Multicomponent Pt-Based Zigzag Nanowires as Selectivity Controllers for Selective Hydrogenation Reactions

Article abstract of DOI:10.1021/jacs.8b03862

The selective hydrogenation of α, β-unsaturated aldehyde is an extremely important transformation, while developing efficient catalysts with desirable selectivity to highly value-added products is challenging, mainly due to the coexistence of two conjugated unsaturated functional groups. Herein, we report that a series of Pt-based zigzag nanowires (ZNWs) can be adopted as selectivity controllers for α, β-unsaturated aldehyde hydrogenation, where the excellent unsaturated alcohol (UOL) selectivity (>95%) and high saturated aldehyde (SA) selectivity (>94%) are achieved on PtFe ZNWs and PtFeNi ZNWs+AlCl₃, respectively. The excellent UOL selectivity of PtFe ZNWs is attributed to the lower electron density of the surface Pt atoms, while the high SA selectivity of PtFeNi ZNWs+AlCl₃ is due to synergy between PtFeNi ZNWs and AlCl₃, highlighting the importance of Pt-based NWs with precisely controlled surface and composition for catalysis and beyond.

Full text of DOI:10.1021/jacs.8b03862

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Communication
Multicomponent Pt-based Zigzag Nanowires as Selectivity
Controllers for Selective Hydrogenation Reactions
Shuxing Bai, Lingzheng Bu, Qi Shao, Xing Zhu, and Xiaoqing Huang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b03862 • Publication Date (Web): 20 Jun 2018
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Multicomponent Pt-based Zigzag Nanowires as Selectivity
Controllers for Selective Hydrogenation Reactions
Shuxing Bai,† Lingzheng Bu,† Qi Shao,† Xing Zhu,‡ and Xiaoqing Huang*†
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†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu, 215123, China.
‡Testing & Analysis Center, Soochow University, Jiangsu, 215123, China.
Supporting Information Placeholder
to enhance the performance of targeted reaction.15-20 Alt-
ABSTRACT: The selective hydrogenation of α, β-
hough high UOL and SA selectivity can be realized separate-
ly,21-24 the simultaneous realization of high UOL and SA se-
lectivity remains a great challenge.
unsaturated aldehyde is an extremely important transfor-
mation, while developing efficient catalysts with desirable
selectivity to highly value-added products is challenging,
mainly due to the coexistence of two conjugated unsaturated
functional groups. Herein, we report that a series of Pt-based
zigzag nanowires (ZNWs) can be adopted as selectivity con-
trollers for α, β-unsaturated aldehyde hydrogenation, where
the excellent unsaturated alcohol (UOL) selectivity (> 95%)
and high saturated aldehyde (SA) selectivity (> 94%) are
achieved on PtFe ZNWs and PtFeNi ZNWs+AlCl3, respective-
ly. The excellent UOL selectivity of PtFe ZNWs is attributed
to the lower electron density of the surface Pt atoms, while
the high SA selectivity of PtFeNi ZNWs+AlCl3 is due to syn-
ergy between PtFeNi ZNWs and AlCl3, highlighting the im-
portance of Pt-based NWs with precisely controlled surface
and composition for catalysis and beyond.
The selective hydrogenation of α, β-unsaturated aldehyde
to unsaturated alcohol (UOL) or saturated aldehyde (SA) is a
vital process in petrochemical, biological and chemical in-
dustries.1,2 Nevertheless, it is a very complex process since α,
β-unsaturated aldehyde has two unsaturated functional and
conjugated alkene bond (C=C) and carbonyl (C=O) groups.3,4
In general, owing to thermodynamic favoring of the C=C
hydrogenation over the C=O hydrogenation, it is extremely
difficult to achieve high selectivity of C=O hydrogenation.5,6
Moreover, when there is a bulky group or an extra unsaturat-
ed group conjugated with C=C, such as cinnamaldehyde
(CAL) and furfural, high selectivity for C=C hydrogenation
also becomes challenging.7
Figure 1. (a) HAADF-STEM image, (b, e) TEM images, (c)
XRD, (d) SEM-EDX, and (f) HRTEM image of Pt ZNWs.
Herein, we show that Pt-based zigzag nanowires (ZNWs)
can be serviced as the selectivity controllers for α, β-
unsaturated aldehyde hydrogenation. While the PtFe ZNWs
can represent excellent UOL selectivity, the PtFeNi ZNWs
exhibit promising SA selectivity by introducing AlCl3. Signifi-
cantly, the excellent activity of Pt-based ZNWs is well pre-
served. The excellent C=O hydrogenation selectivity of PtFe
ZNWs is due to the lower electron density of the surface Pt
atoms, and the high C=C hydrogenation selectivity of PtFeNi
ZNWs+AlCl3, in which PtFeNi ZNWs provide highly active
sites and AlCl3 is used as aldehyde protector.
Many researches about selective hydrogenation catalysts
for α, β-unsaturated aldehyde have been primarily centered
on platinum (Pt)-based catalysts, owing to their excellent
activity, while poor selectivity of pure Pt restricts their prac-
tical applications.8,9 The conventional methods to improve
the selectivity of UOL or SA are modifying the undesirable
active sites by surface ligands, thiolate, oxide or metal-
organic frameworks,1,3,6,10 while the selectivity improvement
is often accompanied by sacrificing activity.1,6 Pt-based alloy
catalysts become the focus of study, which usually offer the
synergistic effects to obtain high selectivity to desired prod-
ucts.11-14 Alloying 3d transition metal with Pt can particularly
alters the d-band center of surface Pt, which has been proved
The Pt-based ZNWs were made through a wet-chemical
process. Taken Pt ZNWs as example, platinum (II) acety-
lacetonate (Pt(acac)2), zinc (II) acetylacetonate (Zn(acac)2),
ribose and cetyltrimethyl ammonium chloride (CTAC) were
dissolved in the mixed solvent of oleylamine (OAm) and
diphenyl ether (DPE). The solution was gradually heated to
160 ºC and maintained for 5 h. The Pt ZNWs are uniform
with the diameter of ~12 nm, as confirmed by the high angle
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annular dark field scanning transmission electron microsco-
PtFe ZNWs (Figure S2).19 The ZNWs were confirmed by
HAADF-STEM and TEM images (Figure S2a-b). The diffrac-
tion peaks of PtFeNi ZNWs (Figure S2c) can be assigned to
fcc structure, while the 2θ of PtFeNi ZNWs shifts to higher
angle than that of fcc Pt3Fe, suggesting the formation of ter-
nary alloys of Pt, Fe, and Ni. The Pt/Fe/Ni atomic ratio of the
PtFeNi ZNWs is 52.3%/33.5%/14.2% (Figure S2d). The crys-
tallinity and high-index facet-bounded surface of PtFeNi
ZNWs were also confirmed by HRTEM (Figure S2e). The
STEM-EDS elemental mappings of PtFeNi ZNWs show that
the Pt, Fe, and Ni distribute evenly in the ZNWs (Figure 2g),
confirming the alloyed structure of the PtFeNi ZNWs.
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py (HAADF-STEM, Figure 1a) and TEM (Figure 1b) images.
Notably, the surface of these ZNWs represent the zigzag
borders.25,26 The X-ray diffraction (XRD) pattern (Figure 1c)
of Pt ZNWs is assigned to face-centered cubic (fcc) phase of
Pt (PDF No. 04-0802). The elemental compositions are
measured by scanning electron microscopy energy-dispersive
X-ray spectroscopy (SEM-EDX, Figure 1d), in which the
Pt/Zn atomic ratio is approaching to 100%/0%. Pt ZNWs can
only be obtained by introducing Zn(acac)2 (Figure S1). The
0.196 nm lattice spacing of Pt ZNWs corresponds to the (200)
facet of Pt, as confirmed by high-resolution TEM image
(HRTEM, Figure 1e-f), in which the steps and high-index
facets ({410}, {310}, {220}, and {210}) can be readily observed.27
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Figure 3. (a) Schematic CAL hydrogenation. CAL hydrogena-
tion performances of (b) Pt ZNWs, (c) PtFe ZNWs, and (d)
PtFeNi ZNWs+AlCl3.
Table 1. Selective hydrogenation by Pt-based ZNWs
catalysts.
Cata-
lyst
Substrate
Tem.
/°C
Time
/h
Con.
/%
Selectivity /%
UOL
SA
SOL
CAL
70
70
70
70
2.5
2
95.7
83.5
77.7
96.0
95.5
93.6
90.4
99.4
1.0
1.4
1.3
0.1
3.5
5.0
8.3
0.5
CAL[a]
CAL[b]
Furfural
PtFe
ZNWs
(3.4
2
3.5
wt%
Pt,
ICP)
Crotonalde
tonalde-
Figure 2. (a) HAADF-STEM image, (b) XRD, (c) SEM-EDX,
(d) HAADF-STEM image and elemental mappings, (e) TEM
image and (f) HRTEM image of PtFe ZNWs. (g) HAADF-
STEM elemental mappings of PtFeNi ZNWs.
40
4
88.3
80.3
2.4
17.3
Guaiacene
CAL
CAL[a]
70
70
70
70
70
5
92.7
94.5
94.4
95.2
95.6
90.0
0.5
0.4
-
1.3
8.7
4.6
6.2
6.8
1.2
3.5
3
94.9
93.4
93.2
98.8
PtFeNi
ZNWs+
AlCl3
(2.9
A synthetic strategy was also developed for PtFe ZNWs
(Supporting information for details). The product was char-
acterized by HAADF-STEM (Figure 2a), where 1D nanostruc-
tures with zigzag borders, average diameter of 12 nm and
length up to micrometers are clearly observed. The XRD pat-
tern of PtFe ZNWs (Figure 2b) matches well with that of fcc
Pt3Fe (PDF No. 29-0717).28 The Pt/Fe atomic ratio of the
ZNWs is 75.8%/24.2%, as determined by SEM-EDX (Figure
2c). Although the PtFe ZNWs have rough surface and zigzag
border, Pt and Fe distribute evenly in the whole ZNWs (Fig-
ure 2d). As shown in Figure 2e-f, the 0.194 nm lattice spac-
ing is assigned to the (200) facet of fcc Pt3Fe and many steps
and high-index facets are also observed.
CAL[b]
3
Furfural
2.5
-
wt%
Pt,
ICP)
Crotonalde
tonalde-
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1
99.5
-
99.9
0.1
Guaiacene
70
1.5
99.0
0.3
97.7
1.0
Selective hydrogenation of the 1st and 5th reaction
[a] [b]
rounds.
To explore catalytic behaviour of these ZNWs for α, β-
unsaturated aldehyde hydrogenation, we initially used CAL
as a model molecule (Figure S3). The widely used and easily
available TiO2 was selected as support (Figure S4).4 Firstly,
CAL is hydrogenated to cinnamyl alcohol (COL) or hydro-
cinnamaldehyde (HCAL), and subsequently generated to
hydrocinnamyl alcohol (HCOL) (Figure 3a). Pt ZNWs hy-
The trimetallic PtFeNi ZNWs can also be synthesized by
introducing additional Ni precursor into the preparation of
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drogenate CAL at 70 °C and 0.1 MPa H2 with selectivity for
PtFe ZNWs are below 5% after 5 h. However, PtFeNi
ZNWs+AlCl3 exhibit promising CAL hydrogenation behav-
iour, with the CAL conversion of 94.5%, HCAL selectivity of
94.9% after 3.5 h (Table 1). Indeed, the C=O stretching vibra-
tion (1692 cm-1) peak disappears after adding AlCl3 (Figure
S8), which ensures the high selectivity of C=C hydrogena-
tion.30 Other Lewis acids can also achieve similar results
(Figure S7c-d).
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COL/HCAL/HCOL of 38.1%/16.8%/45.1% at the CAL conver-
sion of 95.4% after 3.5 h (Figure 3b&Table S1). For compari-
son, the CAL conversion on Pt nanoparticles (NPs) and Pt
NWs with smooth surface (Figure S5) is only 46.0% and
66.4% after 5 h with poor selectivity (Figure S6a-b). Consid-
ering that the CAL conversion of Pt ZNWs (95.4%) is 2.2
folds higher than that of Pt NWs (43.1%) after 3.5 h, the zig-
zag surface structure of Pt ZNWs significantly enhances hy-
drogenation activity. We further examined the catalytic
properties of PtFe ZNWs and PtFeNi ZNWs (Figure
3c&Figure S6c). The PtFe ZNWs exhibit excellent COL selec-
tivity (Figure 3c), with COL selectivity of 95.5% at 95.7%
conversion after 2.5 h (Table 1). Furthermore, PtFeNi ZNWs
exhibit similar selectivity as Pt ZNWs, but higher CAL hy-
drogenation activity (Figure S6c). To assess the intrinsic
reactivity, turnover frequency (TOF) based on Pt was calcu-
lated.1 The TOF of PtFeNi ZNWs (244.9 h-1) is 2.8 and 2.5
folds higher than those of the Pt ZNWs (86.8 h-1) and PtFe
ZNWs (99.5 h-1) (Table S1).
To find out why the high selectivity of C=O and C=C hy-
drogenation obtained by PtFe ZNWs and PtFeNi
ZNWs+AlCl3, the COL and HCAL hydrogenations were ex-
plored over Pt ZNWs, PtFe ZNWs, PtFeNi ZNWs, and PtFeNi
ZNWs+AlCl3 (Figure 4a-b). To better evaluate performances,
the rate constant k was calculated from the rate equation
ln(C/C0) = kt (Figure S9). The ranking for k values of COL
hydrogenation is PtFe ZNWs (0.02) << Pt ZNWs (1.16) <
PtFeNi ZNWs (1.47) << PtFeNi ZNWs+AlCl3 (24.78) (Figure
4c&Table S2). In contrast, the ranking for k values of HCAL
hydrogenation is PtFeNi ZNWs+AlCl3 (0.01) << Pt ZNWs
(0.30) < PtFe ZNWs (0.46) < PtFeNi ZNWs (1.64) (Figure
4d&Table S3). The C=O hydrogenation k value ratio be-
tween PtFe ZNWs and Pt ZNWs is 1.5 and the k value ratio
between C=O and C=C hydrogenation on PtFe ZNWs is 23.0,
indicating that alloying Pt with Fe enhances C=O hydrogena-
tion, meanwhile, deactivates the C=C hydrogenation. While
the C=C hydrogenation k value ratio between PtFeNi ZNWs
and PtFe ZNWs is 73.5 and the k value ratio between C=O
and C=C hydrogenation on PtFeNi ZNWs+AlCl3 is 4.0×10-4,
suggesting the synergism of PtFeNi ZNWs and AlCl3 enhanc-
es the selectivity of C=C hydrogenation, in which PtFeNi
ZNWs provide highly active sites and AlCl3 is used as aldeꢀ
hyde protector (Figure S10).
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Since surface atoms of catalysts have critical influence on
the catalytic behaviour, the electronic properties of surface
Pt were characterized by X-ray photoelectron spectroscopy
(XPS) (Figure 4e). Pt 4f spectrum of Pt-based ZNWs clearly
demonstrates that there are mainly Pt0 with small portion of
Pt2+ on the surface.31,32 Compared with the binding energies
(BE) of Pt0 in Pt ZNWs (70.2 eV) and PtFeNi ZNWs (70.3 eV),
the higher BE in PtFe ZNWs (70.5 eV) indicates the lower
electron density of Pt, mainly caused by the electronic inter-
action between Fe and Pt. The variation tendency of both BE
of Pt0 and COL selectivity at ~ 50% conversion in Pt-based
NWs is similar (Figure 4f), indicating that the lower electron
density of surface Pt in PtFe ZNWs hinders the hydrogena-
tion of C=C, consequently to high selectivity of C=O hydro-
genation.1
Figure 4. (a) COL and (b) HCAL hydrogenation performanc-
es of Pt ZNWs, PtFe ZNWs, PtFeNi ZNWs, and PtFeNi
ZNWs+AlCl3. The rate constant k values of (c) COL and (d)
HCAL hydrogenation by Pt ZNWs, PtFe ZNWs, PtFeNi
ZNWs, and PtFeNi ZNWs+AlCl3. (e) Pt 4f XPS curves and (f)
Pt 4f5/2 BEs and COL selectivity of different ZNWs.
To further study the universality, we used the optimized
PtFe ZNWs and PtFeNi ZNWs+AlCl3 to catalyze other α, β-
unsaturated aldehyde hydrogenation (Table 1&Figure S11).
Significantly, we found that PtFe ZNWs and PtFeNi
ZNWs+AlCl3 are generally highly active and selective for
UOL and SA, respectively. For furfural hydrogenation, the
furfuryl alcohol selectivity is 99.4 % at 96.0% conversion by
using PtFe ZNWs (Figure S11a), whereas PtFeNi ZNWs+AlCl3
exhibits high tetrahydrofurfural selectivity (98.8%) at 95.6%
conversion (Figure S11b). Similar results are also obtained
for crotonaldehyde (Figure S11c-d) and guaiacene (Figure
S11e-f), where PtFe ZNWs and PtFeNi ZNWs+AlCl3 generate
high selectivity to the corresponding UOL and SA products.
Moreover, stability of PtFe ZNWs and PtFeNi ZNWs+AlCl3
was also explored. Both CAL conversion and selectivity for
Although thermodynamical favouring of the C=C hydro-
genation over the C=O hydrogenation, Pt-based materials
with high selectivity of C=C hydrogenation have been rarely
reported.7,29 Since the acid-base interaction between the
Lewis acid and C=O can inhibit C=O hydrogenation to alco-
hol,30 high selectivity of C=C group hydrogenation is ex-
pected to obtain by adding AlCl3 as C=O protector. After
adding Lewis acid, the performances of Pt ZNWs, PtFe ZNWs,
and PtFeNi ZNWs for CAL hydrogenation were investigated
(Figure S7&Figure 3d). CAL conversions on Pt ZNWs and
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COL and HCAL had limited changes after five reaction
rounds (Table 1&Figure S12) and no noticeable differences
in structure and surface property between fresh and used
catalysts (Figures S13-S15).
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To conclude, a series of Pt-based ZNWs were used as selec-
tive catalysts for α, β-unsaturated aldehyde hydrogenation.
The excellent selectivities for UOL and SA were successfully
realized by using the PtFe ZNWs and PtFeNi ZNWs+AlCl3 as
catalysts. The remarkable selectivity of PtFe ZNWs is at-
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ic interaction between Fe and Pt, and PtFeNi ZNWs+AlCl3 is
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
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Ed. 2005, 44, 5279.
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Experimental section, Figures S1−S15, and Tables S1−S3
(PDF)
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J.; Lu, G.; Huang, X. Adv. Mater. 2015, 27, 7204.
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J.; Guo, J.; Huang, X. Nat. Commun. 2016, 7, 11850.
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gaoka, Y.; Cao, Y. C. J. Am. Chem. Soc. 2011, 133, 14327.
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AUTHOR INFORMATION
Corresponding Author
hxq006@suda.edu.cn
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was financially supported by the Ministry of Sci-
ence and Technology (2016YFA0204100, 2017YFA0208200),
the National Natural Science Foundation of China (21571135),
Young Thousand Talented Program, Jiangsu Province Natu-
ral Science Fund for Distinguished Young Scholars
(BK20170003), and the Priority Academic Program Develop-
ment of Jiangsu Higher Education Institutions (PAPD).
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