RUPDWLRQRI'&U\VWDOVZLWK6TXDUH/DWWLFH6WUXFWXUHIURPWKH/LTXLG6WDWH &RPS3K\VLFV/DE+RFKL0LQK&LW\8QLYRI7HFKQRORJ\9LHWQDP1DWO8QLYHUVLW\±+RFKL0LQK&LW\ /\7KXRQJ.LHW6WUHHW'LVWULFW+RFKL0LQK&LW\9LH
Trang 1The 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
Vo Van Hoang, and Hieu Thanh Nguyen
J Phys Chem C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.6b06704 • Publication Date (Web): 26 Jul 2016
Downloaded from http://pubs.acs.org on July 30, 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
Trang 2)RUPDWLRQRI'&U\VWDOVZLWK6TXDUH/DWWLFH6WUXFWXUHIURPWKH/LTXLG6WDWH
&RPS3K\VLFV/DE+RFKL0LQK&LW\8QLYRI7HFKQRORJ\9LHWQDP1DWO8QLYHUVLW\±+RFKL0LQK&LW\ /\7KXRQJ.LHW6WUHHW'LVWULFW+RFKL0LQK&LW\9LHWQDP
VTXDUH LQWHUDWRPLF SRWHQWLDO SURSRVHG E\ 0 5HFKWVPDQ HW DO 3K\V 5HY (
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
,1752'8&7,21
Trang 3LQVXODWRUV PRQROD\HU S\ULWH )H6 ' LFH VTXDUH ' JROG DQG SODWLQXP ,QGHHG WKH
VWDELOLW\ DQG HOHFWURQLF SURSHUWLHV RI SXUH ' )H DQG )H& DOOR\V DUH VWXGLHG YLD ')7
FDOFXODWLRQV,WLVIRXQGWKDWSXUH')HZLWKVTXDUHODWWLFHVWUXFWXUHLVQRWVWDEOHFRPSDUHG
WRWKDWZLWKWULDQJOHRQHZKLOHPRQROD\HU)H&ZLWK)HDWRPVRIGLVWRUWHGVTXDUHODWWLFHKDV
EHHQ IRXQG ,QWHUHVWLQJO\ ' VTXDUH LFH FRQILQHG EHWZHHQ WZR JUDSKHQH VKHHWV KDV EHHQ
LQ OLWHUDWXUH ,W LV FOHDU WKDW ' PDWHULDOV ZLWK VTXDUH ODWWLFH VWUXFWXUH DUH D VSHFLILF QHZ
FODVV RI ' PDWHULDOV +RZHYHU RXU XQGHUVWDQGLQJ RI WKHLU VWUXFWXUDO DQG WKHUPRG\QDPLF
EHKDYLRUV LV DOPRVW FRPSOHWHO\ ODFNLQJ VLQFH PRVW DWWHQWLRQ KDV EHHQ SDLG RQ WKHLU WKHUPDO
Trang 4,Q DGGLWLRQ D ZLGHO\ DFFHSWHG WKHRU\ RI PHOWLQJ RI ' FU\VWDOV LV %HUH]LQVN\
.RVWHUOLW]7KRXOHVV1HOVRQ+DOSHULQ<RXQJ %.71+< RQH LH PHOWLQJ RI ' FU\VWDOV
FRQVLVWV RI WZR FRQWLQXRXV WUDQVLWLRQV ' FU\VWDOV KH[DWLF SKDVH LVRWURSLF OLTXLG+H[DWLFLVDQLQWHUPHGLDWHSKDVHZLWKDTXDVLORQJUDQJHRULHQWDWLRQRUGHU6RPHH[SHULPHQWV
DQG VLPXODWLRQV VXSSRUW %.71+< WKHRU\ KRZHYHU VRPH RWKHU VWXGLHV VKRZ D ILUVWRUGHU
FKDUDFWHULVWLFEHKDYLRURIPHOWLQJRI'FU\VWDOVZLWKRXWDKH[DWLFSKDVHVHHPRUHGHWDLOVLQ
5HIDQGUHIHUHQFHVWKHUHLQ $FFRUGLQJWRVRPHUHFHQWVWXGLHVPHOWLQJRIORZGHQVLW\'
FU\VWDOV ZLWK WULDQJXODU ODWWLFH VWUXFWXUH IROORZV %.71+< WKHRU\ ZKLOH PHOWLQJ RI KLJK
GHQVLW\ ' FU\VWDOV ZLWK D VTXDUH ODWWLFH VWUXFWXUH H[KLELWV D ILUVWRUGHU SKDVH WUDQVLWLRQ
DQG WHPSHUDWXUH &XW RII UDGLXV IRU SRWHQWLDO LV DGRSWHG /HQQDUG-RQHV
UHGXFHGXQLWVDUHXVHGDVIROORZVOHQJWKLQXQLWVRI WHPSHUDWXUH LQXQLWVRI DQG
Trang 5WLPHLQXQLWVRI ZKHUH LVWKH%ROW]PDQQFRQVWDQW LVDQDWRPLFPDVV LVDWRPLFGLDPHWHUDQG LVDGHSWKRI/-OLNHSDUWRISRWHQWLDO9HUOHWDOJRULWKPLVHPSOR\HG
DQG0'WLPHVWHSLV ,QLWLDODWRPLFFRQILJXUDWLRQVRI'VLPSOHVTXDUHODWWLFH
VWUXFWXUH RI WKH VL]H RI DQG DW WKH IL[HG GHQVLW\ KDYH EHHQ
UHOD[HGDWWHPSHUDWXUHDVKLJKDV IRU 0'VWHSVLQRUGHUWRJHWHTXLOLEULXPOLTXLG
VWDWH7KHQWKHV\VWHPLVFRROHGGRZQDWWKHµFRQVWDQWDUHD¶ZKLOHWHPSHUDWXUHLVGHFUHDVHG
OLQHDUO\ ZLWK WLPH DV YLD WKH VLPSOH DWRPLF YHORFLW\ UHVFDOLQJ XQWLO UHDFKLQJ
+HUH SHU0'VWHSLVDFRROLQJUDWHDQG LVWKHQXPEHURI0'VWHSVZH
XVH90'VRIWZDUHIRU'YLVXDOL]DWLRQRIDWRPLFFRQILJXUDWLRQV,QRUGHUWRLPSURYHWKH
VWDWLVWLFVUHVXOWVDUHDYHUDJHGRYHUWZRLQGHSHQGHQWUXQVDQGILQDOFRQILJXUDWLRQVDW KDYHEHHQUHOD[HGIRU 0'VWHSVEHIRUHFDUU\LQJRXWVWUXFWXUDODQDO\VLV:HXVHWKHFXWRII
UDGLXVRI IRUFDOFXODWLRQRIYDULRXVTXDQWLWLHVVXFKDVFRRUGLQDWLRQQXPEHUERQG
DQJOH LQWHUDWRPLF GLVWDQFH HWF 7KLV FXW RII UDGLXV LV HTXDO WR WKH SRVLWLRQ RI WKH ILUVW
PLQLPXP DIWHU WKH ILUVW SHDN LQ 5') RI PRGHO DW ,6$$&6 VRIWZDUH LV XVHG IRU
FDOFXODWLQJULQJVWDWLVWLFVZLWKWKH*XWWPDQ¶VUXOH
5(68/76$1'',6&866,216
7KHUPRG\QDPLFVDQGHYROXWLRQRIVWUXFWXUHXSRQFRROLQJIURPWKHPHOW
7HPSHUDWXUH GHSHQGHQFH RI YDULRXV WKHUPRG\QDPLF TXDQWLWLHV RI WKH V\VWHP XSRQ
FRROLQJ IURP WKH PHOW FDQ EH VHHQ LQ )LJXUH )LJXUH DQG )LJXUH 2QH FDQ VHH WKDW
VROLGLILFDWLRQ FU\VWDOOL]DWLRQ RI WKH V\VWHPDSSHDUV WR EH DILUVWRUGHUOLNH SKDVH WUDQVLWLRQ
DOWKRXJK WKH FKDQJH RI HQHUJ\ DW DURXQG IUHH]LQJ WHPSHUDWXUH LV QRW VKDUS VHH )LJXUH
)RU D SHUIHFW VTXDUH ODWWLFH VWUXFWXUH DQG IRU D IXOO GLVRUGHUHG VWDWH LVHTXDOWR]HUR$VVKRZQLQWKHLQVHWRI)LJXUHLQWKHKLJKWHPSHUDWXUHUHJLRQLQGHHG LVDOPRVW HTXDO WR ]HUR +RZHYHU LW VWURQJO\ LQFUHDVHV LQ WKH FU\VWDOOL]DWLRQ UHJLRQ DURXQG
DQGUHDFKHVDW LQGLFDWLQJDKLJKGHJUHHRIVTXDUHODWWLFHRUGHULQWKHREWDLQHG ' VROLG 4XDQWLW\ LV QRW HTXDO WR IRU RXU ' VTXDUH ODWWLFH LQGLFDWHG WKHH[LVWHQFH RI D VLJQLILFDQW DPRXQW RI VWUXFWXUDO GHIHFWV LQ PRGHOV REWDLQHG µQDWXUDOO\¶ E\FRROLQJIURPWKHPHOW:HZLOOUHWXUQWRWKLVSUREOHPODWHU
6WUXFWXUDOSURSHUWLHVRI'VTXDUHODWWLFHFU\VWDO
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
U 1
Trang 9DQGODUJHPHPEHUUHGULQJVPLJKWEHPRUHUHDFWLYHWKDQIROGRQHV$WRPVZLWK DQG
ULQJVGLIIHUHGIURPIROGFDQEHFRQVLGHUHGDVVWUXFWXUDOGHIHFWVZKLFKFDQSOD\DQLPSRUWDQW
UROHLQYDULRXVSK\VLFRFKHPLFDOSHUIRUPDQFHVRI'PDWHULDOV7KHUHLVQRZRUNUHODWHGWR
WKH DQDO\VLV RI VWUXFWXUDO GHIHFWV LQ ' FU\VWDOV ZLWK VTXDUH ODWWLFH VWUXFWXUH LQ RUGHU WR
FRPSDUH DQG GLVFXVV ,WLV ZHOONQRZQ WKDW LQ JUDSKHQH VWUXFWXUDO GHIHFWV DFW DVFHQWHUV IRU
LPSXULWLHV ZLWK DQ HQKDQFHG FKHPLFDO UHDFWLYLW\ YDULRXV W\SHV RI GHIHFWV LQ JUDSKHQH DQG
WKHLU UROH LQ SK\VLFRFKHPLFDO SHUIRUPDQFHV RI JUDSKHQH FDQ EH IRXQG LQ OLWHUDWXUH6LPLODU UROH RI GHIHFWV IRU ' FU\VWDOV ZLWK VTXDUH ODWWLFH VWUXFWXUH FDQ EH VXJJHVWHG ,W LV
WKH DWRPLF FRQILJXUDWLRQ )RU VLPSOLFLW\ ZH XVH VLPSOH ' QHWZRUN DQG DWRPV DUH
LQWHUVHFWLRQ SRLQWV RI WKH ERQGV IRU GHVFULELQJ RI DWRPLF FRQILJXUDWLRQ VHH )LJXUH DQG
Trang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
$GGLWLRQDO LQIRUPDWLRQ RI VWUXFWXUH RI ' FU\VWDO FRQILJXUDWLRQ REWDLQHG E\ FRROLQJIURPWKHPHOWFDQEHVHHQLQ)LJXUHLHDWRPVZLWKWKHVDPHRUFORVHORFDOERQGRULHQWDWLRQRUGHU DUHPDUNHGE\WKHVDPHFRORU2QHFDQVHHWKDWVWUXFWXUHRI'FU\VWDOVIRUPHGµQDWXUDOO\¶ E\ FRROLQJ IURP WKH PHOW LV QRW KRPRJHQHRXV VLQFH LW FRQWDLQV PLFURVFRSLFFOXVWHUV ZLWK GLIIHUHQW YDOXHV RI ORFDO ERQGRULHQWDWLRQ RUGHU ,W FDQ EH FDOOHG µVWDWLFKHWHURJHQHLW\¶ RI ' FU\VWDOV ,W LV FOHDU WKDW WKH GHJUHH RI µVWDWLF KHWHURJHQHLW\¶ VKRXOGGHSHQGRQV\QWKHVLVPHWKRGRI'PDWHULDOVDQGSK\VLFRFKHPLFDOEHKDYLRUVRI'FU\VWDOVVKRXOGGHSHQGRQWKHGHJUHHRIµVWDWLFKHWHURJHQHLW\¶7KHSUREOHPKDVQRWEHHQPHQWLRQHGLQ OLWHUDWXUH \HW IRU FU\VWDOV DOWKRXJK WKH HYLGHQFH RI µVWDWLF KHWHURJHQHLW\¶ RI OLTXLGV DQGJODVVHVFDQEHVHHQVRPHZKHUH
Trang 11YDULRXV GHILQLWLRQV RI VROLGOLNH DWRPV XVHG LQ OLWHUDWXUH LQFOXGLQJ WKRVH EDVHG RQ WKHLU
G\QDPLFVXVLQJWKHIUHH]LQJOLNH/LQGHPDQQUDWLR$QRWKHUDSSURDFKLVEDVHGRQWKHORFDO
ERQGRULHQWDWLRQ RUGHU RU EDVHG RQ ERWK WKH /LQGHPDQQ UDWLR DQG ERQGRULHQWDWLRQ
RUGHU :H FDQ LQIHU VRPH SRLQWV UHODWHG WR VROLGLILFDWLRQ RI WKH V\VWHP YLD VWXG\LQJ RI
RFFXUUHQFH DQG JURZWK RI KLJKERQGRULHQWDWLRQRUGHUHG +%22 DWRPV ZKLFK FDQ EH
FRQVLGHUHG DV VROLGOLNH DWRPV ZLWK VRPH DSSUR[LPDWLRQV LH WKH DWRPV ZLWK ORFDO ERQG
RULHQWDWLRQ RUGHU ODUJHU WKDQ D FULWLFDO YDOXH VHH (T DQG )LJXUH :H KDYH
WHVWHGDQGIRXQGWKDWWKHYDOXHRIJOREDOERQGRULHQWDWLRQRUGHUDW LH VHH)LJXUHDQG)LJXUH ...
UHIHUHQFH D[LV WKH VXP RYHU LV FDOFXODWHG RYHU DOO QHDUHVWQHLJKERUV 7KH JOREDOERQGRULHQWDWLRQRUGHU LVFDOFXODWHGYLDDYHUDJLQJRYHUDOODWRPVLQWKHV\VWHP... HOHFWURQLF SURSHUWLHV RI SXUH '' )H DQG )H& DOOR\V DUH VWXGLHG YLD '')7
FDOFXODWLRQV,WLVIRXQGWKDWSXUH'')HZLWKVTXDUHODWWLFHVWUXFWXUHLVQRWVWDEOHFRPSDUHG... WKHLU WKHUPDO
Trang 4,Q DGGLWLRQ D ZLGHO\ DFFHSWHG WKHRU\ RI PHOWLQJ RI '' FU\VWDOV LV %HUH]LQVN\