α-Alumina Membranes for

Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, I-87036 ... Giovanni De Filpo , Elvira Pantuso , Katia Armentano , Patr...
0 downloads 0 Views 3MB Size
Subscriber access provided by UNIVERSITY OF ADELAIDE LIBRARIES

Article

Multi-stimuli activation of TiO2/#-alumina membranes for degradation of Methylene Blue Teresa Fina Mastropietro, Carmen Meringolo, Teresa Poerio, Francesca Scarpelli, Nicolas Godbert, Gianluca Di Profio, and Enrica Fontananova Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b02778 • Publication Date (Web): 10 Sep 2017 Downloaded from http://pubs.acs.org on September 12, 2017

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.

Industrial & Engineering Chemistry Research 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 26

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

Industrial & Engineering Chemistry Research

0XOWL VWLPXOL DFWLYDWLRQ RI 7L2 . DOXPLQD PHPEUDQHV IRU GHJUDGDWLRQ RI 0HWK\OHQH %OXH 7HUHVD )LQD 0DVWURSLHWUR D &DUPHQ 0HULQJROR D 7HUHVD 3RHULR *RGEHUW

E

D

)UDQFHVFD 6FDUSHOOL E 1LFRODV

*LDQOXFD 'L 3URILRD DQG (QULFD )RQWDQDQRYDD

D

1DWLRQDO 5HVHDUFK &RXQFLO ,QVWLWXWH IRU 0HPEUDQH 7HFKQRORJ\ ,70±&15 F R 8QLYHUVLW\ RI &DODEULD FXER & 9LD 3LHWUR %XFFL 5HQGH &6 ,WDO\ E

0$7 ,1/$% /DERUDWRULR GL 0DWHULDOL 0ROHFRODUL ,QRUJDQLFL /$6&$00 &5 ,1670 8QLWj ,1670 GHOOD &DODEULD 'LSDUWLPHQWR GL &KLPLFD H 7HFQRORJLH &KLPLFKH 8QLYHUVLWj GHOOD &DODEULD , $UFDYDFDWD GL 5HQGH &6 ,WDO\

W SRHULR#LWP FQU LW )D[

7HO

QLFRODV JRGEHUW#XQLFDO LW 7HO

$%675$&7 7L2 . $O 2 SRURXV PHPEUDQHV ZHUH SUHSDUHG DQG WHVWHG XQGHU GLIIHUHQW VWLPXOL LQFOXGLQJ 89 DQG VLPXODWHG VRODU LUUDGLDWLRQ ZLWK RU ZLWKRXW WKH DGGLWLRQ RI K\GURJHQ SHUR[LGH + 2

DQG E\

XVLQJ 0HWK\OHQH %OXH 0% DV D PRGHO RUJDQLF SROOXWDQW WR SUREH WKH R[LGDWLYH FDWDO\WLF DFWLYLW\ RI WKH PHPEUDQHV $Q XOWUDWKLQ 7L2 OD\HU ZDV FRDWHG RQ SRURXV . $O 2 VXEVWUDWHV E\ FRPELQLQJ VRO JHO SURFHVV ZLWK VSLQ FRDWLQJ WHFKQLTXH 8QLIRUP 7L2 FRDWHG DOXPLQD VXUIDFHV ZHUH REWDLQHG ZKLFK UHVXOWHG LQ DQ LQFUHDVHG SROOXWDQW DGVRUSWLRQ RQ WKH VHPLFRQGXFWRU VXUIDFH D FUXFLDO UHTXLUHPHQW IRU DFKLHYLQJ HQKDQFHG FDWDO\WLF SHUIRUPDQFHV 7KH SKRWRFDWDO\WLF DFWLYLW\ RI WKHVH IXQFWLRQDOLVHG PHPEUDQHV ZDV WHVWHG LQ D 3KRWRFDWDO\WLF 0HPEUDQH 5HDFWRU 305 LUUDGLDWLRQ

E\ PRQLWRULQJ WKH SKRWRGHJUDGDWLRQ RI 0% LQ ZDWHU 8QGHU 89

RI 0% GHJUDGDWLRQ ZDV DFKLHYHG LQ

K &RQFRPLWDQWO\ WKH UHVLGXDO SROOXWDQW LV

FRPSOHWHO\ UHWDLQHG E\ WKH PHPEUDQH LQ WKH IHHG VROXWLRQ DQG D SROOXWDQW IUHH SHUPHDWH FDQ EH UHFRYHUHG 1RWHZRUWK\ WKH 7L2 . $O 2 PHPEUDQHV GLVSOD\HG VHOI FOHDQLQJ SURSHUWLHV DOORZLQJ WKHLU UHXVH LQ VXFFHVVLYH FDWDO\WLF UXQV ZLWKRXW UHGXFWLRQ RI WKHLU SKRWRFDWDO\WLF DFWLYLW\ 8QGHU LUUDGLDWLRQ 89 RU VRODU OLJKW

WKH DGGLWLRQ RI + 2 LQ WKH IHHG VROXWLRQ LQFUHDVHG WKH

HIILFLHQF\ RI 0% GHJUDGDWLRQ )XUWKHUPRUH DQG IRU WKH ILUVW WLPH WKH DELOLW\ RI D 7L2 FRDWHG PHPEUDQH WR SHUIRUP FDWDO\WLF R[LGDWLRQ LQ SUHVHQFH RI + 2 ZDV GHPRQVWUDWHG LQ GDUN FRQGLWLRQV í

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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 2 of 26

(QKDQFHG PHPEUDQH SHUIRUPDQFHV ZHUH REWDLQHG XQGHU VRODU OLJKW LUUDGLDWLRQ H[SHFLDOO\ ZKHQ WKH 7L2 . $O 2 SKRWRFDWDO\WLF DFWLYLW\ ZDV V\QHUJLFDOO\ FRPELQHG ZLWK WKH + 2 DVVLVWHG R[LGDWLYH UHDFWLRQ DOORZLQJ WKH FRPSOHWH 0% GHJUDGDWLRQ LQ RQO\

PLQ 7KH H[FHOOHQW SHUIRUPDQFH RI WKHVH

7L2 . $O 2 PHPEUDQHV XQGHU VRODU OLJKW ZDV PDLQO\ DVFULEHG WR WKH DEVRUSWLRQ DQG LQ VLWX G\H VHQVLWL]DWLRQ RI WKH WKLQ 7L2 OD\HU DOORZLQJ WKH YLVLEOH SKRWRQ KDUYHVWLQJ DV ZHOO DV WR WKH RFFXUUHQFH RI ODWWLFH GLVRUGHU DQG GHIHFWV 7KHVH ILQGLQJV GHPRQVWUDWH WKDW WKHVH FDWDO\WLF PHPEUDQHV SRVVHVV D JUHDW SRWHQWLDO IRU WKH VXQOLJKW GULYHQ GHJUDGDWLRQ RI RUJDQLF FRPSRXQGV WKXV PHHWLQJ WKH UHTXLUHPHQWV IRU IXWXUH HQYLURQPHQWDO DSSOLFDWLRQV

.H\ZRUGV 3KRWRFDWDO\WLF 0HPEUDQH 5HDFWRU 7L2 D $O 2 0HPEUDQH 3KRWRGHJUDGDWLRQ 3KRWRFDWDO\VLV :DVWH :DWHU 7UHDWPHQW

,QWURGXFWLRQ ,Q UHFHQW \HDUV VHPLFRQGXFWRU SKRWRFDWDO\WLF SURFHVVHV KDYH VKRZQ WR KDYH D JUHDW SRWHQWLDO DV ORZ FRVW HQYLURQPHQWDO IULHQGO\ DQG VXVWDLQDEOH WHFKQRORJ\ IRU ZDVWHZDWHU WUHDWPHQW DQG HQYLURQPHQWDO UHPHGLDWLRQ

&RPSDUHG ZLWK RWKHU PDWHULDOV WLWDQLXP GLR[LGH 7L2

EDVHG

SKRWRFDWDO\VWV DUH WKH PRVW DWWUDFWLYH GXH WR WKH PXOWLSOH DGYDQWDJHV WKDW WKH\ GLVSOD\ L KLJK HIILFLHQF\ LL VWUXFWXUDO VWDELOLW\ LLL QRQ WR[LFLW\ DQG LY UHDG\ DYDLODELOLW\

7KHLU

DELOLW\ WR UHPRYH UHIUDFWRU\ RUJDQLF SROOXWDQWV DQG PLFURRUJDQLVPV LQ ZDWHU E\ SKRWRR[LGDWLYH SURFHVVHV KDV EHHQ ZLGHO\ GHPRQVWUDWHG E\ XVLQJ ERWK DUWLILFLDO DQG QDWXUDO OLJKWV

0DLQ UHVHDUFK HIIRUWV KDYH EHHQ DGGUHVVHG WR PRGLI\ WKH 7L2 VWUXFWXUDO DQG

HOHFWURQLF SURSHUWLHV ZLWK WKH DLP RI LPSURYLQJ WKH SKRWRFDWDO\VW HIILFLHQF\ DQG H[WHQGLQJ WKHLU SKRWRUHVSRQVH LQWR WKH YLVLEOH UHJLRQ 7KH PDLQ VWUDWHJLHV DGRSWHG WR UHDFK WKHVH DLPV G\H DQFKRULQJ

FRPSULVH LPSXULW\ GRSLQJ HQJLQHHUHG LQFOXGLQJ 7L &7&V

VXFK DV $O 2

GHVLJQ RI 7L2 QDQR K\EULGV

VHOI GRSHG QDQR SKDVHV

RU GHIHFW

7KH XVH RI FKDUJH WUDQVIHU FDWDO\VWV

WR SUHSDUH 7L2 EDVHG SKRWRFDWDO\VWV LV DQ DOWHUQDWLYH ZD\ RI 7KHVH FRPSRVLWH ELQDU\ R[LGHV IUHTXHQWO\

LPSURYLQJ WKH SKRWRFDWDO\WLF DFWLYLWLHV

H[KLELW XQH[SHFWHG SURSHUWLHV GHULYHG IURP D V\QHUJLVWLF LQWHUDFWLRQ EHWZHHQ WKH WZR FRPSRQHQWV ,QGHHG $O 2

KRVWLQJ PDWHULDOV DUH SURYHG WR WUDS WKH SKRWR JHQHUDWHG

FKDUJHV GHOD\LQJ WKHLU UHFRPELQDWLRQ

DQG WR HQKDQFH WKH DGVRUSWLRQ DELOLW\ RI WKH

SKRWRFDWDO\VW IRU WDUJHW PROHFXOHV $OO WKHVH VWXGLHV PDLQO\ FRQFHUQHG WKH XVH RI 7L2 QDQRSDUWLFOHV DV SDUWLFXODWH VXVSHQVLRQV LQ KHWHURJHQHRXV SKRWRFDWDO\WLF SURFHVVHV (YHQ LI HIILFLHQW SROOXWDQW PLQHUDOL]DWLRQ FDQ EH î

ACS Paragon Plus Environment

Page 3 of 26

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

Industrial & Engineering Chemistry Research

UHDFKHG WKH XVH RI QDQRFDWDO\VWV DV VXVSHQVLRQV LPSOLHV PDQ\ WHFKQLFDO LQFRQYHQLHQFHV LQFOXGLQJ L ORZ VWDELOLW\ RI WKH FDWDO\VW VXVSHQVLRQ LL LQHIILFLHQW OLJKW KDUYHVWLQJ GXH WR VFDWWHULQJ SKHQRPHQD DQG LLL FKDOOHQJLQJ SURFHGXUHV IRU WKH SRVW UHFRYHU\ RI WKH FDWDO\VW SDUWLFOHV DIWHU ZDWHU WUHDWPHQW

3KRWRFDWDO\WLF 0HPEUDQH 5HDFWRUV 305V UHSUHVHQW D

YHU\ SURPLVLQJ WHFKQRORJ\ WR IDFH DOO WKHVH LVVXHV 305V DUH K\EULG UHDFWRUV ZKLFK FRXSOH SKRWRFDWDO\VLV ZLWK D PHPEUDQH EDVHG VHSDUDWLRQ SURFHVV SKRWRUHDFWRUV

:LWK UHVSHFW WR FRQYHQWLRQDO

305V SUHVHQW VHYHUDO DGYDQWDJHV VXFK DV

L

FRQILQHPHQW RI WKH

SKRWRFDWDO\VW ZLWKLQ WKH UHDFWLRQ HQYLURQPHQW LL FRQWURO RI WKH UHVLGHQFH WLPH RI VXEVWUDWH PROHFXOHV LQVLGH WKH UHDFWRU UHDFWLRQ HQYLURQPHQW

LLL VLPXOWDQHRXV FDWDO\VW DQG SURGXFWV VHSDUDWLRQ IURP WKH

LY VHWWLQJ XS RI D FRQWLQXRXV SURFHVV ZKLFK DOORZV HQHUJ\ VDYLQJ

DQG VL]H UHGXFWLRQ RI WKH LQVWDOODWLRQ GXH WR WKH PRGXODULW\ RI WKH PHPEUDQH V\VWHPV Y SRVVLELOLW\ RI UHXVLQJ WKH SKRWRFDWDO\VW RU WKH SKRWRFDWDO\WLF PHPEUDQH ,Q DGGLWLRQ LI WKH FDWDO\VW LV LPPRELOL]HG RQWR RU ZLWKLQ WKH PHPEUDQH VXVSHQVLRQ VWDELOLW\ FRQFHUQV DUH HYDGHG DQG WKH HYHQWXDO IRXOLQJ RI WKH PHPEUDQH FDXVHG E\ WKH DFFXPXODWLRQ RI WKH SKRWRFDWDO\VW SDUWLFOHV LQ WKH PHPEUDQH SRUHV LV HOXGHG

2Q WKH RWKHU KDQG WKH

DFFHVVLEOH DFWLYH VXUIDFH RI WKH SKRWRFDWDO\VW LV VLJQLILFDQWO\ UHGXFHG DV D FRQVHTXHQFH RI LPPRELOL]DWLRQ XVXDOO\ UHVXOWLQJ LQ DQ XQGHVLUDEOH ORVV RI SKRWRDFWLYLW\ DQG DQ DEDWHPHQW RI WKH WUDQV PHPEUDQH IORZ UDWHV ,Q DQ DWWHPSW WR DYRLG WKHVH GUDZEDFNV ZH GHSRVLWHG DQ XOWUD WKLQ SRURXV 7L2 OD\HU RQ WKH WRS VXUIDFH RI SRURXV FHUDPLF VXSSRUWV 7KLV VWUDWHJ\ ZRXOG DOORZ IRU PDLQWDLQLQJ D KLJK VXUIDFH DUHD WR YROXPH UDWLR RI WKH FDWDO\VW WKXV PD[LPL]LQJ WKH QXPEHU RI KLJKO\ UHDFWLYH VXUIDFH

VLWHV

0RUHRYHU

E\

LPSURYLQJ

WKH

VXUIDFH

FRQWDFW

DUHD

EHWZHHQ

WKH

7L2 VHPLFRQGXFWRU DQG WKH $O 2 VXUIDFH D PDMRU QXPEHU RI GHIHFWV FDQ EH FUHDWHG DW WKH LQWHUIDFH ZKLFK ZRXOG DFW DV DFWLYH VLWHV IRU SKRWRGHJUDGDWLRQ

)XUWKHUPRUH KLJKHU

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

([SHULPHQWDO ï

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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 4 of 26

0DWHULDOV 7L&O

6LJPD $OGULFK

(WKDQRO

3OXURQLF )

6LJPD $OGULFK

):

+2

& + &O1 6‡ + 2

J PRO 6LJPD $OGULFK

ZY

YRO

3$

3DQUHDF

$EVROXWH DQG 0%

6LJPD $OGULFK ZHUH XVHG DV UHFHLYHG 6ROYHQWV RI DQDO\WLFDO

JUDGH ZHUH SXUFKDVHG IURP 6LJPD $OGULFK DQG XVHG ZLWKRXW IXUWKHU SXULILFDWLRQ 8OWUDSXUH 'LVN VKDSHG PLFURSRURXV . $O 2 PHPEUDQHV

ZDWHU ZDV SURGXFHG E\ D 0LOOLSRUH (/,; PP RI GLDPHWHU

PP WKLFNQHVV PHDQ SRUH VL]H RI

QP ZHUH SXUFKDVHG IURP

)UDXQKRIHU ,.76

3UHSDUDWLRQ RI WKH SKRWRFDWDO\WLF PHPEUDQHV 7KH 7L2 SUHFXUVRU VROXWLRQ XVHG IRU WKH V\QWKHVLV RI WKH DFWLYH OD\HU RQ WKH . $O 2 PHPEUDQHV ZDV SUHSDUHG DFFRUGLQJ WR D SURFHGXUH UHSRUWHG LQ OLWHUDWXUH J RI 3OXURQLF )

P/ RI 7L&O

P/ RI HWKDQRO DQG VWLUUHG IRU

DQG

J

P/ RI GLVWLOOHG ZDWHU ZHUH PL[HG LQ

PLQXWHV 6XEVHTXHQWO\ D JLYHQ YROXPH RI VROXWLRQ ZDV

GHSRVHG RQ WKH VXUIDFH RI WKH PHPEUDQHV DQG VSLQ FRDWHG DW 6SLQ FRDWHU 0RGHO 3

7\SLFDOO\

USP IRU

PLQXWH ZLWK D

6SHHGOLQH 7HFKQRORJLHV 1RWH WKDW WKH FHUDPLF PHPEUDQHV ZHUH

LPSUHJQDWHG ZLWK ZDWHU SULRU WR GHSRVLWLRQ WR DYRLG SRUH SOXJJLQJ 7KH FRDWHG PHPEUDQHV ZHUH DJHG XQGHU D FRQWUROOHG KXPLGLW\ RI WUHDWPHQWV ZHUH WKHQ DSSOLHG IRU

DW

KRXUV DW

ƒ& IRU

DQG

RYHQ )LQDOO\ PHPEUDQHV ZHUH FDOFLQDWHG DW

KRXUV 7ZR VXFFHVVLYH WKHUPDO

ƒ& UHVSHFWLYHO\ LQ D FRQYHQWLRQDO

ƒ& IRU WZR KRXUV DQG DW

ƒ& IRU

PLQXWHV IRU FRPSOHWHO\ UHPRYLQJ WKH RUJDQLF WHPSODWH

&KDUDFWHUL]DWLRQ 7KH PRUSKRORJ\ RI ERWK SULVWLQH DQG 7L2 D &DPEULGJH =HLVV /(2

PRGLILHG . $O 2 PHPEUDQHV ZDV REVHUYHG ZLWK

VFDQQLQJ HOHFWURQ PLFURVFRSH 6(0

7KH 7L FRQWHQW ZDV

GHWHUPLQHG E\ (QHUJ\ 'LVSHUVLYH ; UD\ ('; SHUIRUPHG ZLWK D 3KHQRP 3UR; 6FDQQLQJ (OHFWURQ 0LFURVFRSH 6(0 PLFURVFRSH DW

7(0 LPDJHV ZHUH FROOHFWHG ZLWK D -(0

N9 7(0 -HRO $NLVKLPD 7RN\R -DSDQ

; 5D\ 3RZGHU 'LIIUDFWLRQ

3;5' DQDO\VLV ZDV FDUULHG RXW RQ FUXVKHG VDPSOHV XVLQJ D ' SRZGHU GLIIUDFWRPHWHU HTXLSSHG ZLWK D &X.. UDGLDWLRQ GHWHFWRU DW

N9 DQG

P$ ZLWK D VWHS VL]H RI

ƒ EHWZHHQ

ð

ACS Paragon Plus Environment

3OXV HOHFWURQ

3KDVHU %UXNHU ; UD\ c DQG D /\Q[H\H DQG

ƒ

5DPDQ

Page 5 of 26

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

Industrial & Engineering Chemistry Research

VSHFWUD ZHUH FROOHFWHG ZLWK D 7KHUPR 6FLHQWLILF ';5 5DPDQ PLFURVFRSH DW URRP WHPSHUDWXUH ZLWK

QP ODVHU H[FLWDWLRQ 7KH ; EDQG (OHFWURQ 3DUDPDJQHWLF 5HVRQDQFH

(35 VSHFWUD ZHUH UHFRUGHG RQ D %UXNHU (0; VSHFWURPHWHU HTXLSSHG ZLWK D F\OLQGULFDO TXDUW] WXEH RSHUDWLQJ DW

N+] ILHOG PRGXODWLRQ $ FUXVKHG VDPSOH RI WKH FDWDO\WLF

PHPEUDQH ZDV DQDO\]HG H[ VLWX XQGHU OLTXLG QLWURJHQ EHIRUH DQG DIWHU WHVWLQJ 7KH FRQFHQWUDWLRQ RI 0% ZDV PRQLWRUHG E\ PHDVXULQJ WKH DEVRUEDQFH DW D ZDYHOHQJWK RI QP E\ XVLQJ D 89 9LVLEOH /DPEGD (=

VSHFWURSKRWRPHWHU 3HUNLQ(OPHU 7RWDO RUJDQLF

FDUERQ 72& ZDV HYDOXDWHG E\ XVLQJ D 72& 9&61 IURP 6KLPDG]X

'HVFULSWLRQ RI WKH 305 DQG WKH SKRWRFDWDO\WLF WHVWV 7KH SKRWRFDWDO\WLF WHVWV ZHUH FDUULHG RXW LQ WKH 305 VFKHPDWL]HG LQ )LJXUH

$FFRUGLQJO\

89 RU VLPXODWHG VRODU OLJKW ZHUH XVHG DV LUUDGLDWLRQ VRXUFH 7KH 89 VRXUFH ZDV D PHGLXP KLJK SUHVVXUH PHUFXU\ YDSRU ODPS =V ODPS +HOLRV ,WDOTXDU] ZLWK DQ LUUDGLDQFH RI 7KH VRODU VRXUFH ZDV D

:P

: 2ULHO ;H $UF ODPS %HIRUH WHVWLQJ WKH IXQFWLRQDOL]HG

PHPEUDQHV ZHUH KRXVHG LQ D IODW VKHHW PHPEUDQH PRGXOH HTXLSSHG ZLWK D TXDUW] ZLQGRZ RQ WKH WRS VLGH DFWLYH PHPEUDQH DUHD

FP

DQG WKHQ SODFHG LQ D OLJKW H[SRVXUH

FKDPEHU 7KH GLVWDQFH EHWZHHQ WKH OLJKW VRXUFH DQG WKH DFWLYH PHPEUDQH VXUIDFH ZDV IL[HG DW

FP $ 0% DTXHRXV VROXWLRQ

ZLWK D SXPS IORZ UDWH RI

0 WRWDO YROXPH

P/ ZDV IHG LQWR WKH FKDPEHU

P/ PLQ DW D WUDQV PHPEUDQH SUHVVXUH VHW DW

EDU 7KH 305

ZDV RSHUDWHG LQ FURVV IORZ ILOWUDWLRQ PRGH DQG WHVWV ZHUH SHUIRUPHG LQ FRQWLQXRXV WKH IHHG UHWHQWDWH DQG WKH SHUPHDWH YROXPHV EHLQJ FROOHFWHG LQ VHSDUDWH FKDPEHUV RU LQ EDWFK E\ UHFRYHULQJ WKH SHUPHDWH VWUHDP

'XULQJ WKH SKRWRGHJUDGDWLRQ SURFHVV

WKH 0%

FRQFHQWUDWLRQ ZDV GHWHUPLQHG LQ UHDO WLPH DFFRUGLQJ WR LWV PD[LPXP DEVRUEDQFH PHDVXUHG ZLWK DQ LQ OLQH 89 YLV VSHFWURSKRWRPHWHU 7KH VWDELOLW\ DQG UHXVDELOLW\ RI WKH 7L2 . $O 2 PHPEUDQHV ZHUH WHVWHG E\ UH XVLQJ WKH VDPH PHPEUDQHV LQ VHYHUDO F\FOHV ZLWK QR DGGLWLRQDO SURFHGXUHV IRU FOHDQLQJ WKH PHPEUDQHV EHWZHHQ HDFK F\FOH 7R WHVW WKH 7L2 . $O 2 PHPEUDQHV LQ WKH + 2 DVVLVWHG SKRWRFDWDO\WLF GHJUDGDWLRQ RI 0% + 2 ZDV GLUHFWO\ DGGHG WR WKH 0% VROXWLRQ WR D ILQDO FRQFHQWUDWLRQ RI

0

)RU DOO WKH H[SHULPHQWDO WHVWV WKH 0% GHJUDGDWLRQ ZDV SORWWHG DV &W & DV D IXQFWLRQ RI WLPH ZKHUH &W LV 0% FRQFHQWUDWLRQ DW W WLPH DQG & LV 0% FRQFHQWUDWLRQ DW WKH VWHDG\ VWDWH DIWHU 0% DGVRUSWLRQ RQ WKH FDWDO\WLF VXUIDFH

ñ

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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

)LJXUH

Page 6 of 26

6FKHPDWLF UHSUHVHQWDWLRQ RI WKH 305

5HVXOWV DQG 'LVFXVVLRQ ,Q WKLV VWXG\

ZH SUHSDUHG SKRWRFDWDO\WLF PHPEUDQHV E\ FRDWLQJ . $O 2

FHUDPLF

PLFURILOWUDWLRQ PHPEUDQHV ZLWK D WKLQ 7L2 OD\HU 7KH LPPRELOL]DWLRQ RI WKH 7L2 FDWDO\VWV RQ SRURXV . $O 2 VXSSRUWV ZRXOG FUHDWH D V\QHUJLVWLF FRXSOLQJ EHWZHHQ WKH 7L2 SKRWRFDWDO\WLF DFWLYLW\ DQG WKH DOXPLQD PHPEUDQH SURSHUWLHV ,QGHHG WKH DEVRUSWLRQ RI VXEVWUDWH PROHFXOHV ZLOO EH SURPRWHG E\ WKH DOXPLQD SRURXV VXSSRUW DQG E\ WKH IRUFHG SHUPHDWLRQ RI UHDJHQWV WKURXJK WKH FDWDO\WLF PHPEUDQH SRUHV

7KH HIILFLHQF\ RI WKH

VXSSRUWHG 7L2 SKRWRFDWDO\VW FRXOG DOVR EH HQKDQFHG VLQFH DOXPLQD LV DEOH WR WUDS WKH SKRWRJHQHUDWHG H EHHQ SURYHG WKDW

DQG K

FKDUJHV GHOD\LQJ WKHLU UHFRPELQDWLRQ

0RUHRYHU LW KDV

E\ H[WHQGLQJ WKH LQWHUIDFLDO FRQWDFW VXUIDFH EHWZHHQ WKH 7L2

VHPLFRQGXFWRU DQG $O 2 VXSSRUW LPSRUWDQW VXUIDFH GHIHFWV DUH FUHDWHG DW WKH DOXPLQD±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ò

ACS Paragon Plus Environment

Page 7 of 26

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

Industrial & Engineering Chemistry Research

FU\VWDOOL]DWLRQ DQG FDOFLQDWLRQ FRQGLWLRQV ZHUH DOO RSSRUWXQHO\ VHOHFWHG DQG RSWLPL]HG ZLWK WKH DLP RI L HQVXULQJ D XQLIRUP VXUIDFH FRYHUDJH RI WKH PHPEUDQH LL FRQWUROOLQJ WKH ILOP WKLFNQHVV LLL GLUHFWLQJ WKH GHJUHH RI FU\VWDOOLQLW\ DQG LY SURPRWLQJ WKH SUHIHUHQWLDO IRUPDWLRQ RI WKH DQDWDVH FU\VWDO SKDVH 3OXURQLF )

LQ SDUWLFXODU ZDV XVHG DV ERWK SRUH

IRUPLQJ DQG VWUXFWXUH GLUHFWLQJ DJHQW ,Q RUGHU WR HYDOXDWH WKH SKRWRFDWDO\WLF HIILFLHQF\ RI WKH 7L2 . $O 2 PHPEUDQHV 0% D]R G\H ZDV XVHG DV ZDWHU SROOXWDQW PRGHO 'LIIHUHQW PHWKRGV KDYH EHHQ LQYHVWLJDWHG WR SUREH WKH R[LGDWLYH EHKDYLRU RI 7L2 LQFOXGLQJ SKRWRDFWLYDWLRQ XVLQJ ERWK 89 RU VRODU OLJKW DQG FKHPLFDO UHDFWLRQ ZLWK + 2 ERWK LQ GDUNQHVV RU XQGHU LUUDGLDWLRQ

6WUXFWXUDO DQG PRUSKRORJLFDO SURSHUWLHV RI WKH PHPEUDQHV 7KH ;5' SDWWHUQV FROOHFWHG RQ WKH SULVWLQH . $O 2 DQG 7L2 . $O 2 PHPEUDQHV DUH VKRZQ LQ )LJXUH D 7KH SUHVHQFH RI WKH W\SLFDO SHDN FRUUHVSRQGLQJ WR WKH UHIOHFWLRQ . $O 2 SHDN DW LQVHW

RI

DQDWDVH

FDQ EH REVHUYHG LQ WKH SDWWHUQ HYHQ LI SDUWLDOO\ FRYHUHG E\ WKH LQWHQVH ƒ FRQVHTXHQWO\ UHVXOWLQJ LQ D VKRXOGHU RI WKH PDLQ GLIIUDFWLRQ SHDN VHH

+LJKHU DQJOH GLIIUDFWLRQ SHDNV FKDUDFWHULVWLF RI WKH DQDWDVH SKDVH FDQ KDUGO\ EH

REVHUYHG GXH WR WKHLU ORZ UHODWLYH LQWHQVLW\ ZLWK UHVSHFW WR WKH GRPLQDQW LQWHQVH VLJQDOV RI WKH DOXPLQD SKDVH +RZHYHU WKH IRUPDWLRQ RI DQDWDVH FU\VWDO SKDVH ZDV FRQILUPHG E\ 0LFUR 5DPDQ VSHFWURVFRS\ )LJXUH

E VKRZV WKH 5DPDQ VSHFWUD RI WKH 7L2 . $O 2

PHPEUDQH EHIRUH DQG DIWHU WKH 89 GULYHQ SKRWRFDWDO\WLF WHVWV FRPSDUHG ZLWK WKH VSHFWUXP RI WKH SULVWLQH . $O 2 PHPEUDQH 7KH VSHFWUD RI 7L2 . $O 2 PHPEUDQHV SUHVHQW D SDWWHUQ RI 5DPDQ DFWLYH WLWDQLD DQDWDVH PRGHV ZLWK W\SLFDO VLJQDOV DW

DQG

FP

7ZR OHVV LQWHQVH SHDNV DUH DOVR SUHVHQW GXH WR WKH $O 2 VXEVWUDWH WKH VWURQJHVW RQH EHLQJ DW FPí 1RWHZRUWK\ QR VWUXFWXUDO YDULDWLRQV DUH REVHUYHG LQ WKH 5DPDQ VSHFWUD DIWHU WKH 89 SKRWRFDWDO\WLF WHVWV GHPRQVWUDWLQJ WKH VWDELOLW\ RI WKH 7L2 FRDWLQJ 6(0 LPDJHV RI WKH VXUIDFH PRUSKRORJ\ RI WKH XQPRGLILHG D DQG RI WKH 7L2 FRDWHG E PLFURSRURXV PHPEUDQH DUH VKRZQ LQ )LJXUH D DQG )LJXUH E UHVSHFWLYHO\ 7KH SUHVHQFH RI D YHU\ WKLQ FRDWLQJ RQ WKH VXUIDFH RI WKH DOXPLQD FU\VWDOOLWHV OLNH D ³VHPL WUDQVSDUHQW YHLO´ FDQ EH QRWLFHG LQ WKH PLFURJUDSK )LJXUH

E

7KH XQLIRUP GLVWULEXWLRQ RI WKH DQDWDVH

SRO\FU\VWDOOLQH OD\HU RQ WKH PHPEUDQH VXUIDFH ZDV FRQILUPHG E\ ('; DQDO\VLV )LJXUH F VKRZV WKH HOHPHQWDO PDSSLQJ FDUULHG RXW RQ D

P PHPEUDQH DUHD WKDW SURYLGHG D PHDQ 7L

ó

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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

FRQWHQW RI

Page 8 of 26

$V D UHVXOW DQG DV H[SHFWHG WKH 7L2 VNLQ OLNH OD\HU UHSURGXFHV WKH

LQWULQVLF PHPEUDQH VXUIDFH URXJKQHVV ZLWK D FRQVHTXHQW LQFUHDVH RI WKH H[SRVHG VXUIDFH

~ •

~ •

)LJXUH

;5' SDWWHUQ RI WKH XQ PRGLILHG UHG OLQH DQG 7L2 . $O 2 EODFN OLQH PHPEUDQH D DQG 5DPDQ

VSHFWUD RI SULVWLQH EODFN OLQH DQG 7L2 . $O 2 PHPEUDQHV EHIRUH JUHHQ OLQH DQG DIWHU UHG OLQH WKH 89 FDWDO\WLF WHVWV E

7(0 LPDJHV ZHUH DOVR FROOHFWHG RQ VRPH IUDJPHQWV RI WKH PHPEUDQH WR VKRZV WKH WKLFNQHVV RI WKH 7L2 FRDWLQJ )LJ

G

7KH 7L2 VXUIDFH LV QRW VPRRWK DQG IHDWXUHV D

³JUDLQ\´ WH[WXUH 7KH WKLFNQHVV RI WKH OD\HU YDULHV EHWZHHQ

ô

ACS Paragon Plus Environment

DQG

QP

Page 9 of 26

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

Industrial & Engineering Chemistry Research





)LJXUH

6(0 LPDJHV RI WKH XQ WUHDWHG D DQG 7L2 PRGLILHG E PLFURSRURXV DOXPLQD PHPEUDQH

F (OHPHQWDO PDSSLQJ DQG ('; DQDO\VLV SHUIRUPHG RQ D

P DUHD RI WKH 7L2 . $O 2 PHPEUDQH

OD\HU G 7(0 LPDJH RI WKH 7L2 FRDWLQJ

3XUH ZDWHU SHUPHDELOLW\ 7KH SXUH ZDWHU IOX[ RI ERWK PRGLILHG DQG XQPRGLILHG PHPEUDQHV ZHUH PHDVXUHG XQGHU GDUN FRQGLWLRQ 7KH SXUH ZDWHU IOX[ YDOXHV DUH FRQVWDQW RYHU WLPH IRU DOO WKH PHPEUDQHV WHVWHG ZLWK D PHDQ YDOXH RI

NJ K P IRU WKH SULVWLQH PHPEUDQH DW DQ DSSOLHG WUDQV PHPEUDQH SUHVVXUH RI

EDU 7KLV YDOXH VLJQLILFDQWO\ GHFUHDVHV IRU WKH 7L2 FRDWHG PHPEUDQH PHDQ YDOXH RI

NJ K P

7KH REVHUYHG GHFUHDVH LV LQGLFDWLYH RI WKH IRUPDWLRQ RI WKH 7L2 ILOP SDUWLDOO\ FRYHULQJ WKH EHQHDWK DOXPLQD SRURXV VWUXFWXUH DQG FRQVHTXHQWO\ DGGLQJ DQ H[WUD UHVLVWDQFH WR WKH ZDWHU SKDVH WUDQVSRUW %\ FRPSDULQJ WKH SXUH ZDWHU IOX[ D PHDQ SRUH VL]H RI

QP FDQ EH H[WLPDWHG IRU WKH PRGLILHG

õ

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

PHPEUDQH +RZHYHU XQGHU 89 LUUDGLDWLRQ DQ LQFUHDVH RI ZDWHU IOX[ LV REVHUYHG RQO\ IRU WKH 7L2 . $O 2 PHPEUDQH SHUPHDELOLW\ PHDQ YDOXH RI

NJ K P

7KLV LQFUHDVH FDQ EH DWWULEXWHG

WR D SKRWRLQGXFHG K\GURSKLOLF HIIHFW ZKLFK HQKDQFHV WKH PHPEUDQH SHUPHDELOLW\ FRQVLVWHQW ZLWK WKH SUHVHQFH RI WKH 7L2 VXUIDFH FRYHUDJH RI WKH PHPEUDQH 7KH SXUH ZDWHU SHUPHDELOLW\ ZDV DOVR PRQLWRUHG DIWHU HDFK SKRWRFDWDO\WLF H[SHULPHQW :DWHU SHUPHDELOLW\ UHPDLQHG EDVLFDOO\ XQDOWHUHG LQ WKH VXFFHVVLYH UXQV ZLWK YDOXHV UDQJLQJ IURP

WR

NJ K P LQ DJUHHPHQW ZLWK WKH LQ VLWX VHOI FOHDQLQJ SURSHUWLHV RI WKH WLWDQLD FRDWLQJ

89 GULYHQ 3KRWRFDWDO\WLF GHJUDGDWLRQ LQ WKH 305 7KH 7L2 . $O 2 PHPEUDQHV ZHUH ILUVW WHVWHG LQ WKH 305 IRU WKH SKRWRFDWDO\WLF GHJUDGDWLRQ WHVWV FRQGXFWHG XQGHU 89 LUUDGLDWLRQ $ FUXFLDO VWHS RI D SKRWRFDWDO\WLF SURFHVV LV WKH SUHOLPLQDU\ DGVRUSWLRQ RI RUJDQLF FRPSRXQGV RQWR WKH FDWDO\VW VXUIDFH ZKHUH WKH VXEVWUDWH PROHFXOHV FDQ EH R[LGL]HG WKDQNV WR WKH IRUPDWLRQ RI UHDFWLYH VSHFLHV 0% DGVRUSWLRQ HIILFLHQF\ RQ SULVWLQH PHPEUDQHV DQG 7L2 . $O 2 PHPEUDQHV ZDV PRQLWRUHG LQ GDUN FRQGLWLRQ E\ XVLQJ ERWK SULVWLQH DQG 7L2 FRDWHG PHPEUDQHV $GVRUSWLRQ UHVXOWV LQGLFDWHG WKDW WKH VWHDG\ VWDWH FRQGLWLRQV ZHUH UHDFKHG DIWHU DQG

PLQ IRU WKH SULVWLQH PHPEUDQH

PLQ IRU WKH 7L2 . $O 2 PHPEUDQH UHVSHFWLYHO\ 1RWHZRUWK\ WKH DPRXQW RI DGVRUEHG 0%

ZDV KLJKHU IRU WKH 7L2 . $O 2 PHPEUDQH

ZLWK UHVSHFW WR WKH SULVWLQH PHPEUDQH

GXH WR WKH V\QHUJLF HIIHFW RI WKH QHJDWLYHO\ FKDUJHG VLWHV RI WKH . $O 2

DQG WKH WUDSSLQJ VLWHV RI

WKH 7L2 FRDWLQJ

íUì ìUô šl ì

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 10 of 26

ìUò ìUð ìUî ìUì ì

)LJXUH

ñì

íìì

íñì š ~u]v•

îìì

îñì

ïìì

0% DGVRUSWLRQ RQ SULVWLQH PHPEUDQH . $O 2 EOXH OLQH DQG 7L2 . $O 2 UHG OLQH PHPEUDQH

VXUIDFH LQ GDUNQHVV

íì

ACS Paragon Plus Environment

Page 11 of 26

)LJXUH

VKRZV WKH GHJUDGDWLRQ RI 0% RYHU WLPH UHG OLQH REVHUYHG LQ WKH 305 RSHUDWLQJ LQ

FRQWLQXRXV FURVV IORZ ILOWUDWLRQ PRGH ZKHQ ERWK SHUPHDWH DQG UHWHQWDWH DUH UHFRYHUHG LQWR WKH IHHG 1RWH WKDW UHVXOWV DUH UHSRUWHG DV D IXQFWLRQ RI &W & ZKHUH &W LV WKH FRQFHQWUDWLRQ DW W WLPH DQG & LV WKH LQLWLDO FRQFHQWUDWLRQ UHDFKHG ZLWKLQ WKH IHHG DIWHU UHDFKLQJ WKH DGVRUSWLRQ HTXLOLEULXP 7R UXOH RXW WKH LQIOXHQFH RI WKH . $O 2 PHPEUDQH RQ WKH SKRWRFDWDO\WLF DFWLYLW\ WHVWV KDYH EHHQ DOVR FDUULHG RXW E\ XVLQJ WKH SULVWLQH PHPEUDQH 5HVXOWV FRQILUPHG WKDW WKH EDUH VXSSRUW DFWV DV D SROOXWDQW DEVRUEHU DQG FRQFHQWUDWRU EXW ZKHQ LUUDGLDWHG QR SKRWRGHJUDGDWLYH DFWLYLW\ ZDV PHDVXUHG )XUWKHUPRUH WR HYDOXDWH WKH HYHQWXDO FRQWULEXWLRQ RI WKH GLUHFW SKRWRGHJUDGDWLYH R[LGDWLRQ RI 0% XQGHU 89 H[SRVXUH EODQFN WHVWV ZHUH FDUULHG RXW LQ WKH 305 ZLWKRXW WKH PHPEUDQHV 'XULQJ WKH H[SHULPHQW RQO\ WKH

RI 0% R[LGDWLRQ ZDV REVHUYHG UHSURGXFLQJ WKH

UHVXOWV REWDLQHG ZLWK WKH SULVWLQH PHPEUDQH WKXV IXUWKHU FRQILUPLQJ WKH LQHUW UROH RI . $O 2 GXULQJ SKRWRGHJUDGDWLRQ )LJXUH

íUì ìUô šl ì

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

Industrial & Engineering Chemistry Research

ìUò ìUð ìUî ìUì ì

ñì

íìì

íñì

îìì

îñì

ïìì

š ~u]v• )LJXUH

89 LUUDGLDWHG GHJUDGDWLRQ RI 0% LQ WKH 305 ZLWKRXW PHPEUDQH GDUN OLQH ZLWK . $O 2 SULVWLQH

PHPEUDQH EOXH OLQH DQG ZLWK 7L2 . $O 2 PHPEUDQH UHG OLQH

:KHQ WKH 7L2 . $O 2 PHPEUDQH LV XVHG XQGHU 89 LUUDGLDWLRQ WKH FRQFHQWUDWLRQ RI 0% FRQWLQRXVO\ GHFUHDVH WKH

RI 0% EHLQJ UHPRYHG DIWHU

K )LJXUH

VKRZV KRZ WKH FDWDO\WLF

PHPEUDQHV DSSHDU GXULQJ D DQG DIWHU E WKH SKRWRFDWDO\WLF WHVWV 3KRWRJUDSKV RI WKH LQLWLDO DQG ILQDO 0% VROXWLRQV DUH UHSRUWHG LQ )LJXUH

F

FOHDUO\ VKRZLQJ WKH HIILFLHQF\ RI WKH

SKRWRGHJUDGDWLRQ

íí

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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

)LJXUH

7L2 . $O 2 PHPEUDQH GXULQJ D DQG DW WKH HQG E RI WKH SKRWRFDWDO\WLF WHVW ,QLWLDO OHIW DQG

ILQDO ULJKW 0% VROXWLRQ F

7KH VDPH 7L2 . $O 2 PHPEUDQH ZDV UHXVHG LQ VXFFHVVLYH UXQV ZLWKRXW SHUIRUPLQJ DQ\ FOHDQLQJ SURFHGXUH )RU HDFK UXQ VLPLODU UHVXOWV LQ WHUPV RI SHUFHQWDJH RI GHJUDGHG 0% ZHUH REWDLQHG DIWHU K RI LUUDGLDWLRQ )LJXUH

7KHVH UHVXOWV GHPRQVWUDWH WKH DELOLW\ RI WKH 7L2 . $O 2 PHPEUDQHV

WR IXOO\ SUHVHUYH UHVWRUH WKHLU LQLWLDO FDWDO\WLF HIILFLHQF\

)LJXUH

3HUFHQWDJH RI GHJUDGHG 0% DIWHU K RI LUUDGLDWLRQ LQ VXFFHVVLYH UXQV

)LQDOO\ WHVWV KDYH EHHQ FRQGXFWHG LQ WKH 305 RSHUDWLQJ LQ FRQWLQXRXV FURVV IORZ ILOWUDWLRQ PRGH E\ VHSDUDWHO\ UHFRYHULQJ WKH SHUPHDWH YROXPH 7KH SHUPHDWH IOX[ - DQG WKH YDULDWLRQ RI 0% FRQFHQWUDWLRQ &W & PHDVXUHG LQ WKH UHWHQWDWH DQG LQ WKH SHUPHDWH VWUHDPV RYHU WLPH DUH VKRZHG LQ )LJXUH

íî

ACS Paragon Plus Environment

Page 12 of 26

Page 13 of 26

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

Industrial & Engineering Chemistry Research

)LJXUH

0% FRQFHQWUDWLRQ RYHU WLPH LQ WKH UHWHQWDWH EOXH OLQH DQG SHUPHDWH UHG OLQH 3HUPHDWH IOX[ RYHU

WLPH JUHHQ OLQH

7KH 0% FRQFHQWUDWLRQ GHFUHDVHV RYHU WLPH LQ WKH UHWHQWDWH EOXH OLQH GHJUDGDWHG DIWHU

WKH

RI 0% ZDV

K ZKLOH WKH SHUPHDWH UHG OLQH LV LQVWDQWDQHRXVO\ GHFRORUHG ZLWK D UHPRYDO RI

0% RI )XUWKHUPRUH DV REVHUYHG LQ )LJXUH

WKH SHUPHDWH IOX[ UHPDLQHG FRQVWDQW DW WKH YDOXH RI

.J K P LQGLFDWLYH RI WKH WKH DQWL IRXOLQJ SURSHUWLHV FRQIHUUHG E\ WKH 7L2 OD\HU WR WKH SRURXV PHPEUDQH VXSSRUW GXULQJ WKH SKRWRFDWDO\WLF GHJUDGDWLRQ 2Q WKH FRQWUDU\ LQ DEVHQFH RI LUUDGLDWLRQ WKH WUDQVPHPEUDQH IOX[ UDSLGO\ IDOOV WR ]HUR 6XFK LQWULQVLF EHKDYLRU FRXOG EH H[SORLWHG LQ WKH YLHZ RI XVLQJ WKHVH PHPEUDQHV LQ VHOI FOHDQLQJ V\VWHPV

1RQ LUUDGLDWHG DQG 89 GULYHQ 3KRWRFDWDO\WLF GHJUDGDWLRQ LQ SUHVHQFH RI + 2 7KH DELOLW\ RI WKH DV SUHSDUHG 7L2 . $O 2 PHPEUDQHV WR PHGLDWH WKH + 2 DFWLYDWLRQ LQ DEVHQFH RI LUUDGLDWLRQ ZDV DOVR WHVWHG ZLWKLQ WKH 305 E\ IHHGLQJ D VROXWLRQ $V VKRZHG LQ )LJXUH DV

DIWHU

0+ 2

0 0%

XQGHU GDUN FRQGLWLRQV WKH GHJUDGDWLRQ RI 0% ZDV DV KLJK

K RI UHDFWLRQ LQ WKH SUHVHQFH RI WKH 7L2 . $O 2 PHPEUDQH VKRZLQJ WKH

LPSRUWDQW FRQWULEXWLRQ RI WKH 7L2 . $O 2 PHPEUDQH WR WKH + 2 DFWLYDWLRQ ,QGHHG LQ GDUN FRQGLWLRQV WKH FRQWULEXWLRQ RI WKH VHOI GLVVRFLDWLRQ RI + 2 WR WKH PHWK\OHQH EOXH ZDV UHJLVWHUHG OHVV WKDQ

DV REVHUYHG DOVR LQ WKH FDVH RI WKH SULVWLQH . $O 2 PHPEUDQH

ZKLFK LV E\ LWVHOI XQDEOH WR IXUWKHU DFWLYDWH + 2 )LJ íï

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

íUìì ìUôì

šl ì

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 26

ìUòì ìUðì ìUîì ìUìì ì

ñì

íìì

íñì

îìì

îñì

ïìì

š ~u]v•

)LJXUH

'HJUDGDWLRQ RI 0% RYHU WLPH FDUULHG RXW LQ DEVHQFH RI LUUDGLDWLRQ DQG LQ SUHVHQFH RI + 2

0 ZLWK . $O 2 SULVWLQH PHPEUDQH EOXH OLQH ZLWK 7L2 . $O 2 PHPEUDQH UHG OLQH DQG ZLWKRXW DQ\ PHPEUDQH EODFN OLQH

3KRWRGHJUDGDWLRQ UHVXOWV REWDLQHG XVLQJ D QRQ LUUDGLDWHG 7L2 . $O 2 + 2 V\VWHP KDYH DOVR EHHQ FRQILUPHG E\ :LHGPHU HW DO

7KH DXWKRUV HYLGHQFHG IRU D 7L2

VXVSHQVLRQ WKH LPSURYHG G\H DGVRUSWLRQ RQWR WKH FDWDO\VWV VXUIDFH GXH WR WKH K\GURJHQ SHUR[LGH SUHVHQFH %HVLGHV WKH\ YHULILHG WKH SUHVHQFH RI K\GUR[\O 2+Ü DQG VXSHUR[LGH UDGLFDOV 2

Üí

22+Ü WKDW SHUPLWWHG WKH GHJUDGDWLRQ RI 0% ZLWKRXW LUUDGLDWLRQ 7KH DFWLYH

VSHFLHV LV UHVXOWLQJ IURP WKH WUDQVLWLRQ PHWDO LRQ 7L UHDFWLRQ ,QGHHG 7L

7L

UHSODFLQJ )H

)H

RI )HQWRQ

KDV EHHQ SURYHG WR EH HIILFLHQW FDWDO\VWV LQ SUHVHQFH RI + 2 DEOH WR

SURYLGH D )HQWRQ OLNH PHFKDQLVP 2Q WKLV EDVLV DQG E\ FRQVLGHULQJ WKH KLJK DGVRUSWLRQ FDSDFLW\ REVHUYHG IRU RXU V\VWHP )LJ ZH FDQ K\SRWKHVL]H WKDW WKH 0% DGVRUSWLRQ RQWR WKH 7L2 . $O 2 PHPEUDQH V\VWHP SRVLWLYHO\ DIIHFWHG WKH UHVXOWDQW + 2 DVVLVWHG QRQ LUUDGLDWHG R[LGDWLYH UHDFWLRQ 7KH SKRWRFDWDO\WLF DFWLYLW\ RI WKH 7L2 . $O 2 PHPEUDQH ZDV DOVR WHVWHG E\ FRPELQLQJ 89 LUUDGLDWLRQ DQG + 2

,Q WKLV FDVH DV H[SHFWHG ZH REVHUYHG D UHPDUNDEOH LPSURYHPHQW RI

WKH SKRWRGHJUDGDWLRQ HIILFLHQF\ OHDGLQJ WR FRPSOHWH 0% GHJUDGDWLRQ ZLWKLQ WKH 305 LQ RQO\

K )LJ

72& PHDVXUHPHQWV SHUIRUPHG RQ WKH 0% VROXWLRQ UHFRYHUHG DW WKH HQG

RI WKH SURFHVV SURYLGH RUJDQLF FDUERQ YDOXH ZLWKLQ WKH UDQJH RI WKH GHWHFWLRQ OLPLW FRQILUPLQJ WKH FRPSOHWH PLQHUDOL]DWLRQ RI WKH G\H íð

ACS Paragon Plus Environment

Page 15 of 26

íUì ìUõ ìUô ìUó ìUò šl ì

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

Industrial & Engineering Chemistry Research

ìUñ ìUð ìUï ìUî ìUí ìUì ì

ñì

íìì

íñì š ~u]v•

îìì

îñì

ïìì

'HJUDGDWLRQ RI 0% UHSRUWHG DV &W & E\ FRPELQLQJ 89 LUUDGLDWLRQ DQG + 2

)LJXUH

ZLWK WKH

7L2 . $O 2 PHPEUDQH

3KRWRFDWDO\WLF WHVWV XQGHU VRODU OLJKW LUUDGLDWLRQ 5HVXOWV RI WKH SKRWRFDWDO\WLF DFWLYLW\ RI WKH 7L2 $O 2 LUUDGLDWLRQ DUH VKRZQ LQ )LJXUH OLJKW LUUDGLDWLRQ ZLWK 1RWHZRUWK\

PHPEUDQH XQGHU VRODU OLJKW

LQGLFDWLQJ DQ HQKDQFHG GHJUDGDWLRQ DFWLYLW\ XQGHU VRODU

RI 0% GHJUDGHG LQ RQO\

PLQXWHV

WKH HIILFLHQW XWLOL]DWLRQ RI VRODU OLJKW REVHUYHG IRU WKHVH WLWDQLD EDVHG

PHPEUDQHV RFFXUV GHVSLWH WKH DEVHQFH RI VXLWDEOH ³RQ SXUSRVH´ LQWURGXFHG GRSDQWV ,QGHHG LW LV ZHOO NQRZQ WKDW WKH UHODWLYHO\ ZLGH EDQG JDS

H9 IRU DQDWDVH SKDVH DQG WKH IDVW

UHFRPELQDWLRQ RI SKRWRJHQHUDWHG HOHFWURQV DQG KROHV LQ XQPRGLILHG SXUH SKDVH WLWDQLD UHVWULFW WKH HIILFLHQW FRQYHUVLRQ RI YLVLEOH HQHUJ\ UXWLOH GXDO SKDVH

DQG 7L

VHOI GRSHG

2Q WKH FRQWUDU\ WKH HIILFDF\ RI DQDWDVH

7L2 SKRWRFDWDO\VW IRU YLVLEOH OLJKW UHVSRQVH

KDYH EHHQ FRQILUPHG LQ D YDULHW\ RI VWXG\ 0RUHRYHU LW KDV EHHQ UHFHQWO\ UHSRUWHG WKDW SKRWRJHQHUDWHG HOHFWURQV FDQ HDVLO\ PLJUDWH DQG EH WUDSSHG DW WKH 7L2 VXUIDFH LQ XOWUDWKLQ QDQRVWUXFWXUHV JHQHUDWLQJ KLJKO\ UHDFWLYH DQG WUDQVLHQW 7L H[LVWHQFH RI 7L

FHQWHUV

,Q RXU FDVH WKH

FHQWHUV JHQHUDWHG LQ VLWX RQ WKH VXUIDFH RI WKH WLWDQLD ILOP ZDV QRW GHWHFWHG

GXH WR WKH DEVHQFH RI WKH W\SLFDO ; EDQG (OHFWURQ 3DUDPDJQHWLF 5HVRQDQFH (35 VLJQDO J +RZHYHU LW DOVR NQRZQ WKDW VXUIDFH 7L

VSHFLHV DUH KLJKO\ XQVWDEOH DQG UHDGLO\

R[LGL]HG E\ ZDWHU DQG 2 IURP DLU DQG WKDW WKHVH WUDQVLHQW VSHFLHV DUH QRW VWUDLJKWIRUZDUGO\ REVHUYDEOH íñ

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

íUî

íXìí ìUô ìXô

šl ì

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 16 of 26

ìXò ìUò ìXð ìUð ìXî ìUî ìXìì

ríì

íì

ïì

ñì

óì

š ~u]v• )LJXUH

'HJUDGDWLRQ RI 0% XQGHU LUUDGLDWLRQ ZLWK VRODU OLJKW GHHS EOXH OLQH DQG ZLWKRXW EOXH OLQH

7L2 . $O 2 PHPEUDQH

7KH VXSHULRU SHUIRUPDQFH RI WKHVH 7L2 . $O 2 PHPEUDQHV XQGHU VRODU OLJKW LUUDGLDWLRQ FDQ EH UHODWHG LQ D ILUVW DWWHPSW WR WKH KLJK DEVRUSWLRQ FDSDFLW\ JXDUDQWHHG E\ WKH FHUDPLF PHPEUDQH VXSSRUW %\ DGVRUELQJ WKH RUJDQLF G\H WKH LQ VLWX VHQVLWL]DWLRQ RI WKH 7L2 VXUIDFH FDQ EH SURGXFHG ZKLFK ILQDOO\ DOORZV YLVLEOH SKRWRQ KDUYHVWLQJ

7KH VROH LQ

VLWX VHQVLWL]DWLRQ PHFKDQLVP KRZHYHU GRHV QRW IXOO\ DFFRXQW IRU WKH DFWLYLW\ RI WKHVH PHPEUDQHV ,QGHHG ZKHQ SKRWRFDWDO\WLF GHJUDGDWLRQ WHVWV DUH SHUIRUPHG E\ FRPSOHWHO\ H[FOXGLQJ WKH 89 O

QP FRQWULEXWLRQ RI WKH VRODU ODPS ZKLFK HVVHQWLDOO\ FRUUHVSRQG

WR WKH 89$ SRUWLRQ RI WKH VRODU VSHFWUXP IURP

WR

QP WKH SKRWRFDWDO\WLF DFWLYLW\ RI

WKH 7L2 . $O 2 PHPEUDQHV VLJQLILFDQWO\ GHFUHDVHV UHVXOWLQJ LQ RQO\

RI 0% UHPRYDO

$FFRUGLQJ WR WKH PRUSKRORJLFDO IHDWXUHV RI WKH YHU\ WKLQ 7L2 FRDWLQJ RQ WKH PHPEUDQH VXUIDFH WKH FDWDO\WLF OD\HU LV OLNHO\ WR EH LQWULQVLFDOO\ DIIHFWHG E\ ODWWLFH GLVRUGHUV GXH WR WKH XVH RI WKH )

VXUIDFWDQW GXULQJ GHSRVLWLRQ $ ODUJH DPRXQW RI ODWWLFH GLVRUGHU LQ

VHPLFRQGXFWRUV FDQ FUHDWH PLG JDS VWDWHV RU EURDGHQHG WDLO VWDWHV H[WHQGLQJ IURP WKH YDOHQFH DQG FRQGXFWLRQ EDQGV ZKLFK QDUURZ WKH IRUELGGHQ EDQG JDS DQG HQKDQFH YLVLEOH DEVRUSWLRQ

)XUWKHUPRUH GHIHFWV VHUYH DV WUDSV IRU SKRWRJHQHUDWHG FKDUJHV SUHYHQWLQJ

WKHLU UHFRPELQDWLRQ

íò

ACS Paragon Plus Environment

Page 17 of 26

)LQDOO\

WKH 7L2 . $O 2

PHPEUDQH ZDV WHVWHG LQ VLPXODWHG VRODU OLJKW GULYHQ

SKRWRGHJUDGDWLRQ WHVWV LQ SUHVHQFH RI + 2

DGGHG WR WKH UHDFWLRQ V\VWHP $V VRRQ DV WKH

LUUDGLDWLRQ LV VZLWFKHG RQ D QRWLFHDEOH HIIHUYHVFHQFH VWDUWV LQ WKH 0% + 2 VROXWLRQ RULJLQDWLQJ IURP WKH VXUIDFH RI WKH FDWDO\WLF PHPEUDQH $Q H\H SHUFHLYDEOH GHFRORUL]LQJ RI WKH 0% VROXWLRQ LV REVHUYDEOH DIWHU IHZ PLQXWHV ([FHOOHQW UHVXOWV KDYH EHHQ REWDLQHG ZKLFK DUH VKRZQ LQ )LJXUH

WRJHWKHU ZLWK D UHIHUHQFH WHVW FRQGXFWHG E\ H[SRVLQJ WKH

0% + 2 VROXWLRQ WR VRODU OLJKW LUUDGLDWLRQ ZLWKRXW DQ\ PHPEUDQH SUHVHQW LQ WKH 305 5HPDUNDEO\ DOPRVW

RI WKH G\H GHJUDGDWLRQ ZDV UHDFKHG LQ

PLQXWHV ZKHQ WKH

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íUîì

íUìì íXì

ìUôì ìXô

šl ì

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

Industrial & Engineering Chemistry Research

ìUòì ìXò

ìUðì ìXð

ìUîì ìXî

ìUìì ìXì

ríì

íì

ïì

ñì

óì

š ~u]v•

)LJXUH

'HJUDGDWLRQ RI 0% UHSRUWHG DV D IXQFWLRQ RI &W & E\ FRPELQLQJ VRODU OLJKW LUUDGLDWLRQ DQG + 2

ZLWK UHG OLQH DQG ZLWKRXW \HOORZ OLQH 7L2 . $O 2 PHPEUDQH

7KH FDWDO\WLF V\VWHPV ZHUH FRPSDUHG LQ WHUPV RI PHDQ GHJUDGDWLRQ UDWH N FDOFXODWHG LQ WKH SRUWLRQ RI WKH FXUYH ZKHUH WKH GHJUDGDWLRQ IROORZV WKH ]HUR RUGHU ODZ DQG SHUFHQWDJH RI

íó

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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

GHJUDGHG 0% LQ 7DEOH

Page 18 of 26

5HVXOWV IXUWKHU KLJKOLJKWHG WKH KLJKHU FDWDO\WLF DFWLYLW\ ZKHQ VRODU

OLJKW LV XVHG 7DEOH

0HDQ GHJUDGDWLRQ UDWH N DQG

RI 0% GHJUDGDWLRQ

&DWDO\WLF 6\VWHP

0HDQ 'HJUDGDWLRQ UDWH PRO / PLQ “

89 7L2 . $O 2 PHPEUDQH

. PRO / PLQ

0% 'HJUDGDWLRQ



+ 2 7L2 . $O 2 PHPEUDQH





89 + 2 7L2 . $O 2 PHPEUDQH





6RODU OLJKW 7L2 . $O 2 PHPEUDQH





6RODU OLJKW + 2 7L2 . $O 2 PHPEUDQH





&RQFOXVLRQV 8OWUD WKLQ SRURXV OD\HU RI 7L2 DQDWDVH ZDV GHSRVLWHG RQWR SRURXV . DOXPLQD VXEVWUDWHV WR REWDLQHG K\EULG SKRWRFDWDO\WLF PHPEUDQHV 7KHVH 7L2 . $O 2 PHPEUDQHV KDYH EHHQ WHVWHG LQ D 305 IRU WKH 89 GULYHQ SKRWRGHJUDGDWLRQ RI 0% LQ ZDWHU %\ D V\QHUJLF FRPELQDWLRQ RI DEVRUSWLRQ UHMHFWLRQ DQG GHJUDGDWLRQ WKH FRPSOHWH LPPHGLDWH EOHDFKLQJ RI WKH SHUPHDWH ZDV REVHUYHG WKH

RI G\H SROOXWDQW LQ WKH UHWHQWDWH ZDV PLQHUDOL]HG ZLWKLQ

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íô

ACS Paragon Plus Environment

Page 19 of 26

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

Industrial & Engineering Chemistry Research

GULYHQ GHJUDGDWLRQ RI RUJDQLFV WKXV PHHWLQJ WKH UHTXLUHPHQWV RI UHDO HQYLURQPHQWDO DSSOLFDWLRQV

$FNQRZOHGJHPHQWV 7KLV ZRUN ZDV VXSSRUWHG E\ 0,85 (/,275232 SURMHFW 321

3(B

5HIHUHQFHV 6HUSRQH 1

(PHOLQH $ 9 6HPLFRQGXFWRU 3KRWRFDWDO\VLVv3DVW 3UHVHQW DQG

)XWXUH 2XWORRN - 3K\V &KHP /HWW /HH $ (ODP - : 'DUOLQJ 6 % 0HPEUDQH 0DWHULDOV IRU :DWHU 3XULILFDWLRQ 'HVLJQ 'HYHORSPHQW DQG $SSOLFDWLRQ (QYLURQ 6FL :DWHU 5HV 7HFKQRO

6HUSRQH 1 (PHOLQH $ 9 .X]QHWVRY 9 1 5\DEFKXN 9 . 7KH 'HYHORSPHQW RI +LJKO\ $FWLYH 3KRWRFDWDO\VWV IRU WKH *HQHUDWLRQ RI &OHDQ (QHUJ\ DQG 7KHLU $SSOLFDWLRQ WR (QYLURQPHQWDO 3UREOHPV 1DQRVWUXFWXUH 6FLHQFH DQG 7HFKQRORJ\ LQ (QYLURQPHQWDO %HQLJQ &DWDO\VW $QSR 0 .DPDW 3 9 (GV 6SULQJHU 9HUODJ 1HZ