Thermally assisted photocatalytic conversion of CO2-H2O to C2H4 over carbon doped In2S3 nanosheets

Article abstract of DOI:10.1039/d0ta01256d

The development of an efficient photocatalyst for selective conversion of CO₂ to ethylene (C₂H₄) is highly desirable. Here, carbon-doped In₂S₃ nanosheet-based spheres (denoted as C-In₂S₃) are reported to be highly efficient for thermally assisted photocatalytic conversion of CO₂-H₂O to C₂H₄ at 150 °C without any cocatalysts or sacrificial agents. The total consumed electron number (TCEN) for CO₂ conversion over C-In₂S₃ can reach 472.7 μmol g^-1 h^-1. The selectivity and production rate of C₂H₄ over C-In₂S₃ are about 50% and 26.6 ± 4.1 μmol g^-1 h^-1, respectively, with a quantum efficiency of 13.3% at 420 nm. Meanwhile, no C₂H₄ can be detected over In₂S₃ without carbon doping. ¹³CO₂ and D₂O isotope labeling experiments confirm the carbon and hydrogen origins of C₂H₄. In situ experimental and theoretical studies reveal that carbon doping accelerates CO₂ adsorption and activation, lowering the energy barrier to form CH?, the key intermediate for C₂H₄, thus leading to high selectivity.

Full text of DOI:10.1039/d0ta01256d

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Materials Chemistry A
Materials for energy and sustainability
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C. Wang, M. Sun, Y. Yu and B. Zhang, J. Mater. Chem. A, 2020, DOI: 10.1039/D0TA01256D.
Volume
Number 12
March 2018
Pages 4883-5230
6
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accepted for publication.
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Journal of
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Materials for energy and sustainability
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ISSN 2050-7488
COMMUNICATION
Zhenhai Wen et al.
An electrochemically neutralized energy-assisted low-cost
acid-alkaline electrolyzer for energy-saving electrolysis
hydrogen generation
rsc.li/materials-a

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DOI: 10.1039/D0TA01256D
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HH+-7,.(7(2) 7+ D2)(E. 6+.)7-,67(+.) +8 6/-S+.AD+H(.E
:;:;> I!%J ?;=?;;:L/.(2=:;?K;[TT@=
6'29(6/0) F(/ :; k= ꢀ'2.> k= %= $= N/72-'+,)2> 3= 5'(> G=P'/+> P= M(> M= P= N,> ꢀ=
H'+7+6/7/04)7) 8+- )4.7'2)(](.E F/0,2A/DD2D ꢀ
:
7
'2-9/004 /))()72D H'+7+6/7/047(6 6+.F2-)(+. +8 ꢀ!
:
AV
:
!=
V= &,.E /.D &= P'/.E> A'H%L!ꢀ01%$!ꢀ7')!ꢀGK!3 :;?K> JYI?[U:\A
[UU?=
? I= M= M(,> ꢀ= V= N/.E> Q= a= Q,> O= V= P'/+> N= ꢀ= N/.E> Q= V= I,
.D O= P'/.E> 01%$3ꢀ:;?K> JI @[`A@\K=
?
:
:
!$<&6/7.ꢀ!<ꢀ6$7)#).7
/
&'2 /,7'+-) D260/-2 .+ 6+9H27(.E 8(./.6(/0 (.72-2)7=
:: P= 5,.> $= &/0-2*/> V= &/+> G= &2<72-> "= ",'02-> G= 57-,.X /.D
G= ꢀ'2.> A'H%L!ꢀ01%$!ꢀ7')!ꢀGK!3 :;?\> JMI [`?;A[`:[=
:
:
@ 5= N/.E> O= Q= k,/. /.D c= N= M+,> !ꢀA$!ꢀ01%$!ꢀ4.5!3ꢀ:;?\>
@*> U;@[AU;T;=
A/V$!,&)80)()$7.
+
T c= Q,> P= Q/.E> O= m(,> 5= k,+> C= Q/.E> O= Q,> V= P'/.E> Q= P'/+>
N2 /6X.+W02DE2 7'2 8(./.6(/0 ),HH+-7 8-+9 7'2 $/7(+./0
/7,-/0 56(2.62 a+,.D/7(+. +8 ꢀ'(./ Y$+= :?\[?:;` /.D $+=
?T::?;TZ /.D 7'2 $/7,-/0 56(2.62 a+,.D/7(+. +8 &(/.*(. ꢀ(74
Y$+= ?[GꢀGmGꢀTT[;;Z=
c= Q/.E> O= V/. /.D P= M(,> A'H%L!ꢀ01%$!ꢀ7')!ꢀGK!3ꢀ:;?K> JYI
$
`
@:A`@`=
:
:
:
U c= V+.E> G= p(9> 5= a= 5'(> Q= P'/.E> ꢀ= G(.> Q= 5,.> 5= &+.E/4> G=
N,> Q= P'/.E /.D a= N/.E> "#)!ꢀ"#'.)%51'.6!3ꢀ:;?T> ZI `\:A
`
\`=
` Q= N/.E> P= P'/.E> M= P'/.E> P= M,+> G= 5'2.> V= M(.> G= M+.E> G=
'
!7).ꢀ%$8ꢀ#)<)#)$/).
ꢀ= 5= N,> c= a,> c= N/.E /.D ꢀ= M(> !ꢀA$!ꢀ01%$!ꢀ4.5!3ꢀ:;?\>
?
"= 56'-2(2-> a= Vn-+E,20> M= 572(2-> 5= ꢁ'9/D> G= 5= M,72-S/6'2->
+
@*I ?TUKUA?TUK\=
"
= &= "/42-> G= M,+ /.D "= k-o7]20> "#)!ꢀG'%-H23 :;?[> >I
[;\[=
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;?U> >I :`?A:[\=
G= 3/.> "= G/-+.(26 /.D 5= P= m(/+> AK=!ꢀ 8#)%-!ꢀ :;?\> F*I
[;T`TK=
:
:
:
[ ꢀ= M(,> O= ꢀ= ꢀ+0q.> "= P(2)/6X> C= ꢁ= 5(0F2- /.D I= k= $+62-/>
5&%'5%3 :;?`> FJ>I ?:?;=
\ m= M,> Q= Q,> m= "/> O= ꢀ'2. /.D V= P'/.E>ꢀAK=!ꢀ8#)%-!3 :;?`>
YI ?K?[A?K@@=
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4
:
@
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>
K M= P'+.E> a= Q,> Q= ꢁ.> Q= P'/+> Q= 5,.> P= M(> &= M(.> Q= M(.> c= m(>
Q= I/(> M= k,> G= V,> 5= G(.> m= 5'2. /.D V= N/.E> "#)*-%3ꢀ:;?`>
JFYI \TA\[=
?
T
U
k= ꢁ= !](.> AK=!ꢀ8#)%-!ꢀ:;?U> >MI ?KU[A?K`@=
I= O= O,-X)> 5= I/F()> 3= N= M/9S> c= M(,> 3= 3= 3+D-(E,2)> $= C=
M(4/./E2> Q= 5,.> ꢀ= ^= N2S)72-> G= V= I206/9H /.D ^= &= C/H()'>
@
@
; c= P',> 5= G(/.E> ꢀ= M(> c= ꢀ'2. /.D ꢀ= Q/.E> 7'KꢀG'H!ꢀ01%$!ꢀM%(!3ꢀ
:
;?@> J>I ?T@``A?T@[U=
01%$!ꢀ0.$$*'!3ꢀ:;?\> J@I @\?KA@\::=
? c= O= P'/+> G= P= M(> C= &(/.> M= Q= N/.E> c= a= M(> 5= a= M(.> c= N=
`
p= M(> O= C2.E /.D &= C2.E> A04ꢀ0#)#6!3ꢀ:;?`> PI [T\UA[U:[[=
k,+ /.D P= "= M(,> A04ꢀ0#)#6!3ꢀ:;?K> ZI @;?[A@;:U=
@
B
!ꢀ"#$%=> :;?:> **> ?A@
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C02/)2 D+ .+7 /D*,)7 9/-E(.)

Page 5 of 6
J oC u0 2r n/ a) 2l oD f +M .a +t e7 r/i aD l* s, C) 7h 9e m/ -i Es t( .r y) A
View Article Online
DOI: 10.1039/D0TA01256D
!
"#$%&ꢀ'%()
ꢀ:=SSX'D:A2D='
@
@
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: C= &(/.> Q= c= N2(> "= Q2 /.D P= "= M(,> A04ꢀ0#)#6!3ꢀ:;?U> JI
K::A?K@\=
?
@ Q= k/+> M= $2/0> I= I(.E> N= N,> ꢀ= O/-+(> ꢁ= "= k/88.24 /.D a=
M(> A04ꢀ0#)#6!3ꢀ:;?K> ZI \UK:A\`:?=
T Q= C/-X> N= p(9> V= C/-X> &= &/6'(X/W/> &= "/*(9/ /.D N= ꢀ'+(>
A,,6!ꢀ0#)#6!ꢀNOꢀG'=&-.'!3ꢀ:;;K> Z+I @UUA@`?=
@
@
U a= ^= !)72-0+'> 01%$!ꢀ4.5!ꢀM%=!3ꢀ:;?@> @>I ::KTA:@:;=
` "= P'2.E> G= 5'(> &= Q,/. /.D c= N/.E> A'H%L!ꢀ01%$!ꢀ7')!ꢀGK!3ꢀ
:
;?\> JMI UT\[AUTK?=
[ ꢁ= %= G= G+)2H' /.D 5= &'(-(H,-/.7'/E/.> !ꢀ "#'.(5&ꢀ
#'.)%51'.6!3ꢀ:;?\> +YI @?U\A@?`T=
\ p= N/.E> m= M(> O= 5= M(,> O= ꢀ'2.E> N= p= V+ /.D G= k= Q,> A,,6!ꢀ
#)#6!ꢀNPG'=&-.'!3ꢀ:;?U> +MPI TTAU:=
K %= 5'+W.> 5= 5/9(-2DD(> Q= ꢀ= ꢀ'/.E> 3= C,7(X/9> C= V= ꢀ'/.E> ꢁ=
/SS/'> a= Q= a,> N= a= ꢀ'2.> ꢀ= %= N,> &= Q= Q,> C= N= ꢀ',.E> "=
= M(.> M= ꢀ= ꢀ'2. /.D p= V= ꢀ'2.> "#)!ꢀ0.$$*'!3ꢀ:;?\> ZI ?`K=
@
@
@
"
0
5
ꢀ
T; &= ^= I+402 /.D G= 3= I2..()+.> 912(!ꢀM%=!ꢀN3ꢀ?KKU> J+I?K`A:;;=
T? G= a,> O= P',> ꢀ= G(/.E> O= ꢀ'2.E> N= Q+, /.D G= Q,> 4$#663ꢀ:;?[>
+
FI ?`;@K@\=
T: p= ꢀ= C(00/(> d= Q= Q+,.E /.D G= != "= O+6X-()> A,,6!ꢀ4*-/!ꢀ45&!3ꢀ
K\@> +PI @::A@TT=
?
T@ I= ꢁ= I+W)> !ꢀ01%$!ꢀ912(!3ꢀ?K`:> FPI :\@@A:\@U=
TT k= a()6'2-> 3= ^= "(002-> C= a= d+'-/0(X /.D 3= != N/77)> !ꢀ01%$!ꢀ
9
12(!3ꢀ?K\U> YFI ?T[?A?T[[=
TU ꢀ= ꢀ= N/.E> C= P(20X2> != a= 5(E,-S*+-.))+.> ꢀ= 3= d(72-( /.D 3=
(E.+-200> !ꢀ912(!ꢀ01%$!ꢀA3ꢀ:;;K> ++FI ???:KA???@[=
5
T` 5= G= ꢀ0/-X> "= I= 52E/00> ꢀ= G= C(6X/-D> C= G= V/).(H> "= G= C-+S2-7>
p= 328)+. /.D "= ꢀ= C/4.2> Q!ꢀC-&()#66.H-!3ꢀ:;;U> >>*I U`[AU[;=
T[ ^= 3= "6$200() /.D G= "242-> p= 32,72-> 912(!ꢀM%=!ꢀN3ꢀ:;;K> Y*I
:
;UT?T=
T\ N= k/+> 3= k/+> Q= a= P'/+> "= C2.E> ꢀ= m= 5+.E> "= P= M(> 5= N=
M(> G= G= M(,> N= P= M(> Q= ꢀ= I2.E> "= &= P'/.E> G= M= c(2> k= V,> P=
5= P'/.E> 3= M+.E> c= I= N2. /.D I= "/> 01%$3ꢀ:;?\> @I :K?[A
:
K:\=
TK Q= N/.E> c= P', /.D Q= M(> !ꢀ912(!ꢀ01%$!ꢀD%))!3ꢀ:;?K> +*I T``@A
T``[=
U; ꢁ= ꢁ= C272-)+.> a= ꢁS(0DAC2D2-)2.> a= 57,D7> G= 3+))92()0 /.D G=
p= $r-)X+F> G'%-H2ꢀG'=&-.'!ꢀ45&!3ꢀ:;?;> FI ?@??A?@?U=
U? Q= G(/+> Q= P'2.E> C= ꢀ'2.> "= G/-+.(26 /.D 5= P= m(/+> !ꢀA$!ꢀ
0
1%$!ꢀ4.5!3ꢀ:;?[> +FZI ?\;K@A?\?;;=
U: V= %'/-/> V= ꢁS2> 5= ^.D+ /.D &= %-(2> 4.6&Kꢀ4)#)%ꢀ0.$$*'!3ꢀ?K[\>
YI U`@AU`U=
>
U@ "= c(.E> Q= P'+,> ꢀ= I+.E> M= ꢀ/(> M= P2.E> O= 5'2.> M= C/.> ꢀ=
I+.E> Q= ꢀ'/(> G= P'/.E /.D Q= Q(.> "#'.ꢀD%))!3 :;?\> +YI @@\TA
@
@K;=
UT ꢀ= I+.E> ꢀ= M(/.> 5= V,> P= I2.E> G= k+.E> "= M(> V= M(,> "= c(.E
.D G= P'/.E> "#)!ꢀ0.$$*'!3 :;?\>ꢀZI ?:U:=
/
UU c= 5+.E> I= V2> N= M(> P= p2> G= M(,> ꢀ= &/.E> M= ꢀ'2.E> ꢀ= G(/.E> P=
N/.E /.D c= c(/+> A'H%L!ꢀ01%$!ꢀ7')!ꢀGK!3 :;?K> JYI ?```;A
?
```[=
U` 5= ꢀ'2.> V= N/.E> P= p/.E> 5= G(.> c= P'/.E> c= P'2.E> P= m(> G=
P',> O= C/. /.D Q= c(2> "#)!ꢀ0.$$*'!3 :;?K> +*I [\\=
U[ G= N/.E> &= c(/> M= N/.E> c= P'2.E> P= m(> ꢀ= k/+> G= P',> P= m= M(>
V= c, /.D Q= c(+.E> A'H%L!ꢀ01%$!ꢀ7')!ꢀGK!3 :;?\> JMI ?`TT[A
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C02/)2 D+ .+7 /D*,)7 9/-E(.)

Journal of Materials Chemistry A
Page 6 of 6
View Article Online
DOI: 10.1039/D0TA01256D
Table of contents
Thermally-Assisted Photocatalytic Conversion of CO -H O to C H over
2
2
2 4
Carbon Doped In S Nanosheets
2
3
a
a
a
a
a
Lei Wang,‡ Bohang Zhao,‡ Changhong Wang, Mengyao Sun, Yifu Yu and Bin
Zhang*ab
H2
CO
CH4
C
1
1
1
80
50
20
C H
C H
2
4
2
6
In
S
9
6
3
0
0
0
0
In S
C-In S3
2
3
2
Carbon-doped In S (C-In S ) is a highly efficient photocatalyst for selectively
2
3
2 3
converting CO -H O to C H at 150 °C without any sacrificial agents or cocatalysts.
2
2
2 4
The carbon doping can enhance water adsorption/dissociation and CO activation,
2
and decrease energy barriers of forming hydrocarbon intermediates for C H , thus
2
4
resulting in high selectivity of C H .
2
4