Unraveling the Growth Mechanism of Silica Particles in the Stöber

May 17, 2017 - Our results reveal that, at the initial stage, the reaction is dictated by TEOS hydrolysis to form silanol monomers, which is denoted a...
2 downloads 23 Views 2MB Size
Subscriber access provided by CORNELL UNIVERSITY LIBRARY

Article

Unravelling the Growth Mechanism of Silica Particles in Stöber Method: In-situ Seeded Growth Model Yandong Han, Ziyang Lu, Zhaogang Teng, Jinglun Liang, Zilong Guo, Dayang Wang, Ming-Yong Han, and Wensheng Yang Langmuir, Just Accepted Manuscript • Publication Date (Web): 17 May 2017 Downloaded from http://pubs.acs.org on May 18, 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.

Langmuir 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 40

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

Langmuir

295x140mm (96 x 96 DPI)

ACS Paragon Plus Environment

Langmuir

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

8QUDYHOOLQJ WKH *URZWK 0HFKDQLVP RI 6LOLFD 3DUWLFOHV LQ 6W|EHU 0HWKRG ,Q VLWX 6HHGHG *URZWK 0RGHO 6L 2(W @

DUH DVVLJQHG WR WKH K\GURO\]HG PRQRPHUV ZLWK GLIIHUHQW DPRXQW

RI VLODQRO JURXSV >6L 2(W 2+ @ >6L 2(W 2+ @ DQG >6L 2& + DQG >6L 2 2(W 2+ @

2+ @ UHVSHFWLYHO\ 7KH SHDNV DW

DUH DVVLJQHG WR SURWRQDWHG GLPHUV FRQWDLQLQJ ERWK HWKR[\O DQG VLODQRO JURXSV >6L 2 2(W 2+ @

>6L 2 2(W 2+ @

>6L 2 2(W 2+ @ 7KH QRWLFHDEO\ VWURQJ SHDN DW P ]

>6L 2 2(W 2+ @

REVHUYHG DW

SURWRQDWHG GLPHUV FRQWDLQLQJ RQO\ HWKR[\O JURXSV >6L 2 2(W @ ,Q WKH DW P ]

PRQRPHUV DV WKH GRPLQDQW

DQG

DUH DVVLJQHG WR SURWRQDWHG WULPHUV >6L 2 2& +

DQG

0 DPPRQLD LV DVVLJQHG WR 0 DPPRQLD UHDFWLRQ WKH SHDNV

2+ @ DQG >6L 2 2& +

ACS Paragon Plus Environment

2+ @

Page 13 of 40

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

Langmuir

DPPRQLD )LJXUH

ULJKW SDQHO ZKLFK LV H[SHFWHG WR EH GHULYHG IURP WKH FRQGHQVDWLRQ RI HLWKHU

WZR DQLRQLF PRQRPHUV FRQWDLQLQJ WKUHH VLODQRO JURXSV 6L 2(W 2+ 2

P]

DQLRQLF PRQRPHUV FRQWDLQLQJ WZR DQG IRXU VLODQRO JURXSV UHVSHFWLYHO\ 6L 2(W DQG 6L 2+

2

P]

XQGHU EDVLF FRQGLWLRQV VXFK DV 6L 2 2(W

2+

DQG 6L 2 2(W

RU WZR

2+

2

P]

ZKLFK DUH XVXDOO\ QRW REVHUYDEOH GXH WR LWV XOWUDKLJK DFWLYLW\

UHVSHFWLYHO\ :LWK IXUWKHU SURFHHGHG UHDFWLRQV PRUH DQLRQLF GLPHUV 2 2+

P] 2

6L 2 2(W 2+ RU 6L 2 2(W

2

2

RU 6L 2 2(W

P]

2+

2

P]

ZKLFK DUH H[SHFWHG WR EH

GHULYHG IURP WKH VLODQRO PRQRPHUV FRQWDLQLQJ DW OHDVW WZR VLODQRO JURXSV VHH (TXDWLRQ SURGXFHG LQ ERWK WKH UHDFWLRQ VROXWLRQV +RZHYHU WULPHUV VXFK DV 6L 2 2(W 6L 2 2(W

2+

2

P]

EHFDPH HYLGHQW DIWHU

DQG 6L 2 2(W PLQ LQ WKH

FDQ QRW EH ZHOO UHFRJQL]HG HYHQ DIWHU

2+

2

RU 6L 2 2(W

0 DPPRQLD UHDFWLRQ )LJXUH PLQ LQ WKH

2+ 2

2+

2

2+

2

RU P]

ULJKW SDQHO ZKLFK

0 DPPRQLD UHDFWLRQ 7KXV ZH FDQ

FRQFOXGH WKDW 7(26 K\GURO\VLV LV VLJQLILFDQWO\ SURPRWHG DW DPPRQLD FRQFHQWUDWLRQ RI • 2Q WKH RWKHU KDQG DOWKRXJK PRUH 6L 2(W

ZHUH

DQG 6L 2(W

2+

2

0

PRQRPHUV DUH

SURGXFHG DV H[SHFWHG YLD 7(26 K\GURO\VLV DW KLJK DPPRQLD FRQFHQWUDWLRQ WKHLU SHDNV P ] DQG

DUH ZHDNHU WKDQ WKDW RI 6L 2(W

2

P]

HYHQ LQ WKH

0 UHDFWLRQ )LJXUH

ULJKW SDQHO 7KLV LV LQGLFDWLYH RI VWURQJ UHDFWLRQ DFWLYLW\ RI WKHVH VLODQRO PRQRPHUV ZLWK WZR RU WKUHH VLODQRO JURXSV DQG WKHLU VWURQJ WHQGHQF\ WR FRQGHQVH LQWR VLOR[DQH QHWZRUNV PXFK TXLFNO\ +HUH WKH FRQGHQVDWLRQ RI WKH VLODQRO PRQRPHUV ZLWK 7(26 DV VKRZQ LQ (TXDWLRQ

LV QRW

FRQVLGHUHG VLQFH WKH VDPH DPRXQW RI 7(26 ZDV FRQVXPHG ZKHQ WKH K\GURO\VLV DQG FRQGHQVDWLRQ RI 7(26 UHDFKHG WKH HTXLOLEULXP DV GLVFXVVHG LQIUD %DVHG RQ WKH WHPSRUDO HYROXWLRQ LQ 7(26 FRQFHQWUDWLRQ DQG FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD )LJXUH

WKH UDWH FRQVWDQWV RI WKH 7(26 K\GURO\VLV ZHUH FDOFXODWHG DQG WKH VXEVHTXHQW

ACS Paragon Plus Environment

Langmuir

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 40

FRQGHQVDWLRQ ZHUH GHULYHG E\ XVLQJ WKH VWHDG\ VWDWH DQG HTXLOLEULXP DSSUR[LPDWLRQ )LJXUH 6 DQG 7DEOH 6

7KH UDWH FRQVWDQW RI WKH K\GURO\VLV LQFUHDVHV IURP

PLQ DQG WKDW RI WKH FRQGHQVDWLRQ LQFUHDVHV IURP FRQFHQWUDWLRQ LQFUHDVLQJ IURP

WR

u

WR

u

u

WR

VHH 6, u

PLQ ZLWK DPPRQLD

0 ,Q DJUHHPHQW ZLWK OLWHUDWXUH WKH K\GURO\VLV RI 7(26

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|EHU PHWKRG $IWHU 7L WKH FRQGHQVDWLRQ RI DQLRQLF VLODQRO PRQRPHUV DSSHDUV WR EHFRPH DVFHQGDQW DQG FRQVXPHV PRUH DQLRQLF VLODQRO PRQRPHUV WKDQ WKRVH QHZO\ IRUPHG YLD WKH K\GURO\VLV RI WKH UHPDLQLQJ 7(26 PROHFXOHV :KHQ WKH DPPRQLD FRQFHQWUDWLRQ LV EHORZ

0 KRZHYHU WKH VPDOO UHGXFWLRQ RI WKH FRQGXFWLYLW\ LQ

WKH UHDFWLRQ PHGLD DIWHU 7L LQGLFDWHV WKDW WKH K\GURO\VLV RI WKH UHPDLQLQJ 7(26 PROHFXOHV PD\ EH PHUHO\ RIIVHW E\ WKH FRQGHQVDWLRQ RI WKH UHVXOWLQJ VLODQRO PRQRPHUV DQG WKH IRUPHU VWLOO SURGXFHV VXIILFLHQW QHZ VLODQRO PRQRPHUV WR FRPSHQVDWH WKH FRQGXFWLYLW\ ORVV FDXVHG E\ WKH ODWWHU 7KLV HIIHFW RI WKH DPPRQLD FRQFHQWUDWLRQ RQ WKH EDODQFH EHWZHHQ 7(26 K\GURO\VLV DQG FRQGHQVDWLRQ

ACS Paragon Plus Environment

Page 15 of 40

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

Langmuir

DIWHU 7L PD\ PDQLIHVW LWVHOI LQ WKH JURZWK RI VLOLFD SDUWLFOHV LQ WKH 6W|EHU PHWKRG DV GLVFXVVHG LQIUD %\ IXUWKHU VFUXWLQL]LQJ WKH FRQVXPSWLRQ NLQHWLFV SURILOH RI 7(26 )LJXUH E I LW LV XQUDYHOOHG WKDW UHJDUGOHVV RI WKH DPPRQLD FRQFHQWUDWLRQ RI WKH UHDFWLRQ PHGLD RQO\ DERXW

RI WKH 7(26

PROHFXOHV LQ WKH UHDFWLRQ PHGLD DUH FRQVXPHG GXULQJ 7L ZKLOH WKH PDMRULW\ RI WKH 7(26 PROHFXOHV DERXW

DUH FRQVXPHG DIWHUZDUGV 6XFK DPPRQLD FRQFHQWUDWLRQ LQGHSHQGHQW FRQVXPSWLRQ RI

7(26 GXULQJ 7L VXJJHVWV WKDW WKH K\GURO\VLV RI RQH HWKR[\O JURXS RI 7(26 PROHFXOHV WR IRUP PRQRYDOHQW DQLRQLF VLODQRO PRQRPHUV ±6L 2(W

2

± LV WKH UDWH OLPLWLQJ VWHS IRU 7(26

K\GURO\VLV 7KLV LV LQ FRQVRQDQFH ZLWK WKH IDFW WKDW WKH PRUH HWKR[\O JURXSV DUH UHPRYHG IURP D 7(26 PROHFXOH WKH PRUH HDVLO\ WKH VXEVHTXHQW K\GURO\VLV RFFXUV ,W LV DOVR SODXVLEOH WR H[SHFW WKDW WKH DQLRQLF VLODQRO PRQRPHUV REWDLQHG WKHUHDIWHU WHQG WR FRXSOH ZLWK HDFK RWKHU VHH (TXDWLRQ UDWKHU WKDQ WR UHDFW ZLWK 7(26 PROHFXOHV VHH (TXDWLRQ

RWKHUZLVH WKH ODWWHU PLJKW PDNH WKH

IUDFWLRQ RI 7(26 FRQVXPHG LQ 7L GHSHQGHQW RQ WKH DPPRQLD FRQFHQWUDWLRQ DV WKH VLODQRO PRQRPHUV REWDLQHG DW KLJKHU DPPRQLD FRQFHQWUDWLRQ KDYH PRUH HWKR[\O JURXSV GLVSODFHG E\ K\GUR[\O JURXSV DQG EHFRPH PRUH DFWLYH 7DNHQ WRJHWKHU ZH K\SRWKHVL]H WKDW WKH FRQGHQVDWLRQV RI VLODQRO PRQRPHUV RFFXUULQJ GXULQJ DQG DIWHU 7L DUH KDUGO\ LQWHUZHDYHG ZLWK HDFK RWKHU ZKLFK VXEVHTXHQWO\ EXW LQGHSHQGHQWO\ UHJXODWH WKH JURZWK RI VLOLFD SDUWLFOHV LQ WKH 6W|EHU PHWKRG .LQHWLF *URZWK RI 6LOLFD 3DUWLFOHV LQ 6W|EHU 0HWKRG ,Q VLWX 6HHGHG *URZWK 0RGHO 6LQFH WKH JURZWK RI VLOLFD SDUWLFOHV LQ WKH 6W|EHU PHWKRG LV WKH UHVXOW RI WKH FRQGHQVDWLRQ RI DQLRQLF VLODQRO PRQRPHUV GHULYHG IURP 7(26 K\GURO\VLV LQWR VLOR[DQH QHWZRUNV KHUH RXU HIIRUW LV GHYRWHG WR FRUUHODWLRQ RI WKH JURZWK RI VLOLFD SDUWLFOHV ZLWK WKH WHPSRUDO HYROXWLRQ RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD ZKLFK WR ODUJH GHJUHH UHIOHFWV WKH FRQWHQW RI DQLRQLF VLODQRO PRQRPHUV SUHVHQW LQ WKH UHDFWLRQ PHGLD )LJXUH

$V VKRZQ LQ )LJXUH 6

ACS Paragon Plus Environment

VHH 6, WKH WHPSRUDO

Langmuir

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 40

HYROXWLRQ SURILOHV RI WKH K\GURG\QDPLF VL]HV RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD DUH VWURQJO\ GHSHQGHQW RQ WKH DPPRQLD FRQFHQWUDWLRQ :KHQ WKH DPPRQLD FRQFHQWUDWLRQ LV 0 ODUJH SDUWLFOHV DSSHDU LQ WKH UHDFWLRQ PHGLD DURXQG

PLQ DIWHU WKH UHDFWLRQ VWDUWV WKH

K\GURG\QDPLF VL]HV RI ZKLFK LV LQ WKH UDQJH RI

QP GHSHQGLQJ RQ WKH DPPRQLD

±

FRQFHQWUDWLRQ &RQFRPLWDQW ZLWK WKH FRQGXFWLYLW\ LQFUHDVH RI WKH UHDFWLRQ PHGLD GXULQJ 7L WKH VXEVWDQWLDO GURS LQ WKH SDUWLFOH VL]HV LV REVHUYHG ZKLFK LV IROORZHG E\ JUDGXDO VL]H LQFUHDVH ZLWK WKH GHFUHDVH RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD DIWHU 7L )LJXUH D 7(0 LPDJLQJ RI WKH DOLTXRWV RI WKH UHDFWLRQ PHGLD LQGLFDWHV WKDW WKH ODUJH SDUWLFOHV REVHUYHG DW WKH EHJLQQLQJ RI WKH

)LJXUH

D F 7HPSRUDO HYROXWLRQ SURILOHV RI WKH K\GURG\QDPLF GLDPHWHUV 'K RI WKH VLOLFD SDUWLFOHV

JURZLQJ LQ WKH UHDFWLRQ PHGLD DW DPPRQLD FRQFHQWUDWLRQV RI

0 D

0 E DQG

0 F YLD

FODVVLF 6W|EHU PHWKRG 7KH FRUUHVSRQGLQJ WHPSRUDO HYROXWLRQ SURILOHV RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD DUH DOVR SUHVHQW IRU WKH EHQHILW RI EHWWHU FRUUHODWLRQ RI WKH JURZWK RI VLOLFD SDUWLFOHV ZLWK WKH FRQGHQVDWLRQ RI VLODQRO PRQRPHUV G 7HPSRUDO HYROXWLRQ RI WKH ]HWD SRWHQWLDO SURILOHV RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD YLD FODVVLF 6W|EHU PHWKRG DW WKH DPPRQLD FRQFHQWUDWLRQ RI FLUFOHV DQG

0 VROLG

0 RSHQ FLUFOHV UHVSHFWLYHO\ 7KH GDVKHG EOXH OLQHV LQ WKH ILJXUHV KLJKOLJKW WKH SRVLWLRQ

RI 7L

ACS Paragon Plus Environment

Page 17 of 40

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

Langmuir

UHDFWLRQV DUH FOXPSV RI ORRVHO\ FRDOHVFHG VPDOO SDUWLFOHV ZKLFK DUH JUDGXDOO\ WUDQVIRUPHG WR VPDOO GHQVH SRO\GLVSHUVH SDUWLFOHV DIWHU 7L )LJXUH

XSSHU SDQHO 7KLV XQGHUOLQHV WKH JURZWK RI VLOLFD

SDUWLFOHV SURFHHGLQJ LQ GLIIHUHQW SDWKZD\V GXULQJ DQG DIWHU 7L DW WKH DPPRQLD FRQFHQWUDWLRQ EHORZ 0 ,Q FRQWUDVW WKH JURZWK RI VLOLFD SDUWLFOHV IROORZV D FRPSOHWH GLIIHUHQW SURFHVV ZKHQ WKH DPPRQLD FRQFHQWUDWLRQ LV DW ZLWK VL]HV RI DERXW

0 DQG DERYH $V VKRZQ LQ )LJXUH E DQG F YHU\ VPDOO SDUWLFOHV

QP DUH IRUPHG LQ DERXW PLQ DIWHU WKH UHDFWLRQ VWDUWV DQG WKH SDUWLFOH VL]HV

UDSLGO\ MXPS WR DERXW

QP ZLWKLQ 7L LQ DFFRPSDQLPHQW ZLWK WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ

PHGLD DSSURDFKLQJ WKH PD[LPXP IROORZHG E\ JUDGXDO EXW VWLOO VXEVWDQWLDO LQFUHDVH ZLWK WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD FRQVLGHUDEO\ GHFUHDVLQJ ZLWK WKH UHDFWLRQ WLPH DIWHU 7L 7KLV FRQWLQXLQJ JURZWK PDQQHU RI VLOLFD SDUWLFOHV ZLWK WKH UHDFWLRQ WLPH LV IXUWKHU FRQILUPHG E\ 7(0 LPDJLQJ )LJXUH

ORZHU SDQHO 7KH TXDVL ORJDULWKPLF JURZWK SURILOH RI WKH SDUWLFOH VL]HV ZLWK

WKH UHDFWLRQ WLPH LV KDUGO\ DIIHFWHG E\ WKH DPPRQLD FRQFHQWUDWLRQ ZKLOH WKH VL]H RI WKH ILQDO SDUWLFOHV LQFUHDVHV IURP 0 WR

QP WR

QP ZLWK WKH DPPRQLD FRQFHQWUDWLRQ LQFUHDVLQJ IURP

0 7KH DIRUHPHQWLRQHG UHVXOWV XQGHUOLQH GLVWLQFWO\ GLIIHUHQW SDWKZD\V IRU VLOLFD SDUWLFOHV

)LJXUH 7(0 LPDJHV RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD DW WKH DPPRQLD FRQFHQWUDWLRQ RI 0 XSSHU SDQHO DQG

0 ORZHU SDQHO UHVSHFWLYHO\ YLD FODVVLF 6W|EHU PHWKRG $IWHU WKH UHDFWLRQV

DUH FDUULHG RXW IRU D JLYHQ WLPH PDUNHG LQ WKH ILJXUHV WKH DOLTXRWV RI WKH UHDFWLRQ PHGLD DUH WDNHQ RXW IRU 7(0 LPDJLQJ

ACS Paragon Plus Environment

Langmuir

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

WR JURZ DW WKH DPPRQLD FRQFHQWUDWLRQ EHORZ DQG DERYH

Page 18 of 40

0 DQG PRUHRYHU WKHUH LV FOHDU

GLIIHUHQWLDWLRQ EHWZHHQ WKH SDUWLFOH JURZWK SDWKZD\V RFFXUULQJ GXULQJ 7L DQG DIWHU 7L )LJXUH DQG 6

7KHVH WZR DVSHFWV DUH KDUGO\ UHYHDOHG LQ OLWHUDWXUH VR IDU 6LQFH WKH FKDQJHRYHU RI WKH

JURZWK SDWKZD\V RI VLOLFD SDUWLFOHV EHIRUH DQG DIWHU WKH SRLQW RI 7L LV FRQFRPLWDQW ZLWK WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD SDVVLQJ WKH PD[LPXP YDOXH )LJXUH

ZH ZHUH LQVSLUHG WR

FRUUHODWH WKH JURZWK NLQHWLFV RI VLOLFD SDUWLFOHV ZLWK WKH NLQHWLFV RI 7(26 K\GURO\VLV DQG VXEVHTXHQW FRQGHQVDWLRQ $V GLVFXVVHG DERYH WKH UHDFWLRQ SURFHVV GXULQJ 7L LV GRPLQDWHG E\ WKH K\GURO\VLV RI 7(26 PROHFXOHV WR DQLRQLF VLODQRO PRQRPHUV ZKLFK LV VLJQLILFDQWO\ SURPRWHG DW WKH DPPRQLD FRQFHQWUDWLRQ RI •

0 )LJXUH

$W WKLV LQGXFWLRQ VWDJH WKH FRQGHQVDWLRQ RI

WKH UHVXOWLQJ DQLRQLF VLODQRO PRQRPHUV WR VLOR[DQH QHWZRUNV LV OHVV HIIHFWLYH ZKLFK LV ZLWQHVVHG QRW RQO\ E\ WKH FRQWLQXLQJ LQFUHDVH RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD )LJXUH E\ WKH IDFW WKDW LW WDNHV DERXW VHYHUDO WR

PLQ GHSHQGLQJ RQ WKH DPPRQLD FRQFHQWUDWLRQ WR

REVHUYH SDUWLFXODWH VSHFLHV LQ WKH UHDFWLRQ PHGLD DIWHU WKH UHDFWLRQV FRPPHQFH )LJXUH VFHQDULR DV VKRZQ LQ 6FKHPH

EXW DOVR

,Q WKLV

LW LV SODXVLEOH WR H[SHFW WKDW ZKHQ WKH VXIILFLHQW DPRXQW RI DQLRQLF

VLODQRO PRQRPHUV DUH SURGXFHG YLD 7(26 K\GURO\VLV GXULQJ 7L WKH VLOR[DQH QHWZRUN FOXVWHUV GHULYHG YLD FRQGHQVDWLRQ RI WKH VLODQRO PRQRPHUV WHQG WR DJJORPHUDWH DQG LQ WXUQ IXVH WRJHWKHU WR WKUHH GLPHQVLRQDO

' SDUWLFXODWH QHWZRUNV ZKLFK RQFH IRUPHG SUHIHUHQWLDOO\ DWWUDFW WKH QHZO\

IRUPHG WKH VLODQRO PRQRPHUV WR FRQGHQVH DWRS DQG RU LQVLGH GXH WR WKHLU KLJK DFWLYLW\ WKXV WUDQVIRUPLQJ WKHPVHOYHV WR GHQVH VROLG SDUWLFOHV DQG DW WKH VDPH WLPH UHWDUGLQJ WKH FRQGXFWLYLW\ LQFUHDVH LQ WKH UHDFWLRQ PHGLD 7KH LQFUHDVH RI WKH DPPRQLD FRQFHQWUDWLRQ FDQ VLJQLILFDQWO\ SURPRWH RI 7(26 K\GURO\VLV LQ WHUPV RI UHDFWLRQ UDWH DQG HIILFLHQF\ HYLGHQFHG E\ WKH KLJK YDOXH DQG UDSLG LQFUHDVH LQ WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD DW KLJKHU DPPRQLD FRQFHQWUDWLRQV )LJXUH

ACS Paragon Plus Environment

DQG E\ WKH IDFW

Page 19 of 40

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

Langmuir

6FKHPH

6FKHPDWLF LOOXVWUDWLRQ IRU QXFOHDWLRQ JURZWK RI VLOLFD SDUWLFOHV DW WKH KLJK •

0 DQG ORZ

0 DPPRQLD FRQFHQWUDWLRQV 7KH JURZWK FDQ EH LQWR WZR FRQVHFXWLYHO\ RFFXUULQJ VWDJHV 3DWKZD\ , QXFOHDWLRQ JURZWK DQG 3DWKZD\ ,, PRQRPHU DGGLWLRQ DW WKH KLJK DPPRQLD FRQFHQWUDWLRQ •

0 RU

3DWKZD\ , QXFOHDWLRQ JURZWK 3DWKZD\ , ,, FRQWLQXRXV QXFOHDWLRQ DQG PRQRPHU DGGLWLRQ DW WKH ORZ 0 DFFRUGLQJ WR WKH UHYHUVLRQ RI WKH K\GURO\VLV UDWH #K DQG FRQGHQVDWLRQ

DPPRQLD FRQFHQWUDWLRQ

UDWH #F FRUUHVSRQGLQJ WKH IRUPDWLRQ RI VHHGV DQG JURZWK RI VHHGV UHVSHFWLYHO\

WKDW 7(26 PROHFXOHV KDYH PRUH HWKR[\O JURXSV GLVSODFHG E\ VLODQRO JURXSV )LJXUH $FFRUGLQJO\ ZKHQ 7(26 K\GURO\VLV LV FDUULHG RXW DW DPPRQLD FRQFHQWUDWLRQ EHORZ VLODQRO PRQRPHUV RI 6L 2(W VRPH RI 6L 2(W 6L 2(W

2+ 2

2+

2

2

0 WKH

W\SH DUH GRPLQDQWO\ SUHVHQW LQ WKH UHDFWLRQ PHGLD DORQJ ZLWK

W\SH HVSHFLDOO\ WDNLQJ LQWR DFFRXQW WKH SRVVLELOLW\ WKDW RQFH SURGXFHG

PRQRPHUV WHQG WR FRQGHQVH ZLWK HDFK RWKHU RU ZLWK H[LVWLQJ VLOR[DQH

QHWZRUNV 7KH VLOR[DQH FOXVWHUV GHULYHG IURP WKHVH 6L 2(W

2

PRQRPHUV DUH ORRVHO\ FRQGHQVHG

DQG KDYH OHVV QHJDWLYHO\ FKDUJHV RQ WKHLU VXUIDFHV WR UHSHO QHLJKERULQJ FOXVWHUV ZKLFK LV HYLGHQFHG

ACS Paragon Plus Environment

Langmuir

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 20 of 40

E\ WKH IDLUO\ ZHDNO\ QHJDWLYH ]HWD SRWHQWLDO DURXQG ± P9 REVHUYHG DIWHU

PLQ RI WKH UHDFWLRQ

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

XSSHU SDQHO

,Q FRQWUDVW WR WKDW RFFXUULQJ DW WKH DPPRQLD FRQFHQWUDWLRQ EHORZ WKH DPPRQLD FRQFHQWUDWLRQ RI • 6L 2(W

2+

2

DQG 6L 2(W

0 7(26 K\GURO\VLV DW

0 PD\ SURGXFH PRQRPHUV ZLWK PRUH VLODQRO JURXSV VXFK DV 2+

2

W\SHV 6RRQ DIWHU WKH UHDFWLRQ FRPPHQFHV WKH UDSLG

MXPS RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD LQWR WKH KLJK YDOXH ZLWK WLPH LV LQGLFDWLYH RI WKH K\GURO\VLV RI PRUH LQGLYLGXDO 7(26 PROHFXOHV GXULQJ 7L 7KHVH 6L 2(W 2+ 6L 2(W

2+

2

2

PRQRPHUV KDYH PXFK KLJKHU UHDFWLRQ DFWLYLW\ WKDQ WKH 6L 2(W 2

DQG RQHV

ZKLFK QRW RQO\ UHVXOWV LQ UDSLG IRUPDWLRQ RI FRQGHQVHG VLOR[DQH FOXVWHUV DV ZLWQHVVHG E\ DERXW QP VROLG SDUWLFOHV FOHDUO\ YLVLEOH LQ WKH UHDFWLRQ PHGLD DIWHU

PLQ RI WKH UHDFWLRQ )LJXUH E EXW

DOVR LPSDUWV PRUH QHJDWLYH FKDUJHV WR WKH UHVXOWLQJ VLOR[DQH FOXVWHUV WR UHSHO HDFK RWKHU DV HYLGHQFHG E\ UHODWLYHO\ ODUJH QHJDWLYH ]HWD SRWHQWLDO FD ± G 6LQFH KLJKO\ DFWLYH 6L 2(W

2+

2

DQG 6L 2(W

P9 RI WKH UHVXOWLQJ FOXVWHUV )LJXUH 2+

2

PRQRPHUV WHQG WR IXVH HDFK

RWKHU WR IRUP KLJKO\ FRQGHQVHG VLOR[DQH QHWZRUNV QHZO\ IRUPHG VLODQRO PRQRPHUV LQ WKH UHDFWLRQ

ACS Paragon Plus Environment

Page 21 of 40

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

Langmuir

PHGLD PD\ SUHIHUHQWLDOO\ DGG RQWR UDWKHU WKDQ GLIIXVH LQWR WKH SUHIRUPHG VLOR[DQH QHWZRUN SDUWLFOHV WKXV HQDEOLQJ WKH VL]H LQFUHDVH ZLWK WKH UHDFWLRQ WLPH 7KH LQIUDUHG VSHFWURVFRSLF DVVHVVPHQW UHYHDOHG WKDW WKH VLOLFD SDUWLFOHV REWDLQHG DW DPPRQLD FRQFHQWUDWLRQ RI • FRQGHQVHG LQWHULRU VLOR[DQH QHWZRUNV

WKDQ WKRVH REWDLQHG DW DPPRQLD FRQFHQWUDWLRQ RI

0 LQ ZKLFK WKH IRUPHU 6L 2 6L VWUHWFKLQJ YLEUDWLRQ EDQG ZDV FHQWHUHG DW DW

FP

0 EHDU PRUH

FP DQG WKH ODWWHU

VHH 6, )LJXUH 6

$OO WKH DIRUHPHQWLRQHG UHVXOWV IXUWKHU VXJJHVW WKDW WKH K\GURO\VLV RI 7(26 LV VLJQLILFDQWO\ IDFLOLWDWHG ZKHQ WKH DPPRQLD FRQFHQWUDWLRQ LQFUHDVHV WR RI VKRUW 7L

PLQ DW

0 YV

PLQ DW

0 DQG DERYH ZKLFK LV FKDUDFWHULVWLF

0 7DNLQJ LQWR DFFRXQW WKDW VKRUW 7L DQG WKH

REVHUYDWLRQ RI XQLIRUP VLOLFD SDUWLFOHV IRUPHG WKHUHLQ LW LV SODXVLEOH WR H[SHFW WKDW 7(26 K\GURO\VLV DW DPPRQLD FRQFHQWUDWLRQ RI •

0 HQDEOHV WKH FRQFHQWUDWLRQ RI KLJKO\ DFWLYH VLODQRO

PRQRPHUV WR UDSLGO\ UHDFK WR WKH OHYHO DW ZKLFK WKH VLODQRO PRQRPHUV XQGHUJR VKDUS FRDOHVFHQFH DQG IXVLRQ WR SURGXFH WKH FOXVWHUV RI KLJKO\ FRQGHQVHG VLOR[DQH QHWZRUNV ZLWK UHODWLYHO\ QDUURZ VL]H GLVWULEXWLRQ ,Q FRQWUDVW WKH VORZ K\GURO\VLV RI 7(26 PROHFXOHV LQWR SRRUO\ DFWLYH VLODQRO PRQRPHUV DW WKH DPPRQLD FRQFHQWUDWLRQ

0 PD\ OHDG WR JUDGXDO DQG FRQWLQXLQJ IRUPDWLRQ

RI VLOR[DQH QHWZRUN FOXVWHUV ZKLFK PDQLIHVWV LWVHOI QRW RQO\ LQ WKH 7L SURORQJDWLRQ ZKLFK LQFUHDVHV IURP

PLQ DW

0 DPPRQLD WR

PLQ DW

0 DPPRQLD EXW DOVR LQ WKH VL]H GLVWULEXWLRQ

EURDGHQLQJ RI WKH VLOLFD SDUWLFOHV REWDLQHG GXULQJ 7L 6LPLODU WR WKDW GXULQJ 7L DV LOOXVWUDWHG LQ 6FKHPH

WKH VLOLFD SDUWLFOH JURZWK DIWHU 7L FDQ EH DOVR

FRUUHODWHG ZLWK WKH DPPRQLD FRQFHQWUDWLRQ GHSHQGHQW UHDFWLRQ NLQHWLFV RI 7(26 K\GURO\VLV DQG VXEVHTXHQW FRQGHQVDWLRQ 7KH DIRUHPHQWLRQHG UHVXOWV UHYHDO WKDW MXVW FD DUH K\GURO\]HG GXULQJ 7L ZKLOH WKH UHVW FD

RI 7(26 PROHFXOHV

DUH FRQVXPHG DIWHU 7L 6LQFH WKH FRQGHQVDWLRQV RI

VLODQRO PRQRPHUV RFFXUULQJ GXULQJ DQG DIWHU 7L WDNH SODFH VXEVHTXHQWO\ EXW LQGHSHQGHQWO\ ZLWK

ACS Paragon Plus Environment

Langmuir

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 22 of 40

OLWWOH RYHUODSSLQJ WKH VLOLFD SDUWLFOHV GHULYHG IURP K\GURO\VLV DQG FRQGHQVDWLRQ RI WKH WRWDO 7(26 PROHFXOHV XVHG DQG WKH UHPDLQLQJ

RI WKH

RI WKH 7(26 PROHFXOHV DUH H[SHFWHG WKH

GRPLQDQW VSHFLHV LQ WKH UHDFWLRQ PHGLD DIWHU 7L 7KH VLOLFD SDUWLFOHV REWDLQHG GXULQJ 7L H[KLELW UHDVRQDEOH FROORLGDO VWDELOLW\ WKH ]HWD SRWHQWLDO RI WKH VLOLFD SDUWLFOHV IRUPHG DW WKH HQG RI 7L DUH DURXQG ±

P9 UHJDUGOHVV RI DPPRQLD FRQFHQWUDWLRQ DW ZKLFK WKH\ DUH SURGXFHG )LJXUH G ,Q

WKLV VFHQDULR WKH VLOLFD SDUWLFOHV SUH IRUPHG GXULQJ 7L DUH H[SHFWHG WR DFW DV VHHGV IRU FRQGHQVDWLRQ RI WKH VLODQRO PRQRPHUV GHULYHG IURP K\GURO\VLV RI WKH UHPDLQLQJ

RI 7(26 PROHFXOHV LQ WKH

UHDFWLRQ PHGLD IRU JURZWK RI ODUJH SDUWLFOH ZKLFK LV UHPLQLVFHQW RI VHHGHG JURZWK 6FKHPH 2Q WKH EDVLV RI WKH VHHGHG JURZWK PRGHO KHUH ZH HQGHDYRUHG WR ILW WKH K\GURG\QDPLF VL]H SURILOHV RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD )LJXUH NLQHWLFV RI 7(26 )LJXUH

ZLWK WKH FRQVXPSWLRQ

)LJXUH D LQGLFDWHV DQ H[FHOOHQW ILWWLQJ IRU WKH JURZWK RI VLOLFD

SDUWLFOHV DW DPPRQLD FRQFHQWUDWLRQ RI •

0 7KLV LV HOXFLGDWHG E\ WDNLQJ LQWR DFFRXQW WKH IDFW

WKDW KLJKO\ DFWLYH VLODQRO PRQRPHUV SURGXFHG YLD 7(26 K\GURO\VLV DW KLJK DPPRQLD FRQFHQWUDWLRQ DIWHU 7L WHQG WR SUHIHUHQWLDOO\ DGG RQWR PRUH DFWLYH VLOR[DQH QHWZRUN RI WKH VLOLFD SDUWLFOH VHHGV IRUPHG GXULQJ 7L )LJXUH E LQGLFDWHV D FOHDU GLVFUHSDQF\ RI WKH JURZWK RI VLOLFD SDUWLFOHV RFFXUULQJ DW DPPRQLD FRQFHQWUDWLRQ RI

0 IURP WKH VHHGHG JURZWK PRGHO ,W

VKRXOG DULVH IURP WKH IDFW WKDW WKH K\GURO\VLV RI 7(26 PROHFXOHV LQWR DQLRQLF PRQRPHUV LV MXVW RIIVHW EXW QRW RYHUZKHOPHG E\ WKH VXEVHTXHQW FRQGHQVDWLRQ FKDUDFWHULVWLF RI VPDOO UHGXFWLRQ RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD ZLWK WKH WLPH DIWHU 7L ,Q WKLV VFHQDULR WKHUHIRUH WKH VXIILFLHQW DPRXQW RI DQLRQLF VLODQRO PRQRPHUV ± DOEHLW EHLQJ OHVV DFWLYH± DUH FRQWLQXRXVO\ IRUPHG LQ WKH UHDFWLRQ PHGLD ZKLFK WKHUHIRUH UHVXOWV LQ XQDYRLGDEOH FRDOHVFHQFH DQG IXVLRQ EHWZHHQ WKHVH IUHH PRQRPHUV IRU FRQWLQXLQJ IRUPDWLRQ RI QHZ VPDOO VLOLFD SDUWLFOHV LQ D ZD\ IDLUO\ VLPLODU WR WKDW RFFXUULQJ GXULQJ 7L ZKLFK LQ WXUQ ZLOO DFW DV VHHGV IRU IXUWKHU JURZWK 7KLV UHPLQGV RI WKH

ACS Paragon Plus Environment

Page 23 of 40

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

Langmuir

VHHGHG JURZWK ZLWK SURPLQHQW VHFRQGDU\ QXFOHDWLRQ DQG JURZWK RI FROORLGDO SDUWLFOHV

2Q WKH RWKHU KDQG

WKH

FRQWLQXLQJ IRUPDWLRQ RI VPDOO SDUWLFOH VHHGV ZLWK WKH UHDFWLRQ WLPH DULVLQJ IURP WKH K\GURO\VLV RI WKH UHPDLQLQJ 7(26 FD

RI WKH WRWDO PROHFXOHV DIWHU 7L

PD\ JUDGXDOO\ LQFUHDVH WKH WRWDO QXPEHU RI WKH SDUWLFOH VHHGV 7KLV VKRXOG EH WKH UDWLRQDOH EHKLQG WKH IRUPDWLRQ RI VPDOO VLOLFD

SDUWLFOHV

ZLWK

EURDG

VL]H

GLVWULEXWLRQ DW WKH DPPRQLD FRQFHQWUDWLRQ RI

)LJXUH 3ORWV RI WKH K\GURG\QDPLF GLDPHWHUV RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD YLD 6W:EHU PHWKRG YHUVXV WKH IUDFWLRQV RI WKH 7(26 PROHFXOHV FRQVXPHG IRU

0

WKH JURZWK RI WKH VLOLFD SDUWLFOHV ZLWK WKH FRUUHVSRQGLQJ VL]HV DW WKH DPPRQLD FRQFHQWUDWLRQ RI

$V VXPPDUL]HG LQ 6FKHPH

WKHUHIRUH

WKH JURZWK RI VLOLFD SDUWLFOHV LQ 6W|EHU

0 E

0 D DQG

UHVSHFWLYHO\ YLD FODVVLF 6W|EHU PHWKRG 7KH

H[SHULPHQWDOO\ PHDVXUHG YDOXHV

VROLG WULDQJOHV

DUH

FRPSDUHG ZLWK WKH WKHRUHWLFDO YDOXHV FDOFXODWHG IURP WKH

PHWKRG

FDQ

EH

GLYLGHG

LQWR

WZR

FRQVXPSWLRQ IUDFWLRQV RI WKH FRQVXPHG 7(26 PROHFXOHV

FRQVHFXWLYH VWDJHV DFFRUGLQJ WR WKH

VROLG FLUFOHV VKRZQ LQ )LJXUH F DQG I EDVHG RQ WKH VHHGHG JURZWK PRGHO VHH 6, )LJXUH 6 IRU PRUH GHWDLOV

NLQHWLF

EDODQFH

EHWZHHQ

7(26

K\GURO\VLV DQG VXEVHTXHQW FRQGHQVDWLRQ 7KH ILUVW JURZWK VWDJH RFFXUV GXULQJ 7L DQG LV GLFWDWHG E\ 7(26 K\GURO\VLV 6RRQ DIWHU UDSLG K\GURO\VLV RI D VPDOO IUDFWLRQ WKH WRWDO 7(26 PROHFXOHV FD WKH VORZ FRQGHQVDWLRQ RI WKH UHVXOWLQJ DQLRQLF VLODQRO PRQRPHUV FDXVHV IRUPDWLRQ RI VPDOO VLOLFD SDUWLFOHV +HUH WKLV K\GURO\VLV GLFWDWHG SDUWLFOH JURZWK LV UHIHUUHG WR DV 3DWKZD\ , 7KH VHFRQG JURZWK VWDJH RFFXUV DIWHU 7L ZKHUH WKH DQLRQLF VLODQRO PRQRPHUV GHULYHG YLD K\GURO\VLV

ACS Paragon Plus Environment

Langmuir

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

RI WKH UHPDLQLQJ 7(26 PROHFXOHV FD

Page 24 of 40

SUHIHUHQWLDOO\ DGG RQWR WKH VLOLFD SDUWLFOHV IRUPHG

GXULQJ 7L YLD FRQGHQVDWLRQ 7KLV FRQGHQVDWLRQ GLFWDWHG SDUWLFOH JURZWK LV UHIHUUHG WR DV 3DWKZD\ ,, :KHQ WKH 6W|EHU SURFHVV LV H[HFXWHG DW DPPRQLD FRQFHQWUDWLRQ RI •

0 WKH KLJK HIILFLHQF\

RI 7(26 K\GURO\VLV DVVRFLDWHG WKHUHRI OHDGV WR FOHDU WHPSRUDO VHSDUDWLRQ EHWZHHQ 3DWKZD\V , DQG ,, GXULQJ DQG DIWHU 7L ZKLFK HQDEOHV WKH IRUPDWLRQ RI PRQRGLVSHUVH VLOLFD SDUWLFOHV LQ D VHHGHG JURZWK IDVKLRQ 3DWKZD\ ,, LV UHVSRQVLEOH IRU WKH VL]H HQODUJHPHQW RI WKH ILQDO SDUWLFOHV DQG KDV OLWWOH LPSDFW RQ 3DWKZD\ , EHIRUH 7L :KHQ WKH 6W|EHU SURFHVV LV FDUULHG RXW DW DPPRQLD FRQFHQWUDWLRQ RI

0 WKH SRRU HIILFLHQF\ RI 7(26 K\GURO\VLV DVVRFLDWHG WKHUHRI FDXVHV

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a

DQG LQGHSHQGHQW RQ WKH DPPRQLD FRQFHQWUDWLRQ

KLJKO\ HIIHFWLYH K\GURO\VLV RI 7(26 DW DPPRQLD FRQFHQWUDWLRQ RI •

0 LV H[SHFWHG WR SURGXFH

VPDOO VLOLFD SDUWLFOHV ZLWK FRPSDUDEOH VL]H DQG FRQFHQWUDWLRQ LQ WKH UHDFWLRQ PHGLD GXULQJ 7L 7KLV DVVXPSWLRQ LV VXSSRUWHG E\ WKH IDFW WKDW WKH K\GURG\QDPLF VL]H SURILOHV RI VLOLFD SDUWLFOHV JURZLQJ DW

0 DQG

0 DUH DOPRVW RYHUODSSHG GXULQJ 7L $V VXFK ZH H[SHFW WKH FRQWLQXRXV LQFUHDVH

RI WKH VL]HV RI ILQDO VLOLFD SDUWLFOHV ZLWK WKH DPRXQW RI 7(26 PROHFXOHV DYDLODEOH LQ WKH UHDFWLRQ PHGLD DIWHU 7L )LJXUH D DQG WKH DPPRQLD FRQFHQWUDWLRQ VHH 6, )LJXUH 6

$V LQGLFDWHG LQ

)LJXUH D WKH VL]HV RI VLOLFD SDUWLFOHV REWDLQHG YLD WKH 6W|EHU PHWKRG GURSV SURPLQHQWO\ ZLWK WKH

ACS Paragon Plus Environment

Page 25 of 40

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

Langmuir

DPPRQLD FRQFHQWUDWLRQ GHFUHDVLQJ EHORZ

0 7KLV FDQ EH UDWLRQDOL]HG DV WKH UHVXOW RI WKH ORZ

HIILFLHQF\ RI 7(26 K\GURO\VLV DW DPPRQLD FRQFHQWUDWLRQ RI

0 ZKLFK FDXVHV UHGXFWLRQ LQ

WKH QXPEHU RI DQLRQLF VLODQRO PRQRPHUV DYDLODEOH ERWK IRU JURZWK RI VPDOO SDUWLFOH VHHGV GXULQJ 7L DQG IRU VHHGHG JURZWK DIWHU 7L ,Q OLQH ZLWK WKH GHFUHDVH LQ WKH QXPEHU RI DQLRQLF VLODQRO PRQRPHUV SURGXFHG GXULQJ 7L KRZHYHU WKH QXPEHU RI VLOLFD SDUWLFOH VHHGV IRUPHG GXULQJ 7L LV H[SHFWHG WR GHFUHDVH ZLWK WKH DPPRQLD FRQFHQWUDWLRQ ZKLFK ZRXOG EH IDYRUDEOH IRU IRUPDWLRQ RI ODUJH SDUWLFOHV YLD VHHGHG JURZWK 7KH GLVDJUHHPHQW RI WKLV H[SHFWDWLRQ ZLWK WKH UHVXOWV VKRZQ LQ )LJXUH D LPSOLHV WKDW WKH VL]HV RI ILQDO VLOLFD SDUWLFOHV DUH UHJXODWHG PDLQO\ E\ KRZ PDQ\ DQLRQLF VLODQRO PRQRPHUV DUH DYDLODEOH WR DGG RQWR WKH SUHIRUPHG VHHGV HVSHFLDOO\ DW WKH UHDFWLRQ VWDJH DIWHU 7L ZKLFK LV FRUUHODWHG ZLWK WKH DPPRQLD FRQFHQWUDWLRQ GHSHQGHQW HIILFLHQF\ RI 7(26 K\GURO\VLV 2YHUDOO LW LV UHDVRQDEOH WR FRQFOXGH WKDW WKH JURZWK RI VLOLFD SDUWLFOHV LQ WKH 6W|EHU PHWKRG SURFHHGV LQ DQ LQ VLWX VHHGHG JURZWK IDVKLRQ LQ ZKLFK 3DWKZD\ , LV UHVSRQVLEOH IRU JURZWK RI VPDOO VLOLFD SDUWLFOHV DV VHHGV GXULQJ 7L DQG 3DWKZD\ ,, IRU WKH VL]H HQODUJHPHQW RI WKHVH VHHGV DIWHU 7L )XUWKHUPRUH WKH UDWH DQG HIILFLHQF\ RI 7(26 K\GURO\VLV SOD\ WKH SLYRWDO UROH LQ UHJXODWLRQ RI WKH VL]H DQG VL]H GLVWULEXWLRQ RI WKH ILQDO VLOLFD SDUWLFOHV REWDLQHG :KHQ 7(26 K\GURO\VLV LV VLJQLILFDQWO\ IDFLOLWDWHG DW DPPRQLD FRQFHQWUDWLRQ RI •

0 WKH FOHDU WHPSRUDO VHSDUDWLRQ

EHWZHHQ 3DWKZD\V , DQG ,, VHOHFWLYHO\ RFFXUULQJ LQ DQG DIWHU 7L HQDEOHV WKH JURZWK RI PRQRGLVSHUVH VLOLFD SDUWLFOHV ZLWK VL]HV DERYH FD

QP YLD LQ VLWX VHHGHG JURZWK $OWKRXJK WKH

VL]HV RI VLOLFD SDUWLFOHV REWDLQHG YLD WKH 6W|EHU PHWKRG FDQ EH UHGXFHG EHORZ

QP HYHQ WR

QP ZLWK WKH DPPRQLD FRQFHQWUDWLRQ GHFUHDVLQJ DV UHPDUNHG E\ 6W|EHU HW DO

WKHLU VL]H

GLVWULEXWLRQV DUH UDWKHU EURDG )LJXUH D ZKLFK DV GLVFXVVHG DERYH LV WKH UHVXOW RI WKH IDFW WKDW WKH ORZ HIILFLHQF\ RI 7(26 K\GURO\VLV DW ORZHU DPPRQLD FRQFHQWUDWLRQ JLYHV ULVH WR SURPLQHQW

ACS Paragon Plus Environment

Langmuir

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 26 of 40

FRQWULEXWLRQ RI 3DWKZD\ , WR WKH JURZWK RI VLOLFD SDUWLFOHV DIWHU 7L 8S WR GDWH LW LV VWLOO D IRUPLGDEOH FKDOOHQJH WR SURGXFH PRQRGLVSHUVH VLOLFD SDUWLFOHV ZLWK VL]HV LQ WKH UDQJH RI

QP GLUHFWO\

YLD WKH 6W|EHU PHWKRG WKHVH VPDOO VLOLFD SDUWLFOHV H[KLELW LQFUHDVLQJO\ WHFKQLFDO LPSOLFDWLRQV LQ KLJK WHFK LQGXVWULHV WKRXJK 7R DGGUHVV WKLV FKDOOHQJH KHUH ZH HQGHDYRUHG WR DSSO\ WKH LQ VLWX VHHGHG JURZWK PRGHO WR SURGXFH PRQRGLVSHUVH VPDOO VLOLFD SDUWLFOHV DW DPPRQLD FRQFHQWUDWLRQ RI 0 ,Q RUGHU WR VXSSUHVV WKH FRQWULEXWLRQ RI 3DWKZD\ , WR WKH VLOLFD SDUWLFOH JURZWK DIWHU 7L ZH DGGHG VHFRQGDU\ VWURQJ DONDOLQH ± /L2+ ± DV D FR FDWDO\VW LQ WKH UHDFWLRQ PHGLD WR SURPRWH 7(26 K\GURO\VLV DW DPPRQLD FRQFHQWUDWLRQ RI

0 :KHWKHU RU QRW PRQRGLVSHUVH VPDOO

VLOLFD SDUWLFOHV FDQ EH SURGXFHG LQ WKH SUHVHQFH RI /L2+ RQ WKH RWKHU KDQG ZLOO YDOLGDWH WKH LQ VLWX VHHGHG JURZWK PRGHO RI WKH 6W|EHU SURFHVV DQG LWV FRUUHODWLRQ ZLWK 3DWKZD\V , DQG ,, /L2+ DVVLVWHG ,Q VLWX 6HHGHG *URZWK RI 6LOLFD 3DUWLFOHV 6LQFH WKH K\GUR[\O LRQV ± 2+± ± DUH WKH DFWLQJ QXFOHRSKLOH WKH K\GURO\VLV RI 7(26 PROHFXOHV WR VLODQRO PRQRPHUV FDQ EH IDFLOLWDWHG LQ WKH SUHVHQFH RI /L2+ LQ WKH UHDFWLRQ PHGLD LQ WKH 6W|EHU SURFHVV ZKHQ WKH DPPRQLD FRQFHQWUDWLRQ LV ORZ EHORZ

0 $OWKRXJK WKH K\GURG\QDPLF VL]H SURILOHV RI VLOLFD SDUWLFOHV

JURZLQJ LQ WKH UHDFWLRQ PHGLD DUH FRPSDUDEOH DW WKH DPPRQLD FRQFHQWUDWLRQ EHORZ K\GURO\VLV RI 7(26 LV QRWLFHDEO\ LPSURYHG DW WKH DPPRQLD FRQFHQWUDWLRQ RI

0 WKH 0 ZKLFK LV

FKDUDFWHULVWLF RI MXPS RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD WR WKH PD[LPXP LQ D VKRUW 7L DERXW PLQ IROORZHG E\ VLJQLILFDQW IDOO DIWHU 7L W\SLFDOO\ REVHUYHG DW WKH DPPRQLD FRQFHQWUDWLRQ RI •

0 VHH 6, )LJXUH 6

,Q RUGHU WR DYRLG WKH FRPSOH[LW\ GXH WR WKH XVH RI LQWHUPHGLDWH

DPPRQLD FRQFHQWUDWLRQ KHUH RXU VWXG\ RI WKH /L2+ HIIHFW RQ WKH JURZWK RI VLOLFD SDUWLFOHV ZDV FDUULHG RXW PDLQO\ DW DPPRQLD FRQFHQWUDWLRQ EHORZ

0 :KHQ WKH DPPRQLD FRQFHQWUDWLRQ LV

ACS Paragon Plus Environment

Page 27 of 40

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

Langmuir

0 DV VKRZQ LQ )LJXUH

D WKH

SUHVHQFH RI D VPDOO DPRXQW RI /L2+ FDQ QRW RQO\ ODUJHO\ UHGXFH 7L WR

PLQ IURP

PLQ LQ WKH DEVHQFH RI /L2+ EXW DOVR VLJQLILFDQWO\ WUDQVIRUP WKH K\GURG\QDPLF VL]H SURILOH RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD %RWK WKH 7L YDOXH DQG WKH K\GURG\QDPLF VL]H SURILOH GDWD QRW VKRZQ DUH FRPSDUDEOH WR WKRVH REVHUYHG DW DPPRQLD FRQFHQWUDWLRQ RI

0 LQ WKH )LJXUH

DEVHQFH RI /L2+ )LJXUH F LQGLFDWLYH RI VLJQLILFDQWO\ HQKDQFHG HIILFLHQF\ RI 7(26 K\GURO\VLV LQ WKH SUHVHQFH RI /L2+ DW WKH ORZ

DPPRQLD

FRQFHQWUDWLRQ

7(0

LPDJLQJ XQGHUOLQHV WKH IRUPDWLRQ RI

D 3ORWV RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ

PHGLD LQ WKH DEVHQFH RSHQ FLUFOHV DQG SUHVHQFH RI /L2+ VROLG FLUFOHV YHUVXV WKH UHDFWLRQ WLPH RYHU WKH FRXUVH RI JURZWK RI VLOLFD SDUWLFOHV YLD 6W|EHU PHWKRG 7KH DPPRQLD FRQFHQWUDWLRQ LV VHW DV /L2+ FRQFHQWUDWLRQ DV

0 DQG WKH

P0 7KH WRWDO YROXPH RI

HWKDQRO LQ WKH UHDFWLRQ PHGLD LV VHW DV LQLWLDO FRQFHQWUDWLRQ RI 7(26 DV

P/ DQG WKH

0 E DQG F 7(0

LPDJHV RI WKH FRUUHVSRQGLQJ VLOLFD SDUWLFOHV REWDLQHG DW

PRQRGLVSHUVH VLOLFD SDUWLFOHV ZLWK VL]HV RI QP DW DPPRQLD FRQFHQWUDWLRQ RI 0 LQ WKH SUHVHQFH RI

DPPRQLD FRQFHQWUDWLRQ RI DEVHQFH F RI

0 LQ WKH SUHVHQFH E DQG

P0 /L2+ 6FDOH EDUV ZHUH

QP

P0 /L2+ )LJXUH

E ZKLFK H[KLELW WKH SRO\GLVSHUVLW\ RI

IDU VPDOOHU WKDQ WKDW

RI WKH SDUWLFOHV

QP

REWDLQHG LQ WKH DEVHQFH RI /L2+ )LJXUH F 7KHVH UHVXOWV KLJKOLJKW WKDW 7(26 K\GURO\VLV DW UDWKHU ORZ DPPRQLD FRQFHQWUDWLRQ FDQ EH VLJQLILFDQWO\ IDFLOLWDWHG WR SURGXFH WKH PRQRPHUV ZLWK PRUH VLODQRO JURXSV DQG LPSURYHG DFWLYLW\ LQ WKH SUHVHQFH RI /L2+ LQ WKH UHDFWLRQ PHGLD ZKLFK WUDQVIRUP WKH JURZWK SURILOH RI VLOLFD SDUWLFOHV WR EH FRPSDUDEOH WR WKDW LPSOHPHQWHG DW KLJK

ACS Paragon Plus Environment

Langmuir

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 28 of 40

DPPRQLD FRQFHQWUDWLRQ DQG PLQLPL]H WKH FRQWULEXWLRQ RI 3DWKZD\ , WR WKH SDUWLFOH JURZWK DIWHU 7L WR SURGXFH KLJKO\ XQLIRUP SDUWLFOHV 7KH /L2+ HQKDQFHG K\GURO\VLV RI 7(26 RXJKW WR \LHOG PRUH VLODQRO PRQRPHUV GXULQJ WKH HQWLUH 6W|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

P0 IRU JURZWK RI

0 )LJXUH D :KHQ VLOLFD

P0 WKH VL]H LQFUHDVH RI WKH ILQDO SDUWLFOHV

ZLWK WKH /L2+ FRQFHQWUDWLRQ FDQ EH UDWLRQDOL]DWLRQ DV D UHVXOW RI DGGLWLRQ RI PRUH DFWLYH VLODQRO PRQRPHUV REWDLQHG YLD 7(26 K\GURO\VLV IRU VL]H HQODUJHPHQW RI WKH SUH IRUPHG VHHGV DIWHU 7L :KHQ VLOLFD SDUWLFOHV DUH JURZQ DW /L2+ FRQFHQWUDWLRQ DERYH

P0 WKH VL]H UHGXFWLRQ RI WKH

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

)RU WKH UHDFWLRQ FDUULHG RXW DW DPPRQLD FRQFHQWUDWLRQ RI

0 VL]H RI WKH

UHVXOWLQJ VLOLFD SDUWLFOHV DOVR LQFUHDVHG DW WKH ORZ /L2+ FRQFHQWUDWLRQ DQG GHFUHDVHG DW WKH KLJK /L2+ FRQFHQWUDWLRQ +RZHYHU SRO\GLVSHUVLW\ RI WKH UHVXOWLQJ VLOLFD SDUWLFOHV NHHS LQFUHDVLQJ ZLWK

ACS Paragon Plus Environment

Page 29 of 40

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

Langmuir

WKH LQFUHDVHG /L2+ FRQFHQWUDWLRQ VHH 6, )LJXUH 6

7KHVH UHVXOWV LQGLFDWH WKDW WKH DGGLWLRQ RI

/L2+ DW WKH KLJK DPPRQLD FRQFHQWUDWLRQ LV OHVV HIIHFWLYH WR LPSURYH WKH DFWLYLW\ RI WKH VLODQRO PRQRPHUV DQG PRUH HIIHFWLYH WR DFW DV HOHFWURO\WH WR VFUHHQ WKH HOHFWURVWDWLF UHSXOVLRQ 7R DYRLG WKDW WKH FRQWHQW RI /L2+ LQ WKH UHDFWLRQ PHGLD VKRXOG EH NHSW ORZ ,Q WKLV FXUUHQW ZRUN WKH PRODU UDWLR RI /L2+ WR DPPRQLD ZDV NHSW DURXQG

VR WKH DPPRQLD

VWLOO SOD\V WKH OHDGLQJ UROH IRU UHJXODWLRQ RI 7(26 K\GURO\VLV DQG LQ WXUQ WKH JURZWK RI VLOLFD

SDUWLFOHV

$W

WKH

RSWLPDO

FRQFHQWUDWLRQ RI /L2+ VHH 6, 7DEOH 6 ZH

KDYH

VXFFHVVIXOO\

SURGXFHG

PRQRGLVSHUVH VPDOO VLOLFD SDUWLFOHV ZLWK VL]HV SUHFLVHO\ UHJXODWHG IURP QP DQG

QP WR

QP E\ VLPSO\

)LJXUH

D 3ORWV RI WKH GLDPHWHU EODFN VROLG FLUFOHV

DQG SRO\GLVSHUVLW\ UHG RSHQ FLUFOHV RI WKH VLOLFD

YDU\LQJ WKH DPPRQLD FRQFHQWUDWLRQ IURP 0 WR

DQG

0

SDUWLFOHV REWDLQHG YLD FODVVLFDO 6W|EHU PHWKRG DW DPPRQLD FRQFHQWUDWLRQ RI

0 YHUVXV WKH

FRQFHQWUDWLRQ RI /L2+ LQ WKH UHDFWLRQ PHGLD E 3ORWV

DOPRVW LQ D OLQHDU PDQQHU )LJXUH E 7KLV DOPRVW OLQHDU LQFUHDVH RI WKH VLOLFD SDUWLFOHV

RI WKH VL]HV DQG SRO\GLVSHUVLW\ RI WKH VLOLFD SDUWLFOHV REWDLQHG YLD FODVVLFDO 6W|EHU PHWKRG LQ WKH SUHVHQFH RI D JLYHQ DPRXQW RI /L2+ LQ WKH UHDFWLRQ PHGLD

ZLWK WKH DPPRQLD FRQFHQWUDWLRQ VKRXOG

OLVWHG LQ 7DEOH 6

IXUWKHU FRQILUP WKDW WKH JURZWK RI VLOLFD

FRQFHQWUDWLRQ 7KH SDUWLFOH VL]H DQG SRO\GLVSHUVLW\ DUH

VHH 6,

YHUVXV WKH DPPRQLD

GHWHUPLQHG EDVHG RQ 7(0 LPDJLQJ VHH 6, )LJXUH

SDUWLFOHV LQ WKH 6W|EHU PHWKRG SURFHHGV LQ

6

DQ LQ VLWX VHHGHG JURZWK IDVKLRQ

ACS Paragon Plus Environment

Langmuir

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 30 of 40

&21&/86,216 :H KDYH VXFFHVVIXOO\ HVWDEOLVKHG WKH FRUUHODWLRQ RI WKH NLQHWLF EDODQFH EHWZHHQ 7(26 K\GURO\VLV DQG VXEVHTXHQW FRQGHQVDWLRQ ZLWK WKH JURZWK RI VLOLFD SDUWLFOHV LQ FODVVLF 6W|EHU PHWKRG 2XU UHVXOWV UHYHDO WKDW WKH ZKROH 6W|EHU SURFHVV FDQ EH GLYLGHG LQWR WZR FRQVHFXWLYHO\ RFFXUULQJ VWDJHV 7KH ILUVW LV WKH LQFXEDWLRQ VWDJH ZKHUH WKH QXFOHDWLRQ DQG JURZWK RI VLOLFD SDUWLFOHV LV GHWHUPLQHG GRPLQDQWO\ E\ 7(26 K\GURO\VLV 3DWKZD\ , ZKLFK LV FKDUDFWHULVWLF RI WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD UHDFKLQJ WKH PD[LPXP RYHU D JLYHQ LQFXEDWLRQ WLPH 7L

7KH VHFRQG LV WKH VWDJH

RI WKH VL]H HQODUJHPHQW RI WKH VLOLFD SDUWLFOHV SURGXFHG DW WKH LQFXEDWLRQ VWDJH E\ DGGLQJ QHZO\ IRUPHG VLODQRO PRQRPHUV DWRS YLD FRQGHQVDWLRQ 3DWKZD\ ,, 7KLV XQUDYHOV LQ VLWX VHHGHG JURZWK QDWXUH RI WKH 6W|EHU SURFHVV +RZHYHU VLQFH WKH 7(26 K\GURO\VLV LV VWURQJO\ DIIHFWHG E\ WKH DPPRQLD FRQFHQWUDWLRQ WKH WUXO\ LQ VLWX VHHGHG JURZWK RI VLOLFD SDUWLFOHV YLD FODVVLF 6W|EHU PHWKRG WDNHV SODFH RQO\ DW WKH DPPRQLD FRQFHQWUDWLRQ RI •

0 DW ZKLFK D FOHDU WHPSRUDO VHSDUDWLRQ

EHWZHHQ 3DWKZD\V , DQG ,, LV LPSOHPHQWHG ZLWK WKH UHDFWLRQ SURFHHGLQJ DV D UHVXOW RI KLJKO\ HIIHFWLYH K\GURO\VLV RI 7(26 PROHFXOHV WR KLJKO\ DFWLYH VLODQRO PRQRPHUV :KHQ WKH DPPRQLD FRQFHQWUDWLRQ LV EHORZ

0 WKH SRRUO\ HIIHFWLYH 7(26 K\GURO\VLV QRW RQO\ SURORQJV 7L EXW DOVR

SURYRNH 3DWKZD\ , WR EH QRWLFHDEO\ HIIHFWLYH DQG LQWHUZHDYH ZLWK 3DWKZD\ ,, WRJHWKHU WR UHJXODWH WKH JURZWK RI VLOLFD SDUWLFOHV DIWHU 7L ZKLFK UHVXOWV LQ XQDYRLGDEOH VHFRQGDU\ QXFOHDWLRQ RI VPDOO VLOLFD SDUWLFOHV WKXV OHDYLQJ EHKLQG SRO\GLVSHUVH VLOLFD SDUWLFOHV ,Q WHUPV RI WKH XQGHUO\LQJ JURZLQJ PHFKDQLVP 3DWKZD\ , UHPLQGV RI WKH ³DJJUHJDWLRQ RQO\´ PRGHO SURSRVHG IRU JURZWK RI VLOLFD SDUWLFOHV LQ WKH 6W|EHU PHWKRG ZKLOH 3DWKZD\ ,, GRHV RI WKH ³PRQRPHU DGGLWLRQ´ PRGHO 0RVW LPSRUWDQWO\ WKH UHYHODWLRQ RI WKH FRQWULEXWLRQ RI 3DWKZD\V , DQG ,, ZLWK WKH UHDFWLRQ WLPH RYHU WKH 6W|EHU SURFHVV HQDEOHV WKHVH WZR FXUUHQWO\ SUHYDLOLQJ JURZWK PRGHOV WR EH FRQVLVWHQWO\ UHFRQFLOHG LQWR DQ LQ VLWX VHHGHG JURZWK PRGHO

ACS Paragon Plus Environment

Page 31 of 40

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

Langmuir

%XLOGLQJ RQ WKH DGYDQFHG XQGHUVWDQGLQJ RI WKH 6W|EHU PHWKRG ZH KDYH VXFFHVVIXOO\ SURGXFHG PRQRGLVSHUVH VSKHULFDO VLOLFD SDUWLFOHV ZLWK VL]HV UDQJLQJ IURP

WR

QP E\ XVLQJ /L2+ WR

IDFLOLWDWH WKH 7(26 K\GURO\VLV DW ORZ DPPRQLD FRQFHQWUDWLRQ ZKLFK KRZHYHU LV KDUGO\ DFKLHYHG RWKHUZLVH LQ OLWHUDWXUH VR IDU ,W LV ZRUWK\ RI QRWLQJ WKDW WKH LQGXFWLRQ WLPH 7L LV D KLJKO\ VHQVLWLYH PHDVXUH IRU WKH HIILFLHQF\ RI K\GURO\VLV 2QO\ ZKHQ WKH 7(26 K\GURO\VLV LV KLJKO\ HIIHFWLYH HLWKHU DW IDLUO\ KLJK DPPRQLD FRQFHQWUDWLRQ • WKH SUHVHQFH RI /L2+ 7L FDQ EH YHU\ VKRUW

0 RU DW ORZ DPPRQLD FRQFHQWUDWLRQ

0 LQ

PLQ RYHU ZKLFK UDSLG DQG VXEVWDQWLDO MXPS DQG

IDOO LQ WKH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD DUH YLVLEOH 7KDW LV D GLVWLQFW LQGLFDWRU RI FOHDU WHPSRUDO VHSDUDWLRQ EHWZHHQ 3DWKZD\V , DQG ,, ZKLFK ZLOO EH D IDLUO\ KHOSIXO JXLGDQFH IRU WKH V\QWKHVLV RI PRQRGLVSHUVH VLOLFD SDUWLFOHV YLD FODVVLF 6W|EHU PHWKRG LQ IXWXUH UHVHDUFK

(;3(5,0(17$/ 6(&7,21 0DWHULDOV (WKDQRO VXOIXULF DFLG K\GURFKORULF DFLG DQG DPPRQLXP PRO\EGDWH K\GUDWH ZHUH SXUFKDVHG IURP %HLMLQJ &KHPLFDO ,QW $PPRQLD VROXWLRQ a

ZW

1+ LQ ZDWHU ZDV SXUFKDVHG

IURP 6LQRSKDUP &KHPLFDO 5HDJHQW &R /LWKLXP K\GUR[LGH /L2+ DQG WHWUDHWK\O RUWKRVLOLFDWH 7(26 ZHUH SXUFKDVHG IURP 7LDQMLQ &KHPLFDO ,QW $OO WKH FKHPLFDOV ZHUH RI DQDO\WLFDO JUDGH :KLOH WKH RWKHU FKHPLFDOV ZHUH XVHG ZLWKRXW IXUWKHU SXULILFDWLRQ 7(26 ZDV GLVWLOOHG SULRU WR XVH +LJK SXULW\ ZDWHU 3DOO 3XUHODE 3OXV ZLWK D UHVLVWLYLW\ RI

0

FP ZDV XVHG LQ DOO WKH

H[SHULPHQWV *URZWK RI 6LOLFD 3DUWLFOHV YLD &ODVVLF 6W|EHU 0HWKRG DW 'LIIHUHQW $PPRQLD &RQFHQWUDWLRQV 7\SLFDOO\ 7(26

P/ HWKDQRO

VROXWLRQ ZLWK D JLYHQ YROXPH YDU\LQJ IURP

P/ ZDWHU

P/ WR

ACS Paragon Plus Environment

P/ DQG WKH DPPRQLD DQG

P/ ZHUH PL[HG

Langmuir

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 32 of 40

LQ D WKUHH QHFN IODVN 7KH PL[WXUHV ZHUH WKHQ NHSW LQ D ZDWHU EDWK DW USP IRU

ƒ& XQGHU PDJQHWLF VWLUULQJ

K IRU JURZWK RI VLOLFD SDUWLFOHV $IWHU SXULILFDWLRQ E\ WZLFH UHSHWLWLRQ RI WKH F\FOH

RI FHQWULIXJDWLRQ

USP

PLQ GHFDQWLQJ RI WKH VXSHUQDWDQWV DQG GLVSHUVLRQ LQ IUHVK

HWKDQRO WKH UHVXOWLQJ SDUWLFOHV ZHUH GLVSHUVHG LQ HWKDQRO IRU WKH IROORZLQJ FKDUDFWHUL]DWLRQV *URZWK RI 6LOLFD 3DUWLFOHV YLD &ODVVLF 6W|EHU 0HWKRG LQ WKH 3UHVHQFH RI /L2+ 7\SLFDOO\ HWKDQRO

P/ 7(26

P/ WR

DQG

P/ DQG DPPRQLD VROXWLRQ ZLWK D JLYHQ YROXPH YDU\LQJ IURP P/ ZHUH PL[HG LQ D WKUHH QHFN IODVN IROORZHG E\ GURSZLVH DGGLQJ

P/ RI /L2+ VROXWLRQ ZLWK FRQFHQWUDWLRQV LQ WKH UDQJH RI ZHUH NHSW LQ D ZDWHU EDWK DW

ƒ& XQGHU PDJQHWLF VWLUULQJ

0 7KH UHDFWLRQ PL[WXUHV USP IRU K IRU JURZWK RI WKH VLOLFD

SDUWLFOHV $IWHU SXULILFDWLRQ E\ WZLFH UHSHWLWLRQ RI WKH F\FOH RI FHQWULIXJDWLRQ

USP

PLQ

GHFDQWLQJ RI WKH VXSHUQDWDQWV DQG GLVSHUVLRQ LQ IUHVK HWKDQRO WKH UHVXOWLQJ SDUWLFOHV ZHUH GLVSHUVHG LQ HWKDQRO IRU WKH IROORZLQJ FKDUDFWHUL]DWLRQV 4XDQWLWDWLYH 'HWHUPLQDWLRQ RI 7(26 7KH FRQFHQWUDWLRQ RI IUHH 7(26 PROHFXOHV UHPDLQLQJ LQ WKH UHDFWLRQ PHGLD ZHUH GHWHUPLQHG E\ PHDQV RI DPPRQLXP PRO\EGDWH VSHFWURSKRWRPHWULF PHWKRG

)LUVWO\

P/ RI FRQFHQWUDWHG + 62 VROXWLRQ

ZDV PL[HG LQWR

ZDWHU IROORZHG E\ GLOXWLRQ ZLWK WR UHDFK WKH WRWDO YROXPH RI 6HFRQGO\

J RI 1+

0R 2

+ 2 ZHUH GLVVROYHG LQ

P/ ZKLFK \LHOGHG 6ROXWLRQ $ P/ RI ZDWHU EHDULQJ

DPPRQLD VROXWLRQ IROORZHG E\ GLOXWLRQ ZLWK ZDWHU WR UHDFK WKH WRWDO YROXPH RI \LHOGHG 6ROXWLRQ % 7KLUGO\

P/ RI 6ROXWLRQ $ DQG

E\ GLOXWLRQ ZLWK ZDWHU WR UHDFK WKH WRWDO YROXPH RI DVVHVV WKH 7(26 FRQFHQWUDWLRQ

P/ RI

P/ RI

P/ ZKLFK

P/ RI 6ROXWLRQ % ZHUH PL[HG IROORZHG P/ ZKLFK \LHOGHG 6ROXWLRQ & ,Q RUGHU WR

—/ RI DOLTXRW ZDV WDNHQ RXW RI WKH UHDFWLRQ PHGLD DIWHU WKH

UHDFWLRQV ZHUH FDUULHG RXW IRU D JLYHQ WLPH DQG VXEVHTXHQWO\ PL[HG ZLWK IROORZHG E\ DGGLWLRQ RI ZDWHU WR DGMXVW WKH WRWDO YROXPH WR

ACS Paragon Plus Environment

P/ RI 6ROXWLRQ &

P/ 7KH DEVRUEDQFH RI WKH

Page 33 of 40

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

Langmuir

UHVXOWLQJ VROXWLRQV DW

QP ZDV XVHG WR GHWHUPLQH WKH DPRXQW RI WKH PRO\EGRVLOLFDWH \HOORZ

IURP ZKLFK RQH FRXOG GHWHUPLQH WKH DPRXQW RI IUHH 7(26 PROHFXOHV LQ WKH UHDFWLRQ PHGLD &KDUDFWHUL]DWLRQV 7KH K\GURG\QDPLF GLDPHWHUV DQG ]HWD SRWHQWLDOV RI WKH VLOLFD SDUWLFOHV JURZLQJ LQ WKH UHDFWLRQ PHGLD YLD FODVVLF 6W|EHU PHWKRG ZHUH DVVHVVHG E\ XVLQJ D %URRNKDYHQ =HWD3$/6 DSSDUDWXV 7KH FRQGXFWLYLW\ RI WKH UHDFWLRQ PHGLD ZDV PHDVXUHG RQ DQ +$11$ (F FRQGXFWLYLW\ PHWHU 7(0 LPDJLQJ ZDV LPSOHPHQWHG RQ D -2(/-(0 RSHUDWLQJ DW

N9 )ROORZLQJ WR WKH SURFHGXUH GHVFULEHG LQ OLWHUDWXUH

HOHFWURQ PLFURVFRSH D VHULHV RI DOLTXRWV

P/ ZHUH WDNHQ RXW RI WKH UHDFWLRQ PHGLD DIWHU WKH UHDFWLRQV ZHUH FDUULHG RXW IRU GLIIHUHQW UHDFWLRQ WLPH IROORZHG E\ PL[LQJ ZLWK

P/ RI HWKDQRO DW

ZHUH GURSSHG RQWR )RUPYDU FRDWHG FRSSHU JULGV

ƒ& WR WHUPLQDWH WKH UHDFWLRQV 7KH PL[WXUHV PHVK DQG GULHG E\ WLVVXH SDSHU IRU 7(0

REVHUYDWLRQV 7KH VL]HV DQG VL]H GLVWULEXWLRQV RI WKH VLOLFD SDUWLFOHV ZHUH FDOFXODWHG E\ FRXQWLQJ DW OHDVW

SDUWLFOHV IRU HDFK VDPSOH DFFRUGLQJ WR WKH PHWKRG UHSRUWHG LQ OLWHUDWXUH

WUDQVIRUP LQIUDUHG )7,5 VSHFWUD ZHUH FROOHFWHG RQ D 1LFROHW WKH UDQJH RI

FP

)RXULHU

VSHFWURSKRWRPHWHU VFDQQLQJ LQ

89 YLVLEOH VSHFWUD ZHUH WDNHQ RQ D 9DULDQ &DU\

VSHFWURPHWHU

0DVV VSHFWURVFRSLF DQDO\VLV ZDV SHUIRUPHG RQ D 7KHUPR )LVKHU 2UELWUDS )XVLRQ 7ULEULG 0DVV 6SHFWURPHWHU ZKLFK ZDV RSHUDWHG LQ SRVLWLYH LRQ GHWHFWLRQ PRGHV 7KH HOHFWURVSUD\ LRQL]DWLRQ (6, YROWDJH ZDV

N9 DQG WKH LRQ WUDQVIHU WXEH WHPSHUDWXUH ZDV

VSHFWUD ZHUH UHFRUGHG ZLWK DQ DYHUDJH WLPH RI

ƒ& 7KH IXOO VFDQ PDVV

V DQG VDPSOHV IORZ UDWH DW

P/ PLQ

$662&,$7(' &217(17 6XSSRUWLQJ ,QIRUPDWLRQ 7(0 LPDJHV RI VLOLFD SDUWLFOHV SUHSDUHG XQGHU GLIIHUHQW FRQFHQWUDWLRQV RI DPPRQLD DQG /L2+ 7HPSRUDO HYROXWLRQ LQ FRQFHQWUDWLRQV RI 7(26 FRQGXFWLYLW\ RI WKH UHDFWLRQ VROXWLRQV DQG

ACS Paragon Plus Environment

Langmuir

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 34 of 40

K\GURG\QDPLF GLDPHWHUV RI VLOLFD SDUWLFOHV SUHSDUHG E\ WKH FODVVLFDO DQG RXU LPSURYHG 6W|EHU PHWKRGV 7KLV PDWHULDO LV DYDLODEOH IUHH RI FKDUJH YLD WKH LQWHUQHW DW KWWS SXEV DFV RUJ $87+25 ,1)250$7,21 &RUUHVSRQGLQJ $XWKRU ZV\DQJ#MOX HGX FQ 1RWHV 7KH DXWKRUV GHFODUH QR FRPSHWLQJ ILQDQFLDO LQWHUHVW $&.12:/('*0(176 7KLV ZRUN ZDV ILQDQFLDOO\ VXSSRUWHG E\ WKH 1DWXUDO 6FLHQFH )RXQGDWLRQ RI &KLQD 1R :H WKDQN 3URI + : &KHQ DQG 0U 7 * =KX IRU DVVLVWDQFH ZLWK PDVV VSHFWURVFRSLF DQDO\VLV

5()(5(1&(6 6W|EHU : )LQN $ %RKQ ( &RQWUROOHG *URZWK RI 0RQRGLVSHUVH 6LOLFD 6SKHUHV LQ WKH 0LFURQ 6L]H 5DQJH - &ROORLG ,QWHUIDFH 6FL YDQ %ODDGHUHQ $

YDQ *HHVW -

±

9ULM $ 0RQRGLVSHUVH &ROORLGDO 6LOLFD 6SKHUHV IURP

7HWUDDONR[\VLODQHV 3DUWLFOH )RUPDWLRQ DQG *URZWK 0HFKDQLVP - &ROORLG ,QWHUIDFH 6FL ±

ACS Paragon Plus Environment

Page 35 of 40

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

Langmuir

:RQJ 6

.LWDHY 9

*HRIIUH\ $ 2]LQ * $ &ROORLGDO &U\VWDO )LOPV $GYDQFHV LQ

8QLYHUVDOLW\ DQG 3HUIHFWLRQ - $P &KHP 6RF

±

*LHVFKH + - 6\QWKHVLV RI 0RQRGLVSHUVHG 6LOLFD 3RZGHUV ,, &RQWUROOHG *URZWK 5HDFWLRQ DQG &RQWLQXRXV 3URGXFWLRQ 3URFHVV - (XU &HUDP 6RF +DUWOHQ . '

$WKDQDVRSRXORV $ 3 7

0RQRGLVSHUVH 6PDOO 6LOLFD 6SKHUHV

WR !

)RUPDWLRQ RI 2UGHUHG $UUD\V /DQJPXLU

± .LWDHY 9 )DFLOH 3UHSDUDWLRQ RI +LJKO\ QP 6XLWDEOH IRU &ROORLGDO 7HPSODWLQJ DQG ±

0DWVRXNDV 7 *XODUL ( '\QDPLFV RI *URZWK RI 6LOLFD 3DUWLFOHV IURP $PPRQLD FDWDO\]HG +\GURO\VLV RI 7HWUD HWK\O RUWKRVLOLFDWH - &ROORLG ,QWHUIDFH 6FL

±

0DWVRXNDV 7 *XODUL ( 0RQRPHU DGGLWLRQ *URZWK ZLWK D 6ORZ ,QLWLDWLRQ 6WHS $ *URZWK 0RGHO IRU 6LOLFD 3DUWLFOHV IURP $ONR[LGHV - &ROORLG ,QWHUIDFH 6FL 0DWVRXNDV 7 *XODUL ( 6HOI VKDUSHQLQJ 'LVWULEXWLRQV 5HYLVLWHG 3RO\GLVSHUVLW\ LQ *URZWK E\ 0RQRPHU $GGLWLRQ - &ROORLG ,QWHUIDFH 6FL /D0HU 9 .

±

'LQHJDU 5 + 7KHRU\ 3URGXFWLRQ DQG 0HFKDQLVP RI )RUPDWLRQ RI

0RQRGLVSHUVHG +\GURVROV - $P &KHP 6RF

±

%RJXVK * + =XNRVNL & ) 6WXGLHV RI WKH .LQHWLFV RI WKH 3UHFLSLWDWLRQ RI 8QLIRUP 6LOLFD 3DUWLFOHV WKURXJK WKH +\GURO\VLV DQG &RQGHQVDWLRQ RI 6LOLFRQ $ONR[LGHV - &ROORLG ,QWHUIDFH 6FL ± %RJXVK * + =XNRVNL & ) 8QLIRUP 6LOLFD 3DUWLFOH 3UHFLSLWDWLRQ $Q $JJUHJDWLYH *URZWK 0RGHO - &ROORLG ,QWHUIDFH 6FL

±

ACS Paragon Plus Environment

Langmuir

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 36 of 40

/HH . 6DWK\DJDO $ 1 0F&RUPLFN $ 9 $ &ORVHU /RRN DW DQ $JJUHJDWLRQ 0RGHO RI WKH 6W|EHU 3URFHVV &ROORLG 6XUI $

±

/HH . /RRN - / +DUULV 0 7 0F&RUPLF $ 9 $VVHVVLQJ ([WUHPH 0RGHOV RI WKH 6W|EHU 6\QWKHVLV 8VLQJ 7UDQVLHQWV XQGHU D 5DQJH RI ,QLWLDO &RPSRVLWLRQ - &ROORLG ,QWHUIDFH 6FL ± GH )HUUL / /RUHQ]L $ /RWWLFL 3 3 2FW7(6 7(26 6\VWHP IRU +\EULG &RDWLQJV 5HDO WLPH 0RQLWRULQJ RI WKH +\GURO\VLV DQG &RQGHQVDWLRQ E\ 5DPDQ VSHFWURVFRS\ - 5DPDQ 6SHFWURVF ± %XFNOH\ $ 0 *UHHQEODWW 0 7KH 6RO JHO 3UHSDUDWLRQ RI 6LOLFD *HOV - &KHP (GXF ± $OLp & -HDQ 3DXO 3LUDUG - 3 3UHSDUDWLRQ RI /RZ GHQVLW\ ;HURJHOV IURP 0L[WXUHV RI 7(26 ZLWK 6XEVWLWXWHG $ONR[\VLODQHV , 1RQ &U\VW 6ROLG

2 105 6WXG\ RI WKH +\GURO\VLV±FRQGHQVDWLRQ 3URFHVV -

±

:DQJ < : +H - 7 /LX & & &KRQJ : + &KHQ + < 7KHUPRG\QDPLFV 9HUVXV .LQHWLFV LQ 1DQRV\QWKHVLV $QJHZ &KHP ,QW (G

±

1DNDED\DVKL +