Direct Observation, Molecular Structure, and Location of Oxidation

Jul 22, 2016 - The insights regarding the existence, molecular structures and attached sites of OD nanoparticles on GO nanosheets provide a theoretica...
0 downloads 7 Views 9MB Size
Subscriber access provided by CORNELL UNIVERSITY LIBRARY

Article

Direct Observation, Molecular Structure and Location of Oxidation Debris on Graphene Oxide Nanosheets Xiaoxiao Chen, and Baoliang Chen Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b01020 • Publication Date (Web): 22 Jul 2016 Downloaded from http://pubs.acs.org on July 22, 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.

Environmental Science & Technology 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 27

Environmental Science & Technology

í

'LUHFW 2EVHUYDWLRQ 0ROHFXODU 6WUXFWXUH DQG /RFDWLRQ RI 2[LGDWLRQ

î

'HEULV RQ *UDSKHQH 2[LGH 1DQRVKHHWV

ï ð ñ ò

;,$2;,$2 &+(1

%$2/,$1* &+(1

'HSDUWPHQW RI (QYLURQPHQWDO 6FLHQFH =KHMLDQJ 8QLYHUVLW\ +DQJ]KRX

.H\ /DERUDWRU\ RI 2UJDQLF 3ROOXWLRQ 3URFHVV DQG &RQWURO +DQJ]KRX

ó ô õ íì íí íî íï íð íñ íò íó

&KLQD

&RUUHVSRQGLQJ $XWKRU 3KRQH

)D[ (PDLO EOFKHQ#]MX HGX FQ

íô íõ îì îí îî îï îð îñ îò í

ACS Paragon Plus Environment

=KHMLDQJ 3URYLQFLDO &KLQD

Environmental Science & Technology

7DEOH RI &RQWHQW 72&

îó îô îõ

2'

D *2

EZ *2

ïì ïí EDVH ZDVKLQJ

ïî 2'

ïï ïð ïñ

/RFDWLRQ D *2

EZ *2

2'

VS VWUXFWXUH

ïò ïó ïô ïõ ðì ðí ðî ðï ðð ðñ ðò ðó ðô ðõ ñì ñí ñî î

ACS Paragon Plus Environment

Page 2 of 27

Page 3 of 27

Environmental Science & Technology

ñï

v $%675$&7

ñð

7KH SUHVHQFH RI R[LGDWLRQ GHEULV 2' FRPSOLFDWHV WKH VWUXFWXUHV DQG SURSHUWLHV RI JUDSKHQH R[LGH

ññ

*2 QDQRVKHHWV WKHUHE\ LPSDFWLQJ WKHLU SRWHQWLDO DSSOLFDWLRQV +RZHYHU WKH RULJLQ RI 2' LV VWLOO LQ

ñò

GLVSXWH 0RUHRYHU FKDUDFWHUL]LQJ WKH VWUXFWXUH DQG ORFDWLRQ RI VXSSRVHG 2' RQ QDQRVKHHWV RI *2

ñó

SURGXFHG GXULQJ WKH R[LGDWLRQ SURFHVV LV GLIILFXOW +HUHLQ WKH DWWDFKHG VWDWH DQG VL]H RI 2' RQ

ñô

JUDSKHQH R[LGH QDQRVKHHWV ZHUH GLUHFWO\ REVHUYHG XVLQJ +57(0 WKH PROHFXODU VWUXFWXUH RI 2' ZDV

ñõ

LQLWLDOO\ SURSRVHG EDVHG RQ WKH VSHFWURVFRSLF FKDUDFWHUL]DWLRQ DQG 4 72) PDVV VSHFWURPHWU\ DQG WKH

òì

ORFDWLRQV RI 2' RQ WKH *2 QDQRVKHHWV ZHUH GHWHFWHG WKURXJK WKH DGVRUSWLRQ RI SUREH PROHFXOHV RQWR

òí

DV SUHSDUHG *2 D *2 DQG EDVH ZDVKHG *2 EZ *2 7KH UHVXOWV LQGLFDWHG WKDW 2' SRVVHVVHV D

òî

KLJKO\ FU\VWDOOLQH VWUXFWXUH DQG FDQ EH GHILQHG DV VHYHUDO QDQRPHWUH VL]HG SRO\DURPDWLF PROHFXOHV

òï

ZLWK D FRQVLGHUDEOH QXPEHU RI R[\JHQ FRQWDLQLQJ IXQFWLRQDO JURXSV DWWDFKHG RQ WKH HGJHV 7KH GDUN

òð

QDQR GRW VHDWHG RQ D *2 ZDV FOHDUO\ REVHUYHG LQ WKH +57(0 LPDJHV ZKHUHDV LW DSSHDUHG DV D FOHDQ

òñ

QDQRVKHHW LQ WKH LPDJH RI EZ *2 LQGLFDWLQJ WKDW 2' LV UHPRYHG E\ EDVH ZDVKLQJ WUHDWPHQW

òò

)ROORZLQJ WKH EDVH ZDVKLQJ WUHDWPHQW WKH FRQWHQWV RI FDUER[\O JURXSV RQ EZ *2 XQH[SHFWHGO\

òó

LQFUHDVHG DQG VXEVHTXHQWO\ FRQWULEXWHG WR WKH GHVRUSWLRQ RI 2' IURP D *2 GXH WR WKH HOHFWURVWDWLF

òô

UHSXOVLRQ EHLQJ VWURQJHU WKDQ SULPDU\ Œ Œ LQWHUDFWLRQV &RPSDUHG ZLWK D *2 WKH DGVRUSWLRQ RI

òõ

SKHQDQWKUHQH DV DQ DURPDWLF SUREH RQWR EZ *2 LQFUHDVHG E\

óì

ZKHUHDV WKH LQFUHDVH LQ WKH DGVRUSWLRQ RI P GLQLWUREHQ]HQH DV D GHIHFW SUREH ZDV QRW DV UHPDUNDEOH

óí

DV WKDW RI SKHQDQWKUHQH 5HDVRQDEO\ WKH 2' QDQRSDUWLFOHV ZHUH SULPDULO\ ORFDWHG DW WKH VS

óî

VWUXFWXUHV RQ WKH *2 QDQRVKHHWV WKURXJK Œ Œ LQWHUDFWLRQV UDWKHU WKDQ DWWDFKHG RQ GHIHFWV HGJHV 7KH

óï

LQVLJKWV UHJDUGLQJ WKH H[LVWHQFH PROHFXODU VWUXFWXUHV DQG DWWDFKHG VLWHV RI 2' QDQRSDUWLFOHV RQ *2

óð

QDQRVKHHWV SURYLGH D WKHRUHWLFDO EDVLV IRU SUHSDULQJ 2' IUHH *2 IRU RSWLPL]LQJ WKH SRWHQWLDO

óñ

DSSOLFDWLRQV RI *2 QDQRVKHHWV

IROG YLD Œ Œ VWDFNLQJ LQWHUDFWLRQV

ï

ACS Paragon Plus Environment

Environmental Science & Technology

Page 4 of 27

óò

v ,1752'8&7,21

óó

*UDSKHQH D VLQJOH DWRPLF OD\HU RI VS K\EULGL]HG FDUERQ ZLWK D KRQH\FRPE FU\VWDO ODWWLFH

óô

FRQVLGHUHG WR EH WKH QH[W ZRQGHU PDWHULDO ZLWK ZLGHVSUHDG SRWHQWLDO DSSOLFDWLRQV

óõ

VWUXFWXUH DQG VXSUHPH PHFKDQLFDO RSWLFDO DQG HOHFWURQLF SURSHUWLHV

ôì

EHHQ ZLGHO\ XVHG LQ WKH DUHDV RI VXSHUFDSDFLWRUV DQG ZHDUDEOH HOHFWURQLFV

ôí

K\GURSKRELFLW\ DQG ODUJH VXUIDFH DUHD JUDSKHQH LV H[SHFWHG WR VHUYH DV D JRRG DGVRUEHQW IRU

ôî

HQYLURQPHQWDO SROOXWDQWV

ôï

PHWKRGV ZKLFK GHWHUPLQH WKH SURSHUWLHV DQG SRWHQWLDO DSSOLFDWLRQV RI JUDSKHQH EDVHG PDWHULDOV

ôð

%RWWRP XS DSSURDFKHV VXFK DV FKHPLFDO YDSRXU GHSRVLWLRQ &9' RQ UHODWLYHO\ LQH[SHQVLYH PHWDO

ôñ

IRLOV DQG WRS GRZQ PHWKRGV XVLQJ PHFKDQLFDO H[IROLDWLRQ FDQ ERWK SURGXFH KLJK TXDOLW\ JUDSKHQH

ôò

QDQRVKHHWV ,Q FRQWUDVW FKHPLFDOO\ PRGLILHG JUDSKHQH &0* KDV EHFRPH DQ DWWUDFWLYH DOWHUQDWLYH

ôó

IRU WKH V\QWKHVLV RI JUDSKHQH RQ D ODUJH VFDOH EHFDXVH LWV SURGXFWLRQ LV UHDGLO\ VFDODEOH

ôô

LV

GXH WR LWV XQLTXH

)RU H[DPSOH JUDSKHQH KDV %HFDXVH RI LWV

7KH VWUXFWXUHV RI JUDSKHQH DUH KLJKO\ GHSHQGHQW RQ WKH SUHSDUDWLRQ

*UDSKHQH R[LGH *2 ZKLFK LV SURGXFHG YLD R[LGDWLRQ DQG VXEVHTXHQW H[IROLDWLRQ RI JUDSKLWH

ôõ

SRZGHU FRQWDLQV ODUJH QXPEHUV RI R[\JHQ FRQWDLQLQJ IXQFWLRQDO JURXSV VXFK DV HSR[LGH K\GUR[LGH

õì

FDUERQ\O DQG FDUER[\O JURXSV

õí

JUDSKHQH JUDSKHQH R[LGH FDQ HDVLO\ EH UHGXFHG WR JUDSKHQH DQG WKH R[\JHQ FRQWDLQLQJ IXQFWLRQDO

õî

JURXSV FDQ EH UHPRYHG E\ DGGLQJ GLIIHUHQW UHGXFLQJ DJHQWV VXFK DV K\GUD]LQH K\GUDWH

õï

1D%+

õð

SUHVVXUHV %HVLGHV DV WKH SUHFXUVRU IRU JUDSKHQH JUDSKHQH R[LGH FDQ EH IXQFWLRQHG DQ HIIHFWLYH

õñ

DGVRUEHQW IRU WKH UHPRYDO RI SROOXWDQWV

õò

WKH EDVLF SK\VLFDO DQG FKHPLFDO VWUXFWXUHV RI JUDSKHQH R[LGH DUH VWLOO XQGHU GLVFXVVLRQ 2YHU WKH SDVW

õó

GHFDGHV GLIIHUHQW PRGHOV IRU WKH VWUXFWXUH RI JUDSKHQH R[LGH KDYH EHHQ SURSRVHG DQG WKHVH PRGHOV

õô

SULPDULO\ FRQVLVW RI D KRPRJHQHRXV R[LGL]HG VWUXFWXUH

õõ

JUDSKLWLF GRPDLQV ZULQNOHV GHIHFWV HGJHV DQG R[\JHQ FRQWDLQLQJ IXQFWLRQDO JURXSV KDYH VLJQLILFDQW

íìì

HIIHFWV RQ WKH FRQGXFWDQFH FDWDO\VLV DGVRUSWLRQ SURSHUWLHV DQG VXEVHTXHQW DSSOLFDWLRQV RI JUDSKHQH

$V WKH PDLQ SUHFXUVRU IRU WKH V\QWKHVLV DQG PRGLILFDWLRQ RI

DQG

XQGHU GLIIHUHQW UHGXFLQJ HQYLURQPHQWV ZLWK GLIIHUHQW S+ YDOXHV WHPSHUDWXUHV DQG

+RZHYHU GHVSLWH WKH H[WHQVLYH XVH RI JUDSKHQH R[LGH

0RUHRYHU WKH VXUIDFH VWUXFWXUHV VXFK DV

ð

ACS Paragon Plus Environment

Page 5 of 27

Environmental Science & Technology

íìí

R[LGH

íìî

JUDSKHQH R[LGH ZRXOG DOWHU WKH DGVRUSWLRQ SURFHVV ([FHSW IRU WKH VS VWUXFWXUHV WKH GHIHFWV HGJHV

íìï

FDQ EH IXQFWLRQDO DFWLYH VLWHV IRU QLWUR DURPDWLF FRPSRXQGV

íìð

IXQFWLRQDO JURXSV &22+ DQG ±2+ DUH HVVHQWLDO IRU WKH KLJK UHWHQWLRQ RI KHDY\ PHWDO LRQV

íìñ

UHFHQWO\ EHHQ UHSRUWHG WKDW DV SURGXFHG *2 D *2 SUHSDUHG YLD D PRGLILHG +XPPHUV PHWKRG LV

íìò

DFWXDOO\ FRPSRVHG RI JUDSKHQH OLNH VKHHWV FRPSOH[HG ZLWK ORZ PROHFXODU ZHLJKW KLJKO\ R[LGL]HG

íìó

IUDJPHQWV ZKLFK DUH QDPHG R[LGDWLRQ GHEULV 2'

íìô íìõ ííì

)RU H[DPSOH GUDPDWLF FKDQJHV LQ WKH FRQIRUPDWLRQ DQG DJJUHJDWLRQ RI WKH VWUXFWXUH RI

,Q DGGLWLRQ WKH R[\JHQ FRQWDLQLQJ ,W KDV

7KH H[LVWHQFH RI 2' KDV TXLWH GUDPDWLF HIIHFWV RQ WKH HOHFWULFDO DQG FDWDO\WLF SURSHUWLHV RI D *2

7KH UHPRYDO RI 2' UHVXOWV LQ DQ LQFUHDVH LQ WKH FRQGXFWLYLW\ RI *2 RQ WKH RUGHU RI 6P

ZKLFK LV DSSUR[LPDWHO\ ILYH RUGHUV RI PDJQLWXGH JUHDWHU WKDQ WKH FRQGXFWLYLW\ RI

ííí

D *2 DQG RQO\ DQ RUGHU RI PDJQLWXGH OHVV WKDQ WKH YDOXHV UHSRUWHG IRU *2 UHGXFHG XVLQJ FKHPLFDO RU

ííî

ORZ WHPSHUDWXUH WKHUPDO WUHDWPHQWV

ííï

R[LGH OD\HUV FDQ DOVR EORFN WKH FRQGXFWLRQ RI HOHFWURQV

ííð

WKH LQKHUHQW HOHFWUR DFWLYLW\ RI JUDSKHQH R[LGH LV DWWULEXWHG WR WKH SUHVHQFH RI R[LGDWLRQ GHEULV

ííñ

UHOHDVH RI R[LGDWLRQ GHEULV LV DJDLQVW WKH LQKHUHQW HOHFWUR DFWLYLW\ RI JUDSKHQH PDWHULDOV .LDQ HW DO

ííò

UHSRUWHG WKDW WKH 2' KDG QR YLWDO UROH LQ WKH FDWDO\WLF DFWLYLW\ DQG WKDW WKH UHPRYDO RI 2' ZDV

ííó

IDYRXUDEOH IRU DHURELF R[LGDWLRQ UHDFWLRQV

ííô

QRQFRYDOHQW FKHPLFDO IXQFWLRQDOL]DWLRQV IRU D *2

,Q DGGLWLRQ 2' KDV VLJQLILFDQW HIIHFWV RQ WKH

ííõ

GLVSHUVLELOLW\ DQG VSHFWURVFRSLF SURSHUWLHV RI *2

7KH OXPLQHVFHQFH IURP D *2 LV DWWULEXWHG WR

íîì

WKH H[LVWHQFH RI 2' DQG D *2 ZLWKRXW 2' LV D QRQ IOXRUHVFHQW PDWHULDO 5HFHQWO\ 3ROVRQ HW DO

íîí

TXHVWLRQHG WKH RULJLQ RI 2' DQG FRQVLGHUHG WKDW VR FDOOHG R[LGDWLRQ GHEULV DOOHJHGO\ SUH H[LVWLQJ RQ

íîî

D *2 LV LQ IDFW GHULYHG IURP D *2 GXULQJ WKH VWURQJ EDVH ZDVKLQJ WUHDWPHQW 7KH\ FRQWHVWHG WKH

íîï

WZR FRPSRQHQW VWUXFWXUDO PRGHO RI JUDSKHQH R[LGH L H *2 QDQRVKHHWV DWWDFKHG ZLWK 2' DQG

íîð

K\SRWKHVL]HG WKDW 2' RULJLQDWHV IURP D *2 VKHHWV E\ EDVH WUHDWPHQW FXWWLQJ YLD D & & ERQG

íîñ

FOHDYDJH UHDFWLRQ DFFRUGLQJ WR WKH ;36 VSHFWUD )7,5 DQG 6(0 FKDUDFWHUL]DWLRQ 7KH RULJLQ RI 2' LV

0RUHRYHU WKH SUHVHQFH RI 2' EHWZHHQ UHGXFHG JUDSKHQH 0DUWLQ HW DO K\SRWKHVL]HG WKDW WKH RULJLQ RI 7KH

)XUWKHUPRUH WKH 2' LQIOXHQFHG WKH FRYDOHQW DQG

ñ

ACS Paragon Plus Environment

Environmental Science & Technology

Page 6 of 27

ZKLFK UHVXOWV IURP WKH ODFN RI GHWHFWLRQ RI 2' E\ DQ\ PLFURVFRSLF RU

íîò

VWLOO LQ GLVSXWH

íîó

VSHFWURVFRSLF DSSURDFKHV 'XH WR WKH WLQ\ SLHFHV GLUHFWO\ LPDJLQJ WKH 2' DGVRUEHG RQ *2 LV

íîô

FKDOOHQJLQJ %HFDXVH WKH SUHVHQFH RI R[LGDWLRQ GHEULV 2' FRPSOLFDWHV WKH VWUXFWXUHV DQG SURSHUWLHV

íîõ

RI JUDSKHQH R[LGH *2 QDQRVKHHWV

íïì

)XUWKHUPRUH LGHQWLI\LQJ WKH ORFDWLRQV RI 2' RQ JUDSKHQH R[LGH QDQRVKHHWV KDV \HW WR EH H[SORUHG

íïí

ZKLFK LV RI SDUWLFXODU VLJQLILFDQFH IRU REWDLQLQJ GHHS LQVLJKWV UHJDUGLQJ WKH VXUIDFH FKHPLVWU\ RI

íïî

JUDSKHQH R[LGH DQG IRU IXUWKHU IXQFWLRQDOL]DWLRQ DQG DSSOLFDWLRQV RI JUDSKHQH R[LGH

íïï

LW LV LPSRUWDQW WR FRQILUP WKH RULJLQ DQG VWUXFWXUH RI 2'

$V UHSRUWHG WKH 2' RQ WKH VXUIDFH RI D *2 FDQ EH ZDVKHG RII ZLWK D EDVLF VROXWLRQ RI 1D2+ RU

íïð

DPPRQLD

íïñ

+HUHLQ ZH GLUHFWO\ LPDJHG WKH VXUIDFHV RI D *2 EZ *2 DQG 2' XVLQJ KLJK UHVROXWLRQ WUDQVPLVVLRQ

íïò

HOHFWURQ PLFURVFRS\ +57(0 DQG FRQILUPHG WKH DWWDFKHG VWDWH DQG VL]H RI 2' RQ JUDSKHQH R[LGH

íïó

QDQRVKHHWV IRU WKH ILUVW WLPH %DVHG RQ WKH VSHFWURVFRSLF FKDUDFWHUL]DWLRQ RI D *2 EZ *2 DQG 2'

íïô

DQG WKH 4 72) PDVV VSHFWURPHWU\ RI 2' WKH PROHFXODU VWUXFWXUH RI 2' ZDV LQLWLDOO\ SURSRVHG WR EH

íïõ

SRO\DURPDWLF PROHFXOHV VLPLODU WR SUHYLRXVO\ UHSRUWHG FDUERQ GRWV

íðì

QDQRVKHHWV ZHUH GHWHFWHG WKURXJK WKH DGVRUSWLRQ RI SKHQDQWKUHQH DV DQ DURPDWLF SUREH DQG

íðí

P GLQLWUREHQ]HQH DV D GHIHFW SUREH RQWR D *2 DQG EZ *2 7KH DGVRUSWLRQ VLWHV RI QDQRVL]HG 2'

íðî

ZHUH SULPDULO\ ORFDWHG DW WKH VS VWUXFWXUHV RQ *2 QDQRVKHHWV WKURXJK Œ Œ LQWHUDFWLRQV UDWKHU WKDQ

íðï

DWWDFKHG RQ GHIHFWV HGJHV

,Q WKLV VWXG\ DV SUHSDUHG *2 D *2 EDVH ZDVKHG *2 EZ *2 DQG 2' ZHUH SUHSDUHG

7KH ORFDWLRQV RI 2' RQ *2

íðð íðñ

v (;3(5,0(17$/ 6(&7,21

íðò

3UHSDUDWLRQ DQG &KDUDFWHUL]DWLRQ RI D *2 EZ *2 DQG 2' 7KH VDPSOH D *2 ZDV V\QWKHVL]HG

íðó

IURP QDWXUDO JUDSKLWH IODNHV

íðô

7KH VDPSOH RI EZ *2 DQG 2' ZDV SUHSDUHG XVLQJ DPPRQLD VROXWLRQ ZDVKLQJ PHWKRG WR WUHDW D *2

íðõ

7KH SUHSDUDWLRQ PHWKRGV ZHUH GHWDLOHG LQ 6XSSRUWLQJ ,QIRUPDWLRQ VHFWLRQ 7KH +57(0 LPDJHV ZHUH

íñì

DFTXLUHG XVLQJ D )(, 7HFQDL * )

PHVV

$OID $HVDU XVLQJ WKH PRGLILHG +XPPHUV PHWKRG

6 7:,1 DW

N9 )RU +57(0 DQDO\VLV GURSV RI D *2

ò

ACS Paragon Plus Environment

Page 7 of 27

Environmental Science & Technology

íñí

EZ *2 DQG 2' VXVSHQVLRQV LQ DFHWRQLWULOH ZDWHU ZHUH SODFHG GLUHFWO\ RQWR D PLFURJULG EHFDXVH WKH

íñî

QDQRVKHHWV FDQ IRUP D VWDEOH GLVSHUVLRQ LQ DQ DFHWRQLWULOH ZDWHU PL[

íñï

VSHFWURVFRS\ ;36 GDWD ZHUH REWDLQHG XVLQJ D 7KHUPR 6FLHQWLILF (6&$/

%$íñð

FRUH OHYHO VSHFWUD ZHUH DQDO\VHG XVLQJ WKH 3HDN)LW Y

íññ

RQ D %UXNHU 9HFWRU

íñò

UHIOHFWLRQ $75 DFFHVVRU\ 2YHUDOO

íñó

ZHUH SHUIRUPHG RQ D /DE5$0 +5 89 VSHFWURPHWHU +RULED -RELQ