Niobium oxide prepared through a novel supercritical-CO2-assisted method as a highly active heterogeneous catalyst for the synthesis of azoxybenzene from aniline

DOI: 10.1039/c9gc02623a

Source and publish data:

Green Chemistry p. 5852 - 5864 (2019)

Update date:2022-08-03

Topics:

Authors:

Tao, Yehan

Singh, Bhawan

Jindal, Vanshika

Tang, Zhenchen

Pescarmona, Paolo P.

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Article abstract of DOI:10.1039/c9gc02623a

High-surface area Nb₂O₅ nanoparticles were synthesised by a novel supercritical-CO₂-assisted method (Nb₂O₅-scCO₂) and were applied for the first time as a heterogeneous catalyst in the oxidative coupling of aniline to azoxybenzene using the environmentally friendly H₂O₂ as the oxidant. The application of scCO₂ in the synthesis of Nb₂O₅-scCO₂ catalyst resulted in a significantly enhanced catalytic activity compared to a reference catalyst prepared without scCO₂ (Nb₂O₅-Ref) or to commercial Nb₂O₅. Importantly, the Nb₂O₅-scCO₂ catalyst achieved an aniline conversion of 86% (stoichiometric maximum of 93% with the employed aniline-to-H₂O₂ ratio of 1?:?1.4) with an azoxybenzene selectivity of 92% and with 95% efficiency in H₂O₂ utilisation in 45 min without requiring external heating (the reaction is exothermic) and with an extremely low catalyst loading (weight ratio between the catalyst and substrate, R_c/s = 0.005). This performance largely surpasses that of any other heterogeneous catalyst previously reported for this reaction. Additionally, the Nb₂O₅ catalyst displayed high activity also for substituted anilines (e.g. methyl or ethyl-anilines and para-anisidine) and was reused in consecutive runs without any loss of activity. Characterisation by means of N₂-physisorption, XRD, FTIR and TEM allowed the correlation of the remarkable catalytic performance of Nb₂O₅-scCO₂ to its higher surface area and discrete nanoparticle morphology compared to the aggregated larger particles constituting the material prepared without scCO₂. A catalytic test in the presence of a radical scavenger proved that the reaction follows a radical pathway.

Full text of DOI:10.1039/c9gc02623a

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DOI: 10.1039/C9GC02623A

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.(*.*X )-4'4-(X .,7#.A.,'04+4-(X %$7 A.,'04+4-(X 0 , A.,'04+4-(X

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>(-R9')14-( N(2( 0*(+ )* *0>*.2).(*X )-4*,'( N)* 0*(+ )*

4-.(2-)' *.)-+)2+ :,2 3)* 6@2,1).,32)8@9 ;h#< )-)'9*4*X N@4'(

)a0(,0* O_CB_CN4.@ +4::(2(-. 6,-6(-.2).4,-* ;SF N._X CF N._X

_6V*b FDSD A -,-A-,>'( 1(.)' 6).)'9*. #0A#(B_CN)* 2(8,2.(+ .,

+4*8')9 @43@(2 )-4'4-( 6,-=(2*4,- )-+ )R,Q9>(-R(-( *('(6.4=4.9

6,18)2(+ ., .@( A3AdB_T6).)'9*. ):.(2 ^ @ N4.@ .@( *)1( _6V*X

)'>(4. 0*4-3 HF L# )* 2()6.4,- .(18(2).02(D^TT#,-.2,' .(*.*

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&'()*( +, -,. )+/0*. 1)234-*

Page 3 of 12

Green Chemistry

View Article Online

DOI: 10.1039/C9GC02623A

&'()*( +, -,. )+/0*. 1)234-*

Green Chemistry

Page 4 of 12

View Article Online

DOI: 10.1039/C9GC02623A

A<=;5>?

@"$*/+1 +%(

)=(2)34-3 ^` *6)-* N4.@ ) *8).4)' 2(*,'0.4,- ,: ` 61^ASD !@( .@( *,'0.4,- N)* )-)'9*(+ >9 h#D !@( 1,')2 )1,0-.* ,: )-4'4-(

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2(6,2+(+ 0*4-3 )- ('(6.2,- 1462,*6,8( #MSC ;&@4'48*<

,8(2).4-3 ). SCF P([D !@( *)18'(* N(2( 32,0-+X .@(-

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1462,*6,89 ;7%M< )-)'9*4* N)* 6)224(+ ,0. ,- ) &@4'48* I$TF

%7%M 1462,*6,8( ,8(2).4-3 ). CF P([D !@( 7%M *)18'(* N(2(

82(8)2(+ >9 324-+4-3 .@( 8,N+(2X +4*8(2*4-3 4. ,- ) 6)2>,-

.)8( )-+ *82)94-3 4. N4.@ 3,'+D %'(1(-.)' )-)'9*4* N)* 6)224(+

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:,2 .@( *('(6.4=4.9 )-+ 94('+ ,: 82,+06.* )-+ :,2 .@(

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&*<, <D "- ) .9846)' (Q8(241(-.X CF 11,' )-4'4-(X SF 11,'

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6).)'9*. N)* )++(+ )-+ .@( 2()6.4,- 14Q.02( N)* *.422(+ :,2 `H

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,- .@( )6.4=( *4.(* ,: .@( 6).)'9*. )-+ .@( 2()6.4,- 6,-+4.4,-*

;(D3D 8OX O_CB_C6,-6(-.2).4,-<D m-.4' -,NX G>_CB_H@)* >((-

)88'4(+ )* @(.(2,3(-(,0* 6).)'9*. 4- 1)-9 2()6.4,-*

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2(8,2.(+ .@). G>_CB_H82(8)2(+ >9 ) 1462,N)=(A)**4*.(+

@9+2,.@(21)' 1(.@,+ 6).)'9*(+ .@( ,Q4+).4,- ,: )-4'4-( N4.@

O_CB_C). CH L# N4.@ 8@(-9'@9+2,Q9')14-( )-+ -4.2,*,>(-R(-(

)* 1)4- 82,+06.*D^S`!, .@( >(*. ,: ,02 P-,N'(+3(X .@(

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6)2(:0''9 2(1,=(+ >9 848(..(D !@(-X 6)D `H 1$ (.@)-,' N)*

)++(+ ., .@( 6(-.24:03( .0>( )-+ .@( .0>( N)* *@)P(-

=43,2,0*'9D A:.(2N)2+*X .@( .0>( N)* 6(-.24:03(+ ). `HFF 281

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6)D `H 1$ :2(*@ (.@)-,' N)* )++(+D !@4* N)*@4-3 82,6(+02(

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G f E! 9 %$DX CFSCX AAX SAT

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&'()*( +, -,. )+/0*. 1)234-*

Green Chemistry

Page 5 of 12

View Article Online

DOI: 10.1039/C9GC02623A

@"$*/+1 +%(

A<=;5>?

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82(*(-6( ,: !%M&B ;S 1,'_ ., O_CB_C< )* 2)+46)' *6)=(-3(2D

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Green Chemistry

Page 6 of 12

View Article Online

DOI: 10.1039/C9GC02623A

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(Q@4>4.* ) *'43@.'9 @43@(2 *8(64:46 *02:)6( )2() 6,18)2(+ .,

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Green Chemistry

Page 7 of 12

View Article Online

DOI: 10.1039/C9GC02623A

@"$*/+1 +%(

A<=;5>?

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>(.N((- CFFFACHFF 61^AS82(*(-. 4- )'' .@2(( *8(6.201* )2( +0( ., )+*,28.4,- ,: #B_C

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6,18)2(+ ., .@( 6,11(264)' 6).)'9*.* +4*8')94-3 =(29 ',N

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!@( 629*.)''4-4.9 ,: *('(6.(+ 6).)'9*.* N)* (Q)14-(+ >9 I J

1()*02(1(-.D Z,.@ 8)..(2-* ,: G>_CB_HA*6#B_C)-+ G>_CB_HA (:

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)-+ HTLX 6,22(*8,-+4-3 ., .@( )1,28@,0* G>_CB_H*.206.02( .@).

6,-*4*.* ,: G>B_`.(.2)@(+2) )-+ G>B_^,6.)@(+2) ;c43D `<D^S`XHH

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Green Chemistry

Page 8 of 12

View Article Online

DOI: 10.1039/C9GC02623A

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Green Chemistry

Page 9 of 12

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DOI: 10.1039/C9GC02623A

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Page 12 of 12

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DOI: 10.1039/C9GC02623A

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