MOFs based on 1D structural sub-domains with Br?nsted acid and redox active sites as effective bi-functional catalysts

Article abstract of DOI:10.1039/d0cy00235f

A novel family of lamellar MOF-type materials, which contain Br?nsted acid sites together with redox active centers, based on assembled 1D organic-inorganic nanoribbons were obtained through direct solvothermal synthesis routes, using specific monotopic benzylcarboxylate spacers with thiol substituents in thepara-position like structural modulator compounds and effective post-synthesis oxidized treatments to generate accessible sulfonic groups. Low-dimensional aluminum metal-organic materials, containing free sulfonic pendant groups (Al-ITQ-SO₃H), were successfully tested in several acid reactions, such as acetalization, esterification and ring opening of epoxides with a significant impact on fine chemistry processes. The direct introduction of stabilized Pd nanoparticles, cohabitating with pendant sulfonic groups, allowed the preparation of active bi-functional MOF-type hybrid materials (Al-ITQ-SO₃H/Pd) capable of carrying out one-pot two-step oxidation-acetalization reactions, exhibiting high yield and high activity during consecutive catalytic cycles.

Full text of DOI:10.1039/d0cy00235f

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21 January 2017
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ISSN 2044-4761
PAPER
Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
nanotubes produced by atomic layer deposition for hydrogen
generation from hydrolysis of ammonia borane
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Catalysis Science & Technology
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DOI: 10.1039/D0CY00235F
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&'()*( +, -,. )+/0*. 1)234-*

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DOI: 10.1039/D0CY00235F

&'()*( +, -,. )+/0*. 1)234-*
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DOI: 10.1039/D0CY00235F
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&'()*( +, -,. )+/0*. 1)234-*

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&'()*( +, -,. )+/0*. 1)234-*
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,P .8( 8:L24+ 1).(24)'* WQ4302( Y^[C A. B\77RB_77 51RB
2)-3(= ) 64L2).4,-)' L)-+ )**43-(+ ., .8( 5)2L,<:').(
32,0>* P2,1 .8( ,23)-45 *>)5(2* L,-+ ., 4-,23)-45
0-4.* S)* ,L*(26(+C ". 4* 2(1)2V)L': .8).= 4- .84* *)1(
2)-3(= *(6(2)' *43-)'* )..24L0.(+ ., )*:11(.245
*.2(.584-3 64L2).4,-* S(2( +(.(5.(+ L(5)0*( ,P
)2,1).45 24-3* >2(*(-. 4- .8( ,23)-45 0-4.*C
Q02.8(21,2(= .8( *>(5.2) *8,S(+ ) L2,)+ *43-)' P,2
*.2(.584-3 64L2).4,- 1,+( ). D^77RD;77 51RB 2)-3(= 5,14-3
P2,1 8:+2,<:' 32,0>* WR@Z[ +0( ., 8:+2).4,- S).(2 )-+
)'014-01 ,<,R8:+2,<4+( *>(54(*= A'@\W@Z[;= >2(*(-. 4- .8( B?
*0LR0-4.*C !8(2(P,2(= " *>(5.2,*5,>: )'*, 5,-P421(+ .8( .,.)'
4-.(324.: ,P .8( ,23)-45 *>)5(2*= P,214-3 .8( *.205.02( ,P .8(
8:L24+ 1).(24)'*= L(4-3 4- )32((1(-. S4.8 OH 2(*0'.*C
f&Y WfR2): &8,.,('(5.2,- Y>(5.2,*5,>:[ *.0+: ,P .8( ,<4+).4,-
*.).( ,P .8( >)'')+401 -)-,>)2.45'(* 4-5,2>,2).(+ 4- .8( 8:L24+
1).(24)'* WA'R"!XRYZF&+ )-+ A'R"!XRY@DZF&+[ S)* >(2P,21(+C
!8( *>(5.201 ,P &+D+ S)* *8,S- 4- Q4302( DC !S, L)-+* S(2(
+(.(5.(+ 5,22(*>,-+4-3 ., 5,1>,-(-.* S4.8 ) L4-+4-3 (-(23:
WTC%C[ ). DD_C; )-+ DDbCB (J P,2 A'R"!XRYZF&+ )-+ A'R"!XR
Y@DZF&+= 2(*>(5.46(':C !84* 2(*0'. 4* .:>45)' ,P .8( >2(*(-5(
,<4+4M(+ >)'')+401 *>(54(*= L(4-3 -,. ,L*(26(+ .8( 1(.)''45
W&+7[ 5,1>,-(-.C\_ @- .8( ,.8(2 8)-+= .8( *>(5.201 ,P Y;&
WQ4302( DW""[[ 5,-P421(+ .8( 8438 (PP(5.46(-(** ,P .8( >,*.R
*:-.8(*4* ,<4+).4,- >2,5(** +0( ., .8( >2(*(-5( ,P .8( L)-+
S4.8 ) TC%C ). B^DCb (J= 5,22(*>,-+4-3 ., .8( .84,'* 32,0>* P,2
A'R"!XRYZF&+ )-+ ,P ) -(S L)-+ S4.8 ) 8438(2 TC%C ). B_7C] (J
)**43-(+ ., *0'P,-45 32,0>* P,2 A'R"!XRY@DZF&+ 8:L24+
1).(24)'CD7= \b
>%$0& DH H)4- .(<.02)' >2,>(2.4(* ,P ')1('')2 8:L24+ 1(.)'R,23)-45 1).(24)'*C
F6A>
K2DI1*L
F23/-(
K2DI1*L% K2DI1*L
F&8,
U>(,
U23/-(
K/2JI1*L
7CBB
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7CD]
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A'R"!XRYZ
;^D
;B]
BEb
]D
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A'R"!XRYZF&+
;_]
7C7E
B;;
7C7;
A'R"!XRY@DZF&+ ;;D
) Y(<. k WYT%!RY1452,[C
B_7
7C7b
Q4-)'':= #@; )+*,2>.4,- 4*,.8(21* WQ4302( YE[ S(2( 1()*02(+ 4-
,2+(2 ., *.0+: .8( )+*,2>.4,- 5)>)54.: ,P .8( )'014-01 8:L24+
1).(24)'*C !8( 2(*0'.* 2(6()'(+ +4PP(2(-5( L(.S((- .8( +4PP(2(-.
8:L24+ *,'4+*= L(4-3 .8( 1).(24)' A'R"!XRYZ S4.8 .8( 8438(*.
)+*,2>.4,- 5)>)54.:= *8,S4-3 8438(2 ,2 *414')2 )+*,2>.4,-
6)'0(* .8)- ,.8(2 *.)-+)2+ .84,' )-+ *0'P,-45 1(.)'R,23)-45
1).(24)'* W!)L'( YB[C ". 4* 41>,2.)-. ., >,4-. ,0. .8). ,<4+4M(+
1).(24)'* >2(*(-.(+ ',S(2 )+*,2>.4,- 6)'0(* >2,L)L': +0( .,
.8( L433(2 *.(245 L0'V4-(** ,P .8( *0'P,-45 32,0>*C
?%,%0;,3/ A/,393,;
Z(2(4- S( 2(>,2.(+ .8( *:-.8(*4* ,P ) -(S ')1('')2 8:L24+
1).(24)'*= A'R"!XRY@DZ= L)*(+ ,- B? *0LR0-4.* S4.8 T2U-*.(+
)54+ *4.(* ,S4-3 .8( >2(*(-5( ,P *0'P,-45 32,0>*C o(
P02.8(21,2( +(*524L(+ .8( >2(>)2).4,- ,P L4RP0-5.4,-)'
1).(24)'* .8)-V* ., .8( 4-5,2>,2).4,- ,P >)'')+401
-)-,>)2.45'(*C !84* -(S 1).(24)'= A'R"!XRY@DZF&+= ,PP(2* L,.8
T2U-*.(+ )54+ )-+ 2(+,< )5.46( *4.(*C Q2,1 ) 5).)':.45 >,4-. ,P
64(S= .84* -(S )-+ 6(2*).4'( 8:L24+ 1).(24)' ,PP(2* 8438
>,.(-.4)' 4- )54+ )-+ 2(+,< 5).)':*(+ >2,5(**(*C !8(2(P,2(= .8(
5).)':.45 )5.464.: ,P .84* 8:L24+ 1).(24)' 8)* L((- (6)'0).(+ P,2
+4PP(2(-. .:>( ,P 2()5.4,-* *058 )* )5(.)'4M).4,-= (*.(24P45).4,-=
24-3 ,>(-4-3 )-+ ,<4+).4,-R)5(.)'4M).4,- .S,R*.(> >2,5(**(* .,
>2,64+( 4-.(21(+4).(* )-+ P4-( 58(145)'* ,P 4-.(2(*. 4-
>8)21)5(0.45)'= >(2P01(2:= *,'6(-.* ,2 )32,58(14*.2:
4-+0*.24(*C
>&8,.-%0 N-(N&-,3&#
!(<.02)' >2,>(2.4(* ,P )'014-01 1(.)'R,23)-45 1).(24)'* S(2(
58)2)5.(24M(+ L: )23,- )+*,2>.4,- 4*,.8(21* WQ4302(* Y_ )-+
Yb[C !:>( " 4*,.8(21* S(2( ,L.)4-(+ P,2 )'' 1).(24)'*= L(4-3
58)2)5.(24*.45 ,P *,'4+* S4.8 )**,54).(+ 1452,>,2,*4.:C ?4PP(2(-.
T%! *>(54P45 *02P)5(* )2()* S(2( +(.(214-(+ P,2 .8( 8:L24+
*,'4+*= +(>(-+4-3 ,- .8( 4-5,2>,2).4,- ,2 -,. ,P .8( >)'')+401
-)-,>)2.45'(*C Y>(54P45)'':= A'R"!XRYZ *8,S(+ ) 8438(2 6)'0(
WYT%!A ;^D 1;F3[ .8)- A'R"!XRYZF&+ WYT%!A B;; 1;F3[= L(4-3 .84*
P)5. )**,54).(+ S4.8 .8( ',5).4,- 4-., .8( >,2(* ,P *,1(
>)'')+401 *>(54(*= )6,4+4-3 .8( 5,22(5. +4PP0*4,- ,P .8( )23,-
1,'(50'(*C H,2(,6(2= .8( P4-)' 1).(24)'*= ,L.)4-(+ )P.(2
,<4+).4,- .2().1(-.*= (<84L4.(+ 8438(2 6)'0(*A ;_] 1;F3 P,2 A'R
"!XRY@DZ )-+ ;;D 1;F3 P,2 A'R"!XRY@DZF&+C !84* (PP(5. S)*
>2,L)L': +0( ., ('414-).4,- ,P .8( 0-2()5.(+ ,23)-45 *>)5(2* ,2
?HQ 1,'(50'(* ,55'0+(+ 4- .8( 1).(24)'*= L(4-3 .8(*( *,'4+*
1,2( )55(**4L'( P,2 .8( )23,- 1,'(50'(* W!)L'( ;[C
A/&,%03G%,3() -&%/,3()#
A5(.)'4M).4,- 4* -,. ,-': ) 0*(P0' .,,' 4- ,23)-45 58(14*.2: *4-5(
4* ) 2(6(2*4L'( >2,.(5.4,- ,P 5)2L,-:' 5,1>,0-+*\E L0. 4* )'*,
S4+(': )>>'4(+ ., >2,+05( 4-.(21(+4).(* ,P 2()5.4,- )-+
5,1>,0-+* ,P 4-.(2(*. 4- 58(145)' 4-+0*.2: *058 )*
>8)21)5(0.45)'=]7 P2)32)-5( )-+ P')6,02*C]B "-+((+= .8(
>2,+05.4,- ,P )5(.)'* 5)- *1,,.8 +,S- .8( *.2,-3 *1('' ,P
+4PP(2(-. 5)2L,-:' 5,1>,0-+*C
K*0)'':= )5(.)'4M).4,- ,P )'+(8:+(* S4.8 )- )'5,8,' ,2 +4,' .)V(*
>')5( 4- .8( >2(*(-5( ,P T2U-*.(+ ,2 $(S4* )54+*C];R]\ Y(6(2)'
1(.8,+* P,2 .8( >2(>)2).4,- ,P 5:5'45 )5(.)'* S(2( 2(>,2.(+
.82,038 ,P 0*4-3 14-(2)' )54+*= 2(*4-*= M(,'4.(*= 1(*,>,2,0*
1).(24)'* ,2 1(.)'R,23)-45 1).(24)'* )* 5).)':*.* P,2 .8(
5,-+(-*).4,- ,P 3':5,'* S4.8 )2,1).45 )'+(8:+(*CD7= ]]R]b
!8(-= ., 4''0*.2).( .8( )L4'4.: ,P )'014-01 1(.)'R,23)-45
1).(24)'* S4.8 *0'P,-45 32,0>* WA'R"!XRY@DZ[ 8(2( *:-.8(*4M(+
)* )54+ 5).)':*.*= S( +(1,-*.2).(+ .8( *04.)L'( 5).)':.45
H,2(,6(2= Zm26).8Rn)S)M,( >,2( *4M( +4*.24L0.4,- (64+(-5(+
.8). .8( 1)/,24.: ,P >,2(* S(2( 5(-.2(+ )2,0-+ ]C] h P,2 )''
1).(24)'* WQ4302( Y_ )-+ Yb[C !84* ',S 6)'0( S)* )**,54).(+ .,
2(+05(+ L)*)' *>)5( +0( ., *8,2. '(-3.8 ,P ,23)-45 0-4. 0*(+ )*
T d PE >!2+C= ;7B;= EE= BRD
!84* /,02-)' 4* e !8( ,:)' Y,54(.: ,P #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 7 of 15
View Article Online
DOI: 10.1039/D0CY00235F
B(.-)%0 C%2&
A=><?@A
(`04'4L2401 >2,5(**= .8( 2(1,6( ,P S).(2 4* 0*0)'': 2(`042(+ .,
*84P. .8( (`04'4L2401 )-+ )584(6( 1)<4101 :4('+ )-+ *('(5.464.:C
T,.8 L(-M)'+(8:+( )-+ 6)-4''4- >2,>:'(-( 3':5,' )5(.)'* )2(
P')6,02 )-+ P2)32)-5( )3(-.*= .8( P42*. +0( ., 4.* P204.: )-+ P',2)'
,+,02 S84'( .8( *(5,-+ ., 6)-4''4- )-+ *S((. ,+,02C !8( 2(*0'.*
>2(*(-.(+ 4- .8( Q4302(* \ )-+ ] +(1,-*.2).(+ .8).= 4-+((+= .,
)584(6( ) 1)<4101 )5(.)' :4('+ )-+ *('(5.464.: WEEj[= .8(
)M(,.2,>45 +4*.4'').4,- ,P S).(2 0*4-3 .,'0(-( )* *,'6(-. S)*
2(`042(+C !8( 5).)':.45 2(*0'.* ,L.)4-(+ P,2 .8( *:-.8(*4* ,P
L(-M)'+(8:+( >2,>:'(-( 3':5,' )5(.)' 2(6()'(+ .8). -(4.8(2 .8(
4-52()*( ,P )1,0-. ,P 5).)':*. 58)23( -,2 .8( 4-52()*( ,P
+4,'FL(-M)'+(8:+( 1,'( 2).4, )'',S(+ ., *84P. .8(
.8(21,+:-)145 (`04'4L2401 )584(6(+= L(4-3 .8( 1)<4101 :4('+
5',*( ., _\jC !8( 2(*0'.* +(1,-*.2).(+ .8( )+(`0).( 5).)':.45
>2,>(2.4(* ,P .8( 8:L24+ 1).(24)'* )* *,'4+ )54+ 5).)':*.* ., 5)22:
,0. )5(.)'4M).4,- >2,5(** S4.8 1(.8)-,' )-+ +4,' ., >2(>)2(
>2,+05.* S4.8 8438 )++(+R6)'0( 4- .8( 4-+0*.2: ,P P')6,02 )-+
P2)32)-5( )3(-.*C
*EE
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"3I.-& MH n4-(.45* ,P L(-M)'+(8:+( >2,>:'(-( 3':5,' )5(.)' >2,+05.4,- 4-
>2(*(-5( ,P A'R"!XRY@DZA Wp[ 2).4, BA;= B7 1,'j Y@DZ ). E7l#= W [ 2).4,
BA;= ;7 1,'j Y@DZ ). E7l#= W![ 2).4, BA^= ;7 1,'j Y@DZ ). E7l# )-+ Wq[
2).4, BA^= ;7 1,'j Y@DZ 0-+(2 *,'6(-. 2(P'0<C !,'0(-( S)* 0*(+ )*
*,'6(-.C ).4, WL(-M)'+(8:+(AB=;R>2,>)-(+4,'[C
A#,&-3:3/%,3() -&%/,3()#
T(5)0*( .8( )5(.)'4M).4,- >2,5(** +,(* -,. 2(`042( *.2,-3 )54+
*4.(*= .8( 5).)':.45 )5.464.: ,P .8( *0'P,-45 )54+ *4.(* ,P A'R"!XR
Y@DZ 8(2( *:-.8(*4*(+ S)* 58(5V(+ 4- *.2,-3 )54+ 5).)':*(+
2()5.4,- *058 )* (*.(24P45).4,-C "- P)5.= .8( (*.(24P45).4,- ,P
)'5,8,'* S4.8 5)2L,<:'45 )54+* 4* ,-( ,P .8( L(*. V-,S- )-+
>2,>(2.4(* +(>',:(+ L: .8( .84* 1).(24)' ., >2,+05( ) *(24(* ,P
)5(.)'* S4.8 )>>'45).4,- 4- >(2P01(2: 4-+0*.2:C Q42*.':= .8(
)5(.)'4M).4,- ,P L(-M)'+(8:+( S4.8 1(.8)-,' S)* *.0+4(+
WY58(1( ;[C T(-M)'+(8:+( +41(.8:' )5(.)' 4* 5,11,-': 0*(+ )*
P')6,02 )-+ P2)32)-5( )3(-.* *4-5( 4. 8)* ) -0..: )-+ P',2)'
,+,02C !8( 2(*0'.* >2(*(-.(+ 4- .8( Q4302( YB7 5,-P421(+ .8).
.8( )5(.)'4M).4,- ,P L(-M)'+(8:+( )-+ 1(.8)-,' S)*
*055(**P0'': >(2P,21(+ 4- .8( >2(*(-5( ,P +4PP(2(-. A'R"!XRY@DZ
',)+4-3= 4- 14'+ 2()5.4,- 5,-+4.4,-*= ). D7l#C H,2(,6(2= ,-':
*'438. 6)24).4,-* 5)- L( ,L*(26(+ P2,1 .8( +4PP(2(-. V4-(.45
5026(*= 4-52()*4-3 .8( 4-4.4)' 2).( S4.8 .8( )1,0-. ,P )5.46(
*4.(*= 3464-3 E7 j :4('+ S4.8 EE j *('(5.464.:C "- .8( *)1( S):=
5:5'45 )5(.)'* ,P L(-M)'+(8:+( )-+ 6)-4''4- 5)- L( *055(**P0'':
>2(>)2(+ 0*4-3 >2,>:'(-( 3':5,' )* +4,'C Y4-5( )5(.)'4M).4,- 4* )-
,'+(*. 58(145)' 2()5.4,-*= L(4-3 L)*(+ -,21)'': ,-
)
-05'(,>84'45 )..)5V ,P .8( )'5,8,' ). .8( 5)2L,<:'45 32,0> ,P .8(
(*.(2C]ER^7 !84* >2,5(** 8)* (<.(-*46(': L((- *.0+4(+= L(4-3
>0L'4*8(+ S,2V* P2,1 8,1,3(-(,0* 5).)':*4* L: 0*4-3 14-(2)'
)54+* *058 )* *0'>80245 )54+ ., 8(.(2,3(-(,0* 5).)':*4* L: 0*4-3
2(*4-*= M(,'4.(*= 1(*,>,2,0* 1).(24)'*= 8(.(2,>,':)54+* ,2
1(.)'R,23)-45 1).(24)'* )* *,'4+ 5).)':*.*C;b=
^BR^\
#022(-.':=
.8(2( 4* ) 32(). 4-.(2(*. 4- .84* 2()5.4,- +0( ., 4.* )>>'45).4,- 4-
+4PP(2(-. 4-+0*.24)' )>>'45).4,-* L(5)0*( ,P ,23)-45 (*.(2* )2(
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"3I.-& SH r4('+ ,P 6)-4''4- >2,>:'(-( 3':5,' )5(.)' 6(2*0* .41(= S8(-
)5(.)'4M).4,- S)* 5)224(+ ,0. 4- .8( >2(*(-5( ,P A'R"!XRY@DZA W [ 2).4,
BA^= ;7 1,'j Y@DZ ). E7l# )-+ W [ 2).4, BA^= ;7 1,'j Y@DZ 0-+(2 *,'6(-.
2(P'0<C !,'0(-( S)* 0*(+ )* *,'6(-.C
F/5&2& DH &2(>)2).4,- ,P +4PP(2(-. P')6,2 )-+ P2)32)-5(* )3(-.* L:
)5(.)'4M).4,-C
!84* /,02-)' 4* e !8( ,:)' Y,54(.: ,P #8(14*.2: ;7<<
PE >!2+C= ;7BD= EE= BRD d W
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 8 of 15
View Article Online
DOI: 10.1039/D0CY00235F
A=><?@A
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2()5.4,- ,P 8(<)-,45 )54+ S4.8 1(.8)-,'= ). ^7l#= S)* P42*.':
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). *8,2. 2()5.4,- .41( L: 0*4-3 B7 1,'j Y@DZ )* 5).)':*.
',)+4-3C "- ,2+(2 ., (-*02( .8). -,. )-: )5.46( *0L*.)-5(
1432).(* P2,1 .8( A'R"!XRY@DZ 1).(24)' ., .8( '4`04+ >8)*( )-+
5,0'+ L( 2(*>,-*4L'(= ). '()*. 4- >)2.= ,P .8( 5).)':.45
>(2P,21)-5(= ) '()584-3 .(*. S)* >(2P,21(+C AP.(2 D 8,02* ,P
2()5.4,- .41(= .8( A'R"!XRY@DZ 5).)':*. S)* 2(1,6(+ L:
P4'.2).4,- )-+ .8( >2,5(** S)* 5,-.4-0(+C AP.(2 .8).= .8(
2()5.4,- S)* 5,-.4-0(+ )-+ *)1>'(* S(2( .)V(- 0-.4' ;7 8,02*
,P 2()5.4,- .41(C Q4302( YBB *8,S(+ .8). .8( :4('+ +4+ -,.
*0PP(2(+ *0L*.)-.4)'': 58)-3(*C !)V4-3 4-., )55,0-. .8( 8438
1(.8:' 8(<)-,).( :4('+ ,L.)4-(+ )-+ .8( *.)L4'4.: ,P A'R"!XR
Y@DZ )* )54+ 5).)':*.= .8( >2(>)2).4,- ,P (*.(2* S4.8
)>>'45).4,-* )* P')6,02* )3(-.* P,2 .8(42 P204.: )-+ *S((.':
,+,02 )-+ >4-()>>'( -0)-5(= 0*4-3 )'5,8,'* S4.8 +4PP(2(-. 58)4-
'(-3.8* *058 )* (.8)-,'= L0.)-,' )-+ 8(<)-,' S)* 5)224(+ ,0.C
!8( :4('+ ,P ()58 (*.(2 6(2*0* .41( S)* >',..(+ 4- .8( Q4302( ^C
o8(- )'5,8,'* S4.8 8438(2 58)4- '(-3.8 S(2( 0*(+= *058 )*
L0.)-,' )-+ 8(<)-,'= .8( :4('+ +(52()*(+ P2,1 EB ., ^]jC A-
4-52()*( ,P .8( -01L(2 ,P 5)2L,- ).,1* 4- .8( )'5,8,' 58)4-
>2,+05(* )- 4-+05.46( (PP(5. 5,-.24L0.4-3 ., 4-52()*( .8(
-05'(,>84'45 2()5.464.: ,P .8( )'5,8,' 32,0>C !8(2(P,2(= .8(
,L*(26(+ +(52()*( ,P :4('+ S)* )..24L0.(+ ., *.(245 (PP(5. )-+
)+*,2>.4,-F+(*,2>.4,- '414.).4,-* .8). 5)- L( 41>2,6(+ S4.8 )-
4-52()*( ,P .(1>(2).02(C !8(2(P,2(= 4. S)* >,**4L'( ., )584(6( )
E7j 8(<:' 8(<)-,).( :4('+ S8(- .8( .(1>(2).02( S)*
4-52()*(+ 0-.4' B;7l#= )P.(2 B^8 ,P 2()5.4,- .41(C
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(PP(5. 5,-.24L0.4-3 ., +(52()*( .8( ('(5.2,>84'45 2()5.464.: ,P .8(
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&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 9 of 15
View Article Online
DOI: 10.1039/D0CY00235F
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!84* >2,5(** 8)* L((- +((>': *.0+4(+ .82,038 +4PP(2(-. 5).)':.45
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.8). )'',S 2()584-3 8438 :4('+* )-+ 2(34,R*('(5.464.: 0-+(2 14'+
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,P *0'P,-45 32,0>* ,P .8( A'R"!XRY@DZ 1).(24)'= 4.* 5).)':.45
L(8)64,02 P,2 ,>(- 24-3 2()5.4,- ,P *.:2(-( ,<4+( S4.8 1(.8)-,'
S)* *.0+4(+ WY58(1( \[C !8( 5).)':*. ',)+4-3 S)* (6)'0).(+
S4.8 .(*.4-3 .82(( +4PP(2(-. 58)23( ,P )54+ *4.(*= 4C (C ]= _C] )-+
B7 1,'j Y@DZC Q4302( YB; +(1,-*.2).(+ .8). P0'' 5,-6(2*4,-
S)* 2()58(+ )P.(2 P(S 8,02* ,P 2()5.4,- .41( )-+ .8). 4-4.4)'
2).( S)* *414')2 P,2 .8( .82(( 58)23(* ,P 5).)':*.C "- 5,1>)24*,-
S4.8 2(*0'.* 2(>,2.(+ 4- .8( L4L'4,32)>8:= 8438(2 )-+ *414')2
5).)':.45 )5.464.: .8)- 5,>>(2 ,2 42,- 1(.)'R,23)-45 1).(24)'*
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1(+401 )-+ S(2( 2(*>,-*4L'( ,P .8( 1,-4.,2(+ 5).)':.45
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&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 10 of 15
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DOI: 10.1039/D0CY00235F
A=><?@A
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&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 11 of 15
View Article Online
DOI: 10.1039/D0CY00235F
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)5.464.: 4- ,-(R>,. .S,R*.(> ,<4+).4,-R)5(.)'4M).4,- 2()5.4,-*
)-+ 8438 *.)L4'4.: *4-5( 4.* )5.464.: S)* 1)4-.)4-(+ P,2 P,02
*055(**46( 20-*C Z(2(4-= S( 2(>,2.(+ .8( *:-.8(*4* ,P ) -(S )-+
>2,14*4-3 2(+,<R)54+ 5).)':*. ., >(2P,21 5,-*(50.46( )-+
5)*5)+( >2,5(**(*C
*
D
J
M
=.)#
"3I.-& *DH Q,02 5,-*(50.46( 0*(* S(2( 2(>2(*(-.(+ P,2 ,<4+).4,-R
)5(.)'4M).4,- >2,5(** 4- >2(*(-5( ,P A'R"!XRY@DZF&+ S4.8 D 1,'j &+
0*(+
)*
5).)':*.C
A* 6)'0)L'( )'.(2-).46(= ) *>(54P45 L4RP0-5.4,-)' 1(.)'R,23)-45
5).)':*. 5,1L4-4-3 T2U-*.(+ )54+ )-+ 2(+,< )5.46( *4.(*= A'R"!XR
Y@DZF&+ S)* >2(>)2(+C !8( *.0+4(+ .S, *.(>* 2()5.4,- 5,-*4*.*
4- .8( P42*. *.(> 4- .8( ,<4+).4,- ,P L(-M:' )'5,8,' WB[ 4-.,
L(-M)'+(8:+( W;[ 0-+(2 @; ).1,*>8(2( 5).)':*(+ L: &+
-)-,>)2.45'(*= )-+ 4- .8( *(5,-+ *.(> 4- .8( )5(.)'4M).4,- ,P
L(-M)'+(8:+( S4.8 1(.8)-,' ., 346( .8( 5,22(*>,-+4-3
+41(.8:')5(.)' WD[ WY58(1( ][C A. P42*.= .8( 4-P'0(-5( ,P .8(
58)23( ,P A'R"!XRY@DZF&+ 5).)':*. S)* *.0+4(+ 0*4-3 B= D )-+ ]
1,'j &+ ., >(2P,21 .8( 5,-*(50.46( 2()5.4,-*C Q4302( BB
*8,S(+ .8). :4('+ 4- .8( P42*. *.(> 4-52()*(+ S4.8 )- 4-52()*( ,P
&+ 1,'j P2,1 b_ j 0> ., E_ jC O(6(2.8('(**= .8( :4('+ 4- .8(
*(5,-+ *.(> +(52()*(+ 0-.4' b7j S4.8 )- 4-52()*( ,P &+ 1,'jC
!8(-= ) 5,1>2,14*( L(.S((- .8( &+ 1,'j )-+ .8( 1)<4101
:4('+ ,P ()58 *.)3( S)* P,0-+ P,2 ) D 1,'j &+= )584(64-3 ) E_j
:4('+ 4- .8( P42*. *.(> )-+ E7j :4('+ 4- .8( *(5,-+ *.(>C "-
5,1>)24*,- S4.8 '4.(2).02(= .8( 5).)':.45 >(2P,21)-5( ,P .8( A'R
"!XRY@DZF&+ S(2( 8438(2 .8)- &+u#0RH@Q* )-+ *414')2 .,
&+uK4@^_ )-+ &+uH"$RB7BC_bRbB Q4-)'':= .8( *.)L4'4.: ,P .8( A'R
"!XRY@DZF&+ S)* (<>',2(+ 0-+(2 .8( 2()5.4,- 5,-+4.4,-* ,P
5,-*(50.46( ,<4+).4,-R)5(.)'4M).4,- >2,5(**(*C A '()584-3 .(*.
S)* >(2P,21(+ P4'.(24-3 ,PP .8( *,'4+ 5).)':*. )P.(2 ] 8 ,P
2()5.4,- .41( W]Ej[C Q2,1 Q4302( Y;; 4. 5)- L( *((- .8). -,
A8N&-32&),%0
?5&23/%0#
Z:L24+ 1(.)'R,23)-45 1).(24)'* S(2( *:-.8(*4M(+ L: 0*4-3 \R
1(25)>.,L(-M,45 )54+ WRYZ= A'+2458[ )* ,23)-45 *,025(C
A'014-01 -4.2).( -,-)8:+2).( WA'WO@D[DCEZ;@= A'+2458[ S)*
0*(+ )* 4-,23)-45 *,025(C H4<.02(* ,P +41(.8:'P,21)14+(
W?HQ= A52,**[ )-+ H4''4X S).(2 S(2( 0*(+ )* *,'6(-.* 4- .8(
*,'6,.8(21)' *:-.8(*4* >2,5(**C T4*WL(-M,-4.24'([>)'')+401 W""[
58',24+( S)* 0*(+ )* >2(502*,2 ,P >)'')+401 -)-,>)2.45'(* )-+
1(.8)-,' S)* 0*(+ ., 2(1,6( '4-V(2* (<5(** )-+ ., (<58)-3(
*,'6(-. 1,'(50'(* ,55'0+(+ +024-3 .8( *:-.8(*4* >2,5(**C
H,2(,6(2= 8:+2,3(- >(2,<4+( WD7 jS.[ S)* 0*(+ ., ,<4+4M(
.84,'* ., *0'P,-45 >(-+4-3 32,0>*C
A01<>\1FO
!84* ,23)-45R4-,23)-45 1).(24)' S)* *:-.8(*4M(+ +4**,'64-3 .8(
,23)-45 *>)5(2 WRYZ= ]CDD 11,'[ 4- ) ?HQFH4''4X S).(2 14<.02(
W;7 )-+ ;] 1$= 2(*>(5.46(':[ ). E7l#C AP.(2 .8).= .8( 4-,23)-45
*,025( WA'WO@D[DCEZ;@= ]CDD 11,'[ S)* ()*4': +4**,'6(+ 4- S).(2
W]1$[ ). 2,,1 .(1>(2).02(C T,.8 *,'0.4,- S(2( 14<(+ )-+ V(>.
!84* /,02-)' 4* e !8( ,:)' Y,54(.: ,P #8(14*.2: ;7<<
PE >!2+C= ;7BD= EE= BRD d **
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 12 of 15
View Article Online
DOI: 10.1039/D0CY00235F
A=><?@A
B(.-)%0 C%2&
0-+(2 2(P'0<(+ ). E7l# +024-3 ] +):*C !8( >2(54>4.).(+ >,S+(2 4-3R,>(-4-3 2()5.4,- S)* 5)224(+ ,0. 4- ) ; 1$ 5,-45 6(**(' .8).
S)* 4*,').(+ L: P4'.2).4,- S4.8 ?HQ )-+ +4*.4''(+ S).(2C !8(-= S)* 58)23(+ S4.8 +4PP(2(-. ',)+4-3 ,P 5).)':*. W]= _C] ,2 B7 1,'j
.8( *,'4+ ,L.)4-(+ S)* S)*8(+ *(6(2)' .41(* S4.8 1(.8)-,' )-+ Y@DZ[ 4- B 1$ ,P 1(.8)-,'C AP.(2 .84*= *.:2(-( ,<4+( W7C;] 11,'[
+24(+ ,6(2-438. ). B77l# 0-+(2 6)5001C
S)* )++(+ )-+ .8( 2()5.4,- 14<.02( S)* *.422(+ ). D7l# P,2 .8(
2(`042(+ .41(C
A01<>\1FOQP'
!83'%,3()1A/&,%03G%,3() -&%/,3()
!8( 8:L24+ 1).(24)' S4.8 >)'')+401 -)-,>)2.45'(* S)* ,L.)4-(+
4- ,-(R>,. *.(> *:-.8(*4*= P,'',S4-3 .8( *)1( >2,5(+02( !8( 2()5.4,- S)* 5)224(+ ,0. 4- ,-(R>,. .S,R*.(> >2,5(** 0*4-3
+(*524L(+ P,2 A'R"!XRYZ= L0. )++4-3 .8( >)'')+401 >2(502*,2 .8( L4RP0-5.4,-)' 8:L24+ 5).)':*. .8). 5,-.)4-* >)'')+401
WT4*WL(-M,-4.24'([>)'')+401 W""[[ S8(- .8( ,23)-45 *>)5(2 S)* -)-,>)2.45'(* 4- .8( P2)1(S,2V WA'R"!XRY@DZF&+[C Q42*.= ; 1$
5,1>'(.(': +4**,'6(+C AP.(2= .8( 4-,23)-45 *,025( S)* 5,-45 6(**(' S)* 58)23(+ S4.8 +4PP(2(-. )1,0-. ,P )5.46( *4.(*
4-.2,+05(+ )-+ ) 5'()2 *,'0.4,- S)* ,L.)4-(+= L(4-3 V(>. 4. P,2 WB= D ,2 ] 1,'j &+[ 4- B 1$ ,P L(-M,-4.24'( )-+ L(-M:' )'5,8,'
] +):*C ". S)* 0*(+ .8( *)1( 1(.8,+ )L,6( +(*524L( ., 4*,').( W7C; 11,'[ S)* 4-.2,+05(+= L(4-3 P4<(+ .8( )+(`0).(
.8( P4-)' 1).(24)'C
.(1>(2).02( WB77l#[ ., 5)22: ,0. .8( P42*. *.(>= S4.8 643,2,0*
*.4224-3 0-+(2 ,<:3(- ).1,*>8(2(C AP.(2 .8). .8( P42*. *.(> S)*
5,1>'(.(+= B 1$ ,P 1(.8)-,' S)* 4-.2,+05(+ )-+ .8(
A01<>\1F!JO %)' A01<>\1F!JO QP'
!8( 1).(24)'* )L,6( +(*524L(+ S(2( .2().(+ 0-+(2 )- ,<4+).4,- .(1>(2).02( 1)4-.)4-(+ ). \]l# 0-+(2 -4.2,3(- ).1,*>8(2(
>2,5(** 4- ,2+(2 ., 5,-6(2. .84,'* 4- *0'P,-45 1,4(.4(*C %)58 S4.8 5,-.4-0,0* *.4224-3C
1).(24)' WD77 13[ S)* 4-.2,+05(+ 4-., ) P')*V L,..'( S4.8 ) BH
*,'0.4,- ,P 8:+2,3(- >(2,<4+( WB] 1$[ 4- (.8)-,' ). E7l# P,2 ;\
?()/0.#3()#
8C AP.(2 ,P .84* .2().1(-.= .8( *,'4+* S(2( 2(5,6(2(+ L: P4'.2).4,-
S4.8 )L0-+)-. (.8)-,' 4- ,2+(2 ., 2(1,6( .8( 30(*. 1,'(50'(*
A -(S ',SR+41(-*4,-)' P)14': ,P )'014-01 1(.)'R,23)-45
,P 8:+2,3(- >(2,<4+( *,'0.4,- )-+ .8( ,23)-45 '4-V(2 ',5).(+
1).(24)'* S4.8 .84,' 1,4(.4(* S(2( +42(5.': ,L.)4-(+ .82,038
,0. ,P .8( P2)1(S,2VC Q4-)'':= .8( *,'4+* S(2( +24(+ ). B77l#
*,'6,.8(21)' *:-.8(*4* 2,0.(*C #8)2)5.(24M).4,- L: f ?=
0-+(2 6)5001C
58(145)' )-)':*4*= !cA= OH = " )-+ f&Y *>(5.2,*5,>:= )-+
!%HFZ !%H 1452,*5,>: 5,22,L,2).(+ .8( ')1('')2 *.205.02(
<@1SJKA0L
>2(*(-. 4- .8( P2)1(S,2V ,P .8( 8:L24+ 1).(24)'* L)*(+ ,- .8(
)**,54).4,- ,P B? ,23)-45R4-,23)-45 -)-,24LL,-R.:>( *0LR
+,1)4-*C !8( )55(**4L'( .84,' 32,0>* S(2( (PP(5.46(':
.2)-*P,21(+ 4- P2(( *0'P,-45 >(-+)-. 5(-.2(* L: ,<4+).4,-
.2().1(-.= L(4-3 .8( 8:L24+ 1).(24)'* *055(**P0'': .(*.(+ 4-
*(6(2)' )54+ 2()5.4,-*= *058 )* )5(.)'4M).4,-= (*.(24P45).4,- )-+
,>(- 24-3 ,P (>,<4+(* S4.8 ')23( *5,>( 4- P4-( 58(14*.2:
>2,5(**(*C !8( 5).)':.45 2(*0'.* 5,-P421(+ .8( 8438 5).)':.45
)5.464.: ,P .8( ')1('')2 1(.)',23)-45 8:L24+ 1).(24)'* )-+ .8(42
2(0*)L4'4.: )-+ 2(5:5')L4'4.:C Q02.8(21,2(= L4RP0-5.4,-)' 8:L24+
5).)':*.* S(2( *:-.8(*4M(+ 4- ,-(R*.(> +42(5. *,'6,.8(21)'
*:-.8(*4* >2,5(**= 5,-.)4-4-3 *0'P,-45 >(-+)-. 32,0>* )-+ &+
-)-,>)2.45'(* 5,8)L4.).4-3 4- .8( *.205.02(= S8458 S(2(
(PP(5.46( ., 5)22: ,0. ,-(R>,. .S,R*.(> ,<4+).4,-R)5(.)'4M).4,-
2()5.4,-*= 2()584-3 8438 :4('+ )-+ )5.464.: +024-3 P,02
5,-*(50.46( 0*(*C ?(P4-4.46(':= ) -(S )-+ >2,14*4-3 2(+,<R)54+
',SR+41(-*4,-)' H@QR.:>( 5).)':*. 5)>)L'( ., >(2P,21
5,-*(50.46( )-+ 5)*5)+( >2,5(**(* S)* +(*524L(+= 0*4-3
1,-,.,>45 P0-5.4,-)' ,23)-45 *>)5(2* .,3(.8(2 S4.8 *.)L4'4M(+
1(.)''45 -)-,>)2.45'(*= ,>(-4-3 .8( >,**4L4'4.4(* ., 3(-(2).(
P02.8(2 8(.(2,3(-(,0* 10'.4RP0-5.4,-)' 8:L24+ 5).)':*.*C
#,-6(-.4,-)' D? H"$R]DWA'[ S)* *:-.8(*4M(+ 0*4-3 B=\R
L(-M(-(+45)2L,<:'45 )54+ )* ,23)-45 '4-V(2 WT?#= A'+2458[= )55,2+4-3
., ) '4.(2).02( >2,5(+02(Cb;
A/&,%03G%,3() -&%/,3()#
Q,21).4,- ,P L(-M)'+(8:+( +41(.8:' )5(.)'
; 1$ 5,-45 6(**(' S)* 58)23(+ S4.8 +4PP(2(-. )1,0-. ,P 5).)':*.
W]= _C] ,2 B7 1,'j Y@DZ[ 4- B 1$ ,P 1(.8)-,'C Q4-)'':=
L(-M)'+(8:+( W7CDD 11,'[ S)* 4-.2,+05(+ )-+ .8( 2()5.4,-
14<.02( S)* *.422(+ P,2 .8( 2(`042(+ .41( ). D7l# 0-+(2 O;
).1,*>8(2(C
Q,21).4,- ,P L(-M)'+(8:+( )-+ 6)-4''4- >2,>:'(-( 3':5,' )5(.)'
()5.4,- S)* .(*.(+ 4- ) .82((R-(5V(+ 2,0-+RL,..,1 P')*V
5,--(5.(+ S4.8 ) 2(P'0< 5,-+(-*(2 )-+ S4.8 ) ?()-RY.)2V .2)>C
A+(`0).( )1,0-. ,P 5).)':*. WB7R;7 1,'j Y@DZ[ )-+ B=;R
>2,>)-(+4,' W2).4, L(-M)'+(8:+(A+4,'= BA; ,2 BA^[ S(2( )++(+ 4-
B7 1$ ,P .,'0(-(C AP.(2 .84*= L(-M)'+(8:+( ,2 6)-4''4- WDCD 11,'[
S)* 4-.2,+05(+ )-+ )+(`0).( 2()5.4,- .(1>(2).02( S)*
)584(6(+ WE7RB]7 l#[ S4.8 643,2,0* *.4224-3 0-+(2 O;
).1,*>8(2(C
A#,&-3:3/%,3() (: %03N5%,3/ %/3'#
?():03/,# (: 3),&-&#,
%*.(24P45).4,- 2()5.4,- ,P )'4>8).45 )54+* S)* 5)224(+ ,0. 4- ) ;
1$ 5,-45 6(**('C !8( >2,5(+02( 5,-*4*.(+ 4- 58)234-3 .8(
2()5.,2 S4.8 .8( )+(`0).( )1,0-. ,P 5).)':*. WB7 1,'j Y@DZ[
)-+ S4.8 B 1$ ,P )'5,8,'C !8(-= )'4>8).45 )54+ W7C\ 11,'[ S)*
)++(+ )-+ *('(5.(+ .(1>(2).02( S)* )584(6(+ W^7RE7l#[ 0-+(2
643,2,0* *.4224-3C
!8(2( )2( -, 5,-P'45.* ., +(5')2(C
A/])(40&'I&2&),#
!8( )0.8,2* )2( 32).(P0' P,2 P4-)-54)' *0>>,2. P2,1 Y>)-4*8
c,6(2-1(-.= HA!;7B_Rb;;bbR#;RBR& )-+ Y(6(2, @58,)
!N&) -3)I -&%/,3()
*D d PE >!2+C= ;7B;= EE= BRD
!84* /,02-)' 4* e !8( ,:)' Y,54(.: ,P #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 13 of 15
View Article Online
DOI: 10.1039/D0CY00235F
B(.-)%0 C%2&
A=><?@A
;EC 9C 94)-3= QC cy-+)2)= rC RTC a8)-3= nC O)= @C HC r)384 )-+ oC cC
n'(1>(2(2= PE A2E :S+2E <)-E3 ;7B\^ *JT= B;b\\C
D7C rC 94-= 9C Y84= QC a8)-3= rC a8,-3 )-+ oC a80= PE \).E :!&!. A :S+2E3
;7B\^ JXJ1JXM= B^_C
%<5(''(-5( &2,32)1 Y%JR;7B^R7^bD= )-+ HK$!r;Zr#A! W%KR
Z,24M,- ;7;7 P0-+(+ >2,/(5. 0-+(2 32)-. )32((1(-. -,C
_;7_bD[C
DBC 9C #8(-= nC $4= $C #8(-= C $40= fC Z0)-3 )-+ ?C r(= V"++$ :S+2E3
;7B\^ *T= ;\E7C
D;C ?C %C Q,33 )-+ %C OC +,* Y)-.,*= :))"*E :S+2E T+5E3 ;77\^ DMX=
;D^]C
DDC &C !C A-)*.)*= :S+2E T+5E3 ;77_^ *EW= ;B^_C
D\C HC 9C #'41(-.= AC #,21)= YC "L,22) )-+ HC 9C Y)L).(2= A:< :!&!.E3
;7B\^ M= b_7C
D]C ?C a8),= ?C 9C !411,-*= ?C r0)- )-+ ZC R#C a8,0= A--E :S+2E T+%E3
;7BB^ MM= B;DC
D^C QC cC #420/)-,= QC fC $')L2(* 4 f)1(-) )-+ AC #,21)= X!.&)$ ,"!$%E3
;7B;^ M*= \;\EC
D_C QC cC #420/)-,= AC $(:6)R&G2(M= AC #,21) )-+ QC fC $')L2G*z4z
f)1(-)= :S+2:!&:S+23 ;7BD^ S= ]DbC
DbC C Y242)1L)')/4= YC Z,-3= C O).)2)/)-= HC r,,-= C Z,.)= rC n41= rC
Z, n, )-+ nC n41= :S+2E :)22($E3 ;7B;^ MX= BB^]7C
C(,&# %)' -&:&-&)/&#
BC !C A*(P)= HC 9C H)5$)58')-= OC #,,1L* )-+ cC AC @M4-= cC AC=
>!&("+3 BEEE^ MED= b^_C
;C KC ?I)M )-+ AC #,21)= AC= :))"*E :S+2E T+5E3 ;7B^^ J**= b]C
DC YC Y(.8 )-+ AC 9C H).M3(2= AC 9C= :"U%E V")W&S X+%E3 ;7B_^ *W= \7\DC
\C ?C 9C !2)-58(1,-.)3-(= 9C $C H(-+,M)R#,2.(*= HC @vn((PP( )-+ @C
HC r)384= :S+2E <)-E T+5E3 ;77E^ JX= B;]_C
]C HC @wn((PP( )-+ @C HC r)384= :S+2E T+5E3 ;7B;^ **D= ^_]C
^C YC $C 9)1(*= :S+2E <)-E T+5E3 ;77D^ JD^ ;_^C
_C AC ZC #8038.)4= OC A81)+= ZC AC r,0-0*= AC $):>V,6 )-+ QC
J(2>,,2.= :S+2E <)-E T+5E3 ;7B]^ MM= ^b7\C
bC YC HC 9C ,33(= AC T)6:V4-)= 9C Z)/(V= ZC c)254)= AC "C @'46,*RY0)2(M=
AC Y(>0'6(+)R%*524L)-,= AC J41,-.= cC #'(.= &C T)M4-= QC n)>.(4/-= HC
?).024= %C JC )1,*RQ(2-)-+(M= QC fC $')L2(* 4 f)1(-)= JC J)-
Y>(:L2,(5V )-+ 9C c)*5,-= :S+2E <)-E T+5E3 ;7B_^ MT= DBD\C
EC 9C R C $4= C 9C n0>>'(2 )-+ ZC R# a8,0= :S+2E <)-E T+5E3 ;77E^ JX=
B\__C
B7C QC RrC r4= ?C #8(-= HC RnC o0= $C Z)- )-+ ZC R$C 94)-3= ZCR$C=
:S+26.(%:S+23 ;7B^^ X*= ^_]C
BBC #C RrC Y0-= #C X4-= fC R$C o)-3 )-+ aC RHC Y0= @Y +"& Z '$')$ )$
X"(/ X+.'5+"U3 ;7BD^ *E= bEC
B;C JC Y.)64')= AC AC !)'4- )-+ HC ?C A''(-+,2P= :S+2E <)-E T+5E3 ;7B\^
MJ= ]EE\C
BDC 9C $((= @C nC Q)28)= 9C ,L(2.*= nC AC Y58(4+.= YC !C O30:(-= 9C !C
Z0>>= :S+2E <)-E T+5E3 ;77E^ JX= B\]7C
B\C AC #,21)= ZC c)254) )-+ QC fC $')L2(* 4 f)1(-)= :S+2E T+5E3 ;7B7^
**E= \^7^C
B]C &C c)254)Rc)254)= HC H0''(2 )-+ AC #,21)= :S+2E <-'E3 ;7B\^ [=
;E_EC
B^C @C nC Q)28)= AC HC Y80'.M= AC AC Y)2/()-.= YC !C O30:(- )-+ 9C !C
Z0>>= PE A2E :S+2E <)-E3 ;7BB^ *JJ= ]^];C
B_C #C a,0= aC a8)-3= fC f0= XC c,-3= 9C $4 )-+ #C R?C o0= PE A2E :S+2E
<)-E3 ;7B;^ *JM= b_C
BbC &C oC Y40= aC 9C T2,S-= @C nC Q)28)= 9C !C Z0>> )-+ nC AC Y58(4+.=
:S+2E :)22($E3 ;7BD^ M[= B7E;7C
BEC HC Z)2.1)-- )-+ HC Q4*58(2= \'-") )")(% \+%) )")(% \!&+"E3
;7B;^ *TM= DbC
DEC AC ?8)V*84-)1,,2.8: )-+ ZC c)254)= :S+2<(%:S+23 ;7B\^
;DE;C
=
\7C ZC R$C 94)-3 )-+ XC f0= :S+2E :)22($E3 ;7BB^ MW= DD]BC
\BC QC o0= $C RcC X40= QC n( )-+ fC 94)-3= #$)"/E :S+2E :)22($E3 ;7BD^
JD= ]C
\;C HC Y)L,= AC Z(-*58('= ZC Q2,+(= %C n'(11 )-+ YC n)*V('= PE \!&+"E
:S+2E3 ;77_^ *W= Db;_C
\DC !C "*84+)= HC O)3),V)= !C AV4.) )-+ HC Z)20.)= :S+2E @("E PE3 ;77b^
*M= b\]^C
\\C AC A4/)M= AC n)2V)1V)2= rC 9C #8,4= OC !*01,24= %C m--(L2,= !C
A0.2(:= ZC Y84,:)1) )-+ XC f0= PE A2E :S+2E <)-E3 ;7B;^ *JM= BDE;^C
\]C ZC R$C 94)-3= TC $40= !C AV4.)= HC Z)20.)= ZC Y)V02)4 )-+ XC f0= PE A2E
:S+2E <)-E3 ;77E^ *J*= BBD7;C
\^C &C Q402)*(V )-+ $C (6(-= ]!$/2('"= ;77_= DJ= ;b]_R;b^^C
\_C oC %C H,++(1)-= oC #C T,S'4-3= ?C #C #)2.(2 )-+ ?C C c2,6(=
<("=E #$&+"=!-+ A$!.E3 BEbb^ **= DB_C
\bC &C oC 90= 9C Z:0-)= $C oC )1= YC 9C ZS)= rC n458(,-= nC T,-3Y,,
)-+ ZC #C Y(,>= A$/+WE :S+2E #$&E @*E3 ;7B]^ SM= ]B\;C
\EC HC AC A6(2:= PE \+*E :S+2E3 BEEE^ MD= ];b]C
]7C HC 9C A*8.,-= #C $)S2(-5(= 9C RAC n)2'**,-= nC AC 9C Y.0..'(= #C cC
O(S.,-= TC rC 9C J)58(2= YC o(LL(2 )-+ HC 9C o4.8-)''= PE \+*E :S+2E3
BEE^^ J[= \bbbC
]BC ZC Y02L023 )-+ 9C &)-.(-= "-+464+0)' Q2)32)-5( )-+ Q')6,2
H).(24)'*C "- :)22)$ ^"!/"!$-+ !$* ^.!5)" \!&+"'!.%= o4'(:RJ#Z
J(2')3 c1LZ { #,C= DEET= _RB_]C
;7C aC Z)*)-= 9C oC 90- )-+ YC ZC 980-3= :S+2E @$/E PE3 ;7B]^ DWX= ;^]C
;BC 9C 94)-3 )-+ @C HC r)384= :S+2E T+5E3 ;7B]^ **S= ^E^^C
;;C HC cC c,(*.(-= 9C 90)-RA'5)x4M= %C JC )1,*RQ(2-)-+(M= nC TC Y)4
Y)-V)2 c0>.)= %C Y.)64.*V4= ZC 6)- T(VV01= 9C c)*5,- )-+ QC n)>.(4/-=
PE :!&!.E3 ;7BB^ DX*^ B__C
;DC ?C T24..= #C $((= QC 9C K24L(R ,1,= ZC Q020V)S) )-+ @C HC r)384=
#$)"/E :S+2E3 ;7B7^ M[= ^Db_C
;\C 9C 90)-RA'5)-4M= 9C c)*5,- )-+ QC n)>.(4/-= PE \!&+"E :S+2E3 ;7B;^
DD = B7B7;C
];C %C o(-V(2. )-+ !C %C c,,+S4-= <U$&SE :)22($E3 BE__^ W= \7EC
]DC !C R9C$0= 9C RQC r)-3= $C R9C Y8(0= PE Z"/E :S+2E3 BEE]^ TE= ;EDBC
]\C HC OC !41,P((6)= JC OC &)-58(-V,= 9C oC 90-= aC Z)*)-= HC HC
H).2,*,6) )-+ YC ZC 980-3= A .E :!&!.E A V+$E3 ;7B\^ MW*= EBC
]]C AC #,21)= HC 9C #'41(-.= ZC c)25I) )-+ 9C &241,= A .E :!&!.E3 BEE7^
S[= DDDC
]^C JC C 04M= AC J('.:= $C $C Y)-.,*= AC $(:6)R&G2(M= HC 9C Y)L).(2= YC
"L,22) )-+ AC #,21)= PE :!&!.E3 ;7B7^ DW*= D]BC
]_C !C n)S)L).)= !C H4M03)V4= nC %L4.)-4 )-+ nC n)-(+)= ,+&"!S+*")$
]+&&E3 ;77B^ MD= bD;EC
]bC HC 9C #'41(-.= AC #,21)= YC "L,22)= HC #C O)6)22, )-+ 9C &241,= PE
:!&!.E3 BEE^^ *T*= _bDC
]EC %*.(24P45).4,-A| H(.8,+*= ()5.4,-* )-+ A>>'45).4,-* T: 9C @.(2)C
o4'(: J#Z=| o(4-8(41= DEEJ= D7D >>C
^7C OC #C ?(-,= PE :S+2E @*(-E3 BE_B^ MX= A;BbC
^BC 9C c41(-(M= 9C #,*.) )-+ YC #(26(2)= #$*E @$/E :S+2E T+%E BEb_^ DT=
BEbC
;]C cC AV4:)1)= C H).*0+)= ZC Y).,= HC !)V).) )-+ YC n4.)3)S)= A*5E
\!&+"E3 ;7BB^ DJ= D;E\C
;^C HC $4- Q,,= YC Z,24V(= !C Q0V0*841)= rC Z4/4V).)= rC n0L,.)= HC
!)V).) )-+ YC n4.)3)S)= X!.&)$ ,"!$%E3 ;7B;^ M*= BD_EBC
;_C YC T4*S)*= 9C a8)-3= aC $4= rC RrC $40= HC c2M:S)= $C Y0-= ?C J,'V1(2
)-+ &C J)- ?(2 J,,2.= X!.&)$ ,"!$%E ;7BD^ MD= \_D7C
;bC rC a)-3= 9C Y84= QC a8)-3= rC a8,-3 )-+ oC a80= :!&!.E <-'E ,+-S$).E3
;7BD^ J= ;7\\C
!84* /,02-)' 4* e !8( ,:)' Y,54(.: ,P #8(14*.2: ;7<<
PE >!2+C= ;7BD= EE= BRD d *J
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Catalysis Science & Technology
Page 14 of 15
View Article Online
DOI: 10.1039/D0CY00235F
A=><?@A
B(.-)%0 C%2&
^;C !C 9C Y584'+8)0(2= "C Z,(V= QC n)>.(4/- )-+ 9C AC H,0'4/-= A .E :!&!.E
A V+$E3 ;77E^ JSX= B\BC
^DC AC A'*)'1(= %C QC n,M8(6-4V,6) )-+ "C JC n,M8(6-4V,6= A .E :!&!.E
A V+$E3 ;77b^ JM[= B_7C
^\C TC C 9(21: )-+ AC &)-+02)-3)-= A .E :!&!.E A V+$E3 ;77]^ DXX=
;]C
^]C cC ?C r)+)6 )-+ HC TC !8).8)3)2= T+!-&E ^($-&E 6).U2E3 ;77;^ SD=
EEC
^^C C YC #,'(1)-= PE )= \+*E :S+2E3 BEE^^ J[= B7B7C
^_C "C J4',.4/(645 )-+ !C QC 9)14*,-= A$/+WE :S+2E #$&E @*E3 ;77E^ MX=
];]7C
^bC 9C c,2M:-*V4 Y14.8= <U$&S+%'%3 BEb\^ X= ^;EC
^EC %C 9C #,2(:= YC Y84L).) )-+ C nC T)V*84= PE Z"/E :S+2E3 BEbb^ SJ=
;b^BC
_7C rC RZC $40= XC RYC $40 )-+ aC RZC a8)-3= PE \).E :!&!.E A :S+2E3 ;77b^
D[T= \;C
_BC HC c04+,..4= C &*)2,=OC )6)*4,= HC Y3,LL)= QC #)2-4).,= #C T4*4,=
cC c)..4 )-+ $C H)258(*(= V"++$ :S+2E3 ;77E^ **= BB_DC
_;C @C H)V,.,= nC H,.,14.*0 )-+ "C r0*0V(= :S+2E ]+&&E3 BEb]^ *M=
__EC
_DC AC ?8)V*84-)1,,2.8:= HC A'6)2, )-+ ZC c)254)= :S+2E @("E PE
;7B7^ *T= b]D7C
_\C AC #C T0(-,= 9C AC c,-})'6(* )-+ %C JC c0*(6*V):)= A .E :!&!.E A
V+$E3 ;77_^ JD[= BC
_]C HC "C J,82)= ?C R9C $4= aC RcC c0 )-+ 9C a8)-3= >!$)%-!.+3 ;7B_^ [=
__D\C
_^C TC HC Y14.8 )-+ AC %C c2)8)1= ,+&"!S+*")$ ]+&&E3 ;77_^ MX= \bEBC
__C fC $4= aC c0,= #C f4),= !C oC c,8= ?C !(*P)3)L(2 )-+ oC Z0)-3= A:<
:!&!.E3 ;7B\^ M= D\E7C
_bC &C c)25I)Rc)25I)= HC H~''(2 )-+ AC #,21)= :S+2E <-'E3 ;7B\^ S=
;E_EC
_EC $C rC #8(-= ZC #8(-= C $0`0( )-+ rC o $4= :S+2E <-'E3 ;7B\^ S=
D_7bC
b7C cC #8(-= YC o0= ZC $40= ZC 94)-3 )-+ rC $4= V"++$ :S+2E3 ;7BD^ *S=
;D7C
bBC cC R9C #8(-= 9C RYC o)-3= QC RaC 94-= HC RrC $40= #C RoC a8),= rC RAC $4
)-+ rC RTC ?,-3= #$)"/E :S+2E3 ;7B^^ SS= D7]bC
b;C cC #)4 )-+ ZCR$C 94)-3= A$/+WE :S+2E3 #$&E @*C= ;7B_= ST= ]^DÄ]^_C
*M d PE >!2+C= ;7B;= EE= BRD
!84* /,02-)' 4* e !8( ,:)' Y,54(.: ,P #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

Page 15 of 15
Catalysis Science & Technology
Low-dimensional MOF-type catalysts containing Brønsted acid and redox active sites, based on assembled
1D organic-inorganic nanoribbons, for one-pot two-step reactions