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ChemComm
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COMMUNICATION
Journal Name
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atomic-level and maintaining the multi-channel structure and
high specific surface area of ZIF-8 for the HD-Ni/N-CMS
catalyst to promote the aqueous-phase HDO of vanillin.
(a) 100
(b)
HMP
MMP
100
100
80
60
40
20
0
HD-Ni/N-CMS
Ni-CNT/NC
Ni-NPs/NC
97.1
87.8
75
50
25
0
0
2
4
6
8
10
HD-Ni/N-CMS Ni-CNT/NC Ni-NPs/NC
Reacton Time (h)
(d)
1041.7
(c)
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
HD-Ni/N-CMS
Ni-CNT/NC
Ni-NPs/NC
1000
800
600
400
200
0
KHD-Ni/NC/KNi-CNT/NC=4
KHD-Ni/NC/KNi-NPs/NC=17
357.1
84.4
HD-Ni/N-CMS Ni-CNT/NC Ni-NPs/NC
0
2
4
6
8
10
Reaction Time (h)
Fig. 4 Catalytic evaluation of HD-Ni/N-CMS, Ni-CNT/NC and Ni-NPs/NC toward convert
vanillin to MMP. (a) Conversion vs reaction time, (b) product selectivity for 10 h, (c) ln
(C0,vanillin/C) vs reaction time, (d) TOF value determined as moles of initial vanillin
converted per mole of exposed active sites per hour in dynamic range. (Reaction
conditions: vanillin/Ni (substrate/catalyst) molar ratio of S/C = 300, defined amount of
water, 130 oC, 2.0 MPa H2).
Moreover, the TOF based on Ni and vanillin conversion was
measured at the initial reaction stage (Fig. 4d). The TOF value
of HD-Ni/N-CMS was 1041.7 h-1, which was 3 and 12 times
higher than that of the Ni-CNT and Ni-NPs/NC. This TOF value
was far larger than that of the conventional Ni/AC catalyst.5a
In summary, we successfully synthesized a HD-Ni/N-CMS
catalyst by a simple thermal ionic-exchange method using ZIF-
8 as a sacrificed template, in which Ni ion exchanged with Zn
nodes during pyrolysis. The unique morphological and
electronic structures of the HD-Ni/N-CMS catalyst were
verified by HAADF-STEM, and XANES. Compared with Ni-
CNT/NC and Ni NPs/NC, the HD-Ni/N-CMS catalyst was capable
of highly selective HDO of vanillin with excellent activity and
aqueous-phase stability. This was mainly caused by the high
dispersion at Ni atomic level via Ni-N coordination, thus
ensuring a high metal-atom utilization, as well as retaining the
original structure of ZIF-8 by N-CMS. Importantly, the derived
zeolite-type N-CMS supplied large surface area and abundant
pore channel, which could create a favourable reaction micro-
environment benefiting aqueous-phase reaction and
overcoming poor stability of traditional carbon-based catalysts.
The discovery of this type of catalyst shed light on rational
design of highly efficient atomically dispersed non-noble metal
catalysts for practical industrial application.
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Grant Nos. 51871209, and
51502297).
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Notes and references
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4 | J. Name., 2012, 00, 1-3
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