WR RQH RI WKH 7L FHQWHUV 7KH

ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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c DQG  c 7KH FDUERQ DWRP VWD\V ERQGHG WR DOO RI WKH WKUHH RULJLQDO R[\JHQ DWRPVRIWKH% , FRQILJXUDWLRQ7KHUHDFWLRQSDWKZD\FRQWLQXHVE\WKHHORQJDWLRQRIWKH&2ERQG IURP WKH R[\JHQ WKDW LV ILOOLQJ WKH 92 R[\JHQ YDFDQF\ 7KH ERQG HORQJDWHV IURP  c LQ WKH LQWHUPHGLDWH VWUXFWXUH WR  c LQ WKH WUDQVLWLRQ VWDWH ,Q WKLV SURFHVV D EDUULHU RI  NFDOPRO QHHGVWREHRYHUFRPH$IWHUKHDOLQJWKHR[\JHQYDFDQF\WKH'B92 , FRQILJXUDWLRQLVIRUPHGDQG WKH GLVVRFLDWLRQ RI &2 ZLOO WKHQ RFFXU WKURXJK WKH SDWKZD\ RI 'B92 ,  7KH RYHUDOO UHDFWLRQ LV H[RWKHUPLFDQGWKHUHDFWLRQHQWKDOS\LVHTXDOWRNFDOPRO7KHUDWHOLPLWLQJVWHSLQWKLVUHDFWLRQ PHFKDQLVP LV WKH HORQJDWLRQ RI WKH &2 ERQG IURP WKH R[\JHQ WKDW LV ILOOLQJ WKH 92 R[\JHQ

ACS Paragon Plus Environment

Page 18 of 25

Page 19 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

YDFDQF\FDXVLQJWKHUHDFWLRQUDWHWRGURSWRVDW.ZKLFKLQFUHDVHVWR[VDW . $OOHQHUJ\EDUULHUVDWDEVROXWH]HUR.DQG.DQGDOOUDWHFRQVWDQWVIRUGLIIXVLRQDQG GLVVRFLDWLRQDW.DQG.DUHJLYHQLQ7DEOH

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

6WDUW

(QG

5F. V 

5F. V 

/ ,  % ,  / ,,  % ,  / ,,,  % ,  % ,  

% ,  / ,  % ,  / ,,  % ,  / ,,,  % ,  

[ [ [ [ [ [ [ 

[ [ [ [ [ [ [ 

'LVVRFLDWHG % ,  'LVVRFLDWHG ,QW'B92 ,  7RWDO 'B92 ,  ,QW'B92 ,  7RWDO 'LVVRFLDWHG

% ,  'LVVRFLDWHG ,QW'B92 ,  'B92 , 

 [ [ [ [ [   

[ [ [ [ [ [ [ [ [

,QW'B92 ,  'LVVRFLDWHG 'B92 ,, 

ǻ*. NFDOPRO         

ǻ*. NFDOPRO         

ǻ(HOHF NFDOPRO         

ǻ(HOHFW]SH NFDOPRO         

   

   

   

   

 

 

 

 









ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

      92

'B92 ,,  'LVVRFLDWHG ,QW'B92 ,,,  7RWDO 'B92 ,,,  ,QW'B92 ,,,  7RWDO 'LVVRFLDWHG 'B92 ,  'LVVRFLDWHG ,QW'B92 ,  'B92 ,  ,QW% ,  7RWDO % ,  ,QW% ,  'B92 ,  ,QW'B92 ,  7RWDO

'LVVRFLDWHG ,QW'B92 ,,,  'B92 ,,,   ,QW'B92 ,,,  'LVVRFLDWHG  'B92 ,  'LVVRFLDWHG ,QW'B92 ,  'B92 ,  ,QW% ,  % ,  ,QW% ,  'B92 ,  ,QW'B92 ,  'LVVRFLDWHG

[ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [  [

[ [ [ [ [ [ [ [  [ [ [ [ [ [ [ [ [ [

Page 20 of 25

            

            

            

            

   

   

   

   

 

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

ACS Paragon Plus Environment

Page 21 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

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ࣟ6\QWKHVLV5HSRUW   2UHVNHV17KH6FLHQWLILF&RQVHQVXVRQ&OLPDWH&KDQJH6FLHQFH±   %DO]DQL9&UHGL$9HQWXUL03KRWRFKHPLFDO&RQYHUVLRQRI6RODU(QHUJ\ &KHP6XV&KHP±   QDWLRQDORFHDQLFDQGDWPRVSKHULFDGPLQLVWUDWLRQ KWWSZZZHVUOQRDDJRYJPGFFJJWUHQGVJOREDOKWPO DFFHVVHG0D\    6QRHFN[5+HLMNHUV69DQ:HVHQEHHFN./HQDHUWV6%RJDHUWV$&2&RQYHUVLRQLQ D'LHOHFWULF%DUULHU'LVFKDUJH3ODVPD1LQWKH0L[DVD+HOSLQJ+DQGRU3UREOHPDWLF ,PSXULW\"(QHUJ\(QYLURQ6FL±   %RJDHUWV$.R]DN7YDQ/DHU.6QRHFN[53ODVPD%DVHG&RQYHUVLRQRI&2&XUUHQW 6WDWXVDQG)XWXUH&KDOOHQJHV)DUDGD\'LVFXVV±   5DPDNHUV00LFKLHOVHQ,$HUWV50H\QHQ9%RJDHUWV$(IIHFWRI$UJRQRU+HOLXP RQWKH&2&RQYHUVLRQLQD'LHOHFWULF%DUULHU'LVFKDUJH3ODVPD3URFHVV3RO\P ±

ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

  $HUWV50DUWHQV7%RJDHUWV$,QIOXHQFHRI9LEUDWLRQDO6WDWHVRQ&26SOLWWLQJE\ 'LHOHFWULF%DUULHU'LVFKDUJHV-3K\V&KHP&±   $HUWV56RPHUV:%RJDHUWV$&DUERQ'LR[LGH6SOLWWLQJLQD'LHOHFWULF%DUULHU 'LVFKDUJH3ODVPD$&RPELQHG([SHULPHQWDODQG&RPSXWDWLRQDO6WXG\&KHP6XV&KHP ±   3DXOXVVHQ69HUKH\GH%7X;%LH&'H0DUWHQV73HWURYLF'%RJDHUWV$6HOV %&RQYHUVLRQRI&DUERQ'LR[LGHWR9DOXH$GGHG&KHPLFDOVLQ$WPRVSKHULF3UHVVXUH 'LHOHFWULF%DUULHU'LVFKDUJHV3ODVPD6RXUFHV6FL7HFKQRO   1H\WV(&%RJDHUWV$8QGHUVWDQGLQJ3ODVPD&DWDO\VLVWKURXJK0RGHOOLQJDQG 6LPXODWLRQD5HYLHZ-3K\V'$SSO3K\V   1H\WV(&2VWULNRY. .HQ 6XQNDUD0.%RJDHUWV$3ODVPD&DWDO\VLV6\QHUJLVWLF (IIHFWVDWWKH1DQRVFDOH&KHP5HY±   '¶$OHVVDQGUR'06PLW%/RQJ-5&DUERQ'LR[LGH&DSWXUH3URVSHFWVIRU1HZ 0DWHULDOV$QJHZ&KHP,QW(G(QJO±   ,QRXH7)XMLVKLPD$.RQLVKL6+RQGD.3KRWRHOHFWURFDWDO\WLF5HGXFWLRQRI&DUERQ 'LR[LGHLQ$TXHRXV6XVSHQVLRQVRI6HPLFRQGXFWRU3RZGHUV1DWXUH±