Photocatalytic one-pot multidirectional N-alkylation over Pt/D-TiO2/Ti3C2: Ti3C2-based short-range directional charge transmission

Article abstract of DOI:10.1002/aoc.6291

Visible-light-induced one-pot, multistep, and chemoselectivity adjustable reactions highlight the economical, sustainable, and green process. Herein, we report Pt nanoparticles dispersed on S and N co-doped titanium dioxide/titanium carbide (MXene) (3%Pt/

Full text of DOI:10.1002/aoc.6291

Received: 6 January 2021
DOI: 10.1002/aoc.6291
Revised: 15 April 2021
Accepted: 29 April 2021
F U L L P A P E R
Photocatalytic one-pot multidirectional N-alkylation over
Pt/D-TiO /Ti C : Ti C -based short-range directional charge
2
3 2
3 2
transmission
Heyan Jiang
| Meilin Sheng
| Yue Li
| Shuzhen Kong
| Fengxia Bian
Key Laboratory of Catalysis Science and
Technology of Chongqing Education
Commission, Chongqing Key Laboratory
of Catalysis and New Environmental
Materials, College of Environmental and
Resources, Chongqing Technology and
Business University, Chongqing, China
Visible-light-induced one-pot, multistep, and chemoselectivity adjustable reac-
tions highlight the economical, sustainable, and green process. Herein, we
report Pt nanoparticles dispersed on S and N co-doped titanium dioxide/tita-
nium carbide (MXene) (3%Pt/D-TiO /Ti C ) heterojunctions as photocatalysts
2 3 2
for the tandem reactions between aromatic nitro compounds and alcohols to
produce N-alkylated products. 3%Pt/D-TiO /Ti C heterojunction was pre-
2
3 2
Correspondence
Heyan Jiang, PhD, and Fengxia Bian, Key
Laboratory of Catalysis Science and
Technology of Chongqing Education
Commission, Chongqing Key Laboratory of
Catalysis and New Environmental Materials,
College of Environmental and Resources,
Chongqing Technology and Business
University, Chongqing 400067, China.
Email: orgjiang@163.com;
pared by in situ grew TiO on Ti C nanosheets, S and N co-doped TiO with
2 3 2 2
thiourea, and then Pt nanoparticles with 2.9 nm average diameter well dis-
persed on D-TiO /Ti C . 3%Pt/D-TiO /Ti C showed excellent activity and
2
3
2
2
3 2
chemoselectivity to N-alkyl amines in the presence of base additive K PO
3
4
under visible-light irradiation; interestingly the chemoselectivity almost
completely switched to N-benzylideneanilines in the presence of base additive
KOH. In comparison, Pt nanoparticles on S and N co-doped TiO prepared
2
bianqian1201@163.com
from titanium carbide (3%Pt/D-TiO @C) showed sharply decreased activity
2
Funding information
and chemoselectivity to N-alkyl amines or N-benzylideneanilines. The
Chongqing Key Laboratory of Catalysis
and New Environmental Materials, Grant/
Award Number: KFJJ2019082; Innovation
Group of New Technologies for Industrial
Pollution Control of Chongqing Education
Commission, Grant/Award Number:
CXQT19023; Key Disciplines of Chemical
Engineering and Technology in
enhanced performance of 3%Pt/D-TiO /Ti C should be attributed to the
2
3 2
improvement in photogenerated electron and hole separation efficiency by
means of charge short-range directional transmission caused by the intimate
contact between the TiO and the conductive Ti C . In situ DRIFTS spectra
2
3 2
further verified that the substrates activation with visible-light irradiation at
ꢀ
25 C was much faster than heating.
Chongqing Colleges and Universities
during the 13th Five Year Plan; Ministry
of Education of Chongqing, Grant/Award
Number: KJQN201900811; Natural
Science Foundation Project of Chongqing,
Grant/Award Numbers:
K E Y W O R D S
MXene, one-pot N-alkylation, photocatalysis, short-range charge transmission, titanium
dioxide
cstc2015jcyjBX0031, cstc2019jcyj-
msxmX0641, cstc2018jcyjAX0735;
Chongqing Technology and Business
University, Grant/Award Number:
9
50119090; National Natural Science
Foundation of China, Grant/Award Number:
1201184; Venture & Innovation Support
2
Program for Chongqing Overseas Returnees,
Grant/Award Number: cx2020113
Appl Organomet Chem. 2021;e6291.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.6291

2
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JIANG ET AL.
1
| INTRODUCTION
(3%Pt/D-TiO /Ti C ) heterojunctions as photocatalysts
2
3 2
for the tandem reactions between aromatic nitro com-
pounds and alcohols to synthesize N-alkylated products;
3%Pt/D-TiO /Ti C heterojunction was prepared by in
Seeking an alternative clean, safer, and more
environment-friendly technology is one of the most
important goals in chemistry.
2
3 2
[1–5]
One-pot tandem/cas-
situ grew TiO on Ti C nanosheets, S and N co-doped
2 3 2
cade reactions typically require multifunctional catalysts
with different catalytically active sites in a site-isolated
way to keep their independent function, provide great
advantage, and spur extensive research interest by simpli-
fying the multistep reaction catalysis process into a single
synthesis operation without having to isolate the interme-
TiO with thiourea, and then Pt nanoparticles with small
2
diameter well dispersed on D-TiO /Ti C ; 3%Pt/D-TiO /
2
3
2
2
Ti C showed excellent activity and chemoselectivity to
3
2
N-alkyl amines in the presence of base additive K PO
3
4
with visible-light irradiation; interestingly, the
chemoselectivity almost completely switched to N-
benzylideneanilines by simply changing the base additive
to KOH. In contrast, Pt nanoparticles dispersed on S and
[6–10]
diate.
Two-dimensional materials have been widely
investigated in different applications due to their unusual
[11–13]
electronic, mechanical, and optical properties.
emerging 2D transition metal carbide/carbonitride family
MXenes), with general formula Mn + 1X T (n = 1, 2, 3;
The
N co-doped TiO prepared from titanium carbide (3%Pt/
2
D-TiO @C) showed sharply decreased activity and
2
(
chemoselectivity
to
N-alkyl
amines
or
N-
n
x
Tx = OH, O, F group), has been extensively studied dur-
benzylideneanilines. The enhanced performance of 3%Pt/
D-TiO /Ti C was owing to the improvement in
ing the past few years due to its excellent structure and
2
3 2
[14–19]
chemical properties.
MXene's excellent electron
photogenerated electron and hole separation efficiency
by means of a short-range directional charge transmis-
sion caused by the intimate contact between the TiO2
and the conductive Ti C . This investigation established
conductivity makes it easier to transfer charge from the
semiconductor to MXene, thereby improving the separa-
tion efficiency of electron and hole, thus achieving direc-
3
2
[20,21]
tional charge transmission.
With the above special
an efficient way to realize N-alkyl amines and N-
benzylideneanilines from aromatic nitro compounds, and
alcohols, moreover, shed some light on the great possibil-
ity of multifunctional catalysis construction in a broad
range of light-induced organic synthesis.
characteristics, MXene is considered as one of the most
promising catalytic material.
N-alkyl products are essential fabricating squares in the
construction of agrochemicals, drugs, and bioactive mole-
cules. Methods such as substitution, addition, cycloaddi-
tion, and cross-coupling have been developed to synthesize
[
22–28]
such intermediates.
Homogeneous Ru and Ir cata-
2 | RESULTS AND DISCUSSION
[
24,25]
lysts along with heterogeneous metal nanoparticles
have been used to N-alkylation reaction to amines.
[26,27]
The X-ray diffraction (XRD) patterns of all prepared cata-
lytic materials were employed to characterize the crystal
phase and phase purity in Figures 1 and S1. Consistent
Using light to drive chemical reactions is very attractive;
various nanometal composite photocatalysts have been
developed to achieve N-alkylation by photocatalytic dehy-
drogenation of alcohols to synthesis of aldehydes and then
[
29–35]
hydrogenation of imines in recent years.
et al.
Shiraishi
[29]
focused on the N-alkylation of primary amines
with alcohols catalyzed by Pd/TiO under photoirradiation
2
and discovered that the catalytic efficiency decidedly
[30]
depended on the size of Pd particles. Zhang et al.
described Cu-Mo/TiO2 catalyzed N-alkylation between
amines and alcohols under UV illumination with ambient
temperature, which was particularly suitable for the alkyl-
ation of anilines with halogen. Not long ago, Wang
[32–34]
et al.
loaded metal nanoparticles onto the outside or
into the pores of certain support materials to form
multifunctional catalysts (Pd/ZnIn S , PdNPs@MIL-100
2
4
(Fe) and PdAu@MIL-100(Fe)) for visible-light-prompted
N-alkyl amines synthesis from alcohols and amines with
excellent catalytic activity and chemoselectivity.
Herein, we report Pt nanoparticles dispersed on S and
N co-doped titanium dioxide/titanium carbide (MXene)
FIGURE 1 X-ray diffraction (XRD) patterns of TiO /Ti C , D-
2
3
2
TiO
2
/Ti
3
C
2
, 3%Pt/D-TiO
2
/Ti
3
C
2
, D-TiO
2
@C and 3%Pt/D-TiO
2
@C

JIANG ET AL.
3 of 12
[
36,37]
with the literature,
the layered TiO /Ti C hetero-
indicating that thiourea has been completely
2
3 2
[
40–42]
junction was successfully prepared on the layered Ti C2
decomposed.
Further loading of the metal Pt, no
3
nanosheets by hydrothermal oxidation. The coexistence
of the peak of anatase TiO and the peak of Ti C indi-
significant Ti C2 peak shift was observed in 3%Pt/D-
3
TiO /Ti C , indicating that the loading of the Pt NPs did
2
3
2
2
3 2
cated successfully partial oxidation of Ti C
not change the structure of D-TiO /Ti C . Meanwhile,
2 3 2
the XRD spectrum of 3%Pt/D-TiO /Ti C had no obvious
2 3 2
3
2
[36,37]
nanosheets.
After TiO /Ti C was N and S doped
2
3
2
with thiourea (D-TiO /Ti C ), the Ti C peak intensity in
diffraction peak of Pt, indicating the small Pt NPs were
well dispersed on D-TiO /Ti C . On the other hand, no
2
3
2
3 2
D-TiO /Ti C was further weakened in comparison with
2
3
2
2
3 2
the precursor TiO /Ti C ; meanwhile, the (002) diffrac-
characteristic peak of Ti C was detected in D-TiO @C.
3 2 2
2
3
2
tion peak of Ti C in D-TiO /Ti C shifted to a lower
Similar to the phenomenon in the 3%Pt/D-TiO /Ti C
2 3 2
3
2
2
3
2
angle, indicating that two-dimensional material struc-
tural expansion happened during the N and S dop-
catalyst, the thiourea doping did not change the lattice
morphology of anatase TiO in D-TiO @C and small Pt
2
2
[14,38]
ing.
The thiourea doping did not change the lattice
NPs were well dispersed on D-TiO @C.
2
morphology of anatase TiO . Except for the diffraction
In the Fourier transform infrared (FTIR) spectrum
(Figure S2), all Ti C T derived TiO /Ti C , D-TiO /
2
peak of TiO , there was no other impurity phase. This
2
3
2
x
2
3
2
2
indicated that N and S dopant atoms were directly incor-
Ti C , 3%Pt/D-TiO /Ti C , D-TiO @C, and 3%Pt/D-
3 2 2 3 2 2
À1
porated into the crystal lattice of TiO and did not form
TiO @C exhibited a broad band in 400–800 cm , which
2
2
[
39–42]
related compounds or other precipitation phase.
should be owing to the characteristic of Ti–O–Ti. With
Meanwhile, no diffraction peak of thiourea was observed,
the doping of TiO /Ti C or TiO @C and then the
2
3
2
2
FIGURE 2 Scanning electron microscope
(
SEM) images of (a) Ti
transmission electron microscopy (TEM) image
c) and corresponding mean diameter (e), high-
3 2 2 3 2
C and (b) TiO /Ti C .
(
resolution TEM (HRTEM) image (d), and TEM
image after three consecutive recycles (f) of 3%
2 3 2
Pt/D-TiO /Ti C

4
of 12
JIANG ET AL.
loading of the metal Pt, the vibration of Ti–O–Ti grad Àu 1-
ally enhanced. Another absorption at 1600–1700 cm
was the hydroxyl group bending vibrations, and the
intensity of the hydroxyl group bending vibrations peak
became stronger from TiO /Ti C to D-TiO /Ti C and
effectively encapsulated by D-TiO . After Pt loading and
2
reduction to nanoparticles (Figure S3c), 3%Pt/D-TiO2/
Ti C almost maintained the feature as observed in D-
3
2
TiO /Ti C as a consequence of the Ti C support. How-
2
3
2
3 2
ever, in the absence of Ti C support, no obvious stacked
2
3
2
2
3
2
3 2
then to 3%Pt/D-TiO /Ti C or from D-TiO @C to 3%Pt/
layers were observed in 3%Pt/D-TiO @C (Figure S4).
2
3
2
2
2
D-TiO @C. This demonstrated the doping of S and N
Energy dispersive X-ray spectroscopy spectra (EDS) and
corresponding mapping for 3%Pt/D-TiO /Ti C were dis-
played in Figure S3d and S2e. O, S, Ti, Pt, and N could be
evidently observed, and these elements exist together uni-
formly in the sample proving the successful doping of N
2
could introduce additional hydroxyl group to the 2D cata-
lytic material surface, which would play crucial role in
the subsequent photocatalytic organic transformation.
Figure 2a is scanning electron microscope (SEM)
image of Ti C with characteristics of many stacked layers.
2
3 2
and S to TiO . The Brunauer–Emmett–Teller (BET) sur-
3
2
2
The TiO nanocrystals could grow on the Ti C surfaces
face areas of Ti C , D-TiO /Ti C , and 3%Pt/D-TiO /Ti C
2
3
2
3
2
2
3
2
2
3 2
2
À1
during the oxidation process of hydrothermal treatment at
were 1.17, 12.60, and 9.45 m Ág , respectively. The D-
ꢀ
[37]
1
60 C (Figure 2b).
After hydrothermal oxidation treat-
TiO /Ti C specific surface area was more than tenfold of
2
3 2
ment and thiourea doping, the surface of the D-TiO /Ti C
Ti C through the formation of S and N co-doped TiO
2
2
3
2
3
2
became rougher and the stacked layers became thicker
Figure S3a and S3b), indicating that 2D Ti C2 was
nanocrystals. After Pt NPs loading, the specific surface
area obviously decreased.
(
3
FIGURE 3 X-ray photoelectron spectroscopy
(
(
(
2 3 2
XPS) spectra of 3%Pt/D-TiO /Ti C : (a) full scan,
b) Pt 4f, (c) Ti 2p, (d) O 1s, (e) C 1s, (f) N 1s, and
g) S 2p

JIANG ET AL.
5 of 12
Detailed characteristics of Pt NPs on D-TiO /Ti C
of D-TiO /Ti C , D-TiO @C, 3%Pt/D-TiO /Ti C , and 3%
2
3
2
2
3
2
2
2
3 2
were analyzed by transmission electron microscopy
TEM). Figure 2c is the TEM image of 3%Pt/D-TiO2/
Ti C , which clearly showed that Pt nanoparticles with
Pt/D-TiO @C samples was characterized by ultraviolet–
2
(
visible (UV-vis) absorption spectroscopy in Figure 4. In
general, the light absorbance of D-TiO @C and 3%Pt/D-
3
2
2
the average particle diameter of 2.9 nm were uniformly
dispersed on D-TiO /Ti C . Although the surface of most
TiO @C in visible-light region was weaker than D-TiO /
2
2
Ti C and 3%Pt/D-TiO /Ti C . The absorption of 3%Pt/D-
2
3
2
3
2
2
3 2
Ti C was covered by TiO and Pt metal NPs after TiO
TiO /Ti C after Pt NPs loading was increased compared
2 3 2
3
2
2
2
growth and Pt metal NPs loading, lattice fringes of Pt
with material D-TiO /Ti C ; however, in comparison
2 3 2
with D-TiO @C, the 3%Pt/D-TiO @C light absorption
2 2
[
14]
NPs (0.23 nm), TiO (0.35 nm), and Ti C (0.27 nm)
2
3
2
were simultaneously observed in high resolution electron
micrographs (Figure 2d). This ensured that these Pt NPs,
TiO nanocrystals, and Ti C would be sufficiently con-
decreased. Band gaps were calculated with the Kubelka–
Munk method. TiO /Ti C , D-TiO /Ti C , D-TiO @C, 3%
2
3
2
2
3
2
2
Pt/D-TiO /Ti C , and 3%Pt/D-TiO @C band gaps were
2
3
2
2
3
2
2
tacted by the reactants and acted as active centers in the
photocatalytic reaction.
around 2.80, 2.59, 2.95, 2.50, and 2.93 eV, respectively.
Obviously, TiO /Ti C formation, S and N co-doping as
2
3 2
The X-ray photoelectron spectroscopy (XPS) charac-
terization was employed to elucidate the nature of 3%Pt/
D-TiO /Ti C . XPS analysis identified the presence of
well as Pt nanoparticles loading were all conducive to the
band gap reduction.
Photocurrent generation and electrochemical imped-
ance spectroscopy were implemented to evaluate the
charge separation and transfer efficiency of D-TiO2/
Ti C , D-TiO @C, 3%Pt/D-TiO /Ti C , and 3%Pt/D-
2
3 2
platinum, titanium, oxygen, carbon, nitrogen, and sulfur
in 3%Pt/D-TiO /Ti C (Figure 3a), which signified the
2
3 2
target heterojunction successfully formed. Pt 4f were dec-
onvoluted into two species; binding energies 71.1 and
3
2
2
2
3 2
TiO @C. Figure 5a is a transient photocurrent graph of
2
7
7
4.5 eV were the 4f7/2 and 4f5/2 peaks of metallic Pt;
2.6 and 75.8 eV were the 4f7/2 and 4f5/2 peaks of
photocatalysts on ITO electrode with visible-light illumi-
nation. The photocurrent response of the D-TiO /Ti C ,
D-TiO @C, 3%Pt/D-TiO /Ti C , and 3%Pt/D-TiO @C
2 2 3 2 2
2
3 2
[43,44]
Pt(II) (Figure 3b).
This suggested that metallic Pt
was the main species along with the existence of a small
amount of Pt(II), which might be brought about by the
evident metal support interaction that promoted the elec-
electrodes was rapid, stable, and repeatable during light-
ing on/off cycles. D-TiO /Ti C with visible light
2
3 2
exhibited improved photocurrent than D-TiO @C, indi-
2
[44,45]
tron transfer from Pt to TiO2.
The spectrum of the Ti
cating the positive synergy between D-TiO and Ti C .
2
3 2
2
p region of 3%Pt/D-TiO /Ti C catalyst was shown in
The fact Ti C acting as a transporter for electrons to
3 2
2
3
2
Figure 3c. The binding energy 458.8 and 464.3 eV of Ti
p in doped catalyst shifted negatively compared with
inhibit the backward diffusion of electrons significantly
improved the separation efficiency of photo-induced
charge carriers ; 3%Pt/D-TiO /Ti C had higher photo-
2 3 2
2
[
37]
TiO . The peak that migrated to lower binding energy
2
might be due to that doping resulted in the formation of
current than that of D-TiO /Ti C , which further
2 3 2
Ti–O–S, O–Ti–N, and O–Ti–S bands in the crystal lat-
[
44,46]
tice.
XPS spectrum of O 1s (Figure 3d) could be dec-
onvoluted into two oxygen components, including
[
39]
5
1
30.2 eV from Ti–O–Ti and 531.9 eV from Ti–OH.
C
s in Figure 3e could be fitted to three peaks at 284.8 eV
(
C–C bond); 286.5 eV, which was assigned to the C–O
[47]
bond ; and 288.2 eV, which was assigned to Ti–O–C
because of the substitution of carbon atoms into titanium
lattice and was also detected in some other Ti AlC deriv-
3
2
[48,49]
ative materials.
XPS spectra of N 1s in Figure 3f
could be fitted to two peaks at 399.5 and 405.1 eV;
3
99.5 eV should be owing to the existence of lattice oxy-
[50]
gen replaced by N atom (O–Ti–N).
resolution spectrum resulted in one peak centered at
The S 2p high-
2
À
1
63.8 eV (Figure 3g), which should be the S species,
2À
comparable with the S-doping in TiO with O
substituted by S
2
2
À [46]
.
In order to clarify the intrinsic reason for the excel-
lent performance of 3%Pt/D-TiO /Ti C , light-harvesting
FIGURE 4 Ultraviolet–visible (UV-vis) absorption spectra of
2
3
2
D-TiO /Ti C , D-TiO @C, 3%Pt/D-TiO /Ti C , and 3%Pt/D-
2
3
2
2
2
3 2
capability was conducted. The light absorption capacity
TiO
2
@C

6
of 12
JIANG ET AL.
FIGURE 5 Transient photocurrent
responses (a) and electrochemical
impedance spectroscopy (b) of D-TiO
Ti , D-TiO @C, 3%Pt/D-TiO /Ti
and 3%Pt/D-TiO @C
2
/
,
3
C
2
2
2
3
C
2
2
indicated that the introduction of strong electron
accepting Pt NPs to D-TiO /Ti C could accelerate the
further investigated the promotion of catalytic reactions
by other bases or salts (Table 1, entries 7–13). With the
carbonate additive, the chemoselectivity to E1 was
sharply decreased accompany with moderate activity;
interestingly, with the alkali metal hydroxide additive,
the chemoselectivity almost completely switched to D1
with good to excellent catalytic activity; moreover, with
other additives like CH COONa or CaCl , both the activ-
2
3 2
separation efficiency of photogenerated electrons and
holes. Smaller radius of the arc in the electrochemical
impedance spectrum represent smaller electron transfer
resistance on the surface of photoelectrode, which as a
rule brings about more efficient separation of
photoelectron-hole pairs as well as speedier interfacial
charge transfer. In Figure 5b, the circular segment span
of the electrical impedance spectroscopy (EIS) Nyquist
curve of 3%Pt/D-TiO /Ti C and 3%Pt/D-TiO @C were
3
2
ity and the chemoselectivity were rather low. Considering
catalytic activity and chemoselectivity were always very
sensitive to the solvent used in heterogeneous
2
3
2
2
[
51–53]
smaller than the radius arc of D-TiO /Ti C and D-
catalysis,
different solvents were investigated
2
3 2
TiO @C, which represented that the resistance of the
(Table 1, entries 14–16). Only aniline was detected with
2
interface charge transfer from the electrode to the electro-
lyte molecule was in the order of 3%Pt/D-TiO2/
Ti C < 3%Pt/D-TiO @C < D-TiO /Ti C < D-TiO @C.
DMF instead of acetonitrile, just 9% E1 was obtained
when acetonitrile was replaced with H O. The
2
chemoselectivity to E1 was substantially maintained with
significantly reduced reactivity when benzyl alcohol dis-
placed acetonitrile.
3
2
2
2
3
2
2
These results of the electrochemical impedance spectros-
copy echo the law of the photocurrent test.
The as-prepared 3%Pt/D-TiO /Ti C catalyst was used
In order to acquire a deeper understanding of the role
of light in the reaction, we investigated the effect of wave-
length on one-pot hydrogenation and N-alkylation. The
catalytic activity was generally maintained with the irra-
diation of UV, white or green LEDs (Table 1, entries 17–
19). However, the chemoselectivity of E1 was signifi-
cantly decreased to 46.3% with UV. The catalytic reaction
gave 82.2% E1 chemoselectivity under the irradiation of
green LED. In comparison with 3%Pt/D-TiO /Ti C, 3%
2
3 2
for one-pot hydrogenation and N-alkylation of nitro com-
pounds and alcohols with visible light. Nitrobenzene and
benzyl alcohol were chosen as the substrates to test the
catalytic performance in Table 1. No product was
detected in the absence of catalyst or without metal Pt
(
Table 1, entries 1 and 2). In the absence of base additive,
hydrogenation and N-alkylation of nitrobenzene were
only converted 36.0% with 9.0% chemoselectivity to N-
benzylideneaniline (D1) and 10.0% chemoselectivity to N-
benzylaniline (E1) (Table 1, entry 3). In the presence of
base additive K PO , hydrogenation and N-alkylation
2
3
Pt/D-TiO @C exhibited lower photocatalytic activity
2
accompanied with decreased chemoselectivity (60.0%) to
E1 with K PO and 75.5% chemoselectivity to D1 with
3
4
3
4
reaction could reach 100% conversion with up to 93.0%
KOH (Table 1, entries 20 and 21). The above results indi-
cated that the combination of Ti C, TiO , and Pt NPs
chemoselectivity to E1 (Table 1, entry 4). When H was
2
3
2
substituted by N , hydrogenation and N-alkylation reac-
together to form heterojunction, with Ti C acting as a
2
3
tion could also be carried out, but the catalytic activity
decreased (Table 1, entry 5). This should be attributed to
the fact that dissociated hydrogen could be easily formed
transporter for electrons to inhibit the backward diffusion
of electrons, significantly improved nitrobenzene and
benzyl alcohol one-pot hydrogenation and N-alkylation.
The 3%Pt/D-TiO /Ti C catalyst could be recovered by
on the surface of Pt NPs with H to accelerate the reduc-
2
2
3 2
tion reaction. The one-pot hydrogenation and N-
alkylation reaction could not be carried out without
simple centrifugation and acetonitrile washing followed
by vacuum drying. No significant photocatalytic activity
and chemoselectivity decrease was observed after
recycling for five times in Figure 6. Additionally, no Pt
visible-light irradiation (Table 1, entry 6). Because K PO4
3
played an important role to promote the reaction, we

JIANG ET AL.
7 of 12
TABLE 1 Visible-light-induced catalytic performance for one-pot hydrogenation and N-alkylation of nitrobenzene with benzyl alcohol
over Pt nanoparticles on N and S co-doped TiO
2
/MXene Ti
3
C
2
heterojunctions
Entry
Catalyst
A1 conv. (%)
-
C1 sel. (%)
D1 sel. (%)
E1 sel. (%)
F (μmol)
1
2
-
-
-
-
-
-
-
-
D-TiO
2
/Ti
3
C
-
-
a
3
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
3%Pt/D-TiO
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
/Ti
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
36.0
100.0
30.6
-
81.0
0.1
6.6
-
9.0
6.9
17.4
-
10.0
51
95
117
-
b
4
93.0
c
5
76.0
-
d
6
e
7
70.2
75.0
96.7
81.0
29.0
17.6
7.2
23.1
16.2
1.2
5.4
0.5
25.0
6.2
100.0
91.0
-
12.0
72.0
35.1
11.8
3.8
75
85
86
80
78
62
29
64
91
153
97
86
90
89
93
f
8
g
h
9
95.0
i
1
1
1
1
1
1
1
1
1
1
2
2
0
1
2
3
4
5
6
7
8
9
0
1
89.5
13.6
68.2
0.3
5.1
j
15.0
6.8
k
l
0.7
m
n
o
p
q
r
100.0
100.0
12.4
95.5
90.0
83.6
75.5
80.2
-
-
-
9.0
15.4
18.8
12.3
18.2
25.8
75.5
84.6
46.3
82.2
71.0
60.0
24.5
34.9
5.5
10.8
14.2
-
@C
@C
g
Note: Reaction conditions: nitrobenzene (0.5 mmol), K
3
PO
4
(0.5 mmol), and solvent (benzyl alcohol 1 ml, acetonitrile 4 ml) were stirred magnetically under H
/MXene Ti heterojunctions catalysts (substrate: Pt = 300) for 24 h, TiO /Ti
thiourea = 1:1 during the doping, 0.75 W cm blue LED (460 nm), “-” = no product or negligible product.
2
(
1 atm) in a reaction tube in the presence of Pt NPs on N, S co-doped TiO
2
3
C
2
2
3 2
C :
À2
a
No K
3
PO
4
.
b
À1
TOF based on 10 h yield was 13.5 h
.
c
N
2
instead of H
Dark.
CO
CO
KOH instead of K
2
.
d
e
K
2
3
instead of K
instead of K
PO
TOF based on 10 h yield was 19.8 h
3
PO
4
.
f
Cs
2
3
3
PO
4
.
g
3
4
.
h
À1
.
i
NaOH instead of K
3
PO
PO
4
.
j
LiOH instead of K
3
4
.
k
l
CH
3
COONa instead of K
instead of K PO
DMF instead of acetonitrile.
O instead of acetonitrile.
3 4
PO .
CaCl
2
3
4
.
m
n
H
2
o
Benzyl alcohol instead of acetonitrile.
p
q
r
UV LED (400 nm).
White LED.
Green LED (517 nm).

8
of 12
JIANG ET AL.
For the electron-withdrawing group substituted nitroben-
zene, the steric hindrance on the aromatic ring also had a
significant effect on the catalytic activity (Table 2, entries
13and 14 vs. 15 and 16). Similar to the law of catalytic
reactivity, substrates with electron-donating groups
tended to be lower than substrates with electron-
withdrawing groups in the chemoselectivity of one-pot
hydrogenation and N-alkylation (Table 2, entries 13–16).
On the other hand, the steric hindrance had a significant
effect on the chemoselectivity, and the ortho-substituted
nitrobenzenes had overall lower chemoselectivity to
corresponding N-alkylamines or N-benzylideneanilines
(
Table 2, entries 3 and 4, 9 and 10, and 13 and 14).
Various benzyl alcohols could react with nitrobenzene
to synthesis corresponding N-alkylamines or N-
benzylideneanilines with good to excellent catalytic
performance over 3%Pt/D-TiO /Ti C (Table 2, entries 19–
FIGURE 6 Cycling visible-light-induced one-pot
hydrogenation and N-alkylation of nitrobenzene with benzyl
2
3
alcohol over 3%Pt/D-TiO
2
/Ti
3
C
2
in the presence of K
3
PO
4
or KOH.
for the
2
4). The one-pot hydrogenation and N-alkylation activity
The reaction conditions were the same as in Table 1, K
synthesis of E1, KOH for the synthesis of D1
3
PO
4
of the substituted benzyl alcohols was universally
maintained, but the chemoselectivity was generally
decreased (Table 2, entries 19–24). It is worth mentioning
that 91.0% chemoselectivity to N-alkylamine and 93.4%
chemoselectivity to N-benzylideneaniline were achieved
with p-methylbenzyl alcohol (Table 2, entries 21 and 22).
When 2-phenylethyl alcohol and 1-phenylethyl alcohol
were used as substrates, the activity and chemoselectivity
of the catalytic reaction could also be well maintained
(Table 2, entries 25, 27, 28, and 30). One-pot hydrogena-
tion and N-alkylation could also be carried out using
nitrobenzene and butanol as the substrate with moderate
to good catalytic activity and chemoselectivity (Table 2,
entries 31 and 32).
loss was detected with inductively coupled plasma optical
emission spectrometry (ICP-OES). Many excellent studies
have been reported on alcohols N-alkylation, and it is
necessary to compare our work with these reports
(Table S1). When compared with traditional thermal
catalysis (Table S1, entries 1–2), photocatalytic N-
alkylation could achieve high catalytic activity under
mild conditions (Table S1, entries 3–6). Recently, the
reaction substrate could be extended from aniline to
nitrobenzene (Table S1, entries 5–6). Furthermore, the N-
alkylation chemoselectivity could be easily switched by
adjust the base additive in this study.
In order to gain insight view about how the catalytic
system achieved highly efficient activation under the
visible-light irradiation, we employed the in situ diffuse
reflectance infrared Fourier transform spectroscopy
(DRIFTS) to dynamically observe and analyze the pri-
mary difference in activation of the catalytic system over
3%Pt/D-TiO /Ti C and 3%Pt/D-TiO @C with visible-
In the visible-light-induced 3%Pt/D-TiO /Ti C cata-
2
3
lytic system, the tandem reaction of aromatic nitro com-
pounds with alcohols to form N-alkylamines or N-
benzylideneanilines could also be extended to various
substrates (Table 2). Aromatic nitro compounds having
different substituents could be reacted with benzyl alco-
hol to prepare N-alkylamines or N-benzylideneanilines
on the irradiated 3%Pt/D-TiO /Ti C with good to excel-
2
3
2
2
light irradiation or heating (Figure 7). The baseline spec-
trum was tested before light irradiation or heating. The
following characteristic peaks weakening were obviously
observed in the DRIFTS between light irradiation and
2
3
lent activity and chemoselectivity. In comparison with
nitrobenzene, aromatic nitro compounds with different
substituents generally had a good catalytic activity; the
electron-donating group on the aromatic nitro compound
was more favorable for catalytic activity than the
electron-withdrawing group (Table 2, entries 3–12 vs. 13–
heating, such as the absorption of the telescopic vibration
À1
of the C–O bond in benzyl alcohol at about 1000 cm
,
the absorption of the in-plane deformation vibration of
hydroxyl group benzyl alcohol around 1200 cm , and
À1
1
8). When the aromatic nitro compounds had methyl
the absorption peak of the symmetrical stretching vibra-
substituent (Table 2, entries 3–8), the reactivity order, o-
nitrotoluene < m-nitrotoluene < p-nitrotoluene, should
be owing to the steric hindrance effect. Nitroanisole with
stronger electron-donating effect than nitrotoluene
exhibited higher catalytic activity (Table 2, entries 9–12).
tion as well as asymmetric stretching vibration of nitro
À1
group in nitrobenzene around 1500 and 1620 cm
,
[
54,55]
respectively.
Meanwhile, the absorption between
À1
3000 and 3700 cm was a telescopic vibration of the
hydroxyl group. In the presence of 3%Pt/D-TiO /Ti C
2
3
2

JIANG ET AL.
9 of 12
TABLE 2 Visible-light-induced catalytic performance for one-pot hydrogenation and N-alkylation of aromatic nitro compounds with
alcohols over 3%Pt/D-TiO /Ti
2
3
C
Entry
Substrates A/B
A conv. (%)
100.0
96.7
C sel. (%)
D sel. (%)
6.9
E sel. (%)
93.0
3.8
F (μmol)
95
1
Nitrobenzene/benzyl alcohol
0.1
1.2
16.6
-
a
2
Nitrobenzene/benzyl alcohol
95.0
12.1
81.0
10.0
97.7
9.0
86
3
o-Nitrotoluene/benzyl alcohol
o-Nitrotoluene/benzyl alcohol
m-Nitrotoluene/benzyl alcohol
m-Nitrotoluene/benzyl alcohol
p-Nitrotoluene/benzyl alcohol
p-Nitrotoluene/benzyl alcohol
2-Nitroanisole/benzyl alcohol
98.1
71.3
19.0
90.0
2.1
110
109
93
a
4
85.0
5
99.5
-
a
6
97.2
0.2
-
105
90
7
100.0
100.0
99.5
91.0
10.0
67.8
18.0
95.0
7.8
a
8
-
90.0
12.6
80.0
5.0
99
9
19.6
2.0
-
89
a
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
2-Nitroanisole/benzyl alcohol
86.1
95
4-Nitroanisole/benzyl alcohol
100.0
100.0
83.0
96
a
a
a
a
a
a
a
a
a
a
4-Nitroanisole/benzyl alcohol
-
92.2
20.5
85.5
20.0
97.5
12.1
80.0
10.0
77.2
8.0
100
81
o-Chloronitrobenzene/benzyl alcohol
o-Chloronitrobenzene/benzyl alcohol
p-Chloronitrobenzene/benzyl alcohol
p-Chloronitrobenzene/benzyl alcohol
p-Fluoronitrobenzene/benzyl alcohol
p-Fluoronitrobenzene/benzyl alcohol
Nitrobenzene/o-methylbenzyl alcohol
Nitrobenzene/o-methylbenzyl alcohol
Nitrobenzene/p-methylbenzyl alcohol
Nitrobenzene/p-methylbenzyl alcohol
Nitrobenzene/p-methoxybenzyl alcohol
Nitrobenzene/p-methoxybenzyl alcohol
Nitrobenzene/2-phenylethyl alcohol
Nitrobenzene/2-phenylethyl alcohol
Nitrobenzene/1-phenylethyl alcohol
Nitrobenzene/1-phenylethyl alcohol
Nitrobenzene/N-butanol
21.7
1.0
-
57.8
13.5
80.0
2.5
95.1
98
93.5
85
99.5
-
99
98.1
16.6
0.5
8.3
0.2
1.0
3.0
1.0
5.6
-
71.3
19.5
81.7
22.6
91.0
3.6
93
90.9
101
89
98.0
96.0
96
99.0
85
98.1
93.4
6.0
89
99.0
93.0
34.1
88.0
0.4
90
96.3
60.3
12.0
99.0
16.0
90.0
16.5
76.3
108
51
100.0
100.0
100.0
93.0
0.6
3.0
6.0
5.5
22.7
66
81.0
4.0
69
72
78.0
78.0
1.0
19
Nitrobenzene/N-butanol
100.0
36
Note: The reaction conditions were the same as in Table 1, entry 4.
a
3 4
KOH instead of K PO .
ꢀ
catalyst at 50 C, telescopic vibration of the C–O bond,
the in-plane deformation vibration of hydroxyl group, the
stretching vibration of nitro group, and the telescopic
vibration of hydroxyl group gradually decreased with the
increase of heating time, which should be related to the
substrate catalytic activation. On the other hand,
the decrease in the C–O bond telescopic vibration,
hydroxyl group in-plane deformation vibration, nitro
group stretching vibration, and hydroxyl group telescopic
ꢀ
vibration with visible-light irradiation at 25 C was much

10 of 12
JIANG ET AL.
FIGURE 7 In situ diffuse reflectance infrared Fourier
transform spectroscopy (DRIFTS) spectra for one-pot
hydrogenation and N-alkylation of nitrobenzene with benzyl
alcohol over 3%Pt/D-TiO
2 3 2 2
/Ti C and 3%Pt/D-TiO @C under
SCHEME 1 Proposed mechanism for visible-light-induced
catalytic performance of one-pot hydrogenation and N-alkylation of
nitrobenzene with benzyl alcohol over 3%Pt/D-TiO /Ti
visible-light irradiation or heating
2
3
C
faster than heating. When comparing the visible-light
illumination with heating in the catalyst system, the acti-
vation efficiency of visible-light irradiation promotion in
either the benzyl alcohol dehydrogenation or the nitro
group reduction was much faster than that of heating,
which should also be the key reason for the evident selec-
tive N-alkylation catalytic efficiency improvement under
benzyl alcohol and the H–H bond cleavage (④) was trans-
ferred to electron-rich Pt to form Pt hydride, and then the
selective hydrogenation of nitro was achieved (⑤). Imine
was formed through the condensation between in situ
generated benzaldehyde and aniline (⑥). Imine could be
further hydrogenated to N-alkyl amine with Pt hydride
(⑦). The interesting chemoselectivity switch to imine or
N-alkyl amine with KOH or K PO base additive might
visible-light irradiation; 3%Pt/D-TiO @C catalyst was
2
also tested under similar conditions. Without the Ti C
3
electron transporter, some difference in substrate activa-
tion was observed. Such as, the decrease in symmetrical
stretching vibration of nitro group in nitrobenzene
became not that obvious accompany with the hydroxyl
group telescopic vibration frequency reduction, which
indicated the decrease in the nitro group reduction
activation.
3
4
be related to the Pt hydride hydrogenation ability
adjusted by the basicity of photocatalytic system.
3 | CONCLUSIONS
Up on above observations, photo-induced one-pot
hydrogenation and N-alkylation of nitrobenzene with
benzyl alcohol over 3%Pt/D-TiO /Ti C was proposed
Two-dimensional transition metal carbide/carbonitride-
derived 3%Pt/D-TiO /Ti C heterojunction was prepared
2
3 2
by in situ grew TiO on Ti C nanosheets, S and N co-
2
3
2
2
3 2
(
Scheme 1). D-TiO /Ti C could be excited to generate
doped TiO with thiourea, and then Pt nanoparticles with
2
3
2
2
electrons and holes under visible-light irradiation.
Charge short-range directional transmission construction
small diameter well dispersed on D-TiO /Ti C ; 3%Pt/D-
2
3 2
TiO /Ti C showed excellent photocatalytic activity and
2
3 2
with the assistance of electron transporter Ti C along
chemoselectivity in the tandem reactions between aro-
matic nitro compounds and alcohols. Interestingly, the
3
with metal NPs supported on D-TiO /Ti C could lead to
2
3 2
efficient electron transfer from excited D-TiO /Ti C
3 2
chemoselectivity
to
N-alkyl
amines
or
N-
2
[37,56]
to metal NPs.
The formation of electron-rich Pt spe-
benzylideneanilines could be easily switched by adjust
the Pt hydride hydrogenation ability through the base
additive change from K PO to KOH under visible-light
cie was achieved by the transfer of photogenerated elec-
trons to Pt nanoparticles after visible-light irradiation of
3
4
3
%Pt/D-TiO /Ti C (①); conversion of benzyl alcohol to
irradiation. In contrast, 3%Pt/D-TiO @C exhibited
2
3
2
2
benzaldehyde undergone electron transfer from benzyl
alcohol to the D-TiO /Ti C along with benzyl alcohol
activation (②) follow up with oxidant-free C-H bond
cleavage to form benzaldehyde (③). Hydrogen from both
sharply decreased activity and chemoselectivity to N-
alkyl amines or N-benzylideneanilines. The photo-
catalytic performance difference was owing to the
improvement in photogenerated electron and hole
2
3 2

JIANG ET AL.
11 of 12
separation efficiency by means of short-range directional
charge transmission caused by the intimate contact
between the TiO and the conductive Ti C . This work
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This work was financially supported by Natural Science
Foundation Project of Chongqing (No. cstc2018jcyjAX0735,
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Innovation Support Program for Chongqing Overseas
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dation of China (No. 21201184), Ministry of Education of
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AUTHOR CONTRIBUTIONS
Heyan Jiang: Conceptualization; data curation; funding
acquisition; supervision. Meilin Sheng: Formal analysis;
methodology; software; validation. Yue Li: Formal analy-
sis; investigation; software; validation. Shuzhen Kong:
Funding acquisition; supervision. Fengxia Bian:
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The data that support the findings of this study are avail-
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ORCID
Heyan Jiang https://orcid.org/0000-0003-1239-7861
Meilin Sheng https://orcid.org/0000-0001-9394-5713
Yue Li https://orcid.org/0000-0002-4318-8037
Shuzhen Kong https://orcid.org/0000-0002-7512-8119
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